KR102371414B1 - Surface-treated metal oxide sol - Google Patents

Abstract

(Project) To provide a surface-treated metal oxide sol capable of realizing a resist film having high refractive index and light transmittance, low haze and beads, high sensitivity, high residual film rate, high resolution, high scratch resistance and high weather resistance, and a method for manufacturing the same.
(Solution) The surface-treated metal oxide sol of the present invention contains surface-treated metal oxide particles in which an organosilicon compound containing a predetermined amount of (meth)acryl group is formed on the surface of the metal oxide particles, and a dispersion medium. The metal oxide particle contains 50 mass % or more _of titania as TiO2. 0.1-60 mass parts of organosilicon compounds containing a (meth)acryl group are formed in the surface-treated metal oxide particle as Rn-SiO _{(4-n)/2 with} respect to 100 mass parts of metal oxide particles.

Description

Surface-treated metal oxide sol {SURFACE-TREATED METAL OXIDE SOL}

The present invention relates to a surface-treated metal oxide sol. Specifically, it relates to a surface-treated metal oxide sol comprising a surface-treated metal oxide in which an organosilicon compound containing a (meth)acryl group is formed on the surface of the metal oxide particles for forming a film having high refractive index and high hardness, and a dispersion medium. .

In recent years, in photolithography used in the manufacture of semiconductor elements, printed circuit boards, printing plates, liquid crystal display panels, plasma display panels, etc., a technique of processing by coating a photosensitive material on a substrate, and exposing and developing it in a pattern shape. is disseminated. The photosensitive material (resist material) used for this photolithography is a material which forms functional films, such as a high refractive index film|membrane, in the pattern shape on the substrate surface, for example. For this reason, high sensitivity, high film remaining rate, high resolution, high transparency, and high film|membrane hardness are calculated|required. This photosensitive material (resist material) is comprised from a resin binder component, and components, such as an acid generator, a crosslinking agent, and a solvent.

As a means of increasing the refractive index and hardness of the coating film, it is known to use a high refractive index particle component such as titania particles for the coating liquid. For example, in Japanese Unexamined Patent Publication No. 5-173319 (Patent Document 1), in order to improve etching resistance as a resist material, fine powder of metal oxide or oxymetal oxide having an average particle diameter of 0.002 to 0.2 µm is used as novolac. The composition for photoresists containing 0.05 to 20 weight% in photosensitive resins, such as resin, is disclosed. In addition, Japanese Patent Application Laid-Open No. 2009-020520 (Patent Document 2) describes a photosensitive resin composition excellent in low dielectric properties, adhesive strength, heat resistance, etc., and discloses the use of an inorganic colloidal nanoparticle surface-treated with an organosilane. has been In addition, Japanese Patent Application Laid-Open No. 2014-152226 (Patent Document 3) discloses that it can be easily dispersed in a hydrophobic medium such as a resin or an organic solvent, has high transparency and hardness, and is excellent in abrasion resistance, adhesion to a substrate, and weather resistance. An inorganic composite oxide particle in which the inorganic composite oxide particle for forming a coating film is surface-treated with an organosilicon compound or a partial hydrolyzate thereof is disclosed.

Japanese Laid-Open Patent Publication No. 5-173319 Japanese Patent Laid-Open No. 2009-020520 Japanese Patent Laid-Open No. 2014-152226

When the titania particles described in Patent Document 1 are used for a resist material, a high refractive index and high film hardness can be expected, but the dispersibility with the resist material resin is not sufficient. For this reason, when a resist film was formed, there existed a problem that particle|grains aggregated, transparency fell, and abrasion resistance fell. In addition, in Patent Documents 2 and 3, the dispersibility in the resist film is improved compared to that of Patent Document 1 by surface treatment of the particles, but the bonding with the resist material resin is insufficient, and the sensitivity and residual film rate at the time of forming the resist film are poor, There was also a problem in that the resolution of the film was also poor.

In order to realize these problems and the requirements for the resist material described above, the present invention provides surface-treated metal oxide particles usable as a component of the resist material. Specifically, the organosilicon compound containing a (meth)acryl group on the surface of the metal oxide particle containing 50 mass % or more of titania as TiO2 is R1n-SiO _(4-n)/2 ⁽ _{provided that} ^R1 is a group containing at least one selected from a methacryl group and an acryl group, and may be the same or different from each other. n is an integer of 1 to 3.) 0.1 to 60 parts by mass of the surface-treated metal oxide formed as an integer, and a dispersion medium. A surface-treated metal oxide sol containing

When the surface-treated metal oxide sol of the present invention is used for a resist material, a resist film having both high refractive index, light transmittance, low haze and bead, high sensitivity, high residual film rate, high resolution, high scratch resistance and high weather resistance can be realized.

The surface-treated metal oxide sol of the present invention contains surface-treated metal oxide particles in which an organosilicon compound containing a (meth)acryl group is formed on the surface of the metal oxide particles, and a dispersion medium. This metal oxide particle is a particle|grain which contains 50 mass % or more _of titania as TiO2. As for the surface-treated metal oxide particles, the above-described organosilicon compound represented by Formula (1) is R ¹ _n -SiO _(4-n)/2 (provided that R ¹ is methacryl with respect to 100 parts by mass of the metal oxide particles). It is a group containing at least one selected from group and an acryl group, and may be the same or different from each other. n is an integer of 1-3.), 0.1-60 mass parts is formed.

R ¹ _n -SiX ¹ _(4-n) (1)

(However, R ¹ is a group containing at least one selected from a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1-3. X ¹ is an alkoxy group.)

About the surface-treated metal oxide sol of such a structure, the detail is demonstrated below.

[Metal Oxide Particles]

In order for a surface-treated metal oxide particle to have a high refractive index, it is preferable to contain 50 mass % or more _of titania as TiO2 so that the metal oxide particle itself may become refractive index 2.0 or more. Specifically, it is preferably titania or a complex oxide containing titanium and another metal. These may be used independently and may be mixed and used for them. Examples of the metal include silicon, tin, iron, and cerium. The number of these metal types may be one, or two or more may be sufficient as them.

By the way, since titania generally has photocatalytic activity, it has photoactivity, and it is known that it decomposes|decomposes the organic substance etc. which coexist in a film|membrane. Therefore, if photoactivity is too strong, the weather resistance of a film|membrane will fall. Therefore, it is preferable to adjust the photoactivity using a complex oxide of titania and silica or tin oxide having a relatively low refractive index. Specifically, composite oxide particles of titania silica (TiO ₂ /SiO ₂ ) and titania silica tin oxide (TiO ₂ /SiO ₂ /SnO ₂ ) are exemplified as preferable ones. As the form of titania, either a rutile type or an anatase type may be used, and a mixture thereof may be used. In particular, as a resist material, in order to make refractive index larger than 1.6, it is preferable to contain 50 mass % or _more of titania in a composite oxide particle as TiO2.

_In the case _of TiO2/SiO2, it is preferable that 75 mass % or more of TiO2 _{and 25} mass % or less of SiO2 contain. Here, when the ratio of TiO ₂ /SiO ₂ is smaller than 75/25, there is a possibility that the refractive index becomes low. _More preferably, TiO2 is 80-90 mass %, _and SiO2 is 10-20 mass %.

_{In the} case _of TiO2/SiO2/SnO2, it is preferable that TiO2 is 50-95 mass %, SiO2 is _3-25 mass %, _and SnO2 is _2-47 mass %. Here, when the ratio _of TiO2/(SiO2 ₊ SnO2) is smaller _than 50/50, refractive index may become low. Conversely, when the ratio of TiO ₂ /(SiO ₂ +SnO ₂ ) is larger than 95/5, the difference from the particles of titania alone becomes difficult to appear, and as a result, photoactivity and weather resistance may become a problem. _More preferably, TiO2 is 70-90 mass %, SiO2 is 10-20 mass %, SnO2 is _2-30 mass %, 70/30-90/ ₁₀ as TiO2/ ₍ SiO2 _{+ SnO2} ) am.

In addition, in order to adjust the photoactivity of a resist material, it is also possible to add 3rd components, such as iron and ceria, to composite oxide particles such as TiO ₂ /SiO ₂ and TiO ₂ /SiO ₂ /SnO ₂ .

Iron or ceria doping treatment is preferable from the viewpoint of suppressing photoactivity. It is preferable that a dope amount is less _{than 10} mass parts as Fe2O3 or CeO2 _with respect to 100 mass parts of particle|grains as object. When the doping amount of iron or ceria is 10 parts by mass or more as Fe ₂ O ₃ or CeO ₂ , the outer appearance of the coating film may be colored. A more preferable dope amount is less than 5 mass parts, More preferably, it is less than 3 mass parts.

