TWI720136B - Surface treatment metal oxide sol - Google Patents

Abstract

The present invention provides a surface-treated metal oxide sol and a manufacturing method thereof. The surface-treated metal oxide sol can achieve both higher refractive index and light transmittance, lower haze and bead, and high sensitivity. A resist film with high residual film rate, high resolution, high scratch resistance and high weather resistance. The surface-treated metal oxide sol of the present invention comprises surface-treated metal oxide particles and a dispersion medium. The surface-treated metal oxide particles are provided with a specific amount of organic (meth)acrylic acid group on the surface of the metal oxide particles. Those with silicon compounds. The metal oxide particles contain 50% by mass or more of titanium dioxide _{in terms of TiO 2.} On the surface-treated metal oxide particles, the organosilicon compound containing (meth)acryloyl group is set to be 0.1-60 with respect to 100 parts by mass of the metal oxide particles, calculated _{as R n} -SiO _(4-n)/2 Mass parts.

Description

Surface treatment metal oxide sol

The present invention relates to a surface-treated metal oxide sol. In detail, the present invention relates to a surface-treated metal oxide sol containing a surface-treated metal oxide and a dispersion medium for forming a high-refractive-index and high-hardness coating. The surface-treated metal oxide is a metal oxide The surface of the particles is provided with an organosilicon compound containing (meth)acrylic acid groups.

In recent years, in the photolithography method used in the manufacture of semiconductor elements, printed substrates, printing plates, liquid crystal display panels, plasma display panels, etc., a photosensitive material is coated on the substrate to expose and expose the pattern. The technology of developing and processing is gradually popularized. The photosensitive material (resist material) used in the photolithography method is a material in which a functional film such as a high refractive index film is formed in a pattern on the surface of a substrate. Therefore, high sensitivity, high residual film rate, high resolution, high transparency and high film hardness are required. The photosensitive material (resist material) contains a resin binder component and components such as an acid generator, a crosslinking agent, and a solvent.

So far, as a method of increasing the refractive index or hardness of the coating, a method of using a high-refractive-index particle component of so-called titanium dioxide particles in the coating liquid has been known. For example, in Japanese Patent Laid-Open No. 5-173319 (Patent Document 1), in order to improve the etching resistance as a resist material, it is disclosed that a photosensitive resin such as phenol resin contains an average particle size of 0.05 to 20% by weight. A photoresist composition of fine powder of metal oxide or hydroxy metal oxide with a diameter of 0.002~0.2μm. In addition, in Japanese Patent Laid-Open No. 2009-020520 (Patent Document 2), a photosensitive resin composition having excellent low dielectric properties, adhesive strength, heat resistance, etc. is described, and it is disclosed that the surface is formed by organosilane. Use of processed colloidal nano-particle inorganic matter. Furthermore, Japanese Patent Laid-Open No. 2014-152226 (Patent Document 3) discloses inorganic composite oxide particles obtained by surface-treating inorganic composite oxide particles with an organosilicon compound or a partial hydrolyzate thereof. Inorganic composite oxide particles are used to form a coating film that is easily dispersed in hydrophobic media such as resins or organic solvents, has high transparency or hardness, scratch resistance, adhesion to the substrate, and excellent weather resistance.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-173319

[Patent Document 2] Japanese Patent Laid-Open No. 2009-020520

[Patent Document 3] Japanese Patent Laid-Open No. 2014-152226

When titanium dioxide particles are used for the resist material described in Patent Document 1, although a higher refractive index and a higher film hardness can be expected, the dispersibility with the resist material resin is insufficient. Therefore, when the resist film is formed, there is a problem that particles agglomerate, the transparency is reduced, and the scratch resistance is reduced. In addition, in Patent Documents 2 and 3, by surface treatment of particles, the dispersibility in the resist film is improved compared to Patent Document 1, but there is insufficient bonding with the resist material resin, resulting in the formation of a resist. The problem that the sensitivity or residual film rate of the film becomes poor, and the resolution of the film also becomes poor.

In order to solve these problems and fulfill the above requirements for resist materials, the present invention provides a surface-treated metal oxide particle that can be used as a component of resist materials. Specifically, the present invention provides a surface-treated metal oxide sol containing a surface-treated metal oxide and a dispersion medium. The surface-treated metal oxide is based on metal oxide particles containing 50% by mass or more of titanium dioxide _{as TiO 2} The surface of the organosilicon compound containing (meth)acrylic acid group is R ¹ _n -SiO _(4-n)/2 (wherein, R ¹ contains at least one selected from the group consisting of methacrylic acid group and acrylic acid group The basis of the two may be the same or different. n is an integer of 1 to 3), and 0.1 to 60 parts by mass is included.

When the surface treatment metal oxide sol of the present invention is used as a resist material, it can achieve both higher refractive index and light transmittance, lower haze and swelling, high sensitivity, and high residual film Resist film with high rate, high resolution, high scratch resistance and high weather resistance.

The surface-treated metal oxide sol of the present invention includes surface-treated metal oxide particles and a dispersion medium provided with an organosilicon compound containing (meth)acryloyl groups on the surface of the metal oxide particles. The metal oxide particles are particles containing 50% by mass or more of titanium dioxide _{in terms of TiO 2.} The surface-treated metal oxide particles relative to 100 parts by mass of the metal oxide particles, the above-mentioned organosilicon compound represented by formula (1) is R ¹ _n -SiO _(4-n)/2 (wherein R ¹ contains the selected The base from at least one of the methacrylic group and the acrylic group may be the same or different from each other. n is an integer of 1 to 3), 0.1 to 60 parts by mass, R ¹ _n -SiX ¹ _(4-n) (1)

(Wherein, R ¹ is a group containing at least one selected from a methacrylic group and an acrylic group, which may be the same or different from each other. n is an integer of 1 to 3. X ¹ is an alkoxy group).

The surface-treated metal oxide sol having such a structure will be described in detail below.

[Metal Oxide Particles]

In order to increase the refractive index of the surface-treated metal oxide particles, it is preferable to include 50% by mass or more of titanium dioxide _{in terms of TiO 2 so that the refractive index of the metal oxide particles itself is 2.0 or more.} Specifically, it is preferably titanium dioxide or a composite oxide containing titanium and other metals. These can be used alone or in combination. Examples of metals include silicon, tin, iron, and cerium. The types of these metals may be one type or plural types.

However, it is known that titanium dioxide generally has a photocatalyst function, so it is photoactive and can decompose the coexisting organic matter in the film. Therefore, if the photoactivity is too strong, the weather resistance of the film will decrease. Therefore, it is preferable to use a composite oxide of titanium dioxide and low refractive index silicon dioxide or tin oxide to adjust the light activity. Specifically, there are preferred composite oxide particles of _{titanium dioxide silicon dioxide (TiO 2} /SiO ₂ ) and titanium dioxide silicon oxide tin oxide (TiO ₂ /SiO ₂ /SnO _{2 ).} As the form of titanium dioxide, both rutile type and anatase type may be used, and a mixture of these types may also be used. In particular, as a resist material, in order to make the refractive index greater than 1.6, it is preferable that the titanium dioxide in the composite oxide particles contains 50% by mass or more _{in terms of TiO 2.}

When in the case of TiO ₂ / SiO ₂ of, preferably containing TiO ₂ 75% by mass or more, containing SiO ₂ 25% by mass or less. Here, _{if the ratio of TiO 2} /SiO ₂ is less than 75/25, the refractive index may become low. More preferably, TiO ₂ is 80 to 90% by mass, and SiO ₂ is 10 to 20% by mass.

In the case of TiO ₂ /SiO ₂ /SnO _2, it is preferable that TiO ₂ is 50 to 95% by mass, SiO ₂ is 3 to 25% by mass, and SnO ₂ is 2 to 47% by mass. Here, if _{the ratio of TiO 2} /(SiO ₂ +SnO ₂ ) is less than 50/50, the refractive index may become low. On the contrary, if _{the ratio of TiO 2} /(SiO ₂ +SnO ₂ ) is greater than 95/5, it is difficult to express the difference between the particle and the titanium dioxide alone, and as a result, the photoactivity and weather resistance become problems. More preferably, TiO ₂ is 70 to 90% by mass, SiO ₂ is 10 to 20% by mass, SnO ₂ is 2 to 30% by mass, and TiO ₂ /(SiO ₂ +SnO ₂ ) is more preferably 70/30 to 90/10 .

