TW495485B - Fine particle, sol having fine particles dispersed, method for preparing said sol an - Google Patents

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 ______ B7 V. Description of the Invention (1) Technical Field The present invention relates to the surface of porous composite oxide particles, which are covered with silica-based inorganic oxide layers. The present invention also relates to a sol in which the fine particles are dispersed in a dispersion medium, and a method for producing the sol. A base material containing the fine particles and an antireflection coating is formed on a surface. BACKGROUND OF THE INVENTION The present inventors have previously invented composite oxide sols such as sand sols, sand gravels-oxides, sand gravels-oxidation pins, and the like dispersed with porous fine particles having a large specific surface area (Japanese Patent Laid-Open No. 5-1 3 2 3 0 Bulletin 9). The composite oxide sol can be used in various applications such as a binder, an adsorbent, and a low-refractive charge filler in addition to a catalyst because of its porous nature. In addition, in order to prevent reflection on the surface of a substrate such as glass or a plastic sheet, it is known that an antireflection film is formed on the surface. For example, fluorine is formed on the surface of a glass or a plastic sheet by a coating method, a deposition method, a CVD method, or the like. Coating of resin, low refractive index material like magnesium fluoride. However, these methods are expensive and have problems in durability and the like. It is also known to apply a coating liquid containing silica fine particles on a glass surface, and form fine anti-reflection coatings having uniform unevenness with the fine particles of syrup. However, this method uses the irregular reflection of light to reduce the regular reflection on the uneven surface formed by the silica particles, and uses the air layer generated by the gap between the particles to prevent the reflection, but the particles are difficult to immobilize on the surface of the substrate and it is difficult to form a single layer. Film, so the reflectivity of the surface cannot be easily controlled. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -4------ Ί --- * 5 ------------ Order ---- ----- line · ^^ · (Please read the note on the back? Matters before filling out this page) 495485 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ______ Β7 ____ V. Description of the invention (2) Furthermore, the invention Sol et al. Have proposed a sol in which low-refractive-index composite oxide fine particles completely covered with silica are dispersed on the surface of porous fine particles (Japanese Patent Application Laid-Open No. 7-1 3 3 105). However, in order to completely cover the fine particles, it is necessary to have a coating process and a heat treatment process again, and a solvent such as water or alcohol is sealed in the coating particles, so there is a limit in reducing the refractive index. In addition, films and resin plates obtained by dispersing the particles in a resin or the like have low adhesion to the resin and the particles, and it is difficult to determine the strength of the antireflection film. The present inventors disclosed in Japanese Patent Application Laid-Open No. 10- 1 9 4 7 2 1 and Japanese Patent Application Laid-Open No. 10- 4 5 4 0 3 that silica particles containing an organic group directly bonded to silicon are disclosed. Organic solvents and resins have high affinity, and can be easily monodispersed in water. Although the silica particles are difficult to cause the particles to fall off from the molded product mixed with the resin, they cannot completely prevent the particles from falling off. In addition, when using a filler for adjusting the refractive index, a low refractive index cannot be obtained sufficiently. Furthermore, even on the surface of substrates such as glass and plastic sheets, low-refractive-index materials such as silica, fluororesin, and magnesium oxide are used to form coatings on the substrates, as well as films and substrates composed of low-refractive-index materials. When there is no compatibility (affinity), the adhesion to the substrate is poor. In addition, depending on the substrate used, the performance of preventing reflection may be insufficient. DISCLOSURE OF THE INVENTION The present invention is to provide a surface of porous composite oxide particles, and a variety of fine particle structures covered with a porous silica-based inorganic oxide layer. The paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 丨 ^ ---- ΙΊ ---! ------------ Order --------- line (Please read the notes on the back before filling in this Page) 495485 Printed clothing A7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _____H7 —_ 5. Description of the invention (3) Purpose. In addition, the present invention is to provide a sol in which the fine particles are dispersed, a method for producing the same, and forming a film containing the fine particles on the surface of a substrate, and having a low refractive index, adhesion to a resin, strength, anti-reflection ability, and the like. Excellent substrates with coatings are used for this purpose. The fine particles of the present invention are porous composite oxide particles composed of silica and inorganic oxides other than silica, and are covered with a porous silica-based inorganic oxide layer having a thickness of 0.5 to 20 nm. For its characteristics. The maximum pore diameter of the silica-based inorganic oxide layer is preferably from 0.5 to 5 nm. The aforementioned fine particles are expressed as Si ◦ 2 in the silica, and the molar ratio M0x / S i〇2 of the inorganic oxides other than silica expressed as Mox is preferably in the range of 0.001 to 0.2. . The fine particles preferably have a pore volume of 0.1 to 1.5 c c / g, and the fine particles preferably have a second silica coating layer on the surface. It is preferable that the microparticles contain an organic group directly bonded to silicon, and the ratio of the molar number (SR) of the directly bonded silicon of the organic group to the molar number (St) of all silicon is Sr / St. 〇1 ～ 09 is preferable. The method for producing a microparticle-dispersed sol of the present invention is characterized by being composed of the following processes (a) to (c). (a) An aqueous solution of an oxalate and / or an acidic oxalic acid solution, a hydrolysate of an organic silicon compound having the chemical formula (1), and an aqueous solution of an inorganic compound that is soluble in alkali, at a base of P Η 10 or more. Aqueous aqueous solution, or alkaline aqueous solution in which P Η 10 or more is dispersed as needed, and the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -----. 1- --1 ----------- Order --------- line (please read the notes on the back before filling this page) 495485 A7 B7 V. Description of the invention (4) plus modulation The process of forming the particle precursor dispersion (please read the note on the back? Matters before filling out this page) (b) 'Add a silica source or a stone evening source and other silica to the core particle precursor dispersion The process of forming an aqueous solution of an inorganic compound salt and forming a first silica-based coating in the precursor of the core particles (c) adding an acid to the aforementioned dispersion and selecting and removing from the elements constituting the precursor of the nuclear particles Engineering of at least a part of elements other than silicon and oxygen R 丨 IS i X (4 Π) ......... (1) [However, R: a non-substituted or Substituted hydrocarbyl group, X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen or hydrogen, η: 1 to 3] In addition, an alkaline aqueous solution is added to the fine particle dispersed sol obtained in the aforementioned process (c), It is preferable that the organosilicon compound represented by the chemical formula (2) and / or a partial hydrolyzate thereof, and a second silica coating layer be formed on the fine particles. R " S i X (4 η) ... ... (2) [However, R: an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, X: an alkoxy group, silanol group, halogen or hydrogen having 1 to 4 carbon atoms, η: 〇 ~ 3] Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and it will form a dispersed sol of fine particles of the second silica coating layer, and heat treatment at 50 ° C ~ 350 ° C to make the second silica It is better that the pores of the coating layer disappear. The film substrate of the present invention is characterized in that a film containing the fine particles and a substrate for film formation is formed on the surface of the substrate. The refractive index of the aforementioned substrate is preferably 1.6 or more. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 495485 A7 B7 V. Description of the invention (5) In the case where the refractive index of the aforementioned substrate is below 1.6, it is better (please (Please read the precautions on the back before filling in this page). Under the surface coating containing the fine particles of the present invention, it has an intermediate coating with a refractive index of 1.60 or more. The intermediate film preferably contains 30 to 95% by weight of metal oxide fine particles having an average particle diameter of 5 to 100 nm. Best Modes of Huanshi Invention Hereinafter, preferred embodiments of the invention will be described. (1) Fine particles In the fine particle core of the present invention, porous composite oxide particles composed of silica and inorganic oxides other than silica are used. Inorganic oxides can be listed-one or two or more of A 1 2 03, B 2 03, T 102.