[Surface-treated metal oxide particles]

<Layer of organosilicon compound containing (meth)acryl group>

As for the surface-treated metal oxide particles, the organosilicon compound represented by Formula (1) as a surface treating agent is coat|covered on the surface of the metal oxide particle.

R ¹ _n -SiX ¹ _(4-n) (1)

(However, R ¹ is a group containing at least one selected from a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1-3. X ¹ is an alkoxy group.)

The organosilicon compound containing this (meth)acryl group is R ¹ _n -SiO _(4-n)/2 (provided that R ¹ is at least selected from a methacryl group and an acryl group with respect to 100 parts by mass of the metal oxide particles) As a group containing one type, it may be mutually the same or different. n is an integer of 1-3.), 0.1-60 mass parts is formed as. By forming the organosilicon compound containing a (meth)acryl group on the surface of a metal oxide particle, the dispersibility and bonding property of a surface-treated metal oxide particle and resin in a resist material improve. Here, when the quantity of an organosilicon compound is less than 0.1 mass part, compatibility with resin is insufficient, aggregation of particle|grains may generate|occur|produce, and a rise of a haze and a total light transmittance may fall. Moreover, the sensitivity at the time of exposure and image development, and a residual film rate may run short. Conversely, on the surface area of the particles, it is difficult to coat more than 60 parts by mass. The preferable amount of the organosilicon compound is 1 to 50 parts by mass, more preferably 3 to 30 parts by mass.

This organosilicon compound may exist freely in the sol as an unreacted material which has not been surface-treated. The amount is R ¹ _n -SiO _(4-n)/2 (provided that R ¹ is a group containing at least one selected from a methacryl group and an acryl group, and is the same as each other or It may differ. n is an integer of 1-3.), and is 99.9 mass parts or less. When the free organosilicon compound is 0 parts by mass, the organosilicon compound in the surface-treated metal oxide sol is only the organosilicon compound formed on the surface of the metal oxide. Moreover, even if it exists in more than 99.9 mass parts, an improvement in dispersibility cannot be hoped for, and the refractive index of a film|membrane also falls. That is, the amount of the organosilicon compound containing a (meth)acryl group in the surface-treated metal oxide sol is the sum of those formed on the surface of the metal oxide particles and those freely present in the sol other than that, with respect to 100 parts by mass of the metal oxide particles, R ¹ _n -SiO _(4-n)/2 (However, R ¹ is a group containing at least one selected from a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1-3.) It is preferable that it is 0.1-100 mass parts as Here, when the amount of the organosilicon compound is less than 0.1 parts by mass, the effect of the surface treatment is not obtained. Conversely, when it is more than 100 mass parts, the refractive index of a film|membrane may fall. The amount of the more preferable organosilicon compound is 1 to 70 parts by mass, still more preferably 5 to 40 parts by mass.

Although it will not designate especially as an organosilicon compound if it is an organosilicon compound containing the (meth)acryl group represented by Formula (1), Especially, 3-methacryloxypropyl dimethoxysilane and 3-methacryloxy propyl trimethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyldiethoxysilane, 3-acryloxypropyltriethoxysilane, etc. are mentioned. Among these, 3-methacryloxypropyl trimethoxysilane is especially preferable.

These organosilicon compounds may be used in the state of a monomer, 1 type of polymer or multiple types of polymers chosen from these organosilicon compounds, or a mixture thereof may be sufficient as them.

In the surface-treated metal oxide particles, between the metal oxide particles and the organosilicon compound containing a (meth)acrylic group on the particle surface, silica zirconia, silica alumina, silica titania, silica complex oxide selected from silica tin oxide At least one of a layer and a layer of a single silica can be formed.

By forming these layers, adjustment of refractive index, sensitivity, resolution, and photoactivity becomes easier than the surface-treated metal oxide particle in which the surface of the metal oxide particle is coat|covered only with the organosilicon compound containing a (meth)acryl group.

<Silica Composite Oxide Layer>

Here, the silica composite oxide layer has a molar ratio of SiO ₂ /MO _X (however, MO _X is any one selected from ZrO ₂ , Al ₂ O ₃ , TiO ₂ and SnO ₂ ), 33.3/66.7 to 99.5/ 0.5 is preferred. By forming this layer, it is possible to mainly adjust the photoactivity and refractive index of the metal oxide particles. Here, when SiO2/ _MOX molar ratio is smaller _than 33.3/66.7, it may be difficult to obtain a uniform coating layer, and a metal oxide particle may aggregate. Conversely, when it is larger than 99.5/0.5, it becomes difficult to distinguish from the silica layer, so it is not necessary to form it separately from the silica layer. A more preferable molar ratio is 50.0/50.0 - 95.2/4.8, More preferably, it is 50.0/50.0 - 76.9/23.1.

In addition, the quantity of a silica composite oxide is 1-180 mass parts as (SiO2 _{+ MOX} ) with respect to 100 mass parts of metal oxide particles. When the amount of the silica composite oxide is less than 1 part by mass, the weather resistance may not be sufficient. Conversely, when it is more than 180 mass parts, a desired refractive index may not be obtained. A preferable amount is 2-30 mass parts, More preferably, it is 3-10 mass parts.

<Silica Layer>

As for a silica layer, the quantity of a silica is 0.1-100 mass parts as SiO2 _with respect to 100 mass parts of metal oxide particles. By forming the silica layer, it is possible to mainly adjust the photoactivity of the metal oxide particles and improve the dispersibility of the particles. Here, when the amount of silica is less than 0.1 mass part, the weather resistance by photoactivity adjustment may not be enough, or the organosilicon compound containing a (meth)acryl group after that may become difficult to coat|cover with a metal oxide. Conversely, when it is more than 100 mass parts, a desired refractive index may not be obtained. A preferable amount is 0.5-30 mass parts, More preferably, it is 1-10 mass parts.

This silica-only layer may be formed of an aqueous alkali silicate solution such as water glass or an inorganic silicon compound such as a silicic acid solution, or formed of an organosilicon compound such as tetraethoxysilicate (TEOS) or tetramethoxysilicate (TMOS). may be

In the surface-treated metal oxide particles, the layer between these metal oxide particles and the organosilicon compound containing a (meth)acryl group on the surface of the particle is, in order from the side closest to the metal oxide particle, a layer of silica composite oxide, then It is more preferable that a layer of silica alone is formed, and a layer of an organosilicon compound containing a (meth)acryl group is formed on the outermost surface thereof. This is because by sequentially combining the three layers, the refractive index, sensitivity, resolution and photoactivity can be adjusted step by step, and in particular, by generating OH groups on the surface of the silica layer, which is the second layer, it is easy to give (meth)acryl groups thereto. This is because dispersibility and bonding properties with the resist material can be improved.

《Average particle diameter》

It is preferable that the average particle diameter of the surface-treated metal oxide particle is 5-500 nm. When the average particle diameter is smaller than 5 nm, it is difficult to produce particles of that size, and when the average particle diameter is larger than 500 nm, it is also dependent on the content, but it becomes difficult to obtain transparency of the resist material. A more preferable average particle diameter is 5-200 nm, More preferably, it is 10-25 nm.

《Refractive Index》

The refractive index of the surface-treated metal oxide particles is preferably 1.7 or more in order to make the refractive index as a resist material larger than 1.6.

[Dispersion medium]

As the dispersion medium of the surface-treated metal oxide sol, a conventionally known organic solvent can be used. In particular, for resist materials, this dispersion medium has a solubility parameter (SP value) of 10 or more in consideration of workability as a resist material, and at least one organic solvent having a boiling point of more than 100° C. under atmospheric pressure is contained in the dispersion medium. use what is It is preferable that 30-95 mass % of this organic solvent is contained in a dispersion medium. Here, when the SP value is less than 10, the dispersibility of the surface-treated metal oxide particles becomes low. Moreover, since drying at the time of coating is quick as it is an organic solvent with a boiling point of 100 degrees C or less, and a film|membrane is produced before leveling, there exists a possibility that a bead may generate|occur|produce in a coating film. And when the quantity of the organic solvent in a dispersion medium is less than 30 mass %, the dispersibility of the surface-treated metal oxide particle will fall. Conversely, when it is more than 95 mass %, it will become difficult to obtain a desired film thickness. A more preferable amount is 40-90 mass %, More preferably, it is 50-80 mass %.