In addition, in order to adjust the photoactivity of the resist material, a third component such as iron or ceria _{can also be added to the so-called TiO 2} /SiO ₂ , TiO ₂ /SiO ₂ /SnO _{2 composite oxide particles.}

Iron or ceria doping treatment is preferable in terms of photoactivity suppression. Preferably, the doping amount is less than 10 parts by mass relative to 100 parts by mass of the target particles, as Fe ₂ O ₃ or CeO _2. If the doping amount of iron or ceria _{is 10 parts by mass or more as Fe 2} O ₃ or CeO ₂ , the appearance of the coating film may be colored. The doping amount is more preferably less than 5 parts by mass, and still more preferably less than 3 parts by mass.

[Surface Treatment Metal Oxide Particles] <Layer of organosilicon compound containing (meth)acrylic acid group>

Surface treatment metal oxide particles are those where the surface of the metal oxide particles is coated with the organosilicon compound represented by formula (1) as a surface treatment agent, R ¹ _n -SiX ¹ _(4-n) (1)

(Wherein, R ¹ is a group containing at least one selected from a methacrylic group and an acrylic group, which may be the same or different from each other. n is an integer of 1 to 3. X ¹ is an alkoxy group).

The organosilicon compound containing (meth)acrylic acid group is R ¹ _n -SiO _(4-n)/2 (wherein, R ¹ contains a methacrylic acid group selected from 100 parts by mass of the metal oxide particles). And at least one of the acryl groups may be the same or different from each other. n is an integer of 1 to 3), 0.1 to 60 parts by mass. Since the surface of the metal oxide particles is provided with an organosilicon compound containing a (meth)acryloyl group, the dispersibility or bonding of the surface-treated metal oxide particles and the resin in the resist material is improved. Here, if the amount of the organosilicon compound is less than 0.1 parts by mass, the compatibility with the resin may be insufficient, the aggregation of particles may occur, the haze may increase, and the total light transmittance may decrease. In addition, the sensitivity and residual film rate during exposure and development may be insufficient. On the contrary, it is difficult to coat more than 60 parts by mass on the surface area of the particles. The amount of the organosilicon compound is preferably 1-50 parts by mass, more preferably 3-30 parts by mass.

The organosilicon compound can freely exist in the sol as an unreacted substance without surface treatment. The amount is relative to 100 parts by mass of the metal oxide particles, based on R ¹ _n -SiO _(4-n)/2 (wherein R ¹ is a group containing at least one selected from the group consisting of methacrylic acid group and acrylic acid group , May be the same or different from each other. n is an integer of 1 to 3), 99.9 parts by mass 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 provided on the surface of the metal oxide. In addition, even if there is more than 99.9 parts by mass, improvement in dispersibility cannot be expected, and the refractive index of the film also decreases. That is, if the amount of the organosilicon compound containing (meth)acryloyl group in the surface-treated metal oxide sol is accumulated on the surface of the metal oxide particles and the amount freely present in the sol, it is preferable For 100 parts by mass of the metal oxide particles, R ¹ _n -SiO _(4-n)/2 (wherein R ¹ is a group containing at least one selected from the group consisting of methacrylic acid group and acrylic acid group, They may be the same or different. n is an integer of 1 to 3), 0.1 to 100 parts by mass are provided. Here, if the amount of the organosilicon compound is less than 0.1 parts by mass, the effect of surface treatment cannot be obtained. On the contrary, if it is more than 100 parts by mass, the refractive index of the film may decrease. The amount of the organosilicon compound is more preferably 1 to 70 parts by mass, and still more preferably 5 to 40 parts by mass.

As the organosilicon compound, if it is the organosilicon compound formula containing (meth)acryloyl group represented by the formula (1), it is not specifically specified. Among them, it can be exemplified: 3-methacryloyloxypropyl dimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methacryloxypropyldiethylmethylsilane, 3-acryloxypropyltriethoxysilane, etc. Among them, 3-methacryloxypropyltrimethoxysilane is particularly preferred.

The organosilicon compounds can be used in the form of monomers, and can also be one polymer or a plurality of polymers selected from the organosilicon compounds, or a mixture of these.

On the surface-treated metal oxide particles, between the metal oxide particles and the (meth)acrylic group-containing organosilicon compound on the surface of the particles, a group selected from silica zirconia, silica alumina, At least one of a layer of silicon dioxide titanium dioxide, a silicon dioxide compound oxide in silicon dioxide tin oxide, and a separate layer of silicon dioxide.

By providing these layers, the surface of the metal oxide particles is only covered with surface-treated metal oxide particles containing (meth)acrylic acid-based organosilicon compounds, and the adjustment of refractive index, sensitivity, resolution, and light activity becomes easy.

<Silica Composite Oxide Layer>

Here, the layer of silicon dioxide composite oxide is calculated by the molar ratio of _{SiO 2} /MO _X (where MO _X is selected from any of ZrO ₂ , Al ₂ O ₃ , TiO ₂ , and SnO _{2 ).} The best range is 33.3/66.7~99.5/0.5. By providing this layer, the photoactivity and refractive index of the metal oxide particles can be adjusted mainly. Here, if the SiO ₂ /MO _X molar ratio is less than 33.3/66.7, it may be difficult to obtain a uniform coating layer and the metal oxide particles may aggregate. On the contrary, if it is greater than 99.5/0.5, it is difficult to distinguish it from the silicon dioxide layer, so there is no need to distinguish it from the silicon dioxide layer. The molar ratio is more preferably 50.0/50.0-95.2/4.8, and still more preferably 50.0/50.0-76.9/23.1.

In addition, the amount of the silicon dioxide composite oxide is 1 to 180 parts by _{mass in terms of (SiO 2} +MO _{X) based on 100 parts by mass of the metal oxide particles.} If the amount of the silicon dioxide composite oxide is less than 1 part by mass, the weather resistance may be insufficient. On the contrary, if it is more than 180 parts by mass, there are cases where the required refractive index cannot be obtained. The amount is preferably 2-30 parts by mass, more preferably 3-10 parts by mass.

<Silicon Dioxide Layer>

The amount of silicon dioxide in the silicon dioxide layer is 0.1-100 _{parts by mass based on SiO 2} relative to 100 parts by mass of the metal oxide particles. By providing the silicon dioxide layer, the optical activity adjustment of the metal oxide particles and the dispersion of the particles can be improved. Here, if the amount of silicon dioxide is less than 0.1 parts by mass, the weather resistance adjusted by photoactivity may be insufficient, and the subsequent organosilicon compound containing a (meth)acryloyl group may be difficult to coat the metal oxide. . On the contrary, if it is more than 100 parts by mass, it may not be possible to obtain the required refractive index. The preferred amount is 0.5 to 30 parts by mass, and more preferably 1 to 10 parts by mass.

The separate layer of silicon dioxide can be set by water glass or other inorganic silicon compounds such as alkali silicate solution or silicic acid solution, or by ethyl orthosilicate (TEOS) or methyl orthosilicate (TMOS), etc. Organosilicon compound set.

On the surface-treated metal oxide particles, the layer between the metal oxide particles and the organosilicon compound containing the (meth)acryloyl group on the surface of the particle is preferably arranged in sequence from the side close to the metal oxide particle It is a layer of silicon dioxide composite oxide, and then a layer of silicon dioxide alone, and its outermost surface is a layer of an organosilicon compound containing a (meth)acryloyl group. It is due to the sequential combination of 3 layers, the refractive index, sensitivity, resolution, and photoactivity can be adjusted step by step, especially the surface OH groups of the second layer of silicon dioxide layer are formed, thereby giving (meth)acrylic acid groups here It becomes easy, so it can improve the dispersibility or bonding with the resist material.

"The average particle size"

The average particle diameter of the surface-treated metal oxide particles is preferably 5 to 500 nm. If the average particle size is less than 5 nm, it is difficult to produce particles of that size. If it is greater than 500 nm, although the content is also in accordance with the content, it is difficult to achieve the transparency of the resist material. More preferably, the average particle size is 5 to 200 nm, and still more preferably 10 to 25 nm.

"Refractive Index"

In order to make the refractive index of the resist material greater than 1.6, the refractive index of the surface-treated metal oxide particles is preferably 1.7 or greater.