Zr〇2, Sn〇2, C e 2 0 a, P205, Sb203,

MoO3, Zn02, W03 and the like. Two or more kinds of inorganic oxides may be listed as Ti02-Al203, Ti02-Zr02, and the like. The molar ratio of the nuclear particles printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to Si is represented by S i Ο2, and the inorganic oxides other than silica are represented by MoX. MoX / SiO2 is 0. · The range of 05 ~ 2 · 0 is preferable. If M〇x / S i〇2 is less than 0.005, the pore volume described later cannot be sufficiently increased, and the reduction in refractive index is insufficient. On the other hand, if "〇 \ / 3 丨 〇2 exceeds 2. 0, the stability of the obtained sol is reduced, so it is not good. The surface of the core particles is covered with a silica-based inorganic oxide layer. The so-called silica-based inorganic oxide layer here includes ① a single layer of silica-8-this paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Printed 495485 Α7 Β7 5. Description of the invention (6), ② a single layer of composite oxide composed of silica and inorganic oxides other than silica, and ③ the double layer of the aforementioned ① layer and ② layer. In the present invention, the thickness of the coating layer must be in a range of 0.5 to 20 nm. If the thickness of the coating layer is less than 0 · 5 nm, it is difficult to obtain a coating effect. Specifically, the resin (including monomers, polymers, and oligomers. The same applies below) may enter the pores of the composite oxide particles. , It is easy to make the refractive index reduction described later insufficient. In addition, in a manufacturing process described later, when at least a part of elements other than sand and oxygen are selectively removed from the particles, the shape of the particles may not be maintained in some cases, which is not preferable. On the other hand, when the thickness of the coating layer exceeds 20 nm, it is difficult to form a coating layer having pores of a suitable size to be described later, and the obtained particles sometimes become nonporous. In addition, it is easy to make it difficult to selectively remove elements in the next process. Furthermore, solvents such as water and alcohols were sealed in the composite oxide particles. As a result, when the film was dispersed in the resin to form a film, the solvent could not be sufficiently removed during drying, and because a gas phase such as air could not be formed, the reduction of the refractive index was insufficient. , So bad. The thickness of the coating film is preferably in the range of 1 to 8 nm. The coating layer must be made porous, and the maximum pore diameter of the coating layer is 0.  A range of 5 to 5 n m is preferred. If the maximum pore diameter is less than 0 · 5 n m, it is difficult for the resin to penetrate the pores in the coating layer, so the adhesiveness with the resin is insufficient. In addition, the solvent in the pores of the composite oxide particles is difficult to escape during drying, so the reduction in the refractive index is not sufficient, which is not preferable. On the other hand, when the maximum pore diameter is larger than 5 nm, not only the resin enters the coating layer and the composite oxide particles that become the core also enter the pores, so the reduction of the refractive index is insufficient. The maximum pore diameter is more within the range of 1 ~ 4 · 5 π m " This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) ----- Ί --- 1 ---- ------- Order --------- line (please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 __ B7 V. Description of the invention ( 7) Good. The pore volume of the composite oxide fine particles is 0 · 1 ~ 1 · 5 J / g, particularly preferably in the range of 0 · 2 ~ 1 · 5 m £ / g. The pore volume is less than 0.  1 / g, the desired porous fine particles cannot be made. On the other hand, if it exceeds 1.  5 2 / g decreases the strength of the fine particles. The average particle diameter of the composite oxide fine particles of the present invention must be in the range of 5 to 300 nm. When the average particle size is less than 5 n m, the volume ratio of the coating layer in the fine particles increases, and the ratio of the pores decreases. On the other hand, if the average particle diameter exceeds 300 nm, it is difficult to obtain a stable dispersed sol, and the transparency of a coating film or the like containing the fine particles is liable to decrease. A more preferable average particle diameter of the composite oxide microparticles is in the range of 10 to 200 nm. Therefore, the average particle diameter of the core particles constituting the composite oxide fine particles must be in the range of 4 · 5 to 280 nm. Alas, the average particle size of fine particles can be obtained by the dynamic light scattering method. The composite oxide fine particles of the present invention preferably contain an organic group directly bonded to silicon. Such an organic group may use an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a hydrocarbon group, a halogenated hydrocarbon group, an alkylene oxide group, an amine alkyl group, an alkyl methacrylate group, and a hydrosulfanyl group. . More specifically, methyl, phenyl, isobutyl, vinyl, trifluoropropyl, Θ- (3,4-epoxycyclohexyl), 7-glycidoxypropyl, T-methyl Allylpropyl, N- / 3- (aminoethyl) r-aminopropyl, τ-aminopropyl, N-benzyl-r-aminopropyl, r-hydrothiopropyl and the like. The ratio Sr / St of the molar number (s R) of the direct-bonded silicon of the organic group to the molar number (St) of the total silicon is 0-1.  Scope of 9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----- Ί ---------------- Order ----- ---- Line (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 485 A7 ^ ______ B7 5. The invention description (8) is better. When Sr / St is less than 0 · 00 1, the amount of organic groups on the surface of the particles is small, so the affinity with organic solvents and resins is insufficient, and the reduction in refractive index caused by containing organic groups is insufficient. On the other hand, if it exceeds 0 · 9, the properties of the organic group become too strong, and the particles are likely to aggregate with each other in water. A more preferable range of Sr / St is 〇1 ～ 0 · 9. S K / S τ is obtained by the following method. The sol was vacuum-dried at 100 ° C for one day and night, and about 5 g of a powder sample obtained by completely removing volatile components such as water was added to 250 ml of a 0.50 N aqueous solution of NaOH. Disperse and continue stirring at room temperature for 10 hours. Through this operation, unreacted hydrolyzable groups in the powder sample were completely hydrolyzed and extracted into the water of the dispersion medium. The powder sample in this dispersion was repeatedly separated by ultracentrifugation, washed with water, and the powder sample dried at 200 ° C for 5 hours was determined by elemental analysis to determine the total carbon content, and the average of the organic groups used in the raw materials was determined. The number of carbons, the mole number (SR) of the directly bonded silicon of the organic group is calculated, and the ratio to the mole number (St) of the total silicon is calculated. (2) Microparticle-dispersed sol The microparticle-dispersed sol of the present invention is obtained by dispersing the microparticles of the present invention in a dispersion medium composed of water or an organic solvent, or a mixed solvent thereof. The organic solvent is not particularly limited, but organic solvents used in conventional organic solvents such as monohydric alcohols such as methanol and ethanol, and polyhydric alcohols such as ethylene glycol and propylene glycol may be used. The above-mentioned fine particle dispersing sol can be used for various purposes, and