Metal oxide particles having a core-shell structure and a method for producing the same

Abstract

The present invention provides: modified metal oxide particles which each have, as a core, metal oxide particles containing titanium oxide and each have, as a shell covering the core, particles of a metal oxide other than titanium oxide, and in which the cores are partially exposed; and a method for producing the modified metal oxide particles.　The core-shell type metal oxide particles each include: a core containing metal oxide particles that have an average primary particle diameter of 3-100 nm; and a shell containing metal oxide particles that have an average primary particle diameter of 1-7 nm and that cover the core surfaces. Said average primary particle diameters have a relationship of (metal oxide particles of the cores) > (metal oxide particles of the shells). When component (a) is titanium oxide and component (b) is a metal oxide other than titanium oxide, the cores are formed of particles comprising component (a) or a combination of component (a) and component (b), and the shells are formed of particles comprising component (b). The mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) is in the range of 0.05-1.0.

Description

[Technical field]

[0001] The present invention relates to modified metal oxide particles in which metal oxide particles containing titanium oxide serve as a core and are coated with metal oxide particles other than titanium oxide, and to a method for producing the particles. [Background technology]

[0002] Plastic molded products are used in large quantities due to their advantages such as light weight, ease of processing, and impact resistance, but on the other hand, they have practical shortcomings for use as eyeglass lenses, window materials, etc., due to insufficient hardness, susceptibility to scratches, susceptibility to solvent attack, electrostatic charge and dust attraction, insufficient heat resistance, etc. Therefore, it has been proposed to apply a protective coating to the plastic molded product. A large number of types of coating solutions for forming the protective coating have been proposed.

[0003] A coating solution for forming a film, whose main component (resin component or coating film-forming component) is an organosilicon compound or its hydrolysate, is used for forming a hard coating film similar to that of an inorganic system for eyeglass lenses (see Patent Document 1).

[0004] Since the scratch resistance of the above-mentioned coating solution for forming a film is still unsatisfactory, a solution containing colloidally dispersed silica sol has been proposed and has been put to practical use for eyeglass lenses (see Patent Document 2).

[0005] Incidentally, conventional plastic eyeglass lenses have mostly been manufactured by casting polymerization of diethylene glycol bisallyl carbonate monomer. This lens has a refractive index of about 1.50, which is lower than the refractive index of glass lenses, which is about 1.52, and therefore has the disadvantage that the edge thickness becomes thick in the case of lenses for myopia. For this reason, 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 (see Patent Documents 3 and 4).

[0006] For such high refractive index resin lenses, a method has been proposed in which a colloidal dispersion of metal oxide fine particles of Sb or Ti is used as a coating material (see Patent Documents 5 and 6).

[0007] Also disclosed is a coating composition consisting of a silane coupling agent and a stable modified metal oxide sol having a primary particle size of 2 to 100 nm, which contains a colloidal particle (a) of a metal oxide having a primary particle size of 2 to 60 nm as a core, and a coating material (b) of an acidic oxide colloidal particle (c) obtained by coating the surface of the colloidal particle (a) with the acidic oxide colloidal particle (b), and contains (c) at a ratio of 2 to 50 mass% in terms of metal oxide. As a specific example of the colloidal particle used, a modified titanium oxide-zirconium oxide-stannic oxide composite colloid coated with alkylamine-containing antimony pentoxide and the like are disclosed (see Patent Document 7). Also disclosed is a titanium oxide-stannic oxide-zirconium oxide composite colloid stabilized with alkylamine and oxycarboxylic acid and the like (see Patent Document 8). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 52-16586 [Patent Document 2] Japanese Patent Application Publication No. 53-111336 [Patent Document 3] Japanese Patent Application Publication No. 55-13747 [Patent Document 4] Japanese Patent Application Publication No. 64-54021 [Patent Document 5] Japanese Patent Application Publication No. 62-151801 [Patent Document 6] Japanese Patent Application Publication No. 63-275682 [Patent Document 7] JP 2001-123115 A [Patent Document 8] Japanese Patent Application Publication No. 10-306258 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention provides modified metal oxide particles, which are core-shell type metal oxide particles used in compositions for obtaining coatings with a high refractive index and high moldability, for example, for nanoimprinting, and which have a core made of metal oxide particles containing titanium oxide and a shell made of metal oxide particles other than titanium oxide, with the core being covered with a part of the core being exposed, and a method for producing the same. [Means for solving the problem]

[0010] According to a first aspect, the present invention provides core-shell type metal oxide particles including a core containing metal oxide particles having an average primary particle diameter of 3 to 100 nm and a shell covering a surface of the core containing metal oxide particles having an average primary particle diameter of 1 to 7 nm, wherein the average primary particle diameters satisfy a relationship of (core metal oxide particles)>(shell metal oxide particles), When component (a) is titanium oxide and component (b) is a metal oxide other than titanium oxide, the core is a particle made of component (a) or a combination of component (a) and component (b), The shell is a particle made of component (b). Requirements A and B below: Requirement A: In a test in which the core-shell metal oxide particles are brought into contact with a compound having a P-OH bond, the formation of a PO-Ti bond in the core-shell metal oxide particles is observed by NMR, Requirement B: The refractive index of the core-shell metal oxide particles is 1.85 or more. The core-shell metal oxide particles satisfy the above requirements. As a second aspect, the core-shell type metal oxide particle according to the first aspect, wherein the component (b) is at least one metal oxide particle selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide; As a third aspect, the core-shell type metal oxide particle according to the first aspect or the second aspect, in which the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) is in the range of 0.05 to 1.0. As a fourth aspect, the core-shell metal oxide particle according to any one of the first to third aspects, in which an intermediate layer is present between the core particle and the shell particle, the intermediate layer being metal oxide particles comprising a combination of at least one selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide as component (D), and the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) is in the range of 0.05 to 1.0; As a fifth aspect, the core-shell type metal oxide particles according to any one of the first to fourth aspects, in which the surfaces of the core-shell type metal oxide particles are coated with a compound having a P-OH bond or a Si-OH bond. As a sixth aspect, a compound having a Si—OH bond is represented by any one of formulas (1) to (3):

[0011] [ka]

[0012] (In formula (1), R 1 each represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom by a Si-C bond; R 2 each represents an alkoxy group, an acyloxy group, or a halogen group; a represents an integer of 1 to 3; In formula (2) and formula (3), R 3 and R 5 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom via a Si-C bond; R 4 and R 6 each represents an alkoxy group, an acyloxy group, or a halogen group, Y represents an alkylene group, an NH group, or an oxygen atom, b is an integer of 1 to 3, c is an integer of 0 or 1, and d is an integer of 1 to 3.) The core-shell type metal oxide particle according to any one of the first to fifth aspects, which is at least one silane compound selected from the group consisting of: As a seventh aspect, a compound having a P-OH bond is represented by any one of formulas (4) to (6):

[0013] [ka]

[0014] (In formulas (4) to (6), X 1 , X 2 , and X 3 each represents an alkylene group having 2 to 20 carbon atoms; f, h, and j each represent an integer of 1 to 100; e, g, and i each represent an integer of 1 to 3; Y 1 , Y 2 , and Y 3 each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a (meth)acrylic group. As an eighth aspect, the core-shell type metal oxide particles according to the seventh aspect, in which the phosphate ester is a polyoxyethylene alkyl (C6-20) ether phosphate ester having an alkyl group having 6 to 20 carbon atoms; As a ninth aspect, a core-shell type metal oxide sol in which the core-shell type metal oxide particles according to any one of the first to eighth aspects are dispersed as a dispersoid in a dispersion medium made of an alcohol, an ester, a ketone, an amide, a hydrocarbon, a silicone, a compound containing an unsaturated bond between linear carbon atoms, an oxirane compound, water, or a combination thereof, which may have an ether bond, and which has an average particle size of 5 to 500 nm as measured by a dynamic light scattering method; According to a tenth aspect, there is provided a core-shell metal oxide sol according to the ninth aspect, which further comprises a surfactant, and the surfactant is an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant. as an eleventh aspect, the core-shell metal oxide sol according to the ninth aspect or the tenth aspect, further containing a secondary amine or a tertiary amine having a total of 5 to 35 carbon atoms; According to a twelfth aspect, there is provided a varnish comprising the core-shell metal oxide particles according to any one of the first to eighth aspects and a thermosetting or photocurable resin. as a thirteenth aspect, the varnish according to the twelfth aspect, which is a hard coating agent or a composition for nanoimprints; As a fourteenth aspect, a method for producing a method comprising the steps of (i) and (ii) below: Step (i): preparing a sol (A) containing metal oxide particles having an average primary particle diameter of 3 to 60 nm as measured by nitrogen gas adsorption and a water-based dispersion medium, and a sol (B) containing metal oxide particles having an average primary particle diameter of 1 to 7 nm as measured by nitrogen gas adsorption and a water-based dispersion medium; Step (ii): mixing the sol (A) and the sol (B) at a rate of 22 to 1000 parts by mass per minute of the solid content of one sol added to the container per 100 parts by mass of the solid content of the other sol; A method for producing a core-shell metal oxide sol according to any one of the ninth to eleventh aspects, As a fifteenth aspect, in the step (i) or (ii), Step (S-1): adding a secondary amine or a tertiary amine having a total of 5 to 35 carbon atoms to an aqueous sol; The method for producing a core-shell metal oxide sol according to a fourteenth aspect, As a sixteenth aspect, the method for producing a core-shell metal oxide sol according to the fourteenth aspect or the fifteenth aspect further comprises adding at least one step selected from the step (T-1), the step (T-2), and the step (T-3) after the step (ii); Step (T-1): adding at least one silane compound selected from the group consisting of formulas (1) to (3) or at least one phosphoric acid ester selected from the group consisting of formulas (4) to (6) to the core-shell metal oxide sol obtained in step (ii); Step (T-2): A step of replacing the dispersion medium of the core-shell type metal oxide sol obtained in step (ii) with a dispersion medium comprising an alcohol, an ester, a ketone, an amide, or a hydrocarbon; Step (T-3): adding a surfactant to the core-shell metal oxide sol obtained in step (ii); and As a seventeenth aspect, there is provided a method for producing a core-shell metal oxide sol according to any one of the fourteenth to sixteenth aspects, in which the steps are step (i), step (S-1), step (ii), step (S-1), step (T-2), step (T-1), and step (T-2), in that order. Effect of the Invention

[0015] The present invention provides modified metal oxide particles in which metal oxide particles containing titanium oxide serve as a core and the core is coated with metal oxide particles other than titanium oxide serve as a shell. Titanium dioxide has a high refractive index and is therefore used as a high refractive index material. However, because titanium dioxide particles have high photoactivity, when mixed with various binders or resin components as a matrix component, they can cause discoloration or deterioration of the matrix components.

[0016] In order to suppress photoactivity, modified core-shell metal oxide particles have been proposed by coating titanium oxide particles with metal oxide particles other than titanium oxide. When titanium oxide particles or metal oxide particles containing titanium oxide particles, which are the cores of the core-shell metal oxide particles, are coated with metal oxide particles other than titanium oxide, which are the shells, the proportion of titanium oxide components decreases due to complete coating, and the refractive index of the core-shell metal oxide particles may not be improved.

[0017] In the present invention, in order to maintain a high refractive index in the core-shell type metal oxide particles, the core particles are not completely covered with shell particles, but rather, core-shell type modified metal oxide particles are provided in which a part of the core particle surface is exposed. The fact that a part of the core is exposed means that in a test in which the core-shell type metal oxide particles are brought into contact with a compound having a P-OH bond, the formation of a PO-Ti bond in the core-shell type metal oxide particles is confirmed.31 By observing the P-NMR spectrum, it can be determined that a PO-Ti bond is present, and it can be confirmed that the particles are core-shell type metal oxide particles with part of the core exposed.

[0018] In the core-shell type metal oxide particles of the present invention, the core-shell type metal oxide particles having a part of the core particle surface exposed are such that when particle A having a part of the exposed core particle surface and a similar particle B are coated on a substrate or on the unevenness of the substrate surface, the exposed part of the core particle interacts with a part of the shell particle, and the coated or filled material functions as an integrated mass, and for example, in the case of a coating on a substrate, the weather resistance is improved.

[0019] Furthermore, when a high refractive index material is produced by combining a core particle having a higher refractive index than the shell particle and a shell particle having a lower refractive index than the core particle, a sol containing core-shell metal oxide particles in which a portion of the core particle surface is exposed does not contain excess shell particles, and therefore when such a sol is used to produce a coating or filling, a decrease in the refractive index of the coating or filling after curing can be suppressed. In the present invention, the refractive index of the core-shell type metal oxide particles is 1.85 or more, and for example, a range of 1.85 to 2.30 can be obtained. [Brief description of the drawings]

[0020] [Figure 1] 31P-NMR spectrum of the core-shell metal oxide particles in the methanol solvent dispersion sol used in Example 1, confirming the presence or absence of PO-Ti bonds by 31P-NMR. [Diagram 2] 31P-NMR spectrum of metal oxide particles having only the core in the methanol solvent dispersion sol used in Comparative Example 1, confirming the presence or absence of PO-Ti bonds by 31P-NMR. [Diagram 3] 31P-NMR spectrum of the core-shell metal oxide particles in the methanol solvent dispersion sol used in Comparative Example 3, confirming the presence or absence of PO-Ti bonds by 31P-NMR. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present invention relates to core-shell metal oxide particles comprising a core containing metal oxide particles having an average primary particle diameter of 3 to 60 nm and a shell covering the surface of the core containing metal oxide particles having an average primary particle diameter of 1 to 7 nm, wherein the average primary particle diameters satisfy the relationship of (core metal oxide particles)>(shell metal oxide particles), When component (a) is titanium oxide and component (b) is a metal oxide other than titanium oxide, the core is a particle made of component (a) or a combination of component (a) and component (b), The shell is a particle made of component (b). Requirements A and B below: Requirement A: In a test in which the core-shell metal oxide particles are brought into contact with a compound having a P-OH bond, the formation of a PO-Ti bond in the core-shell metal oxide particles is observed by NMR, Requirement B: The refractive index of the core-shell metal oxide particles is 1.85 or more. The core-shell type metal oxide particles satisfy the above condition. In the present invention, the refractive index of the core-shell type metal oxide particles is 1.85 or more, and for example, core-shell type metal oxide particles having a refractive index in the range of 1.85 to 2.30 can be obtained.