[Dispersion medium]

The dispersion medium of the surface-treated metal oxide sol can use a previously known organic solvent. Especially when used as a resist material, if the dispersion medium also considers the workability of the resist material, the dispersion medium should contain at least one dissolution parameter (Solubility Parameter: SP Value) is an organic solvent with a boiling point of more than 100°C under atmospheric pressure and 10 or more. The organic solvent preferably contains 30 to 95% by mass in the dispersion medium. Here, if the SP value is less than 10, the dispersibility of the surface-treated metal oxide particles becomes low. In addition, if it is an organic solvent with a boiling point of 100°C or less, since it dries quickly during coating and the film is formed before leveling, swelling may occur on the coating film. Furthermore, if the amount of the organic solvent in the dispersion medium is less than 30% by mass, the dispersibility of the surface-treated metal oxide particles decreases. On the contrary, if it is more than 95% by mass, it is difficult to obtain the required film thickness. More preferably, the amount is 40 to 90% by mass, and still more preferably 50 to 80% by mass.

烷等。其中特佳為丙二醇單甲醚(PGM)。 As an organic solvent with an SP value of 10 or more and a boiling point of more than 100°C, propylene glycol monomethyl ether (PGM), propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol mono-n-butyl ether, acetone, ethylene glycol, diphenyl ether, glycerol, formamide, benzyl alcohol, N-methylpyrrolidone, glycerin, cyclohexanone, diethylene glycol mono Ethyl 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-di

Ethane etc. Among them, propylene glycol monomethyl ether (PGM) is particularly preferred.

In order to further improve the dispersibility, the above-mentioned dispersion medium may contain at least one solvent having an SP value of 13 or more and a boiling point of 100°C or less under atmospheric pressure. The content of the solvent in the dispersion medium is preferably less than 20% by mass. Since the solvent is contained, the solvent is fused and the stability of the sol is improved. If the solvent contains 20% by mass or more, swelling of the coating film may occur and the hardness may become insufficient. More preferably, the amount is 1 to 15% by mass, and still more preferably 3 to 12% by mass.

Examples of solvents having an SP value of 13 or more and a boiling point of 100°C or less include lower alcohols and water. Among them, methanol and ethanol are particularly preferred.

<Impurities>

The surface-treated metal oxide sol may contain sodium, potassium, and ammonia as impurity components. If any one of these is present in a large amount, the stability of the sol will decrease. In addition, the workability as a resist material also deteriorates, and pattern exposure and development are difficult. Therefore, sodium is preferably _{less than 25 ppm in terms of Na 2} O concentration, more preferably less than 20 ppm, potassium is preferably _{less than 0.5% by mass in terms of K 2} O concentration, and ammonia is preferably less than in _{terms of NH 3 concentration.} 1000ppm.

"Concentration of Surface Treatment Metal Oxide Sol"

The solid content concentration of the surface-treated metal oxide sol is preferably 5 to 70% by mass. If the solid content concentration is less than 5% by mass, it may not be possible to obtain the required refractive index or film hardness. If the solid content concentration is higher than 70% by mass, it is difficult to realize the transparency of the resist material. A more preferable amount is 10-60% by mass, and even more preferably 20-40% by mass.

[Method for manufacturing surface-treated metal oxide sol] <Step 1>

The first step is a step of producing metal oxide particles. The manufacturing method will be described below.

<Manufacturing Method of Metal Oxide Sol> ≪Manufacturing of titanic acid aqueous solution≫

The hydrous titanate gel or sol is prepared by a previously known method. The hydrous titanic acid gel is obtained by neutralization by adding an alkali to an aqueous solution of, for example, titanium chloride, titanium sulfate, and the like. In addition, the hydrous titanic acid sol is obtained by passing an aqueous solution of titanium chloride, titanium sulfate, etc. through an ion exchange resin to remove anions. The hydrous titanic acid here means titanium oxide hydrate or titanium hydroxide.

Secondly, hydrogen peroxide is added to the obtained hydrous titanic acid gel or hydrous titanic acid sol or the mixture thereof to dissolve the hydrous titanic acid to prepare a uniform aqueous solution. At this time, heating or stirring is preferable. At this time, if the concentration of hydrated titanic acid becomes too high, it will take a long time to dissolve the hydrated titanic acid, and the undissolved gel will precipitate, or the viscosity of the resulting aqueous solution will increase, which is not preferable. Therefore, the _{concentration of TiO 2} is about 10% by mass or less, preferably about 5% by mass or less. If the amount of hydrogen peroxide to be added is 1 or more based on the mass ratio of _{H 2} O ₂ /TiO _{2, the hydrous titanic acid can be completely dissolved.} If the H ₂ O ₂ /TiO ₂ ratio is less than 1, unreacted gel or sol remains because the hydrous titanic acid is not completely dissolved, which is not preferable. In addition, although the _{larger the H 2} O ₂ /TiO ₂ ratio, the faster the dissolution rate of hydrated titanic acid, and the reaction is completed in a short time. However, if hydrogen peroxide is used excessively, a large amount of unreacted hydrogen peroxide will remain in the system. Inside, it has a bad influence on the subsequent steps, so it is not good. Therefore, it is _{better to use hydrogen peroxide in an amount of H 2} O ₂ /TiO ₂ ratio of 1 to 6, preferably 2 to 6 or so. If hydrogen peroxide is used in this amount, the hydrous titanic acid will be completely dissolved in about 0.5-20 hours. The reaction temperature at this time is 50°C or higher, preferably 70°C or higher.

≪Manufacturing of titanium dioxide (TiO ₂ ) aqueous dispersion≫

Then, the aqueous solution (aqueous titanic acid solution) obtained as described above in which the hydrous titanic acid is dissolved is heated to 60°C or higher, preferably 80°C or higher, to hydrolyze the titanic acid. In this way, an aqueous dispersion of _{TiO 2 particles was obtained.}

≪Manufacturing of titanium dioxide and _{silicon dioxide (TiO 2} /SiO ₂ ) aqueous dispersions≫

The silicon compound is mixed in the above-mentioned titanic acid aqueous solution in a specific amount, and heated to 60°C or higher, preferably 80°C or higher, to hydrolyze the titanic acid. In this way, an aqueous dispersion of _{TiO 2} /SiO _{2 particles is obtained.}

Here, as the silicon compound, a silicic acid solution obtained by debasing an aqueous alkali silicate salt solution with a cation exchange resin, a silica sol obtained by neutralizing an alkali silicate salt with an acid, or alkoxylation such as ethyl silicate are used. A solution or dispersion of a silicon compound such as a substance or its hydrolysate. In addition, commercially available silica sols can also be used. In these cases, the average particle size of silicon dioxide is preferably 500 nm or less. The ratio of TiO ₂ /SiO ₂ is 75/25 or more. In addition, _{the ratio of TiO 2} /SiO ₂ is preferably 80/20 or more.

As a method of adding a solution or dispersion of a silicon compound to an aqueous solution of titanic acid, the solution or dispersion of a silicon compound is slowly added while heating the aqueous solution of titanic acid. The gel precursor and the silicon compound solution or dispersion can be mixed together and then heated. The method should be selected according to the concentration of titanium dioxide and the concentration of silicon dioxide in the solution or dispersion of the silicon compound. Even if the method of mixing the two together does not cause any hindrance when the titanium dioxide concentration is less than 1% by mass and the thinner case, because the titanium dioxide concentration is more than 1% by mass and the thicker case, there is Silica agglomerates titanium dioxide, and if the concentration of silica is higher, the agglomeration and polymerization of silica alone will occur. Therefore, the method of adding slowly is preferred.

In order to promote the reaction between the silicon compound and the titanium dioxide, the temperature during addition or mixing is usually preferably carried out by heating to above about 60°C. However, when alkoxides such as ethyl silicate are used, since the hydrolysis rate of these alkoxides is faster, colloidal particles of silica are easily formed in the mixed solution, so the alkoxides are slowly added at a relatively low temperature below about 40°C. , After the addition, the temperature is raised to a temperature above about 60°C to complete the reaction. The pH of the mixed solution when the silicon compound is added is preferably neutral or alkaline in terms of the stability of the titanic acid aqueous solution and the resulting titanium dioxide sol, and it is usually carried out in the range of about 6-10. In _{the case of concentrating the TiO 2} /SiO ₂ aqueous dispersion, a known method such as an evaporation method and an ultrafiltration method can be used.

≪Manufacturing of titanium dioxide silicon dioxide tin oxide (TiO ₂ /SiO ₂ /SnO ₂ ) aqueous dispersion≫

A specific amount of silicon compound or tin compound is mixed in the above-mentioned titanic acid aqueous solution, and heated to 60°C or higher, preferably 80°C or higher, to hydrolyze titanic acid. In this way, an _{aqueous dispersion of TiO 2} /SiO ₂ /SnO ₂ particles was obtained.