in the case of concentration as necessary, a part of the alkali metal in the sol can be removed in advance ----- Ί ------------- --Order --------- line (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -11- 495485 A7 ____ B7 V. Description of the invention (9) Those who have concentrated the ions, alkaline earth metal ions and ammonium ions, etc., can obtain stable concentrated sol. The removal method can be a known method such as ultrafiltration (please read the precautions on the back before filling this page). (3) Method for producing fine particle-dispersed sol The method for producing fine particle-dispersed sol of the present invention is composed of the aforementioned processes (a) to (c). Hereinafter, description will be made in order. (a) [Preparation of the precursor dispersion of nuclear particles] It is preferable to use one or two or more kinds of silicates selected from the group consisting of alkali metal silicates, ammonium silicates, and organic base silicates. Alkali metal silicates can be [J For example, sodium silicate (water glass) and potassium silicate. Organic bases include quaternary ammonium salts such as tetraethylammonium, monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or organic base silicate also contains alkaline solutions such as hydration ammonia, quaternary ammonium hydroxide, and amine compounds in the silicic acid solution. As the acidic silicic acid solution, a silicic acid solution obtained by removing an alkali aqueous solution of silicic acid with cation exchange resin treatment or the like can be used. In particular, the acidic concentration of p Η 2 to p Η 4 and S i 0 2 is about 7% by weight or less. Silicic acid is preferred. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Specific examples of the organic silicon compound represented by the aforementioned chemical formula (1) include methyltrimethoxysilane, dimethyldimethoxysilane, and phenyltrimethoxysilane. , Diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (/ 3-methoxyethoxy) silane, This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ) 495485 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) 3 '3,3-trifluoropropyltrimethoxysilane, methyl-1,3,3,3- ^ fluoropropyldiamine Methoxysilane, A — (3,4-epoxycyclohexyl) Ethyl hydrazone, r-glycidyloxytripropyltrimethoxytriol, r-glycidyloxypropylmethyldi Ethoxysilane, r-glycidyl, oleoxypropyltriethoxysilane, r-methacryloxy Propylmethyldimethoxysilane, r-methacryloxypropyl-trimethoxysilane, r-methacryloxypropylmethyldiethoxysilane, r-methacryloxypropyl Hydrazone ethoxysilane, n — / 5 (aminoethyl) r monoaminopropylmethyldimethylsilane, N-Θ (aminoethyl) r monoaminopropyltrimethoxysilane, (aminoethyl) 7-aminopropyltriethoxysilane, r-aminopropyltrimethoxysilane, r-aminopropyltriethoxysilane, N-phenyl-r-aminopropyltrimethoxysilane, r-hydrogen Thioyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldiphenyl Chlorosilicon, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, etc. Because the above-mentioned organosilicon compound lacks hydrophilicity, it is preferred to perform hydrolysis in advance so that it can be uniformly mixed in the reaction system. The hydrolysis can be performed by a known hydrolysis method of these organic stone compounds. When hydrolyzing catalysts use alkali metal hydroxides, ammonia, amines, and other test substances, these alkaline catalysts can be removed after hydrolysis and made into alkaline solutions for use. When the hydrolysate is prepared using an acidic catalyst such as an organic acid or an inorganic acid, it is preferable to remove the acidic catalyst by ion exchange or the like after hydrolysis. Alas, the hydrolysate of the obtained organosilicon compound is expected to be used in the form of an aqueous solution. The term "aqueous solution" used herein means that the hydrolysate is not in a cloudy state of the gel but in a state of transparency. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -13- ~ " '" " " "' " ---------- *- ----------- Order --------- line ^^ (Please read the note on the back? Matters before filling out this page) 495485 Α7 Β7 V. Description of the invention (11) (Please (Please read the notes on the back before filling this page) The raw materials of inorganic oxides are preferably alkali-soluble inorganic compounds, and the alkali metal salts or alkaline earth metal salts, ammonium salts, The quaternary ammonium salt, more specifically, sodium aluminate, sodium tetraborate, ammonium zirconium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, ammonium nitrate, sodium phosphate, and the like are suitable. On the precursor dispersion of the prepared nuclear particles, an alkaline aqueous solution of the aforementioned inorganic compound can be prepared individually or a mixed aqueous solution can be prepared, and the aqueous solution corresponds to the composite ratio of the composite oxide, while stirring in an alkaline aqueous solution of ρ Η 10 or more Add slowly. The molar ratio of silica raw materials, organic silicon compounds, and inorganic oxides added to the alkaline aqueous solution is represented by Si 102 as the silica component, and the molar ratio of inorganic oxides other than silica is represented by MoX. MoX / Sio2 is preferably in the range of 0. 05 to 2. 0. M〇x / S i〇2 is less than 0.  0, the aforementioned pore volume cannot be sufficiently increased. On the other hand, if MoX / S 102 exceeds 2.0, the stability of the obtained sol is reduced. It is desirable that the aforementioned Sr / St is in the range of 0. 00 1 to 0. 9. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Adding these aqueous solutions will also change the same solution P ，, but the present invention does not need to control this ρ 于 to a specified range. The aqueous solution finally falls on a fixed ρ 根据 depending on the type of the organic silicon compound and the inorganic oxide and their mixing ratio. When ρ Η is controlled within a specified range, for example, an acid may be added. However, at this time, a raw metal salt of a composite oxide is generated by the added acid, so that the stability of the precursor dispersion of the nuclear particles is reduced. Alas, there is no particular limitation on the addition rate of the aqueous solution at this time. -14- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 Α7 Β7 V. Description of the invention (12) The manufacturing method of the present invention can also be A dispersion of seed particles when preparing a precursor dispersion of core particles was used as a starting material. In this case, as the seed particles, inorganic oxides such as Si02, A12203, Ti02, Zr02, Sn02, and Ce02, or composite oxides thereof, such as Si02-A, can be used. ] _2〇3, Ti〇2 — Algos, Ti〇2—Zr〇2, S π Ο 2 — T i 〇2, S i 〇 2 — T i 〇 2 — A 12〇3 temple particles, and usually use them Sol. A dispersion of such particles can be prepared according to a conventionally known method. For example, it can be obtained by adding an acid or a base to a metal salt, a mixture of metal salts, or a metal alkoxide to hydrolyze the inorganic oxide with respect to the above-mentioned inorganic oxide, and it can be obtained by aging if necessary. Of course, the sol obtained by the production method of the present invention may be used as a seed particle dispersion. The particle dispersion liquid adjusted to a pH of 10 or more was treated with the aqueous solution of the aforementioned compound in the same manner as in the above-mentioned alkaline aqueous solution, and added while stirring. In this case, it may be performed arbitrarily without controlling the ρ Η of the dispersion. In this way, if seed particles are used as seeds to grow the composite oxide particles, the particle size of the grown particles can be easily controlled and the desired particle size can