[0022] The component (a) can be titanium oxide, and the component (b) can be at least one type of metal oxide particle selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide.

[0023] The core particle is preferably a particle composed of component (a) or a combination of components (a) and (b), and examples thereof include titanium oxide particles, composite particles of titanium oxide particles and tin oxide particles, composite particles of titanium oxide particles and zirconium oxide particles, and composite particles of titanium oxide particles, tin oxide particles and zirconium oxide particles.

[0024] The shell particles are preferably particles made of component (b), and can be, for example, particles of at least one metal oxide selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide.

[0025] For example, core-shell metal oxide particles consisting of a combination of a core particle and a shell particle include combinations of core particle / shell particle such as titanium oxide particle / composite particle of tin oxide and silicon dioxide, composite particle of titanium oxide and tin oxide / composite particle of tin oxide and silicon dioxide, composite particle of titanium oxide particle and zirconium oxide particle / composite particle of tin oxide and silicon dioxide, composite particle of titanium oxide particle, tin oxide particle and zirconium oxide particle / composite particle of tin oxide and silicon dioxide, titanium oxide particle / antimony oxide particle, and composite particle of titanium oxide and tin oxide / antimony oxide particle.

[0026] The core-shell type metal oxide particles are obtained with a mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) in the range of 0.05 to 1.0, or 0.1 to 1.0, or 0.15 to 1.0.

[0027] In the present invention, an intermediate layer is present between the core particle and the shell particle, and the intermediate layer is a metal oxide particle composed of a combination of at least one selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide as component (D), and the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) can be set in the range of 0.05 to 1.0, or 0.1 to 1.0, or 0.15 to 1.0. Core-shell type metal oxide particles and metal oxide particles having an intermediate layer between a core particle and a shell particle are characterized in that, in a test in which the oxide particles are brought into contact with a compound having a P-OH bond, the formation of a PO-Ti bond is observed in the metal oxide particles. 31This is observed by P-NMR spectrum. This indicates that there is a PO-Ti bond between the core particle and the compound having a P-OH bond, and it can be confirmed that the core is a core-shell type metal oxide particle with a part of the core exposed. This indicates that the core is a partly exposed particle in the core-shell type metal oxide particle and the metal oxide particle in which an intermediate layer exists between the core particle and the shell particle.

[0028] Examples of metal oxide particles used for the core include titanium oxide, a composite oxide of titanium oxide-tin oxide, a composite oxide of titanium oxide-zirconium oxide, and a composite oxide of titanium oxide-zirconium oxide-tin oxide, which have an average primary particle diameter of 5 to 500 nm, 5 to 300 nm, 5 to 250 nm, or 5 to 60 nm, and preferably 3 to 100 nm, 3 to 80 nm, 3 to 60 nm, 3 to 40 nm, 3 to 20 nm, or 5 to 40 nm, as determined by observation with a transmission electron microscope. For example, the metal oxide particles used for coating can be at least one metal oxide particle selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide, which have an average primary particle size of 1 to 10 nm, 1 to 7 nm, or 1 to 5 nm as observed with a transmission electron microscope.

[0029] Examples of the metal oxide particles include metal oxide particles in which the above-mentioned silicon dioxide, tin oxide, antimony oxide, tungsten oxide, aluminum oxide, and zirconium oxide are present alone, or composite metal oxide particles in which the above-mentioned metal oxides are combined and bonded together. Examples of the composite metal oxide particles include composite metal oxide particles of tin oxide-silicon dioxide, composite metal oxide particles of tin oxide-zirconium oxide-silicon dioxide, composite metal oxide particles of tin oxide-tungsten oxide-silicon dioxide, composite metal oxide particles of antimony oxide-silicon dioxide, etc. When the metal oxide particles used for coating contain silicon dioxide, the ratio of silicon dioxide to other metal oxides can be set to a mass ratio of (silicon dioxide) / (other metal oxide) of 0.1 to 5.0.

[0030] When a core-shell structure is used, coating with a metal oxide component different from the metal oxide of the core or with metal oxide particles having a different metal oxide content can include cases in which the metal oxide components of the core and the coating are different, or cases in which the metal oxide components of the core and the coating partially overlap but the compounding ratio of the metal oxides is different. In the case of a core-shell structure, the mass ratio of the core metal oxide particle to the coated metal oxide particle can be set in the range of (coated metal oxide particle) / (core metal oxide particle)=0.05 to 0.40. For example, in the case of a composite oxide of tin oxide-silicon dioxide used for coating, sodium stannate or potassium stannate can be used as the alkali stannate, with sodium stannate being preferred.

[0031] As the alkali silicate, sodium silicate and potassium silicate can be used. The alkali stannates and alkali silicates are prepared as aqueous solutions containing a silicon dioxide / stannic oxide weight ratio of 0.1 to 5, and the cations present in the aqueous solution can then be removed by cation exchange resins. The alkali stannate and alkali silicate are dissolved in water so that the mass ratio of silicon dioxide to stannic oxide is 0.1 to 5.0. The preferred solid concentration of the aqueous solution is (SnO 2 +SiO 2 ) is 1 to 12 mass %. The prepared aqueous solution is subjected to removal of cations using a cation exchange resin. As the cation exchange resin, a hydrogen-type strongly acidic cation exchange resin is preferable, and for example, Amberlite (trade name) 120B or the like can be used by packing it in a column. By carrying out this cation exchange, the silicic acid component and the stannic acid component are polymerized, and silicon dioxide-stannic oxide composite colloidal particles having an average primary particle size of 1 to 4 nm can be produced.

[0032] The silicon dioxide-stannic oxide composite colloidal particles are poorly stable and will gel within a few hours if left to stand. Therefore, after the cation exchange, an amine compound is promptly added to stabilize the colloidal particles, and the mass ratio of silicon dioxide / stannic oxide is 0.1 to 5.0 and M / (SnO 2 +SiO 2 It is necessary to obtain an aqueous sol of silicon dioxide-stannic oxide composite oxide colloidal particles having an average primary particle size of 1 to 4 nm stabilized by an amine compound present in a molar ratio of (SnO 2 +SiO 2 ) is 0.1 to 10 mass %. The stabilization of the silicon dioxide-stannic oxide composite colloidal particles produced by the cation exchange is carried out by using M / (SnO 2 +SiO 2 It is appropriate to add the amine compound in an amount such that the molar ratio of M / (SnO) (wherein M represents an amine compound) is 0.1 to 1.0. 2 +SiO 2 Addition of an amine compound having a molar ratio of 0.1 to less than 1.0 is not preferred because the composition loses stability and gels after standing for several hours.

[0033] Next, an aqueous sol of colloidal particles (a) of a metal oxide used for the core having an average primary particle size of 5 to 60 nm and an aqueous sol of colloidal particles (b) of a silicon dioxide / stannic oxide having a mass ratio of 0.1 to 5.0 and an M / (SnO 2 +SiO 2 ) (wherein M represents an amine compound) in a molar ratio of 0.05 to 0.40, an aqueous sol of modified metal oxide colloid particles in which the metal oxide colloid particles (a) are coated with the silicon dioxide-stannic oxide composite oxide colloid particles (b) can be obtained by mixing the silicon dioxide-stannic oxide composite oxide colloid particles (b) used for the shell having an average primary particle size of 1 to 4 nm stabilized with an amine compound in a molar ratio of 0.05 to 0.40, the mass ratio of the silicon dioxide-stannic oxide composite oxide colloid particles to the metal oxide colloid particles being (b) / (a). The aqueous sol of the metal oxide colloid particles (a) has a solid content concentration of 0.5 to 50% by mass, and preferably 5 to 30% by mass.

[0034] The aqueous sol of the metal oxide colloidal particles (a) can have a pH of 5 to 11.5, preferably 7 to 11.5. The pH of the aqueous sol can be adjusted as necessary with an alkaline component, and examples of the alkaline component include hydroxides of alkali metals such as lithium, sodium, and potassium, hydroxides of alkaline earth metals such as calcium, magnesium, and strontium, ammonia, alkylamines such as ethylamine, triethylamine, isopropylamine, and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine, and quaternary ammonium hydroxides. The aqueous sol of the metal oxide colloidal particles (a) and the aqueous sol of the coated particles (b) are preferably mixed under stirring.

[0035] The mixing ratio of the silicon dioxide-stannic oxide composite oxide colloid particles (b) to the metal oxide colloid particles (a) is preferably 0.05 to 0.40 as a mass ratio (b) / (a), and if it is less than 0.05, the metal oxide colloid particles (a) as the core cannot be sufficiently covered with the silicon dioxide-stannic oxide composite oxide colloid particles (b), and a stable hydrophilic organic solvent dispersion sol or a hydrophobic organic solvent dispersion sol having a water solubility of 0.05 to 12 mass% cannot be obtained. Moreover, if the mass ratio is 0.40 or more, it is sufficient and there is a possibility that complete coverage can be achieved. The resulting aqueous sol of modified metal oxide colloidal particles is then subjected to cation exchange, preferably using a hydrogen-type strongly acidic cation exchange resin.

[0036] Next, the resulting aqueous sol was mixed with the silicon dioxide-stannic oxide composite oxide colloidal particles (b) in a molar ratio of M / (SnO 2 +SiO 2The amount of the amine compound added is such that the ratio M / (SnO 2 +SiO 2 When the molar ratio of M / (SnO) is less than 0.001, the dispersion stability of the hydrophilic organic solvent dispersion sol of the present invention becomes insufficient, which is not preferable. 2 +SiO 2 If the molar ratio of ) exceeds 0.08, when a silane compound is to be bonded to the particle surface of the modified metal oxide colloidal particles, bonding may be hindered. The metal oxide particles of the present invention are obtained via a metal oxide sol. The metal oxide sol can be obtained by the following method.

[0037] The following steps (i) and (ii): Step (i): preparing a sol (A) containing metal oxide particles having an average primary particle diameter of 3 to 60 nm as measured by nitrogen gas adsorption and a water-based dispersion medium, and a sol (B) containing metal oxide particles having an average primary particle diameter of 1 to 7 nm as measured by nitrogen gas adsorption and a water-based dispersion medium; and (ii) mixing the sol (A) and the sol (B) at a rate of 22 to 1,000 parts by mass, 22 to 500 parts by mass, or 22 to 100 parts by mass of the solid content of one sol added to the container per 100 parts by mass of the solid content of the other sol loaded in the container. Sol (A) is an aqueous sol containing the above-mentioned core particles, and sol (B) is an aqueous sol containing the above-mentioned shell particles. In the present invention, the above step (i) or step (ii) can further include step (S-1): a step of adding a secondary amine or tertiary amine having a total of 5 to 35 carbon atoms to the aqueous sol.

[0038] In the present invention, at least one step selected from steps (T-1), (T-2), and (T-3) can be added after the step (ii) above. Step (T-1) is a step of adding at least one silane compound selected from the group consisting of formulas (1) to (3) or at least one phosphoric acid ester selected from the group consisting of formulas (4) to (6) to the core-shell metal oxide sol obtained in step (ii). The step (T-2) is a step of replacing the dispersion medium of the core-shell type metal oxide sol obtained in the step (ii) with a dispersion medium consisting of an alcohol, an ester, a ketone, an amide, or a hydrocarbon. The step (T-3) is a step of adding a surfactant to the core-shell metal oxide sol obtained in the step (ii).

[0039] In the present invention, the steps can be arranged in the order of step (i), step (S-1), step (ii), step (S-1), step (T-2), step (T-1), and step (T-2).

[0040] In addition, the (T-3) step can be added to any step.

[0041] The present invention may further contain a secondary amine or tertiary amine having a total of 5 to 35 carbon atoms. The above amine content is the SiO 2 The concentration can be set to 0.01 to 10.0 mmol, or 0.01 to 5.0 mmol per 100 g. Examples of the secondary amine include ethyl-n-propylamine, ethylisopropylamine, dipropylamine, diisopropylamine, ethylbutylamine, n-propylbutylamine, dibutylamine, ethylpentylamine, n-propylpentylamine, isopropylpentylamine, dipentylamine, ethyloctylamine, i-propyloctylamine, butyloctylamine, dioctylamine, and the like.