Here, as the silicon compound, the same as those used in the production of the _{above-mentioned TiO 2} /SiO _{2 can be used.}

As the tin compound added to the titanic acid aqueous solution, an aqueous solution or dispersion of a tin compound such as tin chloride, tin sulfate, or tin oxychloride is used. The method of adding this tin compound to the titanic acid aqueous solution can be the same as adding the above-mentioned TiO ₂ /SiO ₂ silicon compound. The order of addition can be either first or simultaneously. TiO ₂ / SiO ₂ / SnO ₂ ratio of of TiO ₂ is 70 to 90 mass%, SiO ₂ of 10 to 20 mass%, SnO ₂ is 2 to 30 _{mass%, TiO 2 / (SiO 2} + SnO 2) of a ratio of Within the range of 50/50~95/5. The other manufacturing conditions are the same as the above-mentioned TiO ₂ /SiO ₂ . Preferably, TiO ₂ is 70 to 90% by mass, SiO ₂ is 10 to 20% by mass, SnO ₂ is 2 to 30% by mass, and _{the ratio of TiO 2} /(SiO ₂ +SnO ₂ ) is 70/30 to 90/10 Within the range.

≪Iron or ceria doping treatment≫

The treatment of TiO ₂ /SiO ₂ or TiO ₂ /SiO ₂ /SnO ₂ doped with iron or cerium oxide is prepared by preparing an aqueous solution of iron or cerium chloride and titanium salt in the production of the above-mentioned titanic acid aqueous solution and adding it to it Obtained by alkali neutralization. The subsequent manufacturing method is the same as 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 . The doping amount is less than 10 parts by mass relative to 100 parts by mass of the _{target TiO 2} /SiO ₂ or TiO ₂ /SiO ₂ /SnO _{2 as Fe 2} O ₃ or CeO _2. The doping amount is preferably less than 5 parts by mass, more preferably less than 3 parts by mass.

≪Organic solvent replacement≫

Before "the second step" described later, the aqueous dispersion of the target metal oxide particles is replaced with a previously known organic solvent. As the organic solvent, alcohols, esters, glycols, and ethers can be used. Specifically, as alcohols, there are methanol, ethanol, propanol, 2-propanol, and the like. As esters, there are methyl acetate, ethyl acetate, isopropyl acetate, propyl acetate, and the like. As the glycols, there are ethylene glycol, hexanediol, and the like. As ethers, there are diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. . These can be used alone, or two or more of them can be mixed and used. Among them, methanol and ethanol which are lower alcohols are particularly preferred.

The solvent replacement can be performed by a conventionally known method such as using an ultrafiltration device. The content of water in the dispersion medium after solvent replacement is preferably at most less than 20% by mass.

<Step 2>

The second step is to treat the surface of the metal oxide particles with an organosilicon compound containing (meth)acrylic acid groups represented by formula (1), and set the surface of the metal oxide particles to contain (meth)acrylic acid The layer of base organosilicon compound. The manufacturing method will be described below.

<Manufacturing of a layer containing (meth)acrylic acid-based organosilicon compound>

The organic solvent dispersion liquid of the metal oxide particles is added with an organosilicon compound containing a (meth)acryloyl group represented by formula (1). Although the method of addition is not particularly limited, it is preferable to add the mixture while stirring the two thoroughly. In addition, in order to promote the reaction, it may be heated to about 40 to 60°C.

The addition amount of the (meth)acryloyl-containing organosilicon compound is only added as follows: relative to 100 parts by mass of the metal oxide particles, the surface of the metal oxide particles is R ¹ _n -SiO _{(4-n)/ 2} (wherein R ¹ is a group containing at least one selected from the group consisting of methacrylic acid group and acrylic acid group, which may be the same as or different from each other. n is an integer of 1 to 3), set 0.1 to 60 Parts by mass; and if the accumulated surface of the metal oxide particles and the other freely existing in the sol, relative to 100 parts by mass of the metal oxide particles, R ¹ _n -SiO _{(4-n) /2} (wherein, R ¹ is a group containing at least one selected from the group consisting of methacrylic acid group and acrylic acid group, which may be the same as or different from each other. n is an integer of 1 to 3), with 0.1-100 Mass parts. The preferred amount of the organosilicon compound is 1 to 70 parts by mass, more preferably 5 to 40 parts by mass.

≪Solvent replacement≫

Then, by a previously known method, an organic solvent having an SP value of 10 or more and a boiling point of more than 100° C. is used for solvent replacement by a previously known method. The organic solvent contains 30 to 95% by mass in the dispersion medium.

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

In the above-mentioned surface-treated metal oxide sol, in order to further improve the dispersibility, the content of the lower alcohol and water may be less than 20% by mass. Among them, sodium is preferably _{25 ppm or less based on Na 2} O concentration, more preferably less than 20 ppm, potassium is preferably _{less than 0.5% based on K 2} O concentration, and ammonia is preferably less than 1000 ppm _{based on NH 3 concentration.} .

<Step 3>

The third step is to provide a layer of silica composite oxide selected from the group consisting of silica zirconia, silica alumina, silica titania, and silica tin oxide on the surface of the metal oxide particles. The manufacturing method will be described below.

<Manufacturing of Silicon Dioxide Composite Oxide Layer>

In order to provide a layer of the silicon dioxide composite oxide provided on the target metal oxide particles, a compound selected from the group consisting of silicon compounds, zirconium compounds, aluminum compounds, titanium compounds, and tin compounds is used as a raw material.

Here, as the silicon compound, a silicic acid solution obtained by debasing an aqueous alkali silicate salt solution with a cation exchange resin, a silica sol obtained by neutralizing an alkali silicate salt with an acid, or alkane such as ethyl silicate can be used. A solution or dispersion of silicon compounds such as oxides or their hydrolysates. In addition, commercially available silica sols can also be used.

As the metal compound other than the silicon compound, aqueous solutions or dispersions of chloride or sulfuric acid compounds, ammonium carbonate compounds, hydroxychlorinated compounds, etc., and metal alkoxides are used. Hydrogen peroxide is added to those obtained by adding alkali to neutralize or hydrolyze to obtain a metal acid aqueous solution selected from zirconium, aluminum, titanium, and tin.

Next, a solution or dispersion of a silicon compound and the above-mentioned metal acid aqueous solution are added to the dispersion of the target metal oxide particles. Although the method of addition is not particularly limited, it is preferable to add while stirring in such a way that the two are thoroughly mixed. In addition, in order to promote the reaction, heating may also be used. The molar ratios of silicon compounds and metal compounds other than silicon compounds in terms of SiO ₂ /MO _X (where MO _X is selected from any of ZrO ₂ , Al ₂ O ₃ , TiO ₂ , and SnO _{2) are respectively} 33.3/66.7~99.5/0.5. The preferred molar ratio is 50.0/50.0-95.2/4.8, more preferably 50.0/50.0-76.9/23.1. In addition, the amount is 1 to 180 parts by _{mass in terms of (SiO 2} +MO _X ) based on 100 parts by mass of the metal oxide particles. The preferred amount is 2-30 parts by mass, more preferably 3-10 parts by mass.

<Step 4>

The fourth step is to provide a silicon dioxide layer on the surface of the metal oxide particles. The manufacturing method will be described below.

<Manufacturing of Silicon Dioxide Layer>

In order to provide the silicon dioxide layer of the metal oxide particles on the object, a silicic acid solution obtained by debasing an aqueous alkali silicate salt solution with a cation exchange resin, and a silica sol obtained by neutralizing the alkali silicate salt with an acid are used , Or a solution or dispersion of a silicon compound such as ethyl silicate or its hydrolyzate as a raw material. In addition, commercially available silica sols can also be used.

Add a solution or dispersion of a silicon compound to the dispersion of the target metal oxide particles. Although the method of addition is not particularly limited, it is preferable to add while stirring in such a way that the two are thoroughly mixed. In addition, in order to promote the reaction, heating may also be used. The silicon compound is 0.1-100 _{parts by mass in terms of SiO 2} with respect to 100 parts by mass of the metal oxide particles. The preferred amount is 0.5 to 30 parts by mass, and more preferably 1 to 10 parts by mass.

"Sequence of Steps"

The surface-treated metal oxide particles constituting the present invention are provided with an organosilicon compound containing a (meth)acryloyl group represented by formula (1) on the surface. If the structure can be realized, the order of the steps is not particularly limited. Among them, if the productivity and quality stability at the time of manufacturing are considered, the "second step" of the implementation is preferably performed last among those implemented in the first to fourth steps. also, The "first step" for producing metal oxide particles is preferably performed first among those implemented in the first to fourth steps.