be obtained. The addition ratio of the silica raw material, the organosilicon compound, and the inorganic oxide added to the seed particle dispersion liquid is in the same range as when it is added to the aforementioned alkaline aqueous solution. The above silica raw materials, organic silicon compounds and inorganic oxide raw materials have high solubility on the alkali side. However, if the two are mixed in the ρ ρ field with high solubility, the solubility of oxyacids such as silicic acid ions and aluminate ions is reduced, and the complex is precipitated and grown in colloidal particles, or the species Particles precipitate and cause particle growth. Therefore, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applicable to the colloidal particle precipitation and cost paper size. -Line · (Please read the notes on the back before filling out this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 Α7 Β7 V. Description of the Invention (I3) For a long time, it is not necessary to control P as in the previous law Η ° Alas, the organic group introduced in the target organic oxide-containing composite oxide microparticles is reactive, and this organic group can also be reacted with a desired compound to modify the surface of the particles. Process (b) [Formation of the first silica-based coating layer] The silica raw material to be added is preferably a silicic acid solution obtained by alkali metal salt (water glass) of silica and dealkaliization. In the case where the dispersion medium of the precursor of the nuclear particles is water alone or the ratio of water to organic solvents is high, it may be treated with a silicic acid solution. In the case of using a silicic acid solution, a specified amount of a silicic acid solution can be added to the dispersion, and at the same time, an alkali is added to cause the silicic acid solution to precipitate on the surface of the core particles. Silica materials can also use hydrolyzable organosilicon compounds. Hydrolyzable organosilicon compounds can use the general formula R n S i (〇R ') 4-η [but, R, R', alkyl, aryl, hydrocarbyl groups such as vinyl 'propenyl, etc. , 2 or 3], and particularly preferred are tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and the like. The addition method can add a small amount of alkali or acid as a catalyst solution to the mixed solution of these alkoxysilanes, pure water, and alcohols, and add it to the dispersion of the precursor of the nuclear particles, and hydrolyze the alkoxy The silicic acid polymer produced by the basic silane sinks on the surface of the precursor. At this time, it is also possible to add the oxygen sand compound, alcohol, and catalyst to the dispersion at the same time. As the alkali catalyst, ammonia water, hydroxides of alkali metals, and amines can be used. In addition, the acid catalyst can use a variety of inorganic acids and the paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) ------ I --- * --------- --- Order --------- line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 B7 V. Description of the invention (14) Organic acids. Alternatively, the alkoxysilane and the silicic acid solution may be coated. In addition, on the first coating layer composed of silica and inorganic oxides other than silica, an inorganic oxide source other than sandstone may be added in the above-mentioned process of forming a silica coating layer. The inorganic oxide source can be added before or after the addition of the silica source, but it is preferably added at the same time. In this case, the addition ratio is an oxide other than Shi Xiite, and the molar ratio to silica is preferably in a range of 0.5 to 20. The aforementioned Morse ratio is less than 0.  5. In the following process (c), the pore volume and pore diameter of the first coating layer formed after removing some components other than silica are too small, and as a result, the adhesion with the resin is likely to be insufficient. On the other hand, when the molar ratio is larger than 20, the pore diameter of the first coating layer is too large, and the resin penetrates into the pores and hardens, so that the effect of reducing the refractive index becomes small. Alas, the addition amount of the silica component when forming the first coating layer, and the oxide components other than silica and silica is a sufficient amount to form a coating layer having a thickness of 0.5 to 20 nm. In addition, the first coating layer may be composed of a plurality of layers including a separate stone slate coating layer, a composite oxide coating layer composed of silica and oxides other than silica. Project (c) [Selective removal of elements] The first coating can be formed by selectively removing at least a part of elements other than sand and oxygen from the elements constituting the precursors of the nuclear particles forming the first coating layer. The pore volume of the precursor particles of the coated core particles increases. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ^ ΤΓ- I ----- I --------------- Order ----- ---- Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 Α7 _ Β7 V. Description of the invention (15) On some elements except silicon and oxygen, The method can be exemplified in a composite oxide fine particle dispersion liquid that forms a shiyanite-based coating layer, and it can be dissolved and removed by adding an inorganic acid and an organic acid, or it can be removed by contact with a cation exchange resin for ion exchange removal. After the elements are selectively removed, M 0 X / S 102 is preferably 0 · oooi to 0 · 2. The dispersion liquid in which the element is selectively removed can be washed by a known washing method such as ultrafiltration. At this time, if the first part of the alkali metal ions, alkaline earth metal ions, and ammonium ions in the dispersion is removed beforehand and ultrafiltration is performed, a sol dispersed with fine particles having high dispersion stability can be obtained. Alas, if needed to be replaced by an organic solvent, an organic solvent dispersed sol can be obtained. The manufacturing method of the microparticle-dispersed sol according to the present invention is a process of forming a second silica coating layer. As the organosilicon compound represented by the aforementioned chemical formula (2) in this process, the same organosilicon compound as used in process (b) can be used. In the chemical formula (2), an organic silicon compound with η = 〇 may be used as it is, and when an organic silicon compound with η = 1 to 3 is used, it is preferable to use the same organic compound used in the aforementioned process (a). Partial hydrolysate of silicon compounds. By forming the second silica coating layer, the thickness of the coating layer can be adjusted, and the thickness of the final coating layer can be 0.5 to 20 nm. In addition, when an organic silicon compound having η = 1 to 3 is used for the formation of the second silica coating layer, a dispersion liquid of an organic solvent is excellent, and a composite oxide fine particle dispersed sol having a high affinity with the resin can be obtained. . Therefore, although a silane coupling agent can be used for surface treatment, but because it has excellent dispersibility for organic solvents and affinity with resin, there is no need for this type of paper. The Chinese National Standard (CNS) A4 standard is applicable. (210 X 297 mm) Ί--. ------------ Order --------- Line (Please read the precautions on the back before filling this page) 495485 90. 12.  