[0042] Examples of the tertiary amine include triethylamine, ethyl di-n-propylamine, diethyl n-propylamine, tri-n-propylamine, triisopropylamine, ethyl dibutylamine, diethyl butylamine, isopropyl dibutylamine, diisopropyl ethylamine, diisopropyl butylamine, tributylamine, ethyl dipentylamine, diethyl pentylamine, tripentylamine, methyl dioctylamine, dimethyl octylamine, ethyl dioctylamine, diethyl octylamine, trioctylamine, benzyl dibutylamine, and diazabicycloundecene. Among the above amines, secondary amines and tertiary amines having an alkyl group having a total of 6 to 35 carbon atoms are preferred, and examples thereof include diisopropylamine, tripentylamine, triisopropylamine, dimethyloctylamine, and trioctylamine.

[0043] In the present invention, the silane compound is a silane coupling agent, and the silane coupling agent can be used to coat the photoactive metal oxide particles (A) with a hydrolysate of at least one silane compound selected from the group consisting of formulas (1) to (3). The obtained hydrophilic organic solvent dispersion sol can be coated with a hydrolyzate of at least one silane compound selected from the group consisting of formulas (1) to (3). In formula (1), R 1 each represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom by a Si-C bond; R 2 each represents an alkoxy group, an acyloxy group, or a halogen group; a represents an integer of 1 to 3; In formula (2) and formula (3), R 3 and R 5 are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom via a Si-C bond; R 4 and R6 each represents an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

[0044] The alkyl group is an alkyl group having 1 to 18 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl- n-Propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl cyclopropyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of the cyclopropyl group include, but are not limited to, 3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. Furthermore, examples of the alkylene group include alkylene groups derived from the above-mentioned alkyl groups.

[0045] The aryl group is an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracene group, and a pyrene group. The alkenyl group is an alkenyl group having 2 to 10 carbon atoms, and examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3 Examples of the aryl group include, but are not limited to, 1-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, and 2-methyl-2-pentenyl group.

[0046] The alkoxy group includes an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, and an n-hexyloxy group, but is not limited to these.

[0047] Examples of the acyloxy group having 2 to 10 carbon atoms include, but are not limited to, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, and a 2-methyl-n-pentylcarbonyloxy group. The halogen group includes fluorine, chlorine, bromine, iodine, and the like.

[0048] An example of an organic group having a polyether group is a polyetherpropyl group having an alkoxy group. For example, (CH 3 O) 3 Silicon Carbide 3 H 6 (OC 2 H 4 )nOCH 3The range of n is from 1 to 100 or from 1 to 10. Examples of the organic group having an epoxy group include a 2-(3,4-epoxycyclohexyl)ethyl group and a 3-glycidoxypropyl group. The above-mentioned (meth)acryloyl group refers to both an acryloyl group and a methacryloyl group. Examples of organic groups having a (meth)acryloyl group include a 3-methacryloxypropyl group and a 3-acryloxypropyl group.

[0049] An example of the organic group having a mercapto group is a 3-mercaptopropyl group. Examples of organic groups having an amino group include a 2-aminoethyl group, a 3-aminopropyl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-(1,3-dimethyl-butylidene)aminopropyl group, an N-phenyl-3-aminopropyl group, and an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group. An example of the organic group having a ureido group is a 3-ureidopropyl group. An example of the organic group having a cyano group is a 3-cyanopropyl group. The above formulas (2) and (3) are preferably compounds capable of forming trimethylsilyl groups on the surface of silica particles. Examples of such compounds include the following.

[0050] [ka]

[0051] In the above formula, R 12 is an alkoxy group, for example, a methoxy group or an ethoxy group. As the silane compound, a silane compound manufactured by Shin-Etsu Chemical Co., Ltd. can be used. This is a process in which the silane compound reacts with the hydroxyl groups on the surface of the silica particles, for example, the silanol groups in the case of silica particles, to coat the surface of the silica particles with the silane compound through siloxane bonds. The reaction temperature can be from 20°C to the boiling point of the dispersion medium, for example, in the range of 20°C to 100°C. The reaction time can be about 0.1 to 6 hours.

[0052] The amount of the silane compound coated on the surface of the silica particles is such that the number of silicon atoms in the silane compound is 0.1 / nm 2 ~6.0 pieces / nm 2 The surface of the silica particles can be coated by adding a silane compound corresponding to the coating amount to the silica sol. Water is necessary for the hydrolysis of the silane compound, and if the sol is an aqueous solvent, the aqueous solvent is used. When the aqueous medium is replaced with the organic solvent (C), the water remaining in the solvent can be used. For example, water present at 0.01 to 1% by mass can be used. The hydrolysis can be performed with or without a catalyst. When the hydrolysis is carried out without a catalyst, the silica particle surface is on the acidic side. When a catalyst is used, examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases. Examples of the metal chelate compounds as the hydrolysis catalyst include triethoxy mono(acetylacetonato)titanium and triethoxy mono(acetylacetonato)zirconium. Examples of the organic acids as the hydrolysis catalyst include acetic acid and oxalic acid. Examples of the inorganic acids as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Examples of the organic bases as the hydrolysis catalyst include pyridine, pyrrole, piperazine, and quaternary ammonium salts. Examples of the inorganic bases as the hydrolysis catalyst include ammonia, sodium hydroxide, and potassium hydroxide.

[0053] The organic acid is at least one organic acid selected from the group consisting of divalent aliphatic carboxylic acids, aliphatic oxycarboxylic acids, amino acids, and chelating agents, the divalent aliphatic carboxylic acids being oxalic acid, malonic acid, and succinic acid, the aliphatic oxycarboxylic acids being glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid, the amino acids being glycine, alanine, valine, leucine, serine, and threonine, and the chelating agents being ethylenediaminetetraacetic acid, L-aspartic acid-N,N-diacetic acid, and diethylenetriaminepentaacetic acid. The organic acid salts include alkali metal salts, ammonium salts, and amine salts of the organic acids. The alkali metals include sodium and potassium.

[0054] The phosphoric acid ester that can be used in the present invention includes at least one phosphoric acid ester compound selected from the group consisting of the formulae (4) to (6). In formulas (4) to (6), X 1 , X 2 , and X 3 each represents an alkylene group having 2 to 20 carbon atoms; f, h, and j each represent an integer of 1 to 100; e, g, and i each represent an integer of 1 to 3; Y 1 , Y 2 , and Y 3 each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a (meth)acrylic group. A polyoxyethylene alkyl (C6-20) ether phosphate ester having an alkyl group with 6 to 20 carbon atoms can be used.

[0055] The phosphate ester can preferably be a polyoxyethylene alkyl ether phosphate ester, and the phosphate ester can be a phosphate ester in which the terminal alkyl group (Y1) of the above formula (4) has 6 to 10 or 12 to 15 carbon atoms. For example, products of this type that can be used include those manufactured by Toho Chemical Industry Co., Ltd., trade names of Phosphanol RA-600 and RS-610. In the present invention, a sol is obtained in which core-shell type metal oxide particles are dispersed as a dispersoid in a dispersion medium consisting of alcohol, ester, ketone, amide, hydrocarbon, silicone, a compound containing an unsaturated bond between chain carbon atoms, oxirane compound, water, or a combination thereof, which may have an ether bond, and the core-shell type metal oxide sol has an average particle size measured by a dynamic light scattering method of 5 to 500 nm, or 10 to 200 nm, or 10 to 100 nm, or 10 to 60 nm, or 10 to 40 nm, or 10 to 30 nm.

[0056] The dispersion medium used in the present invention is water and an organic solvent. The organic solvent is an alcohol having 1 to 10 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, isobutanol, n-pentanol, ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether. The ketone is a linear or cyclic aliphatic ketone having 3 to 30 carbon atoms, and examples thereof include methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, methyl amyl ketone, and cyclohexanone.

[0057] The ether is a linear or cyclic aliphatic ether having 3 to 30 carbon atoms, and examples thereof include diethyl ether and tetrahydrofuran. The ester is a linear or cyclic ester having 2 to 30 carbon atoms, and examples thereof include ethyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, phenyl acetate, phenyl lactate, and phenyl propionate. The amide is an aliphatic amide having 3 to 30 carbon atoms, and examples thereof include dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and N-ethylpyrrolidone. The hydrocarbon is a straight-chain or cyclic aliphatic or aromatic hydrocarbon having 6 to 30 carbon atoms, and examples thereof include hexane, heptane, octane, nonane, decane, benzene, toluene, and xylene.

[0058] The surfactant used in the present invention may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant.

[0059] Anionic surfactants for use in the present invention include sodium and potassium salts of fatty acids, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, α-sulfofatty acid esters, α-olefin sulfonates, monoalkyl phosphates, and alkanesulfonates. For example, alkylbenzenesulfonates include sodium salts, potassium salts and lithium salts, such as sodium C10-C16 alkylbenzenesulfonate, C10-C16 alkylbenzenesulfonic acid, and sodium alkylnaphthalenesulfonate.

[0060] Examples of higher alcohol sulfates include sodium dodecyl sulfate (sodium lauryl sulfate), which has 12 carbon atoms, triethanolamine lauryl sulfate, and triethanolammonium lauryl sulfate.

[0061] Examples of polyoxyethylene alkyl ether sulfates include sodium polyoxyethylene styrenated phenyl ether sulfate, ammonium polyoxyethylene styrenated phenyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, ammonium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, and sodium polyoxyethylene oleyl cetyl ether sulfate. The α-olefin sulfonate salts include sodium α-olefin sulfonate.

[0062] Examples of the alkane sulfonate include sodium 2-ethylhexyl sulfate. Examples of the cationic surfactant that can be used in the present invention include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, and amine salt-based agents. Alkyltrimethylammonium salts are quaternary ammonium salts that have a chloride ion or a bromide ion as a counterion. Examples include dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, coconut alkyltrimethylammonium chloride, and alkyl(C16-18)trimethylammonium chloride.

[0063] Dialkyldimethylammonium salts have two lipophilic main chains and two methyl groups. Examples include bis(hydrogenated tallow)dimethylammonium chloride. Examples include didecyldimethylammonium chloride, dicoconucleic acid alkyldimethylammonium chloride, dihydrogenated tallow alkyldimethylammonium chloride, and dialkyl(C14-18)dimethylammonium chloride. Alkyl dimethyl benzyl ammonium salts are quaternary ammonium salts with one lipophilic main chain, two methyl groups, and a benzyl group, and examples of these include benzauconium chloride. For example, alkyl (C8-18) dimethyl benzyl ammonium chloride is included. Amine salt agents include those in which the hydrogen atom of ammonia has been replaced with one or more hydrocarbon groups, such as N-methylbishydroxyethylamine fatty acid ester hydrochloride.

[0064] The amphoteric surfactants used in the present invention include N-alkyl-β-alanine type alkylamino fatty acid salts, alkylcarboxybetaine type alkylbetaines, and N,N-dimethyldodecylamine oxide type alkylamine oxides, examples of which include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, and lauryl dimethylamine oxide.

[0065] The nonionic surfactant used in the present invention is selected from polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and fatty acid alkanolamides. For example, examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether.

[0066] Examples of polyoxyethylene alkylphenol ethers include polyoxyethylene styrenated phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether.

[0067] The alkyl glucoside includes decyl glucoside and lauryl glucoside.

[0068] Examples of polyoxyethylene fatty acid esters include polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyethylene glycol distearate, polyethylene glycol dioleate, and polypropylene glycol dioleate. Examples of sorbitan fatty acid esters include sorbitan monocaprylate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monosesquioleate, and ethylene oxide adducts thereof.

[0069] Examples of polyoxyethylene sorbitan fatty acid esters include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan triisostearate.

[0070] Examples of fatty acid alkanolamides include coconut oil fatty acid diethanolamide, beef tallow fatty acid diethanolamide, lauric acid diethanolamide, and oleic acid diethanolamide.

[0071] Further examples include polyoxyalkyl ethers or polyoxyalkyl glycols such as polyoxyethylene polyoxypropylene glycol, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil ether, sorbitan fatty acid ester alkyl ethers, alkyl polyglucosides, sorbitan monooleate, and sucrose fatty acid esters.

[0072] In the present invention, a composition (varnish) containing core-shell type metal oxide particles and a thermosetting or photocurable resin is obtained. The composition of the present invention can be further mixed with a thermosetting or photocurable resin to produce a varnish.

[0073] In the present invention, a film-forming composition containing the above organic solvent sol and an organic resin is obtained. The film-forming composition can be obtained by removing the organic solvent from the organic solvent sol to form a film-forming composition containing core-shell metal oxide particles and an organic resin. In the case of the thermosetting film-forming composition, the heat curing agent can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr to the resin containing a functional group such as an epoxy group or a (meth)acryloyl group, and for example, the heat curing agent can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents to the functional group such as an epoxy group or a (meth)acryloyl group. The equivalent of the heat curing agent to the curable resin is represented by the equivalent ratio of the heat curing agent to the functional group. Examples of the heat curing agent include phenol resins, amine-based curing agents, polyamide resins, imidazoles, polymercaptans, acid anhydrides, heat radical generators, heat acid generators, etc. In particular, radical generator-based curing agents, acid anhydride-based curing agents, and amine-based curing agents are preferred. Even if these thermosetting agents are solid, they can be used by dissolving them in a solvent. However, evaporation of the solvent reduces the density of the cured product and creates pores, resulting in reduced strength and reduced water resistance. Therefore, it is preferable for the curing agent itself to be liquid at room temperature and normal pressure. Examples of the phenol resin include phenol novolac resin and cresol novolac resin.

[0074] Examples of the amine curing agent include piperidine, N,N-dimethylpiperazine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 1,3-diaminomethylcyclohexane, xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and diethyltoluenediamine. Of these, liquid diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di(1-methyl-2-aminocyclohexyl)methane, menthenediamine, isophoronediamine, diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, diethyltoluenediamine, etc. can be preferably used.