Examples of the organic solvent having an SP value of 10 or more and a boiling point exceeding 100°C include propylene glycol monomethyl ether (PGM), propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol mononormal butyl ether, acetyl acetone, ethylene glycol, diphenyl ether, glycerol, formamide, benzyl alcohol, N-methylpyrrolidone, glycerin, cyclohexanone, diethylene glycol monoethyl ether, ethylene glycol monophenyl ether , γ-butyrolactone, diethyl phthalate, dimethyl phthalate, dimethyl sulfoxide, 4-hydroxy-4-methyl-2-pentanone (DAA), 1-butanol, 2-butanol, 1,3-butanediol, 1 ,4-butanediol, 1,4-dioxane, etc. are mentioned. Among these, propylene glycol monomethyl ether (PGM) is especially preferable.

In the dispersion medium described above, in order to further improve dispersibility, at least one solvent having an SP value of 13 or more and a boiling point of 100°C or less under atmospheric pressure may be contained. It is preferable that content in the dispersion medium of this solvent is less than 20 mass %. By containing this solvent, it solvates and stability of sol improves. When this solvent contains 20 mass % or more, the bead of a coating film may generate|occur|produce or hardness may become inadequate. A more preferable amount is 1-15 mass %, More preferably, it is 3-12 mass %.

Examples of the solvent having an SP value of 13 or more and a boiling point of 100°C or less include a lower alcohol and water. Among these, methanol and ethanol are especially preferable.

<Impurity>

In the surface-treated metal oxide sol, sodium, potassium, and ammonia may be contained as an impurity. When a large amount of any one of these types exists, the stability of the sol will decrease. Moreover, the workability as a resist material also deteriorates, and it becomes difficult to expose and develop in pattern shape. For this reason, it is preferable that sodium is 25 ppm or less as a Na ₂ O concentration, More preferably, it is less than 20 ppm, potassium is less than 0.5 mass % as a K ₂ O concentration, and ammonia is less than 1000 ppm as an NH ₃ concentration.

<<Concentration of surface-treated metal oxide sol>>

It is preferable that solid content concentration of the surface-treated metal oxide sol is 5-70 mass %. When solid content concentration is lower than 5 mass %, desired refractive index and film|membrane hardness may not be obtained. When the solid content concentration is higher than 70 mass%, it becomes difficult to obtain transparency of the resist material. A more preferable quantity is 10-60 mass %, More preferably, it is 20-40 mass %.

[Method for producing surface-treated metal oxide sol]

<First step>

A 1st process is a process of manufacturing a metal oxide particle. Hereinafter, the manufacturing method is demonstrated.

<Method for producing metal oxide sol>

≪Preparation of aqueous titanic acid solution≫

A gel or sol of hydrous titanic acid is prepared by a conventionally known method. The hydrous titanate gel is obtained, for example, by adding an alkali to an aqueous solution such as titanium chloride or titanium sulfate to neutralize it. The hydrous titanate sol is obtained by passing an aqueous solution such as titanium chloride or titanium sulfate through an ion exchange resin to remove anions. Hydrous titanic acid as used herein means titanium oxide hydrate or titanium hydroxide.

Next, to the obtained hydrous titanate gel, hydrous titanate sol, or a mixture thereof, hydrogen peroxide is added to dissolve the hydrous titanic acid to prepare a uniform aqueous solution. At this time, it is preferable to heat or stir. At this time, if the concentration of hydrous titanic acid is too high, it is not preferable because it takes a long time to dissolve the hydrous titanic acid, furthermore, precipitation of an undissolved gel occurs, or the viscosity of the resulting aqueous solution becomes high. For this reason, as _a TiO2 concentration, it is about 10 mass % or less, It is preferable that it is about 5 mass % or less preferably. If the amount of hydrogen peroxide to be added is 1 or more in the H ₂ O ₂ /TiO ₂ mass ratio, hydrous titanic acid can be completely dissolved. When the H ₂ O ₂ /TiO ₂ ratio is less than 1, the hydrous titanic acid is not completely dissolved, and unreacted gel or sol remains, which is not preferable. In addition, the larger the H ₂ O ₂ /TiO ₂ ratio, the greater the dissolution rate of hydrous titanic acid and the reaction is completed in a short time. It is not desirable because it is crazy. Accordingly, it is preferable to use the hydrogen peroxide in an amount such that the H ₂ O ₂ /TiO ₂ ratio is 1 to 6, preferably 2 to 6 or so. When hydrogen peroxide is used in such an amount, hydrous titanic acid is completely dissolved in about 0.5 to 20 hours. The reaction temperature at this time is 50 degreeC or more, Preferably it is 70 degreeC or more.

≪Preparation of titania (TiO ₂ ) aqueous dispersion≫

Next, the aqueous solution (aqueous titanic acid aqueous solution) obtained as described above in which hydrous titanic acid is dissolved is heated to 60°C or higher, preferably 80°C or higher to hydrolyze titanic acid. Thereby, the aqueous dispersion _of TiO2 particle|grains is obtained.

≪Preparation of titania silica (TiO ₂ /SiO ₂ ) aqueous dispersion≫

A predetermined amount of a silicon compound is mixed with the aqueous titanic acid solution described above, and heated to 60°C or higher, preferably 80°C or higher to hydrolyze titanic acid. Thereby, _the aqueous dispersion _of TiO2/SiO2 particle|grains is obtained.

Here, as the silicon compound, a silicic acid solution obtained by deallkaling an aqueous alkali silicate solution with a cation exchange resin, a silica sol obtained by neutralizing an alkali silicate with an acid, or an alkoxide such as ethyl silicate or a solution of a silicon compound such as a hydrolyzate thereof, or A dispersion is used. A commercially available silica sol may also be used. In these cases, it is preferable that the average particle diameter of silica is 500 nm or less. The ratio of TiO ₂ /SiO ₂ is 75/25 or more. Moreover, _a preferable ratio _of TiO2/SiO2 is 80/20 or more.

As a method of adding the solution or dispersion of the silicon compound to the aqueous titanic acid solution, the solution or dispersion of the silicon compound is gradually added while heating the aqueous titanic acid solution, and after mixing the titania sol precursor and the solution or dispersion of the silicon compound at once, Any of the heating methods may be used, and it should be selected according to the titania concentration and the silica concentration in the solution or dispersion of the silicon compound. When the titania concentration is less than 1 mass %, which is relatively thin, there is no problem even if both are mixed at once. However, when the titania concentration is relatively rich (1 mass % or more), the silica may aggregate titania. When the concentration of , silica is high, it is preferable to add slowly from the viewpoint of aggregation and polymerization by a single silica component.

The temperature at the time of addition or mixing is usually preferably carried out by heating to about 60° C. or higher in order to promote the reaction between the silicon compound and titania. However, when alkoxides such as ethyl silicate are used, their hydrolysis rate is high and silica colloidal particles are easily generated in the mixed solution. Thereafter, a method of raising the temperature to about 60° C. or higher to complete the reaction is adopted. The pH of the mixed solution at the time of adding the silicon compound is preferably neutral to alkaline in view of the stability of the aqueous titanic acid solution and the resulting titania sol, and is usually carried out in the range of about 6 to 10. In the case of concentrating the TiO ₂ /SiO ₂ aqueous dispersion, known methods such as evaporation and ultrafiltration are possible.

≪Preparation of an aqueous dispersion of titania silica tin oxide (TiO ₂ /SiO ₂ /SnO ₂ )≫

A predetermined amount of a silicon compound or a tin compound is mixed with the aqueous titanic acid solution described above, and heated to 60°C or higher, preferably 80°C or higher to hydrolyze titanic acid. Thereby _{, the} aqueous dispersion _of TiO2/SiO2/SnO2 particle|grains is obtained.

Here, as a silicon compound, _the thing similar to what was used by manufacture _of TiO2/SiO2 mentioned above can be used.

As the tin compound added to the aqueous titanic acid solution, an aqueous solution or dispersion of a tin compound such as tin chloride, tin sulfate or tin oxychloride is used. The addition method of such a tin compound to titanic acid aqueous solution can be added similarly to _the silicon compound _of TiO2/SiO2 mentioned above. The order of addition may add either one first, and may add it simultaneously. _The ratio _of TiO2/SiO2/SnO2 is 70-90 mass % _of TiO2 _, 10-20 mass % _of SiO2 _, SnO2 is _2-30 mass %, TiO2/(SiO2 _{+ SnO2} ) The ratio is in the range of 50/50 to 95/5. Other manufacturing conditions are _the same as that _of TiO2/SiO2 mentioned above. Preferably, TiO2 is 70-90 mass %, SiO2 is 10-20 mass %, SnO2 is _2-30 mass % _{, The} ratio _of TiO2/(SiO2 _{+ SnO2} ) is 70/30-90/ It is in the range of 10.