24 A7 B7 V. Description of Invention (16) Processing. (Please read the precautions on the reverse side before filling out this page) The method for manufacturing the fine particle dispersing sol according to the present invention is a heat treatment process. That is, in the organic oxide-containing composite oxide microparticle-dispersed sol forming the second silica coating layer, if necessary, an alkaline aqueous solution is added and the p Η of the dispersed sol is preferably adjusted to a range of 8 to 13; and Perform heat treatment. The heat treatment temperature at this time is in a range of about 50 to 350 ° C, and particularly preferably in a range of 100 to 300 ° C. Through this heat treatment, the porosity of the core particles can be maintained, and the pores of the coating layer can be eliminated, so that a sol dispersed with a closed composite oxide microparticle that seals the core particles through the silica-based coating layer can be obtained. Alas, during the heat treatment, the concentration of the organic oxide-containing composite oxide fine particle dispersed sol obtained in the process (c) may be diluted beforehand or concentrated. In addition, the final treatment (c) is the same as above, and the dispersed sol that is heat-treated can also be washed. (4) Film substrate Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Next, the film substrate of the present invention will be described. This substrate is made of glass, polycarbonate, acrylic resin, PET, TAC and other plastic sheets, plastic films, plastic panels, etc. to form a coating on the surface of the substrate, and the coating solution described below is immersed, sprayed, and rotated. It can be obtained by a known method such as the coating method and the trowel coating method, which can be coated and dried on a substrate and then calcined if necessary. The coating liquid is a mixed liquid of the sol and the substrate for forming a film, and an organic solvent may be mixed if necessary. The so-called substrate for film formation refers to the size of the paper that can form a film on the surface of the substrate. Applicable to China National Standard (CNS) A4 (210X297 mm) _ 19-495485 A7 B7 V. Description of the invention (17) (Please read the back first Please fill in this page again) The ingredients can be selected and used from resins with suitable conditions such as adhesiveness, hardness, and applicability, etc., and examples include polyester resins, acrylic resins, and amines used previously Formate resin, vinyl chloride resin, epoxy resin, melamine resin, fluororesin, polysiloxane resin, butyraldehyde resin, phenol resin, vinyl acetate resin, ultraviolet curing resin, electric, radiation curing resin, latex Resins, water-soluble resins, hydrophilic resins, mixtures of these resins, coating resins for copolymers and modifiers of these resins, or hydrolyzable organosilicon compounds such as the aforementioned alkoxysilanes. In the case of using a coating resin as a substrate, for example, the aforementioned sol dispersion medium can be replaced with an organic solvent such as alcohol, such as an alcohol-dispersed sol, or the fine particles can be treated with a known coupling agent and dispersed in an organic solvent. The organic solvent disperses the sol and the coating resin, and is diluted with an appropriate organic solvent to prepare a coating solution. On the other hand, in the case of using a hydrolyzable organosilicon compound as a matrix, for example, water and an acid or base as a catalyst can be added to a mixed solution of an alkoxysilane and an alcohol to obtain a partial hydrolysis of the alkoxysilane. And mixed with the aforementioned sol, and diluted with an organic solvent as needed to prepare a coating solution. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The weight ratio of fine particles to substrate in the coating liquid is preferably in the range of fine particles / matrix 2/99 ~ 9/1. If the weight ratio exceeds 9/1, the strength of the coating is insufficient and practicality is insufficient. On the other hand, if the weight ratio is less than 1/99, the effect of adding the fine particles cannot be exhibited. The refractive index of the film formed on the surface of the above substrate may vary according to the mixing ratio of fine particles and resin and the refractive index of the resin used, but this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297) Mm) 495485 A7 B7 V. Description of the invention (18) (Please read the precautions on the back before filling out this page) Can be 1 · 28 ~ 1.  Low refractive index of 50. Alas, the microparticles of the present invention have a refractive index of 1.20 to 1.44. This is because the fine particles of the present invention disperse the dispersion medium into voids even when the dispersion medium enters the pores of the particles, and the resin and the like are used to control the pore diameter of the silica-based coating layer within the aforementioned range when the film is dried. The film-forming component is sealed in the silica-based coating layer, and after the resin is hardened, the pores of the silica-based coating layer are kept porous within the closed particles. On the other hand, in the aforementioned porous fine particles (Japanese Patent Application Laid-Open No. 5-1 2 3 309), since a film-forming component such as a resin enters the pores, such a low refractive index cannot be made. In addition, compared with the fine particles whose surface is completely covered with silica and containing a solvent in the pores (Japanese Patent Application Laid-Open No. 7-1 3 3 105), the fine particles of the present invention have a low refractive index. rate. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the above-mentioned film substrate, the refractive index of the substrate is below 1.60, preferably the refractive index of the substrate surface is 1.  The above-mentioned film containing the fine particles of the present invention is formed on a film of 60 or more (hereinafter, also referred to as an intermediate film). If the refractive index of the intermediate film is 1.60 or more, the refractive index difference from the aforementioned film (hereinafter, also referred to as a surface film) containing the fine particles of the present invention is large, and a film substrate having excellent antireflection performance can be obtained. The refractive index of the intermediate film can be adjusted according to the type of the metal oxide fine particles used, the mixing ratio of the metal oxide and the resin, and the refractive index of the resin used. The coating liquid for forming an intermediate film is a mixed liquid of metal oxide particles and a substrate for forming a film, and an organic solvent can be mixed as necessary. The substrate for film formation can be the same as the aforementioned film containing microparticles of the present invention. -ZΓ- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). B7 V. Description of the invention (19) By using the same substrate for film formation, a film substrate with excellent adhesion between the two films can be obtained. The weight ratio of the metal oxide fine particles to the substrate in the coating liquid for forming an intermediate film is fine particles / matrix = 30/70 ~ 95/5, and particularly preferably in a range of 50/50 to 8/20. If the weight ratio exceeds 9 5/5, the strength of the film is insufficient, and the adhesion with the substrate is insufficient and practical. On the other hand, if the weight ratio is less than 30/70, the weight of the intermediate film is insufficient. The refractive index cannot be greater than or equal to 1.60, and the difference in refractive index between the refractive index and the surface film cannot help becoming large. Therefore, the reflection prevention performance is insufficient. The metal oxide fine particles preferably use a refractive index of 1.60 or more, particularly 1.70 or more, and examples thereof include titanium oxide (2.50), zinc oxide (2.0), and chromium oxide (2 · 2 0), oxide planer (2 · 2), tin oxide (2 · 0), hafnium oxide (2 · 1), barium titanate (2 · 4 0), aluminum oxide (1 · 7 3), magnesium oxide ( 1 . 