[0075] The polyamide resin is produced by condensation of dimer acid and polyamine, and is a polyamide amine having a primary amine and a secondary amine in the molecule.

[0076] Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy imidazole adduct.

[0077] The polymercaptan is, for example, one having a mercaptan group at the end of a polypropylene glycol chain or one having a mercaptan group at the end of a polyethylene glycol chain, and is preferably in a liquid form. As the acid anhydride curing agent, the anhydride of the compound having a plurality of carboxyl groups in one molecule is preferable.As these acid anhydride curing agents, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methyl butenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, chlorendic anhydride, etc. can be mentioned. Examples of the thermal acid generator include sulfonium salts and phosphonium salts, with sulfonium salts being preferred. For example, the following compounds can be mentioned.

[0078] [ka]

[0079] R may be an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and is particularly preferably an alkyl group having 1 to 12 carbon atoms. Among these, the following are preferred, which are liquid at room temperature and pressure: methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylhimic anhydride), hydrogenated methylnadic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methylhexahydrophthalic anhydride, and a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride. These liquid acid anhydrides have a viscosity of about 10 mPa·s to 1000 mPa·s when measured at 25°C. Examples of thermal radical generators include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methylpropionate)dimethyl, 2,2'-azobis(2-methylpropionamidine)dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, etc. These can be obtained from Tokyo Chemical Industry Co., Ltd.

[0080] In addition, when obtaining the above-mentioned cured product, a curing assistant may be used in combination as appropriate. Examples of the curing assistant include organic phosphorus compounds such as triphenylphosphine and tributylphosphine, quaternary phosphonium salts such as ethyltriphenylphosphonium bromide and methyltriphenylphosphonium diethyl phosphate, and quaternary ammonium salts such as 1,8-diazabicyclo(5,4,0)undecane-7-ene, salts of 1,8-diazabicyclo(5,4,0)undecane-7-ene and octylic acid, zinc octylate, and tetrabutylammonium bromide. These curing assistants can be contained in a ratio of 0.001 to 0.1 parts by mass per part by mass of the curing agent. The composition is a thermosetting varnish obtained by mixing a resin, a curing agent, and optionally a curing aid, which can be mixed in a reaction vessel using a stirring blade or a kneader.

[0081] The mixing is carried out by a hot mixing method at a temperature of 60°C to 100°C for 0.5 to 1 hour. The obtained curable film-forming composition is a thermosetting coating composition, and has a suitable viscosity for use as, for example, a liquid sealant. The liquid thermosetting film-forming composition can be prepared to any viscosity, and can be partially sealed at any desired location for use as a transparent sealant for LEDs, etc., by casting, potting, dispenser, printing, etc. The liquid thermosetting composition is directly mounted on an LED, etc., in the liquid state, by the above-mentioned method, and then dried and cured to obtain a cured epoxy resin body. The thermosetting film-forming composition (thermosetting coating composition) is applied to a substrate and heated at a temperature of 80 to 200° C. to obtain a cured product. In the case of the photocurable resin composition in the above-mentioned film-forming composition, a photocuring agent (photoradical generator, photoacid generator) can be added in the range of 0.01 to 50 phr or 0.01 to 10 phr to a resin containing a functional group such as an epoxy group or a (meth)acryloyl group, and for example, the photocuring agent (photoradical generator, photoacid generator) can be contained in a ratio of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents, to a functional group such as an epoxy group or a (meth)acryloyl group. The equivalent of the photocuring agent to the curable resin is represented by the equivalent ratio of the photocuring agent to the functional group.

[0082] The photoradical generator is not particularly limited as long as it generates radicals directly or indirectly upon irradiation with light. Examples of photoradical generators include photoradical polymerization initiators such as imidazole compounds, diazo compounds, bisimidazole compounds, N-arylglycine compounds, organic azide compounds, titanocene compounds, aluminate compounds, organic peroxides, N-alkoxypyridinium salt compounds, and thioxanthone compounds. Examples of azide compounds include p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, 4,4'-diazidochalcone, 4,4'-diazidodiphenyl sulfide, and 2,6-bis(4'-azidobenzal)-4-methylcyclohexanone. Examples of the diazo compound include 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene borofluoride, 1-diazo-4-N,N-dimethylaminobenzene chloride, and 1-diazo-4-N,N-diethylaminobenzene borofluoride.

[0083] Examples of the bisimidazole compound include 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetrakis(3,4,5-trimethoxyphenyl)1,2'-bisimidazole, and 2,2'-bis(o-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-bisimidazole. Examples of the titanocene compound include dicyclopentadienyl-titanium-dichloride, dicyclopentadienyl-titanium-bisphenyl, dicyclopentadienyl-titanium-bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-titanium-bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl-titanium-bis(2,4,6-trifluorophenyl), dicyclopentadienyl-titanium-bis(2,6-difluorophenyl), dicyclopentadienyl Examples of such aryl groups include dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl), dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl), dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl), and dicyclopentadienyl-titanium-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl).

[0084] Further examples of photoradical generators include 1,3-di(tert-butyldioxycarbonyl)benzophenone, 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone, 3-phenyl-5-isoxazolone, 2-mercaptobenzimidazole, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

[0085] Examples of these photoradical polymerization agents include Irgacure TPO (product name: 2,4,6-trimethylbenzoyldiphenylphosphine oxide) (c1-1-1) manufactured by BASF, Omnirad819 (product name: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) (c1-1-2), available from IGM RESINS under the trade name Irgacure 184 (the active ingredient is 1-hydroxycyclohexyl phenyl ketone) (c1-1-3).

[0086] [ka]

[0087] The photoacid generator is not particularly limited as long as it generates an acid directly or indirectly upon irradiation with light. Specific examples of the photoacid generator that can be used include triazine-based compounds, acetophenone derivative compounds, disulfone-based compounds, diazomethane-based compounds, sulfonic acid derivative compounds, onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts, metallocene complexes, and iron arene complexes. The onium salt used as the photoacid generator may be, for example, an iodonium salt, such as diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium Examples of the iodonium salt include bis(alkylphenyl)iodonium salts such as bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(alkylphenyl)iodonium salts such as bis(4-t-butylphenyl)iodonium hexafluorophosphate, alkoxycarbonylalkoxy-trialkylaryliodonium salts (e.g., 4-[(1-ethoxycarbonyl-ethoxy)phenyl]-(2,4,6-trimethylphenyl)-iodonium hexafluorophosphate, and bis(alkoxyaryl)iodonium salts (e.g., bis(alkoxyphenyl)iodonium salts such as (4-methoxyphenyl)phenyliodonium hexafluoroantimonate).

[0088] Examples of sulfonium salts include triphenylsulfonium chloride, triphenylsulfonium bromide, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluorophosphate; and sulfonium salts such as (4-phenylthiophenyl)diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl)diphenylsulfonium hexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide-bis-hexafluorophosphate, and (4-methoxyphenyl)diphenylsulfonium hexafluoroantimonate.

[0089] Examples of the phosphonium salt include triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, 4-chlorobenzenediazonium hexafluorophosphate, and benzyltriphenylphosphonium hexafluoroantimonate. Examples include selenium salts such as triphenylselenium hexafluorophosphate, and metallocene complexes such as (η5 or η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) hexafluorophosphate.

[0090] In addition, the following compounds can also be used as the photoacid generator.

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] As the photoacid generator, sulfonium salt compounds and iodonium salt compounds are preferred. The anion species thereof is CF 3 SO 3 - , C 4 F 9 SO 3 - , C 8 F 17 SO 3 -, camphorsulfonate anion, tosylate anion, BF 4 - , P.F. 6 - , AsF 6 - and SbF 6 - In particular, anion species such as phosphorus hexafluoride and antimony hexafluoride, which exhibit strong acidity, are preferred. The film-forming composition of the present invention may contain conventional additives as necessary. Examples of such additives include pigments, colorants, thickeners, sensitizers, defoamers, coating improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light resistance stabilizers, etc.), plasticizers, dissolution promoters, fillers, antistatic agents, etc. These additives may be used alone or in combination of two or more.

[0101] Examples of methods for applying the coating composition of the present invention include flow coating, spin coating, spray coating, screen printing, casting, bar coating, curtain coating, roll coating, gravure coating, dipping, and slit coating. In the present invention, the photo-coating composition (film-forming composition) can be applied onto a substrate and cured by light irradiation, or can be heated before or after light irradiation. The thickness of the coating film can be selected from the range of about 0.01 μm to 10 mm depending on the application of the cured product; for example, when used as a photoresist, it can be about 0.05 to 10 μm (particularly 0.1 to 5 μm), when used as a printed wiring board, it can be about 5 μm to 5 mm (particularly 100 μm to 1 mm), and when used as an optical thin film, it can be about 0.1 to 100 μm (particularly 0.3 to 50 μm). When a transparent coating is obtained, the visible light transmittance of the coating can be 80% or more, or 90% or more, typically 90 to 96%.

[0102] When a photoacid generator is used, the light to be irradiated or exposed may be, for example, gamma rays, X-rays, ultraviolet rays, visible light, etc., and is usually visible light or ultraviolet rays, particularly ultraviolet rays. The wavelength of the light is, for example, about 150 to 800 nm, preferably about 150 to 600 nm, and more preferably about 150 to 400 nm. The amount of irradiation light varies depending on the thickness of the coating film, but is, for example, 2 to 20,000 mJ / cm. 2 , preferably 5 to 5000 mJ / cm 2 The light source can be selected according to the type of light to be exposed, and for example, in the case of ultraviolet light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a deuterium lamp, a halogen lamp, or a laser beam (helium-cadmium laser, excimer laser, etc.) can be used. Such light irradiation causes the curing reaction of the composition to proceed. When a thermal acid generator is used or when a photoacid generator is used, the coating film is heated as necessary after light irradiation, for example at 60 to 350° C., and preferably at about 100 to 300° C. The heating time can be selected within a range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, 5 seconds to 2 hours, preferably about 20 seconds to 30 minutes, and usually about 1 minute to 3 hours (for example, about 5 minutes to 2.5 hours).

[0103] Furthermore, when forming a pattern or an image (for example, when manufacturing a printed wiring board, etc.), the coating film formed on the substrate may be pattern-exposed, and this pattern exposure may be performed by scanning with laser light or by irradiating light through a photomask. A pattern or an image can be formed by developing (or dissolving) the non-irradiated area (unexposed part) generated by such pattern exposure with a developer. The developer may be an aqueous alkaline solution or an organic solvent. Examples of the alkaline aqueous solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine.

[0104] The alkaline developer is generally an aqueous solution of 10% by mass or less, and preferably an aqueous solution of 0.1 to 3.0% by mass, etc. Furthermore, alcohols and surfactants can be added to the developer, and each of these is preferably 0.05 to 10 parts by mass relative to 100 parts by mass of the developer. Of these, an aqueous solution of 0.1 to 2.38 mass % tetramethylammonium hydroxide can be used. In addition, the organic solvent used as the developer can be a general organic solvent, such as acetone, acetonitrile, toluene, dimethylformamide, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, ethyl lactate, cyclohexanone, etc., and these can be used alone or in combination of two or more. In particular, propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, etc. can be preferably used.

[0105] In the present invention, an adhesion promoter can be added for the purpose of improving adhesion to the substrate after development. These adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane, silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole, vinyltrichlorosilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane. silanes such as 3-aminopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(N-piperidinyl)propyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, urea such as 1,1-dimethylurea, 1,3-dimethylurea, or thiourea compounds. The adhesion promoters may be used alone or in combination of two or more. The amount of these adhesion promoters added is usually 18% by mass or less, preferably 0.0008 to 9% by mass, more preferably 0.04 to 9% by mass, based on the solid content.

[0106] In the present invention, a sensitizer may be included. Examples of sensitizers that can be used include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Examples of sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. Anthracene sensitizers are particularly preferred, and when used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), they dramatically improve sensitivity and also have a radical polymerization initiation function, and in the hybrid type in which the cationic curing system of the present invention and the radical curing system are used in combination, the catalyst species can be simplified. Specific examples of anthracene compounds that are effective include dibutoxyanthracene and dipropoxyanthraquinone. The amount of the sensitizer added is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content.

[0107] The composition of the present invention can be photocured or thermally cured using a photoradical generator, a thermal radical generator, a photoacid generator, or a thermal acid generator. When a photoacid generator or a thermal acid generator is used, for example, commonly used epoxy curing agents (e.g., amines or acid anhydrides) are not used, or even if they are used, the content of these agents is extremely small, so that the storage stability of the composition is improved.

[0108] The above composition has been found to be applicable to photocationic polymerization. It has a higher curing speed than conventional liquid epoxy compounds (e.g. alicyclic epoxy compounds with an epoxycyclohexyl ring). Because of the fast curing speed, it is possible to reduce the amount of acid generator added or use a weak acid generator. Reducing the amount of acid generator is important for preventing metal corrosion, as active acid species may remain even after UV irradiation. Because of the fast curing speed, thick film curing is possible. Curing by UV irradiation can be applied to materials (equipment) that are sensitive to heat.

[0109] Thermosetting and photocurable materials using the coating-forming composition of the present invention have characteristics such as rapid curing, transparency, and little cure shrinkage, and can be used for coating and bonding electronic components, optical components (anti-reflective coatings), and precision mechanical components.

[0110] The above composition (varnish) can be suitably used as a hard coat agent or a composition for nanoimprints.