≪Iron or ceria doping treatment≫

_The iron or ceria doping treatment with respect to TiO2/SiO2 or TiO2/SiO2/SnO2 prepares _the aqueous solution _of the _{chloride of} iron or cerium, and a titanium salt in manufacture of the titanic acid aqueous solution mentioned above, this It is obtained by adding an alkali to neutralization. Subsequent manufacturing methods are performed similarly to the manufacturing method of titanic acid aqueous solution, the manufacturing method of TiO ₂ /SiO ₂ , or the manufacturing method of TiO ₂ /SiO ₂ /SnO ₂ . _A dope amount is less _{than 10} mass parts as _Fe2O3 or _{CeO2 with} respect to 100 mass parts _of TiO2/SiO2 or TiO2/SiO2/SnO2 target object _. A preferable dope amount is less than 5 mass parts, More preferably, it is less than 3 mass parts.

≪Organic Solvent Substitution≫

Before the "second step" described later, the aqueous dispersion of the target metal oxide particles is replaced with a conventionally known organic solvent. Alcohols, esters, glycols, and ethers can be used for this organic solvent. Specific examples of alcohols include methanol, ethanol, propanol, and 2-propanol. Examples of the esters include methyl acetate, ethyl acetate, isopropyl acetate, and propyl acetate. Examples of glycols include ethylene glycol and hexylene glycol. Examples of the ethers include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. These may be used independently and may mix and use 2 or more types. Among these, methanol and ethanol which are a lower alcohol especially are preferable.

Solvent substitution can be performed by a conventionally well-known method, such as use of an ultrafiltration apparatus. It is preferable that content of the water in the dispersion medium after solvent substitution shall be less than 20 mass % at most.

<Second process>

In the second step, the surface of the metal oxide particles is treated with an organosilicon compound containing a (meth)acryl group represented by Formula (1), and a layer of an organosilicon compound containing a (meth)acryl group on the surface of the metal oxide particles is formed. It is a process of forming Hereinafter, the manufacturing method is demonstrated.

<Preparation of layer of organosilicon compound containing (meth)acryl group>

The organosilicon compound containing the (meth)acryl group represented by Formula (1) is added to the organic solvent dispersion liquid of this metal oxide particle. Although the method of addition is not specifically limited, It is preferable to add while stirring so that both may be fully mixed. Moreover, in order to accelerate|stimulate reaction, you may heat to about 40-60 degreeC.

The addition amount of this (meth)acryl group-containing organosilicon compound is R ¹ _n -SiO _(4-n)/2 (provided that R ¹ is methacryl with respect to 100 parts by mass of the metal oxide particles on the surface of the metal oxide particles. It is a group containing at least one selected from a group and an acryl group, and may be the same or different from each other. n is an integer of 1 to 3.) in an amount of 0.1 to 60 parts by mass, and other than those formed on the surface of the metal oxide particles R ¹ _n -SiO _(4-n)/2 (provided that R ¹ contains at least one selected from a methacryl group and an acryl group, based on 100 parts by mass of the metal oxide particles by adding up those that are free in the sol The group to be used may be the same or different from each other. n is an integer of 1 to 3), and 0.1 to 100 parts by mass is added by the amount to be formed. The preferable amount of the organosilicon compound is from 1 to 70 parts by mass, more preferably from 5 to 40 parts by mass.

≪Solvent substitution≫

Next, solvent substitution is carried out by a conventionally known method with an organic solvent having an SP value of 10 or more and a boiling point of more than 100°C. It is made so that 30-95 mass % of this organic solvent is contained in a dispersion medium.

Thereby, the surface-treated metal oxide sol of this invention is obtained.

In order to improve dispersibility more in the surface-treated metal oxide sol mentioned above, less than 20 mass % of a lower alcohol and water may contain. However, it is preferable that sodium is 25 ppm or less as a concentration of Na ₂ O, more preferably less than 20 ppm, potassium is less than 0.5% as a concentration of K ₂ O, and ammonia is less than 1000 ppm as a concentration of NH ₃ .

<Third step>

The third step is a step of forming a layer of a silica composite oxide selected from silica zirconia, silica alumina, silica titania, and silica tin oxide on the surface of the metal oxide particles. Hereinafter, the manufacturing method is demonstrated.

<Preparation of layer of silica composite oxide>

In order to form the layer of the silica composite oxide to be formed on the target metal oxide particle, a silicon compound, a zirconium compound, an aluminum compound, a titanium compound, and a tin compound are used as a raw material.

Here, as the silicon compound, a silicic acid solution obtained by deallkaling an aqueous alkali silicate solution with a cation exchange resin, a silica sol obtained by neutralizing an alkali silicate with an acid, or an alkoxide such as ethyl silicate or a solution of a silicon compound such as a hydrolyzate thereof Alternatively, a dispersion may be used. A commercially available silica sol may also be used.

Aqueous solutions and dispersion liquids, such as a chloride, a sulfuric compound, an ammonium carbonate compound, an oxychloride compound, and a metal alkoxide, etc. are used for metal compounds other than a silicon compound. Hydrogen peroxide is added to what was neutralized or hydrolyzed by adding alkali to these to obtain an aqueous solution of a metal acid selected from zirconium, aluminum, titanium and tin.

Next, the solution or dispersion of a silicon compound and the metal acid aqueous solution mentioned above are added to the dispersion liquid of the metal oxide particle which is the object. Although the method of addition is not specifically limited, It is preferable to add while stirring so that both may be fully mixed. Moreover, in order to accelerate|stimulate reaction, you may heat. The silicon compound and the metal compound other than the silicon compound each have a molar ratio of SiO ₂ /MO _X (provided that MO _X is any one selected from ZrO ₂ , Al ₂ O ₃ , TiO ₂ and SnO ₂ ) 33.3/ 66.7 to 99.5/0.5. A preferable molar ratio is 50.0/50.0 - 95.2/4.8, More preferably, it is 50.0/50.0 - 76.9/23.1. In addition, the quantity is 1-180 mass parts as (SiO2 _{+ MOX} ) with respect to 100 mass parts of metal oxide particles. A preferable amount is 2-30 mass parts, More preferably, it is 3-10 mass parts.

<Fourth process>

A 4th process is a process of forming a silica layer on the surface of a metal oxide particle. Hereinafter, the manufacturing method is demonstrated.

<Production of Silica Layer>

In order to form a silica layer to be formed on the target metal oxide particles, as a raw material, a silicic acid solution obtained by deallkaling an aqueous alkali silicate aqueous solution with a cation exchange resin, a silica sol obtained by neutralizing an alkali silicate with an acid, or an alkoxide such as ethyl silicate Alternatively, a solution or dispersion of a silicon compound such as a hydrolyzate thereof is used. A commercially available silica sol may also be used.

A solution or dispersion of a silicon compound is added to the dispersion of the target metal oxide particles. Although the method of addition is not specifically limited, It is preferable to add while stirring so that both may be fully mixed. Moreover, in order to accelerate|stimulate reaction, you may heat. A silicon compound is 0.1-100 mass parts as SiO2 _with respect to 100 mass parts of metal oxide particles. A preferable amount is 0.5-30 mass parts, More preferably, it is 1-10 mass parts.

《Order of Process》

As for the surface-treated metal oxide particle which comprises this invention, the organosilicon compound containing the (meth)acryl group represented by Formula (1) on the surface is formed. The order of the processes does not particularly matter as long as this configuration can be realized. However, considering the productivity and quality stability in manufacturing, it is preferable to carry out the "2nd process" of carrying out this last among those implemented in the 1st - 4th process mentioned above. In addition, it is preferable to implement "the 1st process" of manufacturing a metal oxide particle first among those performed by the 1st - 4th process mentioned above.

In the order of the process of manufacturing the surface-treated metal oxide particles,

When metal oxide particles are produced (first step), and then an organosilicon compound containing a (meth)acryl group is formed on the surface of the metal oxide particles (second step)

A metal oxide particle is prepared (first step), and then a layer of silica complex oxide selected from silica zirconia, silica alumina, silica titania, and silica tin oxide is formed on the surface of the metal oxide particle (third step), In the case of forming an organosilicon compound containing a (meth)acryl group after this (second step)

Metal oxide particles are prepared (first step), then a silica layer is formed on the surface of the metal oxide particles (fourth step), and then an organosilicon compound containing a (meth)acryl group is formed (second step) fair) case

A metal oxide particle is prepared (first step), and then a layer of a silica complex oxide selected from silica zirconia, silica alumina, silica titania, and silica tin oxide is formed on the surface of the metal oxide particle (third step) , In the case of further forming a silica layer (4th step) and then forming an organosilicon compound containing a (meth)acryl group (2nd step)

is exemplified.