As a sequence of the steps of producing surface-treated metal oxide particles, an example is: producing metal oxide particles (first step), followed by providing an organosilicon compound containing (meth)acryloyl groups on the surface of the metal oxide particles ( The sequence of the second step); manufacturing metal oxide particles (the first step), and then the surface of the metal oxide particles is selected from the group consisting of silica zirconia, silica alumina, silica titania, and silica The layer of the silicon dioxide composite oxide in the tin oxide (the third step), and then the sequence of setting the organosilicon compound containing the (meth)acrylic acid group (the second step); the production of metal oxide particles (the first step) , Secondly, a silicon dioxide layer is provided on the surface of the metal oxide particles (the fourth step), and thereafter an organosilicon compound containing (meth)acrylic acid group is provided (the second step); the sequence of manufacturing metal oxide particles (the second step) Step 1), secondly, on the surface of the metal oxide particles, a layer of silicon dioxide composite oxide selected from the group consisting of silicon dioxide zirconia, silicon dioxide aluminum oxide, silicon dioxide titanium dioxide, and silicon dioxide tin oxide (section Step 3), and then set up a silicon dioxide layer (Step 4), and then set up an organosilicon compound containing (meth)acrylic acid groups (Step 2).

≪Dealkalization step≫

In the first to fourth steps described above, in order to advance the reaction, it is preferable to perform a dealkalization treatment as necessary. For the dealkalization treatment, a conventionally known method such as using an ion exchange resin or an ultrafiltration device can be used. In the dealkalization step, the sodium in the surface treatment oxide sol of the present invention obtained in the second step is preferably _{25 ppm or less in terms of Na 2} O concentration, more preferably less than 20 ppm, and potassium is not as high as K ₂ O concentration. 0.5%, an ammonia concentration of NH ₃ to the count of less than 1000ppm manner suitable embodiment.

[Example]

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

[Example 1] <Production of Titanium Dioxide Particles (Using Step 1)>

450 g of a titanium tetrachloride aqueous solution containing 2% by mass of titanium tetrachloride in terms of TiO ₂ and 176 g of 15% by mass of ammonia were mixed to prepare a white slurry liquid with a pH of 8.6. Then, after filtering the slurry, it was washed with pure water to obtain 180 g of a hydrous titanic acid filter cake with a solid content of 5% by mass.

Next, after adding 205.6 g of 35 mass% hydrogen peroxide water and 514.4 g of pure water to 180 g of the filter cake, it was heated at a temperature of 80°C for 1 hour to obtain titanic acid containing 2 mass% _{in terms of TiO 2} 900g of the aqueous solution of titanic acid peroxide. The aqueous solution of titanic acid peroxide is transparent yellow-brown and has a pH of 8.1.

Then, 8.2 g of silica sol (manufactured by Nikkei Catalytic Chemicals Co., Ltd.: CATALOID SN-350) containing 15% by mass of silica particles with an average particle size of 7 nm and pure water were mixed with 450 g of the aqueous solution of titanic acid. 589 g, hydrothermally treated in an autoclave at 165°C for 18 hours.

Next, after cooling the resulting aqueous solution to room temperature, it was concentrated using an ultrafiltration membrane device to obtain an aqueous dispersion of titanium dioxide particles (1-A) having a solid content of 10% by mass.

The refractive index of the particles of the titanium dioxide-based fine particles (1-A) is 2.3.

<Production of silicon dioxide composite oxide layer (using the third step)>

To 263 g of a zirconium oxychloride aqueous solution containing 2% by mass of zirconium oxychloride in terms of ZrO ₂ was slowly added 15% by mass of ammonia under stirring to obtain a slurry liquid containing a hydrate of zirconium with a pH of 8.5. Then, after the slurry was filtered, washed with pure water, to obtain in terms of ZrO ₂ contains 10% by mass of cake was 52.6g of zirconium component.

Next, after adding 180 g of pure water to 20 g of the filter cake, and further adding 12 g of a 10% by mass potassium hydroxide aqueous solution to make it alkaline, 40 g of 35% by mass hydrogen peroxide water was added, and the cake was heated to 50°C to dissolve the filter cake. Furthermore, 148 g of pure water was added to obtain 400 g of a zirconium peroxide aqueous solution _{containing 0.5% by mass of zirconium peroxide in terms of ZrO 2.}

On the other hand, a cation exchange resin (manufactured by Mitsubishi Plastics Co., Ltd.) was slowly added to water glass with 2% by mass _{in terms of SiO 2} for dealkalization, and then the ion exchange resin was separated to obtain 2% by mass _{in terms of SiO 2} Silicic acid aqueous solution.

Next, 320 g of pure water was added to 80 g of a titanium dioxide-based particle (1-A) aqueous dispersion of 10% by mass in terms of TiO _{2 and heated to 90°C.} 26.7 g of the above-mentioned zirconic acid aqueous solution and 21.2 g of silicic acid aqueous solution were slowly added thereto. After the addition was completed, the mixture was maintained at 90°C and stirred for 1 hour, and then the mixed solution was subjected to a hydrothermal treatment at 165°C for 18 hours in an autoclave.

Then, after cooling the mixed liquid to room temperature, it was concentrated by an ultrafiltration membrane device to obtain titanium dioxide particles (1-B) with a composite oxide layer of silicon dioxide and zirconium oxide with a solid content of 10% by mass. ) 128g of water dispersion.

<Fabrication of Silicon Dioxide Layer (Using Step 4)>

After slowly adding a cation exchange resin (manufactured by Mitsubishi Plastics Co., Ltd.) to 117 g of the titanium dioxide-based particle (1-B) aqueous dispersion to perform dealkalization, the ion exchange resin was separated. To this solution was slowly added 126.0 g of a methanol solution in which 8.96 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., SiO ₂ content 28.8% by mass) was dissolved, and heated and stirred at 50°C for 1 hour to obtain titanium dioxide particles ( 1-C) Water/methanol dispersion.

The obtained water/methanol dispersion of titanium dioxide-based particles (1-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. After that, it is concentrated to obtain a solid form with a silicon dioxide layer 40 g of a methanol dispersion of titanium dioxide particles (1-C) with a substance component concentration of 30% by mass.

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

<Production of surface-treated metal oxide sol: surface treatment using organosilicon compounds containing (meth)acrylic acid groups (using the second step)>

After slowly adding 1.47 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) to 40 g of methanol dispersion of titanium dioxide particles (1-C), Heat and stir at 50°C for 19 hours.

After cooling to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain 40 g of a surface-treated metal oxide sol (1-D) having a solid content of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

"Determination of Average Particle Size"

The average particle size is obtained by taking an electron micrograph and measuring the particle size of any 100 particles and taking the average value.

"Method for Measuring the Refractive Index of Particles"

1) Collect the dispersion to an evaporator to evaporate the dispersion medium.

2) Dry it at 120°C to prepare a powder.

3) Drop 2, 3 drops of reference refracting liquid with known refractive index on the glass plate, and mix the above-mentioned powders in it.

4) Perform the operation of 3) with various reference refracting liquids, and make the refractive index of the reference refracting liquid when the mixed liquid becomes transparent as the refractive index of the particles.

<Manufacturing of paint (1) for forming transparent film>

Add 84.1 g of propylene glycol monomethyl ether and ethoxylated bisphenol A diacrylate (Xin Nakamura Chemical (Stock) Manufacturing: NK ESTER ABE-300) 1.2 g, ethoxylated pentaerythritol tetraacrylate (New Nakamura Chemical Co., Ltd.: NK ESTER ATM-4E) 0.6 g are mixed, and mixed thoroughly. Then, 0.05 g of 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF Co., Ltd.: IRGACURE651) and phenylbis(2,4,6-trimethyl Benzyl)-phosphine oxide (manufactured by BASF Co., Ltd.: IRGACURE819) 0.04 g and thoroughly mixed to prepare an adhesive for transparent coating.

Next, 14.0 g of the surface-treated metal oxide sol (1-D) was mixed with the above-mentioned adhesive for transparent coating to prepare a coating (1) for forming a transparent coating with a solid content of 6 mass%.

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

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

The haze, total light transmittance, refractive index, scratch resistance, and weather resistance of the obtained film were evaluated by the following methods.