77), yttrium oxide (1. 92), antimony oxide (2. 0), indium oxide (2 · 0), etc. Among them, conductive fine particles such as titanium oxide, oxide scale, tin oxide, antimony oxide, zirconia, and indium oxide 2 and conductive fine particles in which different elements such as antimony, tin, and fluorine are mixed, because the obtained film is It has better anti-reflection performance and anti-static effect. The refractive index of the metal oxide particles is less than 1.  At 60, the refractive index of the intermediate film cannot be made 1.60 or more, and the refractive index difference from the surface film cannot help becoming large, so the reflection prevention performance becomes insufficient. The average particle diameter of the metal oxide fine particles is 5 to 100 nm, and particularly preferably in the range of 10 to 60 nm. The average particle size is less than 5 The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -22---------- I ------------ ^ ---- I ---- (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 ___ B7 V. Description of the invention (2) nm particle acquisition It is difficult, and if it exceeds 100 nm, the dispersion of visible light becomes significant and the transparency of the coating is reduced, which is not good. When using such metal oxide fine particles to prepare a coating liquid for forming an intermediate film, it is preferable to use a sol in which metal oxide fine particles are dispersed in a dispersion medium, and an organic solvent in which a water-dispersed sol can be dispersed in an organic solvent such as alcohols. After the solvent-dispersed sol or the fine particles are treated with a known coupling agent, the organic solvent-dispersed sol dispersed in an organic solvent is diluted with an appropriate organic solvent to form a coating liquid. Furthermore, a surfactant may be added to the coating liquid in order to improve dispersibility, stability, and the like. The two-layer film base material may be coated and dried by applying a coating liquid for intermediate film formation, and calcined as necessary to form an intermediate film, followed by coating and drying the coating liquid for surface film formation as described above, as necessary. Can be obtained by calcining. Alternatively, the coating liquid for forming a surface film may be applied after the application of the coating liquid for forming an intermediate film or after drying, and may be obtained by firing if necessary. The present invention will be described more specifically based on the examples shown below. Example 1 [Production of composite oxide sol] A mixture of 100 g of silica sol with an average particle diameter of 5 nm and a concentration of S 100 of 20% by weight and 1,900 g of pure water was added at 80 ° C. temperature. The pH of this reaction mother liquor was 10 · 5, and SiO 2 · 1.5 wt% sodium silicate aqueous solution of 9 000 g and A 1 2 0 3 0 were simultaneously added to the same mother liquor. 9000 g of a 5% by weight aqueous sodium aluminate solution. In the meantime, it will reflect that the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----- I ---------------- Order ---- ----- Line (Please read the precautions on the back before filling this page) 495485 A7 _ B7 V. Description of the invention (21) The liquid temperature should be kept at 80 ° C. The p of the reaction solution rose to 1 2 · 5 immediately after the addition, and there was almost no change thereafter. After the addition is complete, cool the reaction solution (please read the precautions on the back before filling in this page), cool to room temperature, and wash and concentrate with a super film to obtain a solid concentration of 20% by weight. A 1 2 0 3 Preoxide of the composite oxide particle (A) 〇 To the previous 500 grams of the protosol (A) was added pure water 1.7 g and warmed to 9 8 ° C, while keeping at At this temperature, 2,000 g of a silicic acid solution (Sio2 concentration 3.5% by weight) obtained by debasing an aqueous sodium silicate solution with a cation exchange resin was added over 5 hours to obtain S coated with silica. 〇2 · A 1 203 composite oxide particle pro-sol (B). In this sol, 500 g of sol having a solid content concentration of 13% by weight was washed with an ultrafiltration membrane, and pure water 1 was added.  1 2 5 grams, and then add concentrated hydrochloric acid (35.5%) to make ρ Η 1.  〇, and perform aluminization treatment 〇 Secondly, while adding 10 liters of hydrochloric acid aqueous solution of P 3 and 5 liters of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated to obtain S 1 coated with silica. 2 · A 1 203 composite oxide particles (P 1) printed disperse sol (c) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This silica-coated composite oxide particle (P 1) has a Μ0 × / Sio2 (molar ratio), an average particle diameter, a pore volume, a thickness of the coating layer, a maximum pore diameter, and a refractive index of the particles. Shown in Table 1. Here, the average particle diameter is measured by a dynamic light scattering method, and the pore volume of the particles is measured by a nitrogen adsorption method. The thickness of the coating layer is to obtain the grains before coating by dynamic light scattering method. -24- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm). Cooperative printed A7 B7 V. Description of the invention (22) diameter, and assuming the weight and true specific gravity of the oxide or composite oxide used to form the coating layer and the pore volume of the coating layer to be 0.5 / g, calculated The volume of the coating is obtained and calculated from these figures. Alas, the true specific gravity of the oxide is S 102 = 2 · 6 and Al 2 03 = 3 · 2, and in the case of a composite oxide, 値 calculated from the composition is used. The maximum pore diameter of the coating layer was measured using an automatic pore distribution measuring device (Autosorb-6, manufactured by Quanta Chrome). The refractive index of the particles in the sol was measured as follows. (1) The porous composite oxide dispersion sol is placed in an evaporator, and the dispersion medium is evaporated. (2) It is dried at 120 ° C and powdered. (3) Drop a standard refracting solution of known refractive index on a glass plate and drop 2 or 3 drops, and mix the above powder into it. (4) Perform the operation (3) above with various standard refracting liquids, and use the refractive index of the standard refracting liquid when the mixed solution (in many cases, paste) is transparent, as the refractive index of the particles. [Manufacture of low-reflection film] Pass the composite oxide sol (c) into the ultrafiltration membrane, and replace the water in the dispersion medium with ethanol. 50 g of this ethanol sol (solid content concentration: 5% by weight) and 3 g of acrylic resin (Heteroid 1 007, manufactured by Hitachi Chemical Co., Ltd.) and a mixed solvent of 1/1 (weight ratio) of isopropyl alcohol and n-butanol 47 g are mixed thoroughly to prepare a coating solution. This coating solution is applied on a PET film by a bar coating method, and the paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -25- --------- ----------- Order --------- line (Please read the precautions on the back before filling this page) Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 One One B7 V. Description of the invention (23) Dry at 80 ° C for 1 minute 'to obtain a low reflection film (F 1). The film (F1), the uncoated PET film (F0), the total light transmittance, the haze, the reflectance of light with a wavelength of 5 50 nm and the refractive index of the coating are shown in Table 2. The total light transmittance and haze were measured with a Haze meter (manufactured by Suga Test Co., Ltd.) and the reflectance was measured with a full-spectrophotometer (Japanese Spectrophotometer, UDest-55). The refractive index of the coating was measured using an Elipso meter (manufactured by ULVAC, E M S — 1). In addition, on the surface of the low-reflection film (F 1), a small knife was cut at a distance of 1 mm in length and width to cut out 11 parallel wounds to make 1000 components, and then bonded them with glass tape, followed by the following, In four stages, the number of components that remained on the film without peeling when the glass tape was peeled was classified, and the adhesiveness was evaluated. The results are shown in Table 2. Number of residual components 9 5 or more: ◎ Number of residual components 9 0 to 9 4: 〇 Number of residual components 85 to 89: △