≪Dealkali Process≫

In the 1st - 4th process mentioned above, in order to advance reaction, it is preferable to dealkalize as needed. A conventionally well-known method, such as use of an ion exchange resin and an ultrafiltration apparatus, can be used for the dealkali treatment. In the dealkalization step, sodium in the surface-treated oxide sol of the present invention obtained in the second step is 25 ppm or less as a Na ₂ O concentration, more preferably less than 20 ppm, potassium is less than 0.5% as a K ₂ O concentration, and ammonia is It carries out suitably so that it may become less than 1000 ppm as NH ₃ concentration.

Example

Hereinafter, Examples will be specifically described. The present invention is not limited by these examples.

[Example 1]

<Production of titania-based particles (according to the first step)>

450 g of titanium tetrachloride aqueous solution containing 2 mass % of titanium tetrachloride in conversion of TiO ₂ and 15 mass % aqueous ammonia 176 g were mixed, and the white slurry liquid of pH 8.6 was prepared. Next, after filtering this slurry, it wash|cleaned with pure water, and obtained 180 g of hydrous titanic acid cakes whose solid content is 5 mass %.

Next, after adding 205.6 g of 35 mass % hydrogen peroxide solution and 514.4 g of pure water to 180 g of this cake, it heats at the temperature of 80 degreeC for 1 hour, and the titanic acid peroxide aqueous solution which contains ₂ mass % of titanic acid peroxide in conversion of TiO2. 900 g were obtained. This aqueous titanic acid solution was transparent yellow-brown and had a pH of 8.1.

Next, 8.2 g of silica sol (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN-350) containing 15 mass % of silica particles with an average particle diameter of 7 nm is mixed with 450 g of this aqueous titanic acid solution and 589 g of pure water Thus, hydrothermal treatment was performed in an autoclave at 165°C for 18 hours.

Next, after cooling the obtained aqueous solution to room temperature, it concentrated using the ultrafiltration membrane apparatus, and obtained the titania-type particle|grain (1-A) aqueous dispersion whose solid content concentration is 10 mass %.

The refractive index of the particles of the titania-based fine particles (1-A) was 2.3.

<Production of silica composite oxide layer (according to the third step)>

To 263 g of zirconium oxychloride aqueous solution containing 2 mass % of zirconium oxychloride in terms of ZrO ₂ , 15 mass % aqueous ammonia was gradually added under stirring to obtain a slurry liquid of pH 8.5 containing the hydrate of zirconium. Then, after filtering this slurry, pure water wash|cleaned and 52.6 g of cakes containing 10 mass % of zirconium components in conversion _of ZrO2 were obtained.

Next, after adding 180 g of pure water to 20 g of this cake, and also adding 12 g of 10 mass % potassium hydroxide aqueous solution and making it alkaline, 40 g of 35 mass % hydrogen peroxide solutions are added, and it heats at 50 degreeC, and a cake was dissolved. And 148 g of pure water was added, and 400 g of zirconic-acid aqueous solutions containing 0.5 mass % of zirconic _- acid peroxides as ZrO2 were obtained.

On the other hand, a cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was gradually added to a 2 mass % water glass as SiO ₂ , and dealkalization was performed, followed by separation of the ion exchange resin to obtain a 2 mass % silicic acid aqueous solution as SiO ₂ . .

Next, 320 g of pure water was added to 80 g of a 10 mass % aqueous dispersion of titania-type particle|grains ( ₁ -A) as TiO2, and it heated at 90 degreeC. 26.7 g of the said zirconic acid aqueous solution and 21.2 g of silicic acid aqueous solution were gradually added to this. After the addition was completed, the mixture was stirred for 1 hour while maintaining 90°C, and then hydrothermal treatment was performed on this liquid mixture in an autoclave at 165°C for 18 hours.

Subsequently, after cooling this liquid mixture to room temperature, it concentrated with the ultrafiltration membrane apparatus, and obtained 128 g of titania-type particle|grains (1-B) aqueous dispersion with a solid content concentration of 10 mass % which formed the composite oxide layer of silica zirconia.

<Production of silica layer (according to the fourth step)>

To 117 g of the aqueous dispersion of titania particles (1-B), a cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was gradually added to dealkalization, and then the ion exchange resin was isolated. To this solution, 126.0 g of a methanol solution in which 8.96 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., SiO ₂ component 28.8 mass%) was dissolved was slowly added, heated and stirred at 50° C. for 1 hour, and titania-based particles A water/methanol dispersion of (1-C) was obtained.

The obtained water/methanol dispersion of titania-based particles (1-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. Thereafter, it concentrated to obtain 40 g of a methanol dispersion of titania-based particles (1-C) having a solid content concentration of 30 mass% in which a silica layer was formed.

The amount of water contained in the thus obtained methanol dispersion of titania-based particles (1-C) was 0.3 mass%.

<Preparation of surface-treated metal oxide sol: surface treatment with an organosilicon compound containing a (meth)acryl group (according to the second step)>

To 40 g of titania-based particles (1-C) methanol dispersion, 1.47 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was slowly added, followed by 19 at 50°C Time was heated and stirred.

After cooling to room temperature, the dispersion medium was substituted with propylene glycol monomethyl ether (PGME) using the ultrafiltration membrane, and 40 g of surface-treated metal oxide sol (1-D) with a solid content concentration of 30 mass % was obtained. Table 1 shows the composition of the obtained surface-treated metal oxide sol.

<Measurement of average particle diameter>

The average particle diameter is obtained as an average value by taking an electron microscope photograph, measuring the particle diameter of 100 arbitrary particles.

<<Measuring Method of Refractive Index of Particles>>

1) The dispersion is taken in an evaporator, and the dispersion medium is evaporated.

2) It is dried at 120 degreeC, and it is made into powder.

3) 2 or 3 drops of a standard refractive solution for which the refractive index is known in advance is dropped onto a glass plate, and the powder is mixed thereto.

4) The operation of 3) above is performed with various standard refractive solutions, and the refractive index of the standard refractive solution when the mixed solution becomes transparent is used as the refractive index of the particles.

<Production of paint (1) for forming a transparent film>

84.1 g of propylene glycol monomethyl ether and 1.2 g of ethoxylated bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester ABE-300), and ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical) : NK ester ATM-4E) 0.6 g was added and mixed well. Subsequently, 0.05 g of 2,2-dimethoxy-1,2-diphenylethan-1-one (manufactured by BASF Co., Ltd.: IRGACURE 651) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ( BASF Co., Ltd. product: IRGACURE 819) 0.04 g was added and mixed well to prepare a binder for a transparent film.

Next, 14.0 g of surface-treated metal oxide sol (1-D) was mixed with the said binder for transparent films, and the coating material (1) for transparent film formation with a solid content concentration of 6 mass % was prepared.

<Production of base material (1-FA) with transparent film>

The coating material for forming a transparent film (1) is applied to an easily-adhesive PET film (manufactured by Toyobo: Cosmoshine A-4300, thickness 188 µm, total light transmittance 92.0%, haze 0.7%) by a bar coater method (bar #10), After drying at 80° C. for 1 minute, it was cured by irradiating 120 mJ/cm 2 with a high-pressure mercury lamp (manufactured by Nippon Battery: UV irradiation device CS30L21-3) to prepare a base material (1-FA) with a transparent film. The thickness of the transparent film at this time was 400 nm.

The following method evaluated the haze, total light transmittance, refractive index, abrasion resistance, and weather resistance of the obtained film|membrane.

<< haze, measurement of total light transmittance >>

The haze and total light transmittance of the obtained transparent film were measured with the haze meter (Nippon Denshoku Co., Ltd. product: NDH-2000). A haze and a total light transmittance are evaluated by the following references|standards, and a result is shown in a table|surface.

<Evaluation criteria>

haze;

1.0% or less: ◎

1.1 to 2.0%: ○

2.1% or more: ×

<Evaluation criteria>

total light transmittance;

85 to 100%: ◎

75 to 84%: ○

74% or less: ×

《Measurement of refractive index》

The refractive index of the film was measured with a spectroscopic ellipsometer (manufactured by Nippon Semi-Labo Corporation: SE-2000). The following reference|standard evaluated refractive index, and a result is shown in a table|surface.

<Evaluation criteria>

1.70 or higher: ◎

1.60 ∼ 1.69 : ○

1.59 or less: ×

《Measurement of scratch resistance》

Using #0000 steel wool, it was slid 50 times under a load of 500 g/cm 2 , and the surface of the membrane was visually observed. The following criteria evaluated abrasion resistance, and a result is shown in a table|surface.