"Determination of Haze and Total Light Transmittance"

The haze and total light transmittance of the obtained transparent film were measured with a haze meter (manufactured by Nippon Denshoku Co., Ltd.: NDH-2000). The haze and total light transmittance were evaluated according to the following standards, and the results are shown in the table.

<Evaluation Criteria>

Haze

Below 1.0%: ◎

1.1~2.0%: ○

2.1% or more: ×

<Evaluation Criteria>

Total light transmittance;

85~100%: ◎

75~84%: ○

74% or less: ×

"Measurement of Refractive Index"

The refractive index of the coating was measured with a spectroscopic ellipsometer (manufactured by SEMILAB, Japan: SE-2000). The refractive index was evaluated according to the following criteria, and the results are shown in the table.

<Evaluation Criteria>

Above 1.70: ◎

1.60~1.69: ○

Below 1.59: ×

"Determination of Scratch Resistance"

Use # 0000 steel wool to slide 50 times with a load of 500 g/cm ² and visually observe the surface of the film. The scratch resistance was evaluated according to the following criteria, and the results are shown in the table.

<Evaluation Criteria>

Can't see tendon scratches: ◎

A small amount of tendon scratches can be seen: ○

A lot of tendon scrapes can be seen: △

Overall friction of the surface: ×

"Determination of Weatherability"

The substrate (1-FA) with a transparent conductive film was irradiated with ultraviolet light by a mercury lamp (manufactured by Toshiba Co., Ltd.: H400-E) for 24 hours by a fading test, and the color was visually confirmed. The weather resistance was evaluated according to the following criteria, and the results are shown in the table. Furthermore, the irradiation distance between the lamp and the test piece is set to 70mm, and the lamp output is adjusted in such a way that the surface temperature of the test piece is 45±5°C.

<Evaluation Criteria>

No discoloration: ◎

A little discoloration can be seen: ○

Obvious discoloration can be seen: ×

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

The paint (1) for forming a transparent film was coated on a 6-inch silicon wafer by a spin coater, dried at 80°C for 1 minute, and then irradiated with ArF using the exposure device NSR-S302 (manufactured by Nikon) Excimer laser (193nm) hardened it to prepare a substrate (1-FB) with transparent coating. At this time, the thickness of the transparent coating is 400 nm.

The swelling and sensitivity of the obtained film were evaluated by the following methods.

"Determination of Uplift"

Observe the cross-section of the substrate with transparent conductive film (1-FB) with a scanning electron microscope, and measure the width of the end of the film that is 10% thicker than the film thickness at the center of the film. The swelling was evaluated according to the following evaluation criteria, and the results are shown in the table.

<Evaluation Criteria>

The width of the end of the film with a thickness of more than 10% is less than 0.5mm: ◎

The width of the end of the film with a thickness of more than 10% is 0.5~1.0mm: ○

The width of the end of the film with a thickness of more than 10% is more than 1.1mm: ×

"Determination of Sensitivity and Residual Film Rate" <Evaluation Criteria>

After immersing the base material (1-FB) with a transparent conductive film in a 1% by mass Na ₂ CO ₃ aqueous solution for 10 minutes to remove the unhardened part, it is dried at 80°C for 1 night, depending on the quality difference before and after immersion The sensitivity and residual film rate were evaluated, and the results are shown in the table.

<Evaluation Criteria>

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

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

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

<Manufacturing of base material (1-FC) with transparent coating>

The paint (1) for forming a transparent film was coated on a 6-inch silicon wafer by a spin coater, dried at 80°C for 1 minute, and then separated by an exposure device NSR-S302 (manufactured by Nikon) The photomask (line graph with a ratio of 1:1) is irradiated with an ArF excimer laser (193nm) to harden it. After that, a 1% by mass Na ₂ CO ₃ aqueous solution was sprayed to dissolve and remove the unexposed part, and heated at 150° C. for 3 minutes to prepare a substrate with a transparent film (1-FC).

Using the obtained substrate with a transparent film (1-FC), the resolution was evaluated by the following method.

"Determination of Resolution"

The width of the gap between the masks when the transparent conductive film-attached substrate (1-FC) was produced was changed, and the minimum gap width normally formed with the gap width was used as the value of the resolution to evaluate as follows, and the results are shown in the table.

<Evaluation Criteria>

Pitch width less than 30μm: ◎

Pitch width 31μm~50μm: ○

Pitch width above 51μm: ×

[Example 2]

Except that in the second step, 0.06 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was used, the same procedure as in Example 1 was performed to obtain a surface treatment Metal oxide sol (2-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (2-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 3]

In the second step, except that 7.2 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was used, the same procedure as in Example 1 was performed to obtain a surface treatment Metal oxide sol (3-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (3-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 4]

In the second step, after adding 0.06 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503), 0.29 g of a 2.9% by mass aqueous ammonia solution was added, except for this Otherwise, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (4-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (4-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 5]

In the second step, after adding 7.2 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503), 0.29 g of a 2.9% by mass aqueous ammonia solution was added, except for this Otherwise, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (5-D).

Except having used the surface-treated metal oxide sol (5-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 6]

Except that in the fourth step, 126.0 g of a methanol solution in which 0.90 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., _{28.8% by mass of SiO 2} ) was dissolved was used, the same procedure as in Example 1 was carried out to obtain a surface treatment. Metal oxide sol (6-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (6-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 7]

In the fourth step, 126.0 g of a methanol solution in which 44.8 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd., _{28.8% by mass) of SiO 2 was} dissolved was used, the same procedure as in Example 1 was carried out to obtain a surface-treated metal Oxide sol (7-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (7-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 8]

In the third step, except for using 7.6 g of the zirconium peroxide aqueous solution and 6.1 g of the silicic acid aqueous solution, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (8-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (8-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 9]

Except for using 171.6 g of zirconium peroxide aqueous solution and 142.3 g of silicic acid aqueous solution in the 3rd step, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (9-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (9-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 10]

Except for using 6.02 g of zirconium peroxide aqueous solution and 23.7 g of silicic acid aqueous solution in the third step, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (10-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (10-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, in the same manner as in Example 1, a transparent film was produced The base material and evaluate it.

[Example 11]

Except having used 120.5 g of zirconium peroxide aqueous solution and 9.8 g of silicic acid aqueous solution in the 3rd step, it carried out similarly to Example 1, and obtained the surface-treated metal oxide sol (11-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (11-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 12]

Except that in the third step, 11.5 g of sodium aluminate aqueous solution with 1.0% by mass converted to _{Al 2} O ₃ and 14.8 g of sodium silicate aqueous solution with 3.0% by mass converted _{to SiO 2 were used instead of the aqueous solution of zirconium peroxide and aqueous silicic acid.} In the same manner as in Example 1, an aqueous dispersion of titanium dioxide particles (12-B) with a solid content concentration of 10% by mass in a composite oxide layer of silica and alumina was obtained.

After that, the same procedure as in Example 1 was performed to obtain a surface-treated metal oxide sol (12-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (12-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 13]

Divide in step 3. Same as Example 1, except that 11.5 g of sodium aluminate aqueous solution with 1.0% by mass converted to Al ₂ O _{3 and 14.8 g of sodium silicate aqueous solution with 3.0% by mass converted to SiO 2 were used} instead of the aqueous solution of zirconium peroxide and the aqueous solution of silicic acid. Proceeding to obtain an aqueous dispersion of titanium dioxide particles (13-B) with a solid content concentration of 10% by mass in a composite oxide layer of silica alumina.

Then, except that the dealkalization treatment using the cation exchange resin in the fourth step was repeated, the same procedure as in Example 1 was carried out to obtain titanium dioxide-based particles with a solid content of 30% by mass provided with a silicon dioxide layer (13 -C) Methanol dispersion.

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (13-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (13-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 14]

Except that in the third step, 9.5 g of a titanium tetrachloride aqueous solution with a concentration of 1.0% by mass converted to _{TiO 2} and 15.5 g of a sodium silicate aqueous solution with a concentration of 3.0% by mass converted _{to SiO 2 were used instead of the zirconium peroxide aqueous solution and the silicic acid solution} In the same manner as in Example 1, an aqueous dispersion of titanium dioxide-based particles (14-B) with a solid content concentration of 10% by mass of the composite oxide layer provided with silicon dioxide and titanium dioxide was obtained.