The number of remaining components is 8 or less: X [Made of low-reflection glass] A mixed solution of 20 g of ethyl silicate (S 102 concentration 28% by weight), 45 g of ethanol, and 5.33 g of pure water A small amount of hydrochloric acid was added to obtain a matrix containing a partial hydrolyzate of ethyl silicate. In this substrate, a coating solution was prepared by mixing the mixed oxide sol (c) with an ethanol solvent (solid content concentration: 18% by weight) with an ethanol solvent. The coating solution was applied on the surface of a transparent glass plate at 500r P m ′. The paper size was in accordance with China National Standard (CNS) A4 (210 X 297 mm) -26- --------- -------------- Order --------- line ^^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 B7 V. Description of the invention (24) After applying the spinner method for 10 seconds, heat treatment was performed at 160 ° C for 30 minutes to obtain a low reflection glass (G 1). The glass (G 1) and the uncoated glass (G 0) have the total light transmittance, fog, and reflectance of light with a wavelength of 5 50 nm and the refractive index of the coating are not shown in Table 2. Example 2 [Production of composite oxide sol] To 100 g of the dispersed sol (c) of the silica-coated composite oxide particles (P 1) obtained in Example 1 was added pure water 1,90. 0 g and heating at 95 ° C, and while maintaining this temperature, an aqueous sodium silicate solution (Sio2 is 1.5 g% by weight) 2 7.0 g and an aqueous sodium aluminate solution (A 1 2 0 3 is 0.5% by weight) 27.0 g are slowly added at the same time, so that the particles (P 1) are grown into cores. After the addition was completed, the mixture was cooled to room temperature, washed with an ultrafiltration membrane, and then concentrated to obtain a silica-alumina-coated SiO 2 · A 1 2 03 composite with a solid content concentration of 20% by weight. Preoxide oxide sol (D). 500 grams of this composite oxide precursor sol (D) was collected and subjected to dealumination treatment in the same manner as in Example 1 to obtain the si02 · A 12〇3 composite covered with stone cutting as shown in Table 1. Disperse sol (E) of oxide particles (P 2). [Manufacturing of low-reflection film] In Example 1, except that the composite oxide sol (C) was changed so that the paper size was adapted to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ---- 11-- -------------- Order --------- line (please read the precautions on the back before filling this page) Printed by the Employee Consumption Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 B7 V. Description of the invention (25) Except using the composite oxide sol (E), the same treatment as in Example 1 was performed to obtain a low reflection film (F 2). [Production of low reflection glass] In Example 1, except that the composite oxide sol (C) was changed to use the composite oxide sol (E), the same treatment as in Example 1 was performed to obtain a low reflection film (G 2). Example 3 [Production of composite oxide sol] The same method as in Example 1 was used except that 9.0 g of a potassium stannate aqueous solution of 9,0 g was used instead of sodium aluminate of Example 1. , To obtain a solid SiO 2 · S η02 composite oxide precursor sol (Η) with a solid content concentration of 20% by weight, and then perform a de-S η treatment and a coating treatment in the same manner as in Example 1 to obtain a table. The dispersive sol (I) of S 1〇2 · S η〇2 composite oxide particles (P 3) ° [Manufacture of low-reflection film] In Example 1, except that the composite oxide sol (c) Except changing the use of the composite oxide sol (I), the same treatment as in Example 1 was performed to obtain a low-reflection film (F3). [Manufacturing of Low-Reflection Glass] This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------- t -------- Order ----- ---- Line · (Please read the precautions on the back before filling this page) 495485 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (26) In Example 1, except for the complex oxide The sol (C) was changed except that the composite oxide sol (I) was used. The same treatment as in Example 1 was carried out to obtain a low-reflection film (G 3). Dou Example 4 Warm 500 grams of the S 1202 · A 1 2 03 composite oxide particles protosol (A) obtained in Example 1 at 90 ° C, and keep it at this temperature, While the sodium silicate solution was dealkaliated with a cation exchange resin, the silicic acid solution (Sio2 concentration 3.5% by weight) 3'000 g and the aqueous solution of sodium oxalic acid (A1 2003 concentration 3.5% by weight) %) 100 g was added over 2 hours to obtain a silica-alumina-coated S i02 · A 1 2 03 composite oxide particle prosol (J). The sol was washed with an ultrafiltration membrane to 500 grams of sol having a solid content concentration of 13% by weight. Pure water 1. · 125 grams were added, and concentrated hydrochloric acid (35 · 5%) was added dropwise to pH l · 0. And dealumination treatment. Next, while adding 10 liters of hydrochloric acid aqueous solution of P Η 3 and 5 liters of pure water, the aluminum salt dissolved from the filter membrane was separated to obtain S 1 02 · A 1 2 coated with silica-alumina. 3 Disperse sol (K) of composite oxide particles (P 4). [Production of Low-Reflection Film] In Example 1, except that the composite oxide sol (c) was changed to use a composite oxide sol (?), The same treatment as in Example 1 was performed to obtain a low-reflection film (F4). This paper size applies to China National Standard (CNS) A4 (21〇χ 297 mm) ----------------------- Order ------ --- Line ^^ (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 Α7 Β7 V. Description of the invention (27) [Manufacture of low reflection glass] In Example 1 In addition, except that the composite oxide sol (c) was changed to use the composite oxide sol (K), a low-reflection glass (G4) was obtained in the same manner as in Example 1. Comparative Example 1 [Production of composite oxide sol] The same treatment as in Example 1 was used to prepare a SiO 2 · A 1 2 03 composite oxide particle precursor sol (A). To this 32.5 grams of sol (A) was added 1,300 grams of condensed water, and then concentrated hydrochloric acid (35.5%) was added dropwise to ρ Η 1.0, and dealumination treatment was performed. Next, while adding 10 liters of a hydrochloric acid aqueous solution of P 3 and 5 liters of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated, and si0 2 • A 1 2 03 composite oxide particles (P ′ 1) were obtained. Dispersion sol (L) [Manufacture of low-reflection film] In Example 1, except that the composite oxide sol (c) was changed to use the composite oxide sol (L), the same treatment as in Example 1 was performed to obtain a low-reflection film ( F '1). [Manufacturing of low-reflection glass] In Example 1, except that the composite oxide sol (C) was changed so that the paper size applied the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -30- -1-- -------------- ^ --------- (Please read the notes on the back before filling this page) ^^ 485