<Evaluation criteria>

Scratches on stripes are not recognized: ◎

Slight scratches are recognized in the form of stripes: ○

Many scratches are recognized in the form of stripes: △

The whole face is chamfered : ×

《Measurement of weather resistance》

The substrate (1-FA) on which the transparent conductive film was formed was irradiated with ultraviolet rays for 24 hours using a mercury lamp for a discoloration test (manufactured by Toshiba Corporation: H400-E), and the color was visually confirmed. Weather resistance was evaluated on the basis of the following criteria, and the results are shown in the table. Moreover, the irradiation distance of a lamp|ramp and the test piece was 70 mm, and the output of a lamp|ramp was adjusted so that the surface temperature of a test piece might be set to 45±5 degreeC.

<Evaluation criteria>

Not much discoloration is recognized: ◎

Slight discoloration is recognized: ○

Obvious discoloration is recognized: ×

<Production of base material (1-FB) with transparent film>

The coating material (1) for forming a transparent film was applied to a 6-inch silicon wafer by a spin coater, dried at 80°C for 1 minute, and then an ArF excimer laser (193 nm) was applied using an exposure apparatus NSR-S302 (manufactured by Nikon Corporation). It was irradiated and hardened|cured, and the base material (1-FB) with a transparent film was prepared. The thickness of the transparent film at this time was 400 nm.

The bead and sensitivity of the obtained membrane were evaluated by the following method.

《Measurement of beads》

The cross section of the substrate (1-FB) on which the transparent conductive film was formed was observed with a scanning electron microscope, and the width of the film end portion which was 10% or more thicker than the film thickness of the film center portion was measured. The beads were evaluated by the following evaluation criteria, and the results are shown in the table.

<Evaluation criteria>

Thickness of 10% or more, the width of the end of the membrane is less than 0.5 mm: ◎

0.5-1.0 mm in width at the end of the 10% or more thick film: ○

Thickness of 10% or more The width of the end of the membrane is 1.1 mm or more: ×

《Measurement of sensitivity and film remaining rate》

<Evaluation criteria>

The substrate (1-FB) on which the transparent conductive film was formed was immersed in a 1 mass% Na ₂ CO ₃ aqueous solution for 10 minutes to remove the uncured portion, then dried at 80° C. overnight, and the sensitivity and the remaining film rate were determined from the mass difference before and after immersion. It evaluates and shows a result in a table|surface.

<Evaluation criteria>

The difference in mass before and after immersion in Na ₂ CO ₃ aqueous solution is 0 to 3%: ◎

The difference in mass before and after immersion in Na ₂ CO ₃ aqueous solution is 4 to 10%: ○

The mass difference before and after immersion in Na ₂ CO ₃ aqueous solution is 11% or more: ×

<Production of base material with transparent film (1-FC)>

The coating material for forming a transparent film (1) was applied to a 6-inch silicon wafer with a spin coater, dried at 80° C. for 1 minute, and then a photomask (1:1 ratio) was used using an exposure apparatus NSR-S302 (manufactured by Nikon Corporation). irradiated with an ArF excimer laser (193 nm) through a line pattern of Then, the ₁ mass % _Na2CO3 aqueous solution was sprayed, the unexposed part was dissolved and removed, and it heated at 150 degreeC for 3 minute(s), and the base material (1-FC) with a transparent film was prepared.

From the obtained transparent film-formed substrate (1-FC), the resolution was evaluated by the following method.

《Measurement of resolution》

The minimum pitch width at which the pitch width is normally formed by changing the pitch width of the photomask when manufacturing the base material (1-FC) on which the transparent conductive film is formed is evaluated as a value of resolution as follows, and the results are shown in the table .

<Evaluation criteria>

Pitch width 30 μm or less: ◎

Pitch width 31 μm to 50 μm: ○

Pitch width 51 μm or more: ×

[Example 2]

In the second step, in the same manner as in Example 1 except that 0.06 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was used, the surface-treated metal oxide sol (2- D) was obtained. Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (2-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate with a transparent film was prepared and evaluated.

[Example 3]

In the second step, in the same manner as in Example 1 except that 7.2 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was used, the surface-treated metal oxide sol (3- D) was obtained. Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (3-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 4]

After adding 0.06 g of 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. make: KBM-503) in a 2nd process, Example 1 except having added 0.29 g of 2.9 mass % ammonia aqueous solution It carried out similarly to the above, and obtained the surface-treated metal oxide sol (4-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (4-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 5]

After adding 7.2 g of 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co., Ltd. make: KBM-503) in a 2nd process, Example 1 except having added 0.29 g of 2.9 mass % ammonia aqueous solution It carried out similarly to the above, and obtained the surface-treated metal oxide sol (5-D).

Except having used the surface treatment metal oxide sol (5-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 6]

In the 4th process, it carried out similarly to Example 1, and surface-treated metal oxide sol except having used 126.0 g of methanol solutions in which 0.90 g of tetraethoxysilane ( _The Tama Chemical Co., Ltd. product, SiO2 component 28.8 mass %) was dissolved. (6-D) was obtained. Table 1 shows the composition of the obtained surface-treated metal oxide sol.

A coating material for forming a transparent film was prepared in the same manner as in Example 1 except that the surface-treated metal oxide sol (6-D) was used. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 7]

In the 4th process, it carried out similarly to Example 1, except having used the methanol solution 126.0g in which 44.8g of tetraethoxysilane (The Tama Chemical Co., Ltd. product, SiO2 component 28.8 mass %) was dissolved, It surface _- treated metal oxide sol (7-D) was obtained. Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (7-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 8]

The 3rd process WHEREIN: Except having used 7.6 g of zirconic-acid aqueous solution and 6.1 g of silicic-acid aqueous solution, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (8-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (8-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 9]

The 3rd process WHEREIN: Except having used 171.6g of zirconic-acid aqueous solutions and 142.3g of silicic-acid aqueous solutions were used, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (9-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (9-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 10]

At the 3rd process, it carried out similarly to Example 1 except having used 6.02g of zirconic-acid aqueous solution and 23.7g of silicic-acid aqueous solution, and obtained the surface-treated metal oxide sol (10-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (10-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 11]

At the 3rd process, it carried out similarly to Example 1 except having used 120.5g of zirconic-acid aqueous solution and 9.8g of silicic-acid aqueous solution for the aqueous solution of zirconic acid, and obtained the surface-treated metal oxide sol (11-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (11-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 12]

In the third step, in place of the aqueous zirconic acid solution and the aqueous silicic acid solution, 11.5 g of an aqueous sodium aluminate solution having an Al ₂ O ₃ concentration of 1.0 mass% and 14.8 g of an aqueous sodium silicate solution having a concentration of 3.0 mass% in terms of SiO ₂ were used. In the same manner as in Example 1, an aqueous dispersion of titania-based particles (12-B) having a solid content concentration of 10% by mass in which a silica-alumina composite oxide layer was formed was obtained.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (12-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (12-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 13]

In the third step, in place of the aqueous zirconic acid solution and the aqueous silicic acid solution, 11.5 g of an aqueous sodium aluminate solution having an Al ₂ O ₃ concentration of 1.0 mass% and 14.8 g of an aqueous sodium silicate solution having a concentration of 3.0 mass% in terms of SiO ₂ were used. In the same manner as in Example 1, an aqueous dispersion of titania-based particles (13-B) having a solid content concentration of 10% by mass in which a silica-alumina composite oxide layer was formed was obtained.

Next, in the same manner as in Example 1, except that the dealkalization treatment using the cation exchange resin in the fourth step was repeatedly performed, a silica layer was formed and the titania-based particles (13-C) methanol dispersion having a solid content concentration of 30% by mass got

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (13-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (13-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 14]

In the third step, in place of the aqueous zirconic acid solution and the aqueous silicic acid solution, 9.5 g of a titanium tetrachloride aqueous solution having a concentration of 1.0 mass% in terms of TiO ₂ and 15.5 g of an aqueous sodium silicate solution having a concentration of 3.0% by mass in terms of SiO ₂ were used. Similarly, an aqueous dispersion of titania-based particles (14-B) having a solid content concentration of 10% by mass in which a silica titania composite oxide layer was formed was obtained.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (14-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (14-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 15]

In the third step, the same as in Example 1 except that 15.5 g of an aqueous potassium stannate solution having a concentration of 1.0 mass% in terms of SnO ₂ and 13.5 g of an aqueous solution of silicic acid having a concentration of 2.0 mass% in terms of SiO ₂ were used instead of the aqueous zirconic acid solution and the aqueous solution of silicic acid Thus, an aqueous dispersion of titania-based particles (15-B) having a solid content concentration of 10% by mass in which a composite oxide layer of silica tin oxide was formed was obtained.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (15-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (15-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate with a transparent film was prepared and evaluated.