[0111] Other applications include bonding of mobile phone and camera lenses, optical elements such as light-emitting diodes (LEDs) and semiconductor lasers (LDs), liquid crystal panels, biochips, camera lenses and prisms, magnetic components in hard disks of computers and other devices, pickups in CD and DVD players (the part that captures the optical information reflected from the disc), speaker cones and coils, motor magnets, circuit boards, electronic components, and internal components of automobile engines.

[0112] As a hard coating material for surface protection of automobile bodies, lamps, electrical appliances, building materials, plastics, etc., it can be applied to, for example, automobile and motorcycle bodies, headlight lenses and mirrors, plastic lenses for glasses, mobile phones, game consoles, optical films, ID cards, etc.

[0113] Examples of ink materials for printing on metals such as aluminum and plastics include credit cards, membership cards, and other cards, switches for electrical appliances and office equipment, printing ink for keyboards, and inkjet printer ink for CDs, DVDs, etc.

[0114] Examples of applications include a technology that can be used in combination with 3D CAD to harden resin and create complex three-dimensional objects, photolithography for producing models of industrial products, and optical fiber coatings, adhesives, optical waveguides, and thick-film resists. The film-forming composition of the present invention can also be suitably used as an insulating resin for electronic materials, such as anti-reflection films, semiconductor encapsulation materials, adhesives for electronic materials, printed wiring board materials, interlayer insulating film materials, and encapsulants for power modules, as well as an insulating resin for use in high-voltage equipment, such as generator coils, transformer coils, and gas-insulated switchgear. EXAMPLES

[0115] [Total metal oxide concentration] The sol was weighed using a crucible, and pre-dried by heating at 110° C. for 30 minutes to remove the solvent. This was then fired at 600° C. for 30 minutes. The crucible was weighed, and the total metal oxide concentration was calculated from the weight of the residue.

[0116] [X-ray diffraction measurement] The sol was dried on a hot plate at 110°C and ground for 15 minutes using a mortar and pestle to obtain a dry powder, which was measured using an XRD device (MiniFlex600, manufactured by Rigaku Co., Ltd.) to obtain an X-ray diffraction pattern.

[0117] 〔viscosity〕 Measured using a BM type viscometer (25°C).

[0118] [Average particle size by dynamic light scattering (Dynamic Light Scattering particle size, DLS average secondary particle size)] The sol was diluted with a dispersion solvent, and the parameters of the solvent were used to measure the dispersion using a dynamic light scattering measuring device (manufactured by Malvern Instruments Ltd., trade name: Zetasizer).

[0119] [Average primary particle size measured by transmission electron microscope] The sol was dropped onto a copper mesh and dried, and observed using a transmission electron microscope (manufactured by JEOL Ltd., product name JEM-1020) at an accelerating voltage of 100 kV. The average value of measurements for 100 particles was calculated as the average primary particle size.

[0120] [ 31 P-NMR Test of colloidal particles in a sol 31P-NMR was measured according to the following procedure. (Preparation of phosphoric acid-treated colloidal particle dry powder) 10.0 g of the sol was added with 85% aqueous phosphoric acid solution (3.0 mass% based on the solid content of the colloid particles) and stirred for 0.5 hours to phosphoric acid-treated the colloid particle surface. The resulting sol was then thoroughly washed by ultrafiltration to remove phosphoric acid not bound to the particles. The washed sol was dried on a hot plate at 60°C for 3 hours, and the dried powder was ground in an agate mortar for 10 minutes to produce a dry powder of phosphoric acid-treated colloid particles.

[0121] (Solid-state NMR 31 P-NMR analysis) The dry powder was sealed in a sample tube (diameter 2.5 mm) used for solid-state NMR measurement, and the DD / MAS method was used. 31 P solid-state NMR measurement was performed using a nuclear magnetic resonance device (product name AVANCE3, manufactured by Bruker, 500 MHz) under the following conditions. Probe diameter: 4.0mm Rotation speed: 30000Hz Relaxation waiting time: 10s Accumulation count: 8000 times From the obtained spectrum, peaks originating from the metal species to which phosphate is bound were divided, and the presence or absence of a main peak originating from Ti atoms (Ti-OP), which are the core components of colloidal particles, was examined. Ti-OP: δ=3~5ppm Particles in which the Ti-OP peak was confirmed were marked with "◯", and particles in which the peak was not confirmed were marked with "×".

[0122] [Color retention rate of dyes after UV irradiation at 490 nm] To an aqueous dispersion or a methanol dispersion of inorganic oxide fine particles in an amount equivalent to 0.05 g in terms of solid content, a suitable solvent was added so that the water / methanol ratio was 1 / 1 (weight ratio) and the solid content concentration was 0.5% by weight. Next, the obtained dispersion was mixed with a glycerin solution of a sunset yellow dye with a solid content concentration of 0.02% by weight in a weight ratio (weight of dispersion liquid / weight of glycerin solution) of 1 / 3 to prepare a sample, which was then placed in a quartz cell with a depth of 1 mm, width of 1 cm, and height of 5 cm. Next, an ultraviolet lamp (SLUV-6 manufactured by ASONE) with a wavelength range of I-line (wavelength 365 nm) was used to illuminate the quartz cell with an intensity of 0.4 mW / cm on the surface of the quartz cell with a width of 1 cm and height of 5 cm. 2 The sample was irradiated with ultraviolet light at a wavelength of 490 nm (calculated as 365 nm wavelength) for 30 minutes at 25° C. The absorbance (A0) of the sample before and after ultraviolet light irradiation at a wavelength of 490 nm (A1) was measured using a UV-Vis-NIR spectrophotometer (Shimadzu Corporation, product name UV-3600), and the dye color retention rate was calculated using the following formula.

[0123] Remaining color rate (%) = A1 / A0×100

[0124] [Particle Refractive Index] The refractive index of the colloidal particles in the sol was measured by the following procedures i) to iii).

[0125] i) Preparation of a coating solution containing colloidal particles dispersed in an organic solvent 20.00 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Momentive, product name SILQUEST A-187T) was weighed into a plastic container, 18.57 g of methanol and 4.57 g of 0.01N hydrochloric acid solution were added thereto, and the mixture was stirred at room temperature for 5 hours. 3 ) in methanol (10% by mass Al(acac) 3 ) (6.00 g) was added as a curing agent and stirred for 10 minutes to prepare a partial hydrolysate of 3-glycidoxypropyltrimethoxysilane (concentration: 43% by mass). The prepared partial hydrolysate of 3-glycidoxypropyltrimethoxysilane, colloid particle dispersion sol, water, methanol, and 0.25 g of a methanol solution (10 mass% L-7604) of a leveling agent (DOWSIL trade name, L-7604) were weighed into a brown bottle so that the total amount was 25.00 g, the final solvent composition was the sum of water / solvent other than water = 1 / 4 by weight, and the amount of colloid particles in the organic solvent dispersion sol was 50 phr, 100 phr, and 150 phr, and the mixture was stirred at room temperature for 30 minutes to prepare a coating liquid containing colloid particle organic solvent dispersion sol (solid concentration was 10.0 mass%, amount of colloid particles: 50 phr, 100 phr, and 150 phr).

[0126] ii) Preparation of particle-loaded membrane i) The obtained colloidal particle organic solvent dispersion sol-containing coating liquid is subjected to UV-O 3 Approximately 0.5 mL was dropped onto the treated Si substrate and coated using a spin coater (Mikasa Co., Ltd., product name Opticoat MS-B100) so that the film thickness after coating was 1.0 μm. After that, the substrate was baked on a hot plate at 80°C for 5 minutes and heat-treated in an oven at 120°C for 1 hour to prepare particle-blended films (particle blending amounts: 50 phr, 100 phr, and 150 phr).

[0127] iii) Measurement of refractive index of particle-containing film and calculation of refractive index of particles The refractive index of the particle-blended films obtained in ii) (particle blending amounts: 50 phr, 100 phr, and 150 phr) was measured using an ellipsometer (multiple incidence angle spectroscopic ellipsometer, product name VASE, manufactured by J.A. Woollam Japan, Inc.). The refractive index of a film containing no particles, which was prepared in the same manner using only the partial hydrolysate of 3-glycidoxypropyltrimethoxysilane, was also measured. The measured refractive index of the blended film was plotted against the particle blending amount, and the particle refractive index was calculated by extrapolating so that the particle blending amount was 100 mass%.

[0128] [Dispersion stability] After the dispersion was stored at 50°C for one week, samples whose particle size as measured by dynamic light scattering was less than 1.2 times that before the storage test were marked with an "O" (good), whereas samples whose particle size as measured by dynamic light scattering was 1.2 times or more that before the storage test were marked with an "X".

[0129] The cured film was formed on a urethane plastic lens substrate or a glass substrate by the method described below in (Example 9 Cured Film Evaluation-A1) or (Example 13 Cured Film Evaluation-A5), and evaluated at 25°C and 50% humidity.

[0130] (1) Film refractive index The reflectance of the cured film formed on the glass substrate was measured using a reflectance measuring device (manufactured by Olympus Corporation, trade name USPM-RU). From the measured reflectance, the refractive index of the cured film was calculated using optical simulation.

[0131] (2) Transparency The cured film formed on the urethane plastic lens substrate or the glass substrate was visually inspected under fluorescent light in a dark room for the presence or absence of cloudiness. The evaluation criteria were as follows: ○: Almost no clouding occurs ×: Cloudiness occurs and whitening is evident

[0132] (3) Light resistance Using an ultraviolet fluorescent lamp type accelerated weathering tester (QUV, manufactured by Q-Lab) equipped with a UV-A lamp, 0.89 W / m 2 The cured film formed on a urethane plastic lens or a glass substrate was irradiated with ultraviolet light for 24 hours under the conditions of (340 nm). The evaluation criteria are as follows. ◯: No cracks or peeling of the film were observed. ×: Cracks or peeling of the film were observed.

[0133] (4) Scratch resistance The surface of the cured film formed on a urethane plastic lens substrate or a glass substrate was rubbed with steel wool #0000, and the cured film was visually inspected for scratches in a bright room under fluorescent lighting. The scratch resistance test conditions were 1 time / 10 seconds, with a load of 1 kg. The evaluation criteria were as follows: ○: No scratches were found with the naked eye. ×: Scratches are visible.

[0134] (5) Nanoimprintability A coating liquid containing colloidal particles dispersed in an organic solvent was spin-coated onto a quartz substrate, and heated on a hot plate at 100°C for 1 minute to produce a film from which the solvent had been removed. The film obtained was irradiated with ultraviolet light using a nanoimprinter (Meisho Kiko Co., Ltd., product name NM-0801HB) while a release-treated quartz mold (Kyodo International Co., Ltd., product name DTM-2-1) was pressed against it at 1000N, and the uneven pattern was transferred and cured. The mold was peeled off from the obtained cured film, and the formed pattern was observed with a SEM (JEOL Ltd., product name JSM-6010LV). The criteria for evaluation were as follows: ◯: The pattern was transferred and the imprinting property was good. ×: The pattern was not transferred, and the imprinting properties were poor.

[0135] (Reference Example 1): Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (A1) as the core 319.5 g of 25% by mass tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water, and then 7.4 g of metastannic acid (SnO 2 6.3g), titanium tetraisopropoxide 236.6g (TiO 2To the mixture, 82.0 g of oxalic acid dihydrate (containing 66.6 g of stannic oxide equivalent) and 82.0 g of oxalic acid dihydrate (containing 58.5 g of oxalic acid equivalent) were added under stirring. The mixed solution was held at 80°C for 2 hours, and then further reduced in pressure to 580 Torr and held for 2 hours to prepare a mixed solution. The mixed solution was placed in a glass-lined autoclave vessel, subjected to hydrothermal treatment at 140°C for 5 hours, cooled to room temperature, and then removed. The obtained sol was a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloidal particles (A1), and had a total metal oxide concentration (TiO 2 , and SnO 2 The sol had a molecular weight of 5.0 mass%, and the average primary particle size was 10 nm when observed with a transmission electron microscope. The sol was dried at 110°C and the powder was subjected to X-ray diffraction analysis, which confirmed that it was a rutile crystal.

[0136] (Reference Example 2): Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (A2) as the core 319.5 g of 25% by mass tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water, and then 14.8 g of metastannic acid (SnO 2 12.5g), titanium tetraisopropoxide 236.6g (TiO 2 To the mixture, 82.0 g of oxalic acid dihydrate (containing 66.6 g in terms of oxalic acid) and 82.0 g of oxalic acid dihydrate (containing 58.5 g in terms of oxalic acid) were added under stirring. The mixed solution was held at 80°C for 2 hours, and then further reduced in pressure to 580 Torr and held for 2 hours to prepare a mixed solution. The mixed solution was placed in a glass-lined autoclave vessel, subjected to hydrothermal treatment at 140°C for 5 hours, cooled to room temperature, and then removed. The obtained sol was a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloidal particles (A2), and had a total metal oxide concentration (TiO 2 , and SnO 2 The average primary particle size was 10 nm when observed with a transmission electron microscope. The obtained sol was dried at 110°C, and the powder was subjected to X-ray diffraction analysis, which confirmed that it was a rutile crystal.