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (14-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (14-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 15]

Except that in the third step, 15.5 g of potassium stannate aqueous solution with 1.0% by mass conversion of _{SnO 2 and 13.5 g of silicic acid aqueous solution with 2.0% by mass of SiO 2 were used} instead of the aqueous solution of zirconium peroxide and the aqueous solution of silicic acid. In the same manner as in Example 1, an aqueous dispersion of titanium dioxide particles (15-B) with a solid content concentration of 10% by mass in a composite oxide layer of silicon dioxide tin oxide was obtained.

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (15-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (15-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 16]

Except that in the first step, 599 g of pure water was mixed without using silica sol in 450 g of a 2% by mass aqueous solution of titanic acid per _{TiO 2 converted to TiO 2, the same procedure as in Example 1 was carried out to obtain a solid content concentration of 10} Mass% titanium dioxide particles (16-A) aqueous dispersion.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (16-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (16-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 17]

In addition to the first step, in 450 g of a 2% by mass aqueous solution of titanic acid _{in terms of TiO 2 is mixed with a silica sol containing 15% by mass of SiO 2} and silica particles with an average particle diameter of 7 nm (Japanese volatile Catalyzer Chemicals (stock) manufacturing: CATALOID SN-350) 17.9g and pure water 581g, the same as in Example 1, to obtain a solid content concentration of 10% by mass of titanium dioxide particles (17-A) aqueous dispersion .

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (17-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 1.

Except having used the surface-treated metal oxide sol (17-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 18]

In the first step, in the same manner as in Example 1 manufactured in terms of TiO ₂ to 2 mass% aqueous solution of 729.0g of titanium peroxide in the mixed acid cation exchange resin 35.0 g, to which was added slowly with stirring terms of SnO ₂ After 91.0 g of 1% by mass potassium stannate aqueous solution, the cation exchange resin was separated.

Then, _{8.0 g of silica sol (manufactured by Nikkei Catalytic Chemicals Co., Ltd.: CATALOID SN-350) containing 15% by mass of SiO 2} and silicon dioxide particles with an average particle size of 7 nm were mixed with 180.0 g of pure water. Hydrothermal treatment was performed in the autoclave at 165°C for 18 hours.

Next, after cooling the resulting aqueous solution to room temperature, it was concentrated by an ultrafiltration membrane device to obtain an aqueous dispersion of titanium dioxide-based fine particles (18-A) with a solid content of 10% by mass.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (18-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (18-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 19]

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 an aqueous ferric chloride solution of 2% by mass _{in terms of Fe 2} O _{3 were mixed, and mixed for 15} Except for 176 g of ammonia water of 176 g by mass, the same procedure as in Example 1 was carried out to obtain an aqueous dispersion of iron-doped titanium dioxide particles (19-A) having a solid content of 10% by mass.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (19-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except for using the surface-treated metal oxide sol (19-D), the same procedure as in Example 1 was carried out to produce a paint for forming a transparent film. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 20]

In the first step, 404.0 g of a titanium tetrachloride aqueous solution containing 2% by mass of titanium tetrachloride _{in terms of TiO 2 and 46.0 g of an aqueous ferric chloride solution of 2% by mass in terms of Fe 2} O ₃ were mixed, and mixed for 15 Except for 176 g of ammonia water of mass %, the same procedure as in Example 1 was carried out to obtain 104.9 g of an aqueous dispersion of iron-doped titanium dioxide particles (20-A) with a solid content of 10 mass %.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (20-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (20-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it 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 cerium chloride aqueous solution of 2% by mass _{in terms of CeO 2 were mixed, and mixed with 15% by mass} Except for this, the same procedure as in Example 1 was carried out to obtain an aqueous dispersion of cerium-doped titanium dioxide particles (21-A) with a solid content of 10% by mass.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (21-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (21-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 22]

In the first step, 404.0 g of a titanium tetrachloride aqueous solution containing 2% by mass of titanium tetrachloride _{in terms of TiO 2 and 46.0 g of a cerium chloride aqueous solution of 2% by mass in terms of CeO 2} were mixed, and mixed with 15% by mass Except for this, the same procedure as in Example 1 was carried out to obtain an aqueous dispersion of cerium-doped titanium dioxide particles (22-A) with a solid content of 10% by mass.

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (22-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (22-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 23]

In addition to the first step, in 450 g of a 2% by mass aqueous solution of titanic acid _{in terms of TiO 2 is mixed with a silica sol containing 15% by mass of SiO 2} and silica particles with an average particle diameter of 7 nm (Japanese volatile Catalyzer Chemicals (Stock) Manufacturing: CATALOID SN-350) 8.2 g and 239.1 g of pure water were carried out in the same manner as in Example 1 to obtain water dispersion of titanium dioxide particles (23-A) with a solid content of 10% by mass liquid.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (23-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (23-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 24]

In addition to the first step, in 450 g of a 2% by mass aqueous solution of titanic acid _{in terms of TiO 2 is mixed with a silica sol containing 15% by mass of SiO 2} and silica particles with an average particle diameter of 7 nm (Japanese volatile Catalytic Chemicals (Stock) Manufacturing: CATALOID SN-350) 8.2 g and pure water 1637.1 g, the same as in Example 1 was carried out to obtain a water dispersion of titanium dioxide particles (24-A) with a solid content concentration of 10% by mass liquid.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (24-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (24-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 25]

In addition to the first step, in 450 g of a 2% by mass aqueous solution of titanic acid _{in terms of TiO 2 is mixed with a silica sol containing 15% by mass of SiO 2} and silica particles with an average particle diameter of 7 nm (Japanese volatile Catalytic Chemicals (Stock) Manufacturing: CATALOID SN-350) Except for 8.2 g of pure water and 122.6 g of pure water, the same procedure as in Example 1 was carried out to obtain water dispersion of titanium dioxide particles (25-A) with a solid content of 10% by mass. liquid.

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (25-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (25-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 26]

In addition to the first step, in 450 g of a 2% by mass peroxy titanic acid aqueous solution calculated as _{TiO 2 is mixed a silica sol containing 15% by mass as SiO 2} and silica particles with an average particle diameter of 7 nm (Nippon-catalyst Kasei Co., Ltd. product: CATALOID SN-350) 8.2 g and 122.6 g of pure water were carried out in the same manner as in Example 1 to obtain an aqueous dispersion of titanium dioxide particles (26-A) having a solid content of 10% by mass.

After that, except that the dealkalization treatment using the cation exchange resin in the fourth step was repeated, the same procedure as in Example 1 was performed to obtain a surface-treated metal oxide sol (26-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (26-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 27]

In the first step and the third step, a cation exchange resin (Mitsubishi resin (stock ) Manufacturing) After dealkalizing, the ion exchange resin is separated. After that, the dispersion medium was replaced with methanol using an ultrafiltration membrane. After that, it was concentrated to obtain a methanol dispersion of titanium dioxide-based fine particles (27-B) having a solid content of 30% by mass. The amount of water contained in the obtained titanium dioxide-based particles (27-B) methanol dispersion was 0.3% by mass.

Furthermore, in the second step, in 40 g of the titanium dioxide-based particles (27-B) methanol dispersion Slowly add 1.47 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503). Thereafter, it was heated and stirred at 50°C for 19 hours. Then, after cooling it to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain a surface-treated metal oxide sol (27-D) having a solid content of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 2. Furthermore, in this embodiment, the fourth step is not performed.

Except having used the surface-treated metal oxide sol (27-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 28]

In the first step, a cation exchange resin (manufactured by Mitsubishi Plastics Co., Ltd.) was slowly added to 117 g of an aqueous dispersion of titanium dioxide particles (1-A) with a solid content concentration of 10% by mass produced in the same manner as in Example 1. After the dealkalization is performed, the ion exchange resin is separated.

Next, in the fourth step of manufacturing the silicon dioxide layer, slowly add 126.0 g of a methanol solution in which 8.96 g of tetraethoxysilane (manufactured by Tama Chemical Co., Ltd.) is dissolved in the solution, and heat and stir at 50°C. In 1 hour, a water/methanol dispersion of titanium dioxide-based particles (28-C) was obtained. The water/methanol dispersion of the titanium dioxide-based particles (28-C) was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. After that, it was concentrated to obtain a methanol dispersion of titanium dioxide-based particles (28-C) having a solid content of 30% by mass. The amount of water contained in the obtained titanium dioxide-based particles (28-C) methanol dispersion was 0.3% by mass.

Furthermore, in the second step, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM- 503) 1.47g. Thereafter, it was heated and stirred at 50°C for 19 hours. Then, cool it down to After room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain a surface-treated metal oxide sol (28-D) with a solid content of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 2. Furthermore, in this embodiment, the third step of manufacturing the silicon dioxide composite oxide layer is not performed.