[Example 16]

In the 1st process, it carried out similarly to Example 1 except having mixed 599 g of pure water without using a silica sol with 450 g of 2 mass % aqueous titanic acid peroxide solution in conversion of TiO ₂ , and solid content concentration of 10 mass % titania An aqueous dispersion of particles (16-A) was obtained.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (16-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (16-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 17]

Silica sol containing 15 mass % of silica particles with an average particle diameter of ₇ nm as SiO2 in 450 g of ₂ mass % titanic acid aqueous solution in conversion of TiO2 in a 1st process (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN-350) was carried out similarly to Example 1 except mixing 17.9 g and pure water 581 g, and solid content concentration obtained the titania type particle|grain (17-A) aqueous dispersion of 10 mass %.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (17-D). Table 1 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (17-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate with a transparent film was prepared and evaluated.

[Example 18]

In the first step, 35.0 g of a cation exchange resin was mixed with 729.0 g of a 2 mass % aqueous titanic acid solution in terms of TiO ₂ prepared in the same manner as in Example 1, and 91.0 g of a 1 mass % aqueous potassium stannate solution in terms of SnO ₂ was mixed thereto. was added slowly under stirring, and the cation exchange resin was separated.

Next, 8.0 g of silica sol (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN-350) containing silica particle of 7 nm in average particle diameter 15 mass % as SiO2 and 180.0g _of pure water are mixed, and in an autoclave Hydrothermal treatment was performed at 165 degreeC for 18 hours.

Next, after cooling the obtained aqueous solution to room temperature, it concentrated using the ultrafiltration membrane apparatus, and obtained the titania type microparticles|fine-particles (18-A) aqueous dispersion with a solid content concentration of 10 mass %.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (18-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (18-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 19]

In the first step, 444.9 g of titanium tetrachloride aqueous solution containing 2% by mass of titanium tetrachloride in terms of TiO ₂ and 5.1 g of aqueous solution of 2% by mass of iron chloride in terms of Fe ₂ O ₃ are mixed, and 176 g of 15% by mass of aqueous ammonia is mixed. Except having carried out, it carried out similarly to Example 1, and obtained the iron-doped titania type particle|grain (19-A) aqueous dispersion with a solid content concentration of 10 mass %.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (19-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (19-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 20]

In the first step, 404.0 g of titanium tetrachloride aqueous solution containing 2% by mass of titanium tetrachloride in terms of TiO ₂ and 46.0 g of aqueous solution of 2% by mass of iron chloride in terms of Fe ₂ O ₃ are mixed, and 176 g of 15% by mass of aqueous ammonia is mixed. Except having carried out similarly to Example 1, 104.9 g of iron-doped titania-type particle|grains (20-A) aqueous dispersion with a solid content concentration of 10 mass % were obtained.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (20-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (20-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate with a transparent film was prepared and evaluated.

[Example 21]

In the first step, 444.9 g of a titanium tetrachloride aqueous solution containing 2% by mass of titanium tetrachloride in terms of TiO ₂ and 5.1 g of a 2% by mass of cerium chloride aqueous solution in terms of CeO ₂ were mixed, and 176 g of 15% by mass of aqueous ammonia was mixed. Except for that, it carried out similarly to Example 1, and obtained the aqueous dispersion of cerium-doped titania type particle|grains (21-A) with a solid content concentration of 10 mass %.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (21-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (21-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate with a transparent film was prepared and evaluated.

[Example 22]

In the first step, 404.0 g of a titanium tetrachloride aqueous solution containing 2 mass% of titanium tetrachloride in terms of TiO ₂ and 46.0 g of a 2 mass % aqueous cerium chloride solution in terms of Fe ₂ O ₃ are mixed, and 176 g of 15 mass % aqueous ammonia It carried out similarly to Example 1 except having mixed, and obtained the aqueous dispersion of cerium-doped titania type particle|grains (22-A) with a solid content concentration of 10 mass %.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (22-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (22-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 23]

1st process WHEREIN: The silica sol which contains 15 mass % of silica particles with an _average particle diameter as SiO2 in 450 g of ₂ mass % titanic acid aqueous solution in conversion of TiO2 (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN) -350) except having mixed 8.2 g and pure water 239.1 g, it carried out similarly to Example 1, and obtained the titania type particle|grain (23-A) aqueous dispersion with a solid content concentration of 10 mass %.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (23-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (23-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 24]

1st process WHEREIN: The silica sol which contains 15 mass % of silica particles with an _average particle diameter as SiO2 in 450 g of ₂ mass % titanic acid aqueous solution in conversion of TiO2 (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN) -350) was carried out in the same manner as in Example 1 except that 8.2 g and 1637.1 g of pure water were mixed to obtain an aqueous dispersion of titania-based particles (24-A) having a solid content concentration of 10% by mass.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (24-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (24-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 25]

1st process WHEREIN: The silica sol which contains 15 mass % of silica particles with an _average particle diameter as SiO2 in 450 g of ₂ mass % titanic acid aqueous solution in conversion of TiO2 (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN) -350) was carried out similarly to Example 1 except having mixed 8.2 g and 122.6 g of pure water, and solid content concentration obtained the titania type particle|grain (25-A) aqueous dispersion of 10 mass %.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (25-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (25-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 26]

Silica sol containing 15 mass % of silica particles with an average particle diameter of ₇ nm as SiO2 in 450 g of ₂ mass % titanic acid aqueous solution in conversion of TiO2 of a 1st process (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN -350) was carried out similarly to Example 1 except having mixed 8.2 g and 122.6 g of pure water, and solid content concentration obtained the titania type particle|grain (26-A) aqueous dispersion of 10 mass %.

After that, except having repeatedly performed the dealkalization process using the cation exchange resin in a 4th process, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (26-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (26-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 27]

In the first step and the third step, a cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was gradually added to the aqueous dispersion of titania-based particles (1-B) having a solid content concentration of 10 mass% prepared in the same manner as in Example 1, , and then the ion exchange resin was separated. Thereafter, the dispersion medium was replaced with methanol using an ultrafiltration membrane. Then, it concentrated and obtained the methanol dispersion liquid of titania type microparticles|fine-particles (27-B) with a solid content concentration of 30 mass %. The water content contained in the obtained titania particle (27-B) methanol dispersion liquid was 0.3 mass %.

Then, in the second step, 1.47 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was slowly added to 40 g of the methanol dispersion of the titania particles (27-B). . After that, the mixture was heated and stirred at 50°C for 19 hours. Then, after cooling this to room temperature, the dispersion medium was substituted with propylene glycol monomethyl ether (PGME) using the ultrafiltration membrane, and the surface-treated metal oxide sol (27-D) with a solid content concentration of 30 mass % was obtained. Table 2 shows the composition of the obtained surface-treated metal oxide sol. In addition, in this Example, the 4th process was not implemented.

Except having used the surface-treated metal oxide sol (27-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 28]

In the first step, a cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was gradually added to 117 g of an aqueous dispersion of titania-based particles (1-A) having a solid content concentration of 10% by mass, prepared in the same manner as in Example 1, followed by de-alkaliization. After performing the ion exchange resin was separated.

Next, in the production of the silica layer in the fourth step, 126.0 g of a methanol solution in which 8.96 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.) was dissolved in this solution was slowly added, followed by heating and stirring at 50°C for 1 hour. Thus, a water/methanol dispersion of titania-based particles (28-C) was obtained. The water/methanol dispersion of this titania particle (28-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. Then, it concentrated and obtained the methanol dispersion liquid of titania type particle|grains (28-C) with a solid content concentration of 30 mass %. The water content contained in the obtained titania particle (28-C) methanol dispersion liquid was 0.3 mass %.

Then, in the second step, 1.47 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was slowly added to 40 g of this titania-based particle (28-C) methanol dispersion solution. . After that, the mixture was heated and stirred at 50°C for 19 hours. Then, after cooling this to room temperature, the dispersion medium was substituted with propylene glycol monomethyl ether (PGME) using the ultrafiltration membrane, and the surface-treated metal oxide sol (28-D) with a solid content concentration of 30 mass % was obtained. Table 2 shows the composition of the obtained surface-treated metal oxide sol. In addition, in this Example, manufacture of the silica composite oxide layer of 3rd process was not performed.