[0137] (Reference Example 3): Preparation of titanium oxide colloidal particles (A3) as cores 319.5 g of 25% by mass tetramethylammonium hydroxide aqueous solution was dissolved in 947.1 g of pure water, and 236.6 g of titanium tetraisopropoxide (TiO 2 To the mixture, 82.0 g of oxalic acid dihydrate (containing 66.6 g in terms of oxalic acid) and 82.0 g of oxalic acid dihydrate (containing 58.5 g in terms of oxalic acid) were added under stirring. The mixed solution was held at 80°C for 2 hours, and then further reduced in pressure to 580 Torr and held for 2 hours to prepare a mixed solution. The mixed solution was placed in a glass-lined autoclave vessel, subjected to hydrothermal treatment at 140°C for 5 hours, cooled to room temperature, and then removed. The obtained sol was a water-dispersed sol of titanium oxide colloidal particles (A3), and had a total metal oxide concentration (TiO 2 The average primary particle size was 10 nm when observed with a transmission electron microscope. The obtained sol was dried at 110°C, and the powder was subjected to X-ray diffraction analysis, which confirmed that it was anatase type crystals.

[0138] (Reference Example 4): Preparation of silicon dioxide-stannic oxide composite oxide colloidal particles (B1) to be used as coating material JIS No. 3 sodium silicate (SiO 2 77.2 g of sodium stannate (containing 29.8% by mass in terms of sodium stannate equivalent) was dissolved in 668.8 g of pure water, and then sodium stannate NaSnO 3 H 2 O(SnO 2 In the aqueous solution, 20.9 g of stannic oxide-stannic oxide composite oxide colloidal particles (B1) was dissolved in the aqueous solution (55.1% by mass in terms of total metal oxide content). The resulting aqueous solution was passed through a column packed with a hydrogen cation exchange resin (Amberlite (trade name) IR-120B). Next, 7.2 g of diisopropylamine was added to the resulting aqueous dispersion sol. The resulting sol was an aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1), with a pH of 8.0 and a total metal oxide concentration (SiO 2 , and SnO 2 ) 1.7% by mass, and the average primary particle diameter was 3 nm when observed with a transmission electron microscope.

[0139] (Reference Example 5): Preparation of antimony pentoxide colloidal particles (B2) to be used as coating material Add antimony trioxide (Sb 2 O 3To the mixture were added 125 g of potassium hydroxide (containing 99.5% by mass as diantimony pentoxide), 660 g of pure water, and 125 g of potassium hydroxide (containing 95% by mass as KOH), and 84 g of 35% hydrogen peroxide was gradually added under stirring. The resulting aqueous solution of potassium antimonate was diluted to 2.2% by mass and passed through a column packed with hydrogen cation exchange resin. To the solution of antimonic acid after ion exchange, 2.5 g of diisopropylamine was added under stirring. The resulting sol was an aqueous dispersion sol of antimony pentoxide colloidal particles (B2), and had a pH of 10.8 and Sb 2 O 5 The concentration was 1.5% by mass, and the average primary particle diameter was 6 nm when observed with a transmission electron microscope.

[0140] (Production Example 1): Preparation of colloidal particles of titanium dioxide-stannic oxide composite oxide modified with silicon dioxide-stannic oxide composite oxide (C1) 1,500.0 g of the aqueous dispersion sol of titanium dioxide-stannic oxide composite oxide colloidal particles (A1) prepared in Reference Example 1 was added to 661.8 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 with stirring, and the mixture was heated at 95° C. for 3 hours, and then passed through a column packed with a cation exchange resin (Amberlite (trade name) IR-120B, manufactured by Organo Corporation). The solid content of the sol that would become the core to be added to the container was 667 parts by mass per 100 parts by mass of the coating sol solid content filled in the container, and the addition was carried out over 10 minutes at a rate of 66.7 parts by mass per minute. To the obtained water-dispersed sol, 2.5 g of tri-n-pentylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol was kept at pH 5.2, total metal oxide (TiO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 5.0 mPa s, and DLS average secondary particle size was 15 nm.

[0141] (Production Example 2): Preparation of titanium dioxide-stannic oxide composite oxide colloidal particles (C2) modified with silicon dioxide-stannic oxide composite oxide 1500.0 g of the aqueous dispersion sol of titanium dioxide-stannic oxide composite oxide colloidal particles (A1) prepared in Reference Example 1 was added to 330.9 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 with stirring, and the mixture was heated at 95° C. for 3 hours, and then passed through a column packed with a cation exchange resin (Amberlite (trade name) IR-120B, manufactured by Organo Corporation). The solid content of the sol to be added to the container as the core was 1,340 parts by mass per 100 parts by mass of the coating sol solid content filled in the container, and the addition was carried out over 20 minutes at a rate of 67 parts by mass per minute. To the obtained water-dispersed sol, 2.0 g of tri-n-pentylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloidal particles (C2) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol was kept at pH 5.2, total metal oxide (TiO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 6.0 mPa s, and DLS average secondary particle size was 18 nm.

[0142] (Production Example 3): Preparation of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles modified with silicon dioxide-stannic oxide composite oxide (C3) Zirconium oxychloride (ZrO 2 82.7 g of zirconium oxychloride (containing 21.2% by mass in terms of pure water) was diluted with 501.1 g of pure water to obtain 583.8 g of an aqueous solution of zirconium oxychloride (ZrO 2 A water-dispersed sol of titanium oxide-stannic oxide composite oxide colloid particles (A2) prepared in Reference Example 2 was added under stirring to a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles (A2) prepared in Reference Example 2. Next, hydrolysis was carried out by heating at 95° C. for 5 hours to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles having a thin film layer of zirconium oxide formed on the surface. To 2330.0 g of the obtained water-dispersed sol, 1852.9 g of the water-dispersed sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 was added under stirring, and the mixture was passed through a column packed with 500 mL of anion exchange resin (Amberlite (trade name) IRA-410, manufactured by Organo Corporation). Next, the water-dispersed sol after passing through was heated at 95° C. for 5 hours, and then passed through a column packed with cation exchange resin (Amberlite (trade name) IR-120B, manufactured by Organo Corporation). The solid content of the coating sol added to the container was 30 parts by mass per 100 parts by mass of the core sol filled in the container, and the addition was carried out over one minute at a rate of 30 parts by mass per minute. 3.5 g of tri-n-pentylamine was added to the obtained water-dispersed sol, which was then concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C3) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol had a pH of 5.2 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 5.0 mPa s, and DLS average secondary particle size was 20 nm.

[0143] (Production Example 4): Preparation of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles modified with silicon dioxide-stannic oxide composite oxide (C4) Zirconium oxychloride (ZrO 2 82.7 g of zirconium oxychloride (containing 21.2% by mass in terms of pure water) was diluted with 501.1 g of pure water to obtain 583.8 g of an aqueous solution of zirconium oxychloride (ZrO 2 A water-dispersed sol of titanium oxide-stannic oxide composite oxide colloid particles (A1) prepared in Reference Example 1 was added under stirring to a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles having a thin film layer of zirconium oxide formed on the surface thereof. To 2330.0 g of the obtained water-dispersed sol, 2470.6 g of the alkaline water-dispersed sol of silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 was added under stirring, and the mixture was passed through a column packed with 500 mL of anion exchange resin (Amberlite (trade name) IRA-410, manufactured by Organo Corp.). The water-dispersed sol after passing through was then heated at 95° C. for 5 hours, and then passed through a column packed with cation exchange resin. The solid content of the coating sol added to the container was 40 parts by mass per 100 parts by mass of the core sol filled in the container, and the addition was carried out over one minute at a rate of 40 parts by mass per minute. To the obtained water-dispersed sol, 5.6 g of tri-n-pentylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol was kept at pH 5.1, with a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 5.0 mPa s, and DLS average secondary particle diameter was 25 nm.

[0144] (Production Example 5): Preparation of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles modified with silicon dioxide-stannic oxide composite oxide (C5) Zirconium oxychloride (ZrO 2 82.7 g of zirconium oxychloride (containing 21.2% by mass in terms of pure water) was diluted with 501.1 g of pure water to obtain 583.8 g of an aqueous solution of zirconium oxychloride (ZrO 2 A water-dispersed sol of titanium oxide-stannic oxide composite oxide colloid particles (A1) prepared in Reference Example 1 was added under stirring to a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles having a thin film layer of zirconium oxide formed on the surface thereof. To 2330.0 g of the obtained water-dispersed sol, 3088.2 g of the water-dispersed sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 was added under stirring, and the mixture was passed through a column packed with 500 mL of anion exchange resin (Amberlite (trade name) IRA-410, manufactured by Organo Corp.). The water-dispersed sol after passing through was then heated at 95° C. for 5 hours, and then passed through a column packed with cation exchange resin. The solid content of the coating sol added to the container was 50 parts by mass per 100 parts by mass of the core sol filled in the container, and the addition was carried out over 2 minutes at a rate of 25 parts by mass per minute. To the obtained water-dispersed sol, 6.2 g of tri-n-pentylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C4) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol was kept at pH 5.0 and had a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 5.4 mPa s, and DLS average secondary particle diameter was 24 nm.

[0145] (Production Example 6): Preparation of titanium oxide-stannic oxide composite oxide colloidal particles modified with antimony pentoxide colloidal particles (C6) 1500.0 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (A1) prepared in Reference Example 1 was added to 1500.0 g of the aqueous dispersion sol of alkaline antimony pentoxide colloidal particles (B2) prepared in Reference Example 5 with stirring, and the mixture was heated at 95°C for 3 hours, and then passed through a column packed with a cation exchange resin. The solid content of the sol that would become the core to be added to the container was 333 parts by mass per 100 parts by mass of the coating sol solids filled in the container, and the addition was carried out over 10 minutes at a rate of 33.3 parts by mass per minute. To the obtained water-dispersed sol, 1.8 g of diisobutylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloid particles (C6) modified with antimony pentoxide colloid particles. This water-dispersed sol had a pH of 5.6 and a total metal oxide (TiO 2 , SnO 2 , and Sb 2 O 5 ) concentration was 30.5 mass%, viscosity was 5.5 mPa s, and DLS average secondary particle size was 18 nm.

[0146] (Production Example 7): Preparation of anatase-type titanium dioxide colloidal particles modified with silicon dioxide-stannic oxide composite oxide (C7) 1,500.0 g of the aqueous dispersion sol of the anatase type titanium dioxide colloidal particles (A3) prepared in Reference Example 3 was added to 1,764.7 g of the aqueous dispersion sol of the alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 with stirring, and the mixture was heated at 95° C. for 3 hours, and then passed through a column packed with a cation exchange resin. The solid content of the sol that would become the core to be added to the container was 250 parts by mass per 100 parts by mass of the coating sol solid content filled in the container, and the addition was carried out over 10 minutes at a rate of 25.0 parts by mass per minute. To the obtained water-dispersed sol, 4.5 g of diisobutylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of anatase-type titanium oxide colloidal particles (C7) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol had a pH of 5.2 and a total metal oxide (TiO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 6.5 mPa s, and DLS average secondary particle diameter was 28 nm.

[0147] (Production Example 8): Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (C8) whose cores are surface-modified with polyoxyethylene alkyl ether phosphate To 1,500.0 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (A1) prepared in Reference Example 1, 15.0 g of polyoxyethylene alkyl ether phosphate (RS-710, manufactured by Toho Chemical Industry Co., Ltd.) was added as a surface modifier under stirring to modify the surface of the particles. The obtained sol was concentrated by ultrafiltration membrane method to obtain a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloidal particles (C8) whose cores were surface-modified with polyoxyethylene alkyl ether phosphate. This water-dispersed sol was kept at pH 2.8 and had a total metal oxide (TiO 2 , SnO 2 ) concentration was 30.0 mass%, viscosity was 6.5 mPa s, and DLS average secondary particle diameter was 26 nm.

[0148] (Production Example 9): Preparation of titanium oxide-stannic oxide composite oxide colloidal particles (C9) modified with silicon dioxide-stannic oxide composite oxide 1,500.0 g of the aqueous dispersion sol of titanium dioxide-stannic oxide composite oxide colloid particles (A1) prepared in Reference Example 1 was added to 4,411.8 g of the aqueous dispersion sol of alkaline silicon dioxide-stannic oxide composite oxide colloid particles (B1) prepared in Reference Example 4 under stirring, and the mixture was heated at 95° C. for 3 hours, and then passed through a column packed with a cation exchange resin (Amberlite (trade name) IR-120B, manufactured by Organo Corporation). For every 100 parts by mass of solids of the coating sol filled in the container, 100 parts by mass of the solids of the sol to be the core was added to the container, and the addition was carried out over 10 minutes at a rate of 10 parts by mass per minute. 3.1 g of tri-n-pentylamine was added to the obtained water-dispersed sol, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol was kept at pH 5.2, total metal oxide (TiO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 5.0 mPa s, and DLS average secondary particle size was 20 nm.