Except having used the surface-treated metal oxide sol (28-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 29]

Except for the second step, use 3-propenoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-5103) 1.47g instead of 3-methacryloxypropyltrimethoxysilane Except for (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503), the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (29-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (29-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 30]

Except for the second step, use 3-propenoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE-503) 1.47g instead of 3-methacryloxypropyltrimethoxysilane Except for silane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503), the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (30-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except for using the surface-treated metal oxide sol (30-D), proceed in the same way as in Example 1. Line to manufacture coatings for transparent film formation. Then, a substrate with a transparent coating film was manufactured and evaluated.

[Example 31]

In the second step, 1.47g of 3-propenyloxypropyldiethylmethylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE-502) was used instead of 3-methacryloxypropyltrimethoxy Except for silane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503), the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (31-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (31-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 32]

Except that in the second step, propylene glycol monomethyl ether acetate (PGMEA) was used instead of propylene glycol monomethyl ether (PGME), the same procedure as in Example 1 was performed to obtain a surface treatment metal oxide with a solid content of 30% by mass. Material sol (32-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (32-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Example 33]

In the fourth step, a cation exchange resin (manufactured by Mitsubishi Plastics Co., Ltd.) was slowly added to the water/methanol dispersion of titanium dioxide particles (1-C) produced in the same manner as in Example 1, and then the ions were separated. Exchange resin. Disperse the obtained titanium dioxide particles (33-C) in water/methanol The liquid was cooled to room temperature, and the dispersion medium was replaced with methanol using an ultrafiltration membrane. After that, it was concentrated to obtain 40 g of a methanol dispersion of titanium dioxide-based fine particles (33-C) having a solid content of 30% by mass.

After that, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (33-D). The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (33-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Comparative Example 1]

In the fourth step, in the methanol dispersion of titanium dioxide particles (1-C) with a solid content concentration of 30% by mass produced in the same manner as in Example 1, the dispersion medium was replaced with propylene glycol monomethyl ether ( PGME). Thereby, 40 g of a metal oxide sol (C1-D) with a solid content concentration of 30% by mass without surface treatment with an organosilicon compound containing a (meth)acryloyl group was obtained. The composition of the obtained metal oxide sol is shown in Table 3.

Except having used the surface-treated metal oxide sol (C1-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Comparative Example 2]

Except that in the second step, the amount of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was set to 15.6 g, the same procedure as in Example 1 was performed. , To obtain a surface-treated metal oxide sol (C2-D). The composition of the obtained metal oxide sol is shown in Table 3.

Except having used the surface-treated metal oxide sol (C2-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the transparent film was produced in the same manner as in Example 1. The base material and evaluate it.

[Comparative Example 3]

In addition to the first step, in the same manner as in Example 1 manufactured in terms of TiO ₂ to 2 mass% of the titanium peroxide aqueous acid mixture comprising 450g of 15 mass% average particle diameter of the silicon particles of the silicon dioxide 7nm Sol (manufactured by Nikkei Catalyst Chemical Co., Ltd.: CATALOID SN-350) 65.0 g and 532 g of pure water were carried out in the same manner as in Example 1 to obtain titanium dioxide particles (C3-A) with a solid content of 10% by mass. Water dispersion.

After that, the same procedure as in Example 1 was performed to obtain a surface-treated metal oxide sol (C3-D). Table 3 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (C3-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Comparative Example 4]

In the first step, in the same manner as in Example 1 manufactured in terms of TiO ₂ to 2 mass% aqueous solution of 280.4g of titanium peroxide in the mixed acid cation exchange resin 35.0 g, to which was added slowly with stirring terms of SnO ₂ After being 527.8 g of 1% by mass potassium stannate aqueous solution, the cation exchange resin was separated.

Then, 8.0 g of silica sol (manufactured by Nikkei Catalytic Chemicals Co., Ltd.: CATALOID SN-350) containing 15% by mass of silicon dioxide particles with an average particle diameter of 7 nm was mixed with 180.0 g of pure water, and placed in an autoclave at 165 The hydrothermal treatment was carried out at ℃ for 18 hours.

Next, after cooling the resulting aqueous solution to room temperature, it was concentrated by an ultrafiltration membrane device to obtain an aqueous dispersion of titanium dioxide-based fine particles (C4-A) with a solid content of 10% by mass.

Thereafter, the same procedure as in Example 1 was carried out to obtain a surface-treated metal oxide sol (C4-D). Table 3 shows the composition of the obtained surface-treated metal oxide sol.

Except having used the surface-treated metal oxide sol (C4-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

[Reference example 1]

In the first step, the cation exchange resin (manufactured by Mitsubishi Plastics Co., Ltd.) was slowly added to the aqueous dispersion of titanium dioxide-based fine particles (1-A) with a solid content concentration of 10% by mass produced in the same manner as in Example 1. After dealkalization, the ion exchange resin is separated. After that, the dispersion medium was replaced with methanol using an ultrafiltration membrane. After that, it was concentrated to obtain a methanol dispersion of titanium dioxide particles (R1-A) having a solid content of 30% by mass. The moisture content in the obtained methanol dispersion of titanium dioxide-based particles (R1-A) was 0.3% by mass.

Furthermore, in the second step, 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM- 503) 1.47g. Thereafter, it was heated and stirred at 50°C for 19 hours. Then, after cooling it to room temperature, the dispersion medium was replaced with propylene glycol monomethyl ether (PGME) using an ultrafiltration membrane to obtain a surface-treated metal oxide sol (R1-D) having a solid content of 30% by mass. The composition of the obtained surface-treated metal oxide sol is shown in Table 2.

Except having used the surface-treated metal oxide sol (R1-D), it carried out similarly to Example 1, and produced the coating material for transparent film formation. Then, the base material with a transparent coating film was manufactured similarly to Example 1, and it evaluated.

Claims (5)

A surface-treated metal oxide sol, characterized in that it contains a surface-treated metal obtained by treating the surface of metal oxide particles by an organosilicon compound containing (meth)acrylic acid groups represented by formula (1) Oxide particles and a dispersion medium, wherein the metal oxide particles contain _{50% by mass or more of titanium dioxide based on TiO 2} and the organosilicon compound is based on 100 parts by mass of the metal oxide particles as R ¹ _n -SiO _{(4 -n)/2} (wherein, R ¹ is a group containing at least one selected from the group consisting of methacrylic acid group and acrylic acid group, which may be the same or different from each other, and n is an integer of 1 to 3). The surface of the metal oxide particles is 0.1-60 parts by mass. If the organosilicon compound is accumulated on the surface of the metal oxide particles and the other is present in the surface-treated metal oxide sol, it will be relative to the surface of the metal oxide sol. 100 parts by mass of metal oxide particles, based on R ¹ _n -SiO _(4-n)/2 , containing 0.1-100 parts by mass, between the metal oxide particles and the organosilicon compound containing (meth)acrylic acid groups There is at least one of a layer of silicon dioxide composite oxide selected from the group consisting of silicon dioxide zirconia, silicon dioxide alumina, silicon dioxide titanium dioxide and silicon dioxide tin oxide, and a silicon dioxide layer, Sodium is less than 25ppm based on Na ₂ O concentration, potassium is less than 0.5% by mass _{based on K 2} O concentration, ammonia is less than 1000 ppm _{based on NH 3} ^{concentration, R 1} _n -SiX ¹ _(4-n) (1) (where , R ¹ is a group containing at least one selected from a methacrylic group and an acrylic group, which may be the same or different from each other, n is an integer of 1 to 3, and X ¹ is an alkoxy group). The surface-treated metal oxide sol according to claim 1, wherein the metal oxide particles are titanium dioxide or a composite oxide containing at least one of titanium and silicon, tin, iron, and cerium. The surface-treated metal oxide sol according to claim 1, wherein the average particle size of the surface-treated metal oxide particles is 5 to 500 nm, and contains 5 to 70% by mass based on the solid content. According to the surface treatment metal oxide sol of claim 1, wherein the dispersion medium contains at least one organic solvent with an SP value of 10 or more and a boiling point exceeding 100° C. The organic solvent contains 30-95% by mass in the dispersion medium. For example, the surface treatment metal oxide sol of claim 1, wherein sodium does _{not reach 20 ppm based on Na 2} O concentration, potassium does _{not reach 0.5 mass% based on K 2} O concentration, and ammonia does not reach 1000 ppm _{based on NH 3 concentration.}