Except having used the surface-treated metal oxide sol (28-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 29]

In the second step, in place of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503), 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM) -5103) Except having used 1.47 g, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (29-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (29-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 30]

In the second step, 3-acryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE) instead of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) -503) Except having used 1.47 g, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (30-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (30-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, a base material with a transparent film was prepared and evaluated.

[Example 31]

In the second step, 3-acryloxypropyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE-) instead of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) 502) Except having used 1.47 g, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (31-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (31-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 32]

In the second step, in the same manner as in Example 1 except that propylene glycol monomethyl ether acetate (PGMEA) was used instead of propylene glycol monomethyl ether (PGME), a surface-treated metal oxide sol having a solid content concentration of 30 mass% (32 -D) was obtained. Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (32-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Example 33]

In the fourth step, a cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was gradually added to the water/methanol dispersion of titania-based particles (1-C) prepared in the same manner as in Example 1, followed by dealkalization followed by ion exchange. The resin was isolated. The obtained water/methanol dispersion of titania-based particles (33-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. After that, it concentrated to obtain 40 g of a methanol dispersion of titania-based fine particles (33-C) having a solid content concentration of 30% by mass.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (33-D). Table 2 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface treatment metal oxide sol (33-D), it carried out similarly to Example 1, and manufactured the coating material for transparent film formation. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Comparative Example 1]

In the fourth step, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) with an ultrafiltration membrane for the methanol dispersion of titania-based particles (1-C) having a solid content concentration of 30% by mass, prepared in the same manner as in Example 1. Thereby, 40 g of metal oxide sol (C1-D) of 30 mass % of solid content concentration which is not surface-treated with the organosilicon compound containing a (meth)acryl group was obtained. Table 3 shows the composition of the obtained metal oxide sol.

A coating material for forming a transparent film was prepared in the same manner as in Example 1 except that the surface-treated metal oxide sol (C1-D) was used. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Comparative Example 2]

Surface-treated metal oxide sol was carried out in the same manner as in Example 1 except that the amount of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was 15.6 g in the second step. (C2-D) was obtained. Table 3 shows the composition of the obtained metal oxide sol.

A coating material for forming a transparent film was prepared in the same manner as in Example 1 except that the surface-treated metal oxide sol (C2-D) was used. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Comparative Example 3]

Silica sol containing 15 mass % of silica particles with an average particle diameter of 7 nm in 450 g of a 2 mass % aqueous titanic acid solution in terms of TiO ₂ prepared in the same manner as in Example 1 (Nikki Catalyst Chemical Co., Ltd.) Manufacture: Cataloid SN-350) was carried out similarly to Example 1 except having mixed 65.0 g and pure water 532 g, and solid content concentration obtained the titania type particle|grain (C3-A) aqueous dispersion of 10 mass %.

After that, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (C3-D). Table 3 shows the composition of the obtained surface-treated metal oxide sol.

A coating material for forming a transparent film was prepared in the same manner as in Example 1 except that the surface-treated metal oxide sol (C3-D) was used. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Comparative Example 4]

In the first step, 35.0 g of a cation exchange resin was mixed with 280.4 g of a 2 mass % aqueous titanic acid solution in terms of TiO ₂ prepared in the same manner as in Example 1, and 527.8 g of a 1 mass % aqueous potassium stannate solution in terms of SnO ₂ was mixed thereto. was added slowly under stirring, and the cation exchange resin was separated.

Next, 8.0 g and pure water 180.0g are mixed for the silica sol (Nikki Catalyst Chemical Co., Ltd. product: Cataloid SN-350) containing 15 mass % of silica particles with an average particle diameter of 7 nm, 165 degreeC in autoclave For 18 hours, hydrothermal treatment was performed.

Next, after cooling the obtained aqueous solution to room temperature, it concentrated using the ultrafiltration membrane apparatus, and obtained the titania type microparticles|fine-particles (C4-A) aqueous dispersion with a solid content concentration of 10 mass %.

Thereafter, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (C4-D). Table 3 shows the composition of the obtained surface-treated metal oxide sol.

A coating material for forming a transparent film was prepared in the same manner as in Example 1 except that the surface-treated metal oxide sol (C4-D) was used. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

[Reference Example 1]

In the first step, to the aqueous dispersion of titania-based fine particles (1-A) having a solid content concentration of 10 mass% prepared in the same manner as in Example 1, a cation exchange resin (manufactured by Mitsubishi Resin Co., Ltd.) was gradually added to remove alkali. After carrying out, the ion exchange resin was separated. Thereafter, the dispersion medium was replaced with methanol using an ultrafiltration membrane. Then, it concentrated and obtained the methanol dispersion liquid of titania type particle|grains (R1-A) with a solid content concentration of 30 mass %. The water content contained in the obtained titania particle (R1-A) methanol dispersion liquid was 0.3 mass %.

Then, in the second step, 1.47 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was slowly added to 40 g of this methanol dispersion of titania particles (R1-A). . After that, the mixture was heated and stirred at 50°C for 19 hours. Then, after cooling this to room temperature, the dispersion medium was substituted with propylene glycol monomethyl ether (PGME) using the ultrafiltration membrane, and the surface-treated metal oxide sol (R1-D) with a solid content concentration of 30 mass % was obtained. Table 2 shows the composition of the obtained surface-treated metal oxide sol.

A coating material for forming a transparent film was prepared in the same manner as in Example 1 except that the surface-treated metal oxide sol (R1-D) was used. Next, in the same manner as in Example 1, a substrate provided with a transparent film was prepared and evaluated.

Claims (7)

A surface-treated metal oxide sol comprising a surface-treated metal oxide particle in which the surface of the metal oxide particle is treated with an organosilicon compound containing a (meth)acryl group represented by Formula (1), and a dispersion medium,
The metal oxide particles are a composite oxide, the composite oxide is titania silica or titania silica tin oxide, and contains 50 mass% or more of titania as TiO ₂ ,
The said organosilicon compound is R ¹ _n -SiO _(4-n)/2 (provided that R ¹ is a group containing at least one selected from a methacryl group and an acryl group with respect to 100 parts by mass of the metal oxide particles, , may be the same or different from each other. n is an integer of 1 to 3.) 0.1 to 60 parts by mass is formed on the surface of the metal oxide particles,
R ¹ _n -SiO _{(4-n) /} with respect to 100 parts by mass of the metal oxide particles by adding the organosilicon compound formed on the surface of the metal oxide particles and those present in the surface-treated metal oxide sol. ₂ , 0.1 to 100 parts by mass contained,
The surface-treated metal oxide particles have a silica complex oxide layer selected from silica zirconia, silica alumina, silica titania and silica tin oxide between the metal oxide particles and the organosilicon compound containing a (meth)acrylic group,
A surface-treated metal oxide sol for a resist material, wherein sodium is 25 ppm or less as Na ₂ O concentration, potassium is less than 0.5 mass% as K ₂ O concentration, and ammonia is less than 1000 ppm as NH ₃ concentration.
R ¹ _n -SiX ¹ _(4-n) (1)
(However, R ¹ is a group containing at least one selected from a methacryl group and an acryl group, and may be the same as or different from each other. n is an integer of 1-3. X ¹ is an alkoxy group.) The method of claim 1,
The surface-treated metal oxide sol for a resist material, wherein the composition of the silica composite oxide layer is 33.3/66.7 to 99.5/0.5 when the molar ratio of the formula (2) is expressed.
SiO ₂ /MO _X (2)
(However, MO _X is any ₁ type selected from ZrO2, Al2O3 _, TiO2 _{, SnO2 .} ) The method of claim 1,
The said metal oxide particle further contains at least 1 sort(s) of iron and cerium, The surface-treated metal oxide sol for resist materials characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
The said surface-treated metal oxide particle has an average particle diameter of 5-500 nm, and contains 5-70 mass % as solid content, The surface-treated metal oxide sol for resist materials characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
The said dispersion medium contains at least 1 sort(s) of organic solvent which has an SP value of 10 or more and a boiling point exceeds 100 degreeC, 30-95 mass % of this organic solvent is contained in the said dispersion medium, The surface-treated metal oxide sol for resist materials characterized by the above-mentioned . 4. The method according to any one of claims 1 to 3,
A surface-treated metal oxide sol for a resist material, characterized in that sodium is less than 20 ppm as a concentration of Na ₂ O, potassium is less than 0.5 mass% as a concentration of K ₂ O, and ammonia is less than 1000 ppm as a concentration of NH ₃ . 4. The method according to any one of claims 1 to 3,
The surface-treated metal oxide sol for a resist material, wherein the surface-treated metal oxide particles further include a silica layer between the layer of the silica composite oxide and the organosilicon compound containing the (meth)acryl group. .