[0149] (Production Example 10): Preparation of titanium dioxide-stannic oxide-zirconium oxide composite oxide colloidal particles modified with silicon dioxide-stannic oxide composite oxide (C10) Zirconium oxychloride (ZrO 2 82.7 g of zirconium oxychloride (containing 21.2% by mass in terms of pure water) was diluted with 501.1 g of pure water to obtain 583.8 g of an aqueous solution of zirconium oxychloride (ZrO 2 A water-dispersed sol of titanium oxide-stannic oxide composite oxide colloid particles (A1) prepared in Reference Example 1 was added under stirring to a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloid particles having a thin film layer of zirconium oxide formed on the surface thereof. To 2330.0 g of the obtained water-dispersed sol, 6176.4 g of the water-dispersed sol of alkaline silicon dioxide-stannic oxide composite oxide colloidal particles (B1) prepared in Reference Example 4 was added under stirring, and the mixture was passed through a column packed with 500 mL of anion exchange resin (Amberlite (trade name) IRA-410, manufactured by Organo Corp.). The water-dispersed sol after passing through was then heated at 95° C. for 5 hours, and then passed through a column packed with cation exchange resin. The solid content of the coating sol added to the container was 100 parts by mass relative to 100 parts by mass of the core sol filled in the container, and the addition was carried out over 5 minutes at a rate of 20 parts by mass per minute. To the obtained water-dispersed sol, 10.2 g of tri-n-pentylamine was added, and the mixture was concentrated by ultrafiltration to obtain a water-dispersed sol of titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C10) modified with silicon dioxide-stannic oxide composite oxide. This water-dispersed sol had a pH of 5.4 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 ) concentration was 30.5 mass%, viscosity was 5.8 mPa s, and DLS average secondary particle size was 21 nm.

[0150] Example 1 The dispersion medium of 100 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 1 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide. 1.52 g of polyoxyethylene alkyl ether phosphate (manufactured by Toho Chemical Industry Co., Ltd.: trade name RS-710) was added as a surface modifier to 100 g of the obtained sol under stirring, and the particles were surface-modified by heating under reflux at 65°C for 5 hours. This surface-modified methanol dispersion sol was prepared by subjecting the particles to a pH of 4.5, total metal oxide (TiO 2 , SnO 2 , and SiO 2 The concentration was 20.5% by mass, the viscosity was 2.3 mPa s, and the DLS average secondary particle size was 16 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 54%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.26, the particle refractive index was 2.25, and the dispersion stability was “○.”

[0151] FIG. 1 shows the titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide used in Example 1. 31 This is a P-NMR spectrum, and there are areas where the coating of the shell layer covering the core is partially missing, exposing the core, and when this core-shell type modified metal oxide particle is contacted with an aqueous phosphoric acid solution, a peak is confirmed near δ=3-5 ppm, which is due to a (Ti-OP) bond between the Ti atom of the core and the P atom in the phosphoric acid of the shell layer via an oxygen atom, and the (Ti-OP) bond is determined to be "present." In other words, in the core-shell type metal oxide particle, there are areas where part of the shell layer covering the core is missing, exposing the core.

[0152] Example 2 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C2) obtained in Production Example 2. The methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 4.2 and a total metal oxide (TiO 2, SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 4.5 mPa s, and the DLS average secondary particle size was 45 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 22%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.18, the particle refractive index was 2.30, and the dispersion stability was “good.”

[0153] Example 3 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C3) obtained in Production Example 3. The methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 4.5 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 4.5 mPa s, and the DLS average secondary particle size was 28 nm. 31 P-NMR analysis of PO-Ti showed that it was "bonded," the residual color rate was 88%, (metal oxide other than titanium oxide) / (titanium oxide) was 0.85, the particle refractive index was 2.10, and the dispersion stability was "○."

[0154] Example 4 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C4) obtained in Production Example 4. The methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 4.6 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 4.5 mPa s, and the DLS average secondary particle size was 21 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 98%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.83, the particle refractive index was 2.10, and the dispersion stability was “○.”

[0155] Example 5 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C5) obtained in Production Example 5. The methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 4.4 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 4.5 mPa s, and the DLS average secondary particle size was 29 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the color retention rate was 98%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.97, the particle refractive index was 2.00, and the dispersion stability was “○.”

[0156] Example 6 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C6) obtained in Production Example 6. The methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 4.0 and a total metal oxide (TiO 2 , SnO 2 , and Sb 2 O 5 The concentration was 20.5% by mass, the viscosity was 2.5 mPa·s, and the DLS average secondary particle size was 20 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 10%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.42, the particle refractive index was 2.25, and the dispersion stability was “good.”

[0157] Example 7 A sol was prepared in the same manner as in Example 1, except that the colloidal particles were changed to (C7) obtained in Production Example 7. The methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 4.2 and a total metal oxide (TiO 2 , SnO 2 , and SiO 2 ) concentration was 20.5 mass%, viscosity was 2.3 mPa s, and DLS average secondary particle diameter was 29 nm. Also 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 40%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.40, the particle refractive index was 2.20, and the dispersion stability was “○.”

[0158] Example 8 A sol was prepared in the same manner as in Example 1, except that the surface modifier was changed to 2.0 g of phenyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-103). At this time, the methanol dispersion sol was prepared in the same manner as in Example 1, with a pH of 5.9 and a total metal oxide (TiO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 2.0 mPa·s, and the DLS average secondary particle size was 16 nm. 31 P-NMR analysis of PO-Ti showed that it was "bonded," the residual color rate was 54%, (metal oxide other than titanium oxide) / (titanium oxide) was 0.26, the particle refractive index was 2.25, and the dispersion stability was "○."

[0159] (Example 9, Evaluation of Cured Film-A1) A PGME dispersion sol was prepared by again replacing the dispersion medium of 100 g of a methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide and surface-modified with polyoxyethylene alkyl ether phosphate (manufactured by Toho Chemical Industry Co., Ltd.: product name RS-710) obtained in Example 1 with propylene glycol monomethyl ether (PGME) using a rotary evaporator. At this time, the PGME dispersion sol was prepared at a pH of 4.7, a total metal oxide (TiO 2 , SnO 2 , and SiO 2 The concentration was 20.5% by mass, the viscosity was 4.5 mPa s, and the DLS average secondary particle size was 12 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 54%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.26, the particle refractive index was 2.25, and the dispersion stability was “○.”

[0160] This sol was then used to prepare a cured film according to the following procedure. In a brown bottle equipped with a magnetic stirrer, 2.0 g of a mixture of dipentaerythritol hexa- and pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a resin binder and 4.9 g of PGME were added, and 22.9 g of the sol of this Example 9 was added while stirring. Next, 0.02 g of a photoradical polymerization initiator (manufactured by BASF Co., Ltd., trade name Irgacure OXE01) and 0.3 g of a PGME solution (KP-412 concentration is 10.0 mass%) of a methacrylic group type surface modifier (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KP-412) were added, and the mixture was stirred for 0.5 hours to prepare a coating liquid. Glass substrates were prepared, and the coating liquid was applied to them by spin coating at room temperature of 25°C and humidity of 50% (film thickness 1 μm), and the solvent was evaporated at 100°C for 1 minute, and then the accumulated light amount was 1000 mJ / cm 2 The coating was then cured with ultraviolet light from a high pressure mercury lamp until a cured film was formed. The obtained cured film had a refractive index of 1.80, transparency of "good", and light resistance of "good". In addition, when the same coating liquid was used to evaluate the imprintability, it was rated as "good".

[0161] (Example 10: Evaluation of Cured Film-A2) To 100 g of the methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with silicon dioxide-stannic oxide composite oxide surface-modified with polyoxyethylene alkyl ether phosphate (manufactured by Toho Chemical Industry Co., Ltd.: trade name RS-710) obtained in Example 1, 1.5 g of RS-710 was further added, and the dispersion medium was again replaced with propylene glycol monomethyl ether acetate (hereinafter, PGMEA) using a rotary evaporator to prepare a PGMEA dispersion sol. At this time, the PGMEA dispersion sol was kept at pH 4.1, total metal oxide (TiO 2 , SnO 2 , and SiO 2 The concentration was 20.5% by mass, the viscosity was 5.5 mPa·s, and the DLS average secondary particle size was 20 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 54%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.26, the particle refractive index was 2.20, and the dispersion stability was “good.”

[0162] Next, a cured film was prepared in the same manner as in Example 9, Cured Film Evaluation-A1, except that the sol in Example 9, Cured Film Evaluation-A1 was changed to the sol of this Example 10. The obtained cured film had a refractive index of 1.80, transparency of "good", and light resistance of "good". In addition, when the same coating liquid was used to evaluate the imprintability, it was rated as "good".

[0163] (Example 11 Cured Film Evaluation-A3) The cured film of Example 9, Cured Film Evaluation-A1 was prepared in the same manner as in Example 9, Cured Film Evaluation-A1, except that the resin binder was changed to a urethane acrylate (trade name: UA4200, manufactured by Shin-Nakamura Chemical Co., Ltd.). The obtained cured film had a refractive index of 1.80, transparency of "good", and light resistance of "good". In addition, when the same coating liquid was used to evaluate the imprintability, it was rated as "good".

[0164] (Example 12: Evaluation of cured film-A4) The cured film of Example 9, Cured Film Evaluation-A1 was prepared in the same manner as in Example 9, Cured Film Evaluation-A1, except that the resin binder was changed to Aronix MT-3010 (manufactured by Toagosei Co., Ltd.). The obtained cured film had a refractive index of 1.80, transparency of "good", and light resistance of "good". In addition, when the same coating liquid was used to evaluate the imprintability, it was rated as "good".

[0165] (Example 13: Evaluation of cured film-A5) A sol was prepared in the same manner as in Example 3, except that the surface modifier was changed to 2.5 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-503). The methanol dispersion sol was prepared in the same manner as in Example 3, with a pH of 5.7 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 1.8 mPa s, and the DLS average secondary particle size was 16 nm. 31P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 88%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.85, the particle refractive index was 2.00, and the dispersion stability was “○.”

[0166] This sol was then used to prepare a cured film according to the following procedure. 25.8 g of γ-glycidoxypropyltrimethoxysilane was added to a glass container equipped with a magnetic stirrer, and 6.2 g of 0.01N hydrochloric acid was added dropwise while stirring. After the dropwise addition, stirring was continued for 0.5 hours to obtain a partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, 22.5 g of propylene glycol monomethyl ether, 7.0 g of methanol, 85.6 g of the methanol dispersion sol of this Example 13, and 2.2 g of aluminum acetylacetonate as a curing agent were added to 32.0 g of the partial hydrolyzate of γ-glycidoxypropyltrimethoxysilane described above, and the mixture was stirred for 2 hours to prepare a coating liquid for hard coat. A urethane-based plastic lens (refractive index n D =1.67) and a glass substrate were prepared, and the hard coat coating liquid was applied to them by dip coating (film thickness 3 μm). The solvent was evaporated at 80°C for 10 minutes, and then the coating was hardened by heating at 120°C for 2 hours. The obtained cured film was evaluated as having a refractive index of 1.67, transparency "good", light resistance "good", and scratch resistance "good".

[0167] (Example 14: Evaluation of cured film-A6) A sol was prepared in the same manner as in Example 3, except that the surface modifier was changed to 3.7 g of an allyl isocyanurate-based silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., product name X-12-1290). The methanol dispersion sol was prepared in the same manner as in Example 3, with a pH of 5.7 and a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 1.9 mPa s, and the DLS average secondary particle size was 18 nm. 31P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 88%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.85, the particle refractive index was 2.00, and the dispersion stability was “○.”

[0168] Next, a cured film was prepared in the same manner as in Example 13, Cured Film Evaluation-A5, except that the sol in Example 13, Cured Film Evaluation-A5 was changed to the sol of this Example 14. The obtained cured film was evaluated as having a refractive index of 1.67, transparency "good", light resistance "good", and scratch resistance "good".

[0169] (Example 15: Evaluation of Cured Film-A7) A methanol dispersion sol of 100 g of titanium oxide-stannic oxide composite oxide colloidal particles (C3) modified with silicon dioxide-stannic oxide composite oxide and surface-modified with 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-503) used in Example 13 was used again to replace the dispersion medium with methyl ethyl ketone (hereinafter, MEK) to prepare an MEK dispersion sol. The obtained MEK dispersion sol had a pH of 6.0, a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 2.1 mPa s, and the DLS average secondary particle size was 17 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 88%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.85, the particle refractive index was 2.00, and the dispersion stability was “○.”

[0170] This sol was then used to prepare a cured film according to the following procedure. In a brown bottle equipped with a magnetic stirrer, 17.6 g of a mixture of dipentaerythritol hexa- and pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a resin binder, 5.2 g of methanol, and 18.3 g of PGME were added, and 57.2 g of the sol of this Example 15 was added while stirring. Next, 0.9 g of a photoradical polymerization initiator (manufactured by BASF Co., Ltd., trade name Irgacure OXE01) and 0.9 g of a PGME solution of polyether-modified silicone oil (manufactured by Toray Dow Corning Co., Ltd., trade name L-7001) (L-7001 concentration is 2.0 mass%) were added, and the mixture was stirred for 0.5 hours to prepare a coating liquid. Glass substrates were prepared, and the coating liquid was applied to them by spin coating (film thickness 3 μm), and the solvent was evaporated at 80 ° C for 2 minutes, and then the accumulated light amount was 1000 mJ / cm. 2 The coating was then cured with ultraviolet light from a high pressure mercury lamp until a cured film was formed. The obtained cured film was evaluated as having a refractive index of 1.67, transparency "good", light resistance "good", and scratch resistance "good".

[0171] (Example 16: Evaluation of cured film-A8) An MEK dispersion sol was prepared by again replacing the dispersion medium of 100 g of a methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C1) modified with a silicon dioxide-stannic oxide composite oxide surface-modified with an allyl isocyanurate-based silane coupling agent (X-12-1290 manufactured by Shin-Etsu Chemical Co., Ltd.) used in Example 14 with MEK using a rotary evaporator. The obtained MEK dispersion sol had a pH of 5.9, a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 1.7 mPa s, and the DLS average secondary particle size was 15 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 88%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.85, the particle refractive index was 2.00, and the dispersion stability was “○.”

[0172] Next, a cured film was prepared in the same manner as in Example 15, Cured Film Evaluation-A7, except that the sol in Example 15, Cured Film Evaluation-A7 was changed to the sol of this Example 16. The obtained cured film was evaluated as having a refractive index of 1.67, transparency "good", light resistance "good", and scratch resistance "good".

[0173] (Comparative Example 1: Evaluation of Cured Film-B1) The dispersion medium of 100 g of the aqueous dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C8) whose cores have been surface-modified with polyoxyethylene alkyl ether phosphate obtained in Production Example 8 was replaced with methanol using a rotary evaporator to obtain a methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C8) whose cores have been surface-modified with polyoxyethylene alkyl ether phosphate. This methanol dispersion sol was dissolved in 100 g of water at pH 3.5, total metal oxide (TiO 2 , and SnO 2 The concentration was 20.5% by mass, the viscosity was 2.3 mPa s, and the DLS average secondary particle size was 32 nm. 31 P-NMR analysis of PO-Ti showed that it was “bonded,” the residual color rate was 0%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 0.10, the particle refractive index was 2.10, and the dispersion stability was “×.”

[0174] FIG. 2 shows the titanium oxide-stannic oxide composite oxide colloidal particles (A1) obtained in Production Example 8 used in Comparative Example 1. 31 This is a P-NMR spectrum, and although there is no shell layer covering the core and the phosphoric acid aqueous solution comes into direct contact with the core, a peak was confirmed near δ=3-5 ppm, which is attributable to the (Ti-OP) bond between the Ti atom of the core and the P atom in the phosphoric acid via an oxygen atom, and the (Ti-OP) bond was determined to be "present." In other words, the (Ti-OP) bond was present in the metal oxide particle consisting of the core alone.

[0175] Next, a cured film was prepared in the same manner as in Example 13, cured film evaluation-A5, except that the weight of the metal oxide in this Comparative Example 1 was changed so that the weight of the metal oxide was the same as that in Example 13, cured film evaluation-A5. The obtained cured film had a refractive index of 1.70, transparency of "good", light resistance of "poor", and scratch resistance of "good".

[0176] (Comparative Example 2: Evaluation of Cured Film-B2) The dispersion medium of 100 g of the aqueous dispersion sol of the titanium oxide-stannic oxide composite oxide colloidal particles (C9) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 9 was replaced with methanol using a rotary evaporator. The solvent was then replaced again with PGME to obtain a PGME dispersion sol. The PGME dispersion sol was then heated to 300° C. for 1 hour at a temperature of 4.7° C. and 100° C. for 2 hours at a temperature of 4.7° C. and 100° C. for 2 hours at a temperature of 4.7° C. 2 , SnO 2 , and SiO 2 The concentration was 20.5% by mass, the viscosity was 4.5 mPa s, and the DLS average secondary particle size was 21 nm. 31 P-NMR analysis of PO-Ti showed "no bonds," color retention rate was 98%, mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 1.38, particle refractive index was 1.78, and dispersion stability was "○."

[0177] This sol was then used to prepare a cured film according to the following procedure. In a brown bottle equipped with a magnetic stirrer, 1.3 g of a mixture of dipentaerythritol hexa- and pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a resin binder and 3.0 g of PGME were added, and 25.3 g of the sol of this Comparative Example 2 was added while stirring. Next, 0.01 g of a photoradical polymerization initiator (manufactured by BASF Co., Ltd., trade name Irgacure OXE01) and 0.3 g of a PGME solution (KP-412 concentration 10.0 mass%) of a methacrylic group type surface modifier (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KP-412) were added, and the mixture was stirred for 0.5 hours to prepare a coating liquid. Glass substrates were prepared, and the coating liquid was applied to them by spin coating (film thickness 1 μm), and the solvent was evaporated at 100 ° C for 1 minute, and then the accumulated light amount was 1000 mJ / cm. 2 The coating was then cured with ultraviolet light from a high pressure mercury lamp until a cured film was formed. The obtained cured film had a refractive index of 1.65, transparency of "good", and light resistance of "good". In addition, when the imprint property was evaluated using the same coating liquid, it was rated as "poor".

[0178] (Comparative Example 3: Evaluation of Cured Film-B3) A sol was prepared in the same manner as in Example 13, cured film evaluation-A5, except that the sol was changed to the titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C10) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 10. The methanol dispersion sol was prepared in the same manner as in Example 13, cured film evaluation-A5, except that the sol was changed to the titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C10) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 10. 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 1.6 mPa s, and the DLS average secondary particle size was 22 nm. 31 P-NMR analysis of PO-Ti showed "no bonds," the color retention rate was 98%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 1.85, the particle refractive index was 1.70, and the dispersion stability was "good."

[0179] FIG. 3 shows the results of the titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C10) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 10 used in Comparative Example 3. 31 This is a P-NMR spectrum, and titanium oxide-stannic oxide-zirconium oxide composite oxide colloidal particles (C10) modified with silicon dioxide-stannic oxide composite oxide obtained in Production Example 10 were used, but the shell layer covering the core was sufficiently coated and there was no part where the core was exposed, so when this core-shell type modified metal oxide particle was contacted with an aqueous phosphoric acid solution, a peak at about δ=3 to 5 ppm due to the (Ti-OP) bond between the Ti atom of the core and the P atom present in the phosphoric acid via an oxygen atom could not be confirmed, and the (Ti-OP) bond was marked as "no bond." That is, in the core-shell type metal oxide particle, there was no part where the shell layer covering the core was missing and the core was exposed, and the core was completely covered with the shell layer.

[0180] Next, a cured film was prepared in the same manner as in Example 13, Cured Film Evaluation-A5, except that the sol in Example 13, Cured Film Evaluation-A5 was changed to the sol of this Comparative Example 13. The obtained cured film was evaluated as having a refractive index of 1.56, transparency "good", light resistance "good", and scratch resistance "good".

[0181] (Comparative Example 4, Evaluation of Cured Film-B4) In Comparative Example 3, cured film evaluation B3, 100 g of a methanol dispersion sol of titanium oxide-stannic oxide composite oxide colloidal particles (C10) modified with silicon dioxide-stannic oxide composite oxide and surface-modified with 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-503) was used again to replace the dispersion medium with MEK using a rotary evaporator, thereby preparing an MEK dispersion sol. The obtained MEK dispersion sol had a pH of 6.2, a total metal oxide (TiO 2 , ZrO 2 , SnO 2 , and SiO 2 The concentration was 30.5% by mass, the viscosity was 2.0 mPa·s, and the DLS average secondary particle size was 25 nm. 31P-NMR analysis of PO-Ti showed "no bonds," the color retention rate was 98%, the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) was 1.85, the particle refractive index was 1.70, and the dispersion stability was "good."

[0182] Next, a cured film was prepared in the same manner as in Example 15, Cured Film Evaluation-A7, except that the sol in Example 15, Cured Film Evaluation-A7 was changed to the sol of this Comparative Example 4. The obtained cured film was evaluated as having a refractive index of 1.56, transparency "good", light resistance "good", and scratch resistance "good". [Industrial Applicability]

[0183] The present invention provides modified metal oxide particles, which are core-shell type metal oxide particles used in compositions for obtaining coatings with a high refractive index and high moldability, for example, for nanoimprinting, and which have a core made of metal oxide particles containing titanium oxide and a shell made of metal oxide particles other than titanium oxide, with the core being covered with a part of the core being exposed, and a method for producing the same.

Claims

1. a core-shell type metal oxide particle including a core containing metal oxide particles having an average primary particle diameter of 3 to 100 nm and a shell covering the surface of the core containing metal oxide particles having an average primary particle diameter of 1 to 7 nm, wherein the average primary particle diameter satisfies the relationship of (core metal oxide particles)>(shell metal oxide particles); When the component (a) is titanium oxide and the component (b) is a metal oxide other than titanium oxide, the core is a particle made of the component (a) or a combination of the component (a) and the component (b), The shell is a particle made of component (b). The following requirements A and B: Requirement A: In a test in which the core-shell metal oxide particles are brought into contact with a compound having a P-OH bond, the formation of a P-O-Ti bond in the core-shell metal oxide particles is observed by NMR, Requirement B: The refractive index of the core-shell metal oxide particles is 1.85 or more. The above core-shell metal oxide particles satisfy the above requirements.

2. 2. The core-shell type metal oxide particles according to claim 1, wherein the component (b) is at least one metal oxide particle selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide.

3. 2. The core-shell type metal oxide particles according to claim 1, wherein the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) is in the range of 0.05 to 1.

0.

4. 2. The core-shell metal oxide particle according to claim 1, wherein an intermediate layer is present between the core particle and the shell particle, the intermediate layer being metal oxide particles comprising a combination of at least one selected from the group consisting of zirconium oxide, silicon dioxide, aluminum oxide, tin oxide, zinc oxide, iron oxide, niobium oxide, tantalum oxide, antimony oxide, and tungsten oxide as component (D), and the mass ratio of (metal oxide other than titanium oxide) / (titanium oxide) is in the range of 0.05 to 1.

0.

5. 2. The core-shell type metal oxide particles according to claim 1, wherein the surfaces of the core-shell type metal oxide particles are coated with a compound having a P-OH bond or a Si-OH bond.

6. The compound having a Si—OH bond is represented by formula (1) to formula (3): 【Chemistry 1】 (In formula (1), R １ each represents an alkyl group, a halogenated alkyl group, an alkenyl group, an aryl group, or an organic group having a polyether group, an epoxy group, a (meth)acryloyl group, a mercapto group, an amino group, a ureido group, or a cyano group, and is bonded to a silicon atom via a Si-C bond; R ２ each represents an alkoxy group, an acyloxy group, or a halogen group; a represents an integer of 1 to 3; In formula (2) and formula (3), R ３ and R ５ are each an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 30 carbon atoms and bonded to a silicon atom by a Si—C bond; R ４ and R ６ each represents an alkoxy group, an acyloxy group, or a halogen group; Y represents an alkylene group, an NH group, or an oxygen atom; b is an integer of 1 to 3; c is an integer of 0 or 1; and d is an integer of 1 to 3.

2. The core-shell type metal oxide particles according to claim 1, which is at least one silane compound selected from the group consisting of:

7. The compound having a P-OH bond is represented by formula (4) to formula (6): 【Chemistry 2】 (In formulas (4) to (6), X １ , X ２ , and X ３ each represents an alkylene group having 2 to 20 carbon atoms; f, h, and j each represent an integer of 1 to 100; e, g, and i each represent an integer of 1 to 3; Y １ , Y ２ , and Y ３ each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a (meth)acrylic group.

8. 8. The core-shell type metal oxide particles according to claim 7, wherein the phosphate ester is a polyoxyethylene alkyl (C6-20) ether phosphate ester having an alkyl group having 6 to 20 carbon atoms.

9. 9. A sol in which the core-shell metal oxide particles according to any one of claims 1 to 8 are dispersed as a dispersoid in a dispersion medium comprising an alcohol, an ester, a ketone, an amide, a hydrocarbon, a silicone, a compound containing an unsaturated bond between linear carbon atoms, an oxirane compound, water, or a combination thereof, which may have an ether bond, and the core-shell metal oxide sol has an average particle size of 5 to 500 nm as measured by a dynamic light scattering method.

10. The core-shell metal oxide sol according to claim 9, further comprising a surfactant, the surfactant being an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.

11. The core-shell metal oxide sol according to claim 9, further comprising a secondary amine or a tertiary amine having a total of 5 to 35 carbon atoms.

12. A varnish comprising the core-shell type metal oxide particles according to any one of claims 1 to 8 and a thermosetting or photosetting resin.

13. The varnish according to claim 12, which is a hard coat agent or a composition for nanoimprints.

14. The following steps (i) and (ii): Step (i): preparing a sol (A) containing metal oxide particles having an average primary particle diameter of 3 to 60 nm as determined by a nitrogen gas adsorption method and water as a dispersion medium, and a sol (B) containing metal oxide particles having an average primary particle diameter of 1 to 7 nm as determined by a nitrogen gas adsorption method and water as a dispersion medium; Step (ii): mixing the sol (A) and the sol (B) at a rate of 22 to 1000 parts by mass per minute of the solid content of one sol added to the container per 100 parts by mass of the solid content of the other sol; The method for producing the core-shell metal oxide sol according to claim 9, comprising:

15. In the above step (i) or step (ii), Step (S-1): adding a secondary amine or a tertiary amine having a total of 5 to 35 carbon atoms to an aqueous sol; The method for producing a core / shell metal oxide sol according to claim 14, further comprising the step of:

16. After the step (ii), the following steps (T-1), (T-2), and (T-3) are further performed: Step (T-1): adding at least one silane compound selected from the group consisting of formulas (1) to (3) or at least one phosphoric acid ester selected from the group consisting of formulas (4) to (6) to the core-shell metal oxide sol obtained in step (ii); Step (T-2): A step of replacing the dispersion medium of the core-shell type metal oxide sol obtained in step (ii) with a dispersion medium consisting of an alcohol, an ester, a ketone, an amide, or a hydrocarbon; Step (T-3): adding a surfactant to the core-shell metal oxide sol obtained in step (ii); The method for producing a core / shell metal oxide sol according to claim 15, further comprising the step of:

17. The method for producing a core-shell metal oxide sol according to claim 16, wherein the steps are step (i), step (S-1), step (ii), step (S-1), step (T-2), step (T-1), and step (T-2) in this order.

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