V. Description of the invention (28) Use a complex oxide sol (other than L) The same as in Example 1 and obtain low-cost printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Reflective film (G is also described in Example 2 [Production of swell of composite oxide] The same treatment as in Comparative Example 1 was performed to prepare a dispersed sol (L ·) of S 1 〇 2 · A 1 2 03 composite oxide particles (P, 1) ), And this mixture of 1500 g of gluten, 500 g of pure water, 1,750 g of ethanol and 28% ammonia water 6 2 6 g is heated at 3 5 ° C. 'Ethyl oxalate is added (S 10% concentration 2 8% by weight) 104%, the surface of the composite oxide particles (P'1) was coated with a hydrolyzed polycondensate of ethyl silicate. Next, it was concentrated by an evaporator to a solid content concentration of 5 After weight percent, 15% ammonia water was added to PΡ10, and heat treated at 180 ° C for 2 hours with an autoclave to obtain S 1 02 · A 1 2 03 composite completely covered with silica. Dispersion sol (M) of oxide particles (P'2). [Production of low-reflection film] In Example 1, the same operation was performed except that the composite oxide sol (c) was changed to use the composite oxide sol (M). Example 1 was processed to obtain a low-reflection film (F'2). [Production of low-reflection glass] In Example 1, except for the complex oxide sol (C) In addition to using the composite oxide sol (M), the same treatment as in Example 1 was achieved (please read the precautions on the back before filling in this page) --------- Order -------- -Line 1 paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -31-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 ______B7 V. Description of the invention (29) Reflective glass (G '2). Example 5 [Manufacture of low-reflection coating resin base material] The dispersed sol (I) of the S i〇2 · S η〇2 composite oxide particles (P 3) obtained in Example 3 was passed through an ultrafiltration membrane A solid content concentration of 20% by weight was prepared, and 25 grams of the solid content concentration was mixed with 5 grams of UV resin (manufactured by Dainippon Ink Co., Ltd .: UnIDICK V5 5 00) and 70 grams of ethanol to prepare a coating solution for forming a surface film. . 20 g of titanium oxide colloidal particles (manufactured by Catalytic Chemical Industries, Ltd., Optolake 1130Z, refractive index 2.2, average particle size 20 nm, concentration 20% by weight), and UV resin (Dayokuben Ink Co., Ltd.) Production: Unidick V5500) 5 g and 11 g of ethanol were mixed well to prepare a coating liquid for forming an intermediate film. This coating liquid for forming an intermediate film was coated on an acrylic board (manufactured by Mitsubishi Leon Co., Ltd .: AcryUte, refractive index = 1.49), and was applied using a bar coater, and dried at 70 t for 1 minute to prepare Resin base material for intermediate film. The refractive index of the intermediate film at this time is 1. 6 4. Next, the previously prepared coating liquid for forming a surface film is coated with a bar coater and dried at 70 ° C for 1 minute. Then, it was irradiated with a high-pressure mercury lamp (80 w / cm) for 1 minute to harden it to obtain a resin substrate (R 1) forming a two-layer film. Table 2 shows the total light transmittance, fog, and reflectance of light with a wavelength of 5 50 n m of the resin substrate (R 1). Alas, the folding ratio of the surface coating is not to form an intermediate coating, and to directly form the surface coating on an acrylic sheet. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -32- ---- ------------------ Order --------- line (please read the precautions on the back before filling this page) 495485 Employee Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed clothes A7 B7 V. Description of the invention (30), measured by Elipso meter (manufactured by ULVAC: EMS — 1), and the results are shown in Table 2. g. Example 6 [Manufacture of low-reflection coating resin substrate] The dispersed sol (C) of the SiO 2 · A 1 2 03 composite oxide particles 孑 (P 1) obtained in Example 1 was solidified by an ultrafiltration membrane. The component concentration was 20% by weight, and 25 grams thereof was sufficiently mixed with 5 grams of an acrylic resin (Hitachid 1007 manufactured by Hitachi Chemical Co., Ltd.) and 70 grams of ethanol to prepare a coating solution for forming a surface film. In addition, 20 g of titanium oxide colloidal particles (manufactured by Catalytic Chemical Industries, Ltd .: Optolake 1130Z, refractive index 2.2, average particle diameter 20 nm, concentration 20% by weight) and UV resin (manufactured by Daiichi Ink Co., Ltd .: Unidick V5500) 5 g and isopropyl alcohol 75 g were thoroughly mixed to prepare a coating liquid for forming an intermediate film. This coating solution for forming an intermediate film was coated on an acrylic plate (manufactured by Mitsubishi Leon Co., Ltd .: Acirylite 'refractive index = 1.49'), applied by a dipping method, and dried at 70 ° C for 1 minute. An intermediate film resin substrate is prepared. At this time, the refractive index of θ Wu is 1.80. Next, the previously prepared coating liquid for surface film formation was applied using a bar coater, and dried at 70 ° C for 1 minute, and then irradiated with a high-pressure mercury lamp (80 w / cm) for 1 minute to harden it to obtain A resin substrate (R 2) forming a two-layer film. Table 2 shows the total light transmittance, fog, and reflectance of light with a wavelength of 5 50 nm for the resin substrate (R 2). Alas, the refractive index of the surface coating is to form the surface coating directly on the acrylic plate without forming an intermediate coating. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -33- ----- 1 ---------------- Order --------- line ^^ (Please read the precautions on the back before filling out this page) 495485 Employee Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Cooperatives printed A7 B7 V. Description of the invention (31) 'and measured by Elipso meter (manufactured by ULVAC: EMS-1)' and the results are shown in Table 2. In Example 5, except for the use of the dispersed sol (L) of the S i〇2 · A 1 2 0 3 composite oxide fine particles (p '1) obtained in Comparative Example 1 instead of the S i〇 2 · s 〇 2 composite oxidation Except for the dispersed sol (Ϊ) of the object particles (P 3), the same treatment as in Example 5 was performed to obtain a two-layer film resin substrate (R ′ 1). Table 2 shows the total light transmittance, fog, and reflectance of light with a wavelength of 5 50 n m of the resin substrate (R ′ 1). That is, the refractive index of the surface film was not formed with an intermediate film, and the surface film was directly formed on an acrylic plate, and was measured with an Elipso meter (manufactured by ULVAC: E M S — 1). The results are shown in Table 2. ------ I ---------------- Order --------- line ^^ · (Please read the precautions on the back before filling this page) Table 1 Particles MoX / Sio2 average particle diameter pore volume coating layer refractive index (molar ratio) (nm) (ml / g) thickness maximum pore (nm) diameter (nm) PI 4.7 X ΙΟ '3 27 0.17 3.5 2.0 1.36 P2 4.3 X 10 3 54 0.42 2.0 3.5 1.34 P3 4 · 8 X l0 · 3 25 0.14 2.5 1.5 1.39 P4 3.6 X l〇'3 35 0.23 7.5 4.0 1.37 p / 1 20 X 10' 3 20 0.12 0 8.0 1.47 P'2 8.0 X ΙΟ 3 27 0 7.0 0 1.40 This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -34- 495485 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Garment A7 _B7 V. Description of the invention (32) Table 2 Refractive index adhesiveness of the substrate's total light transmittance, haze reflectance (%) (%) (%) F0 90.7 2.0 7.0 — F1 95.8 0.6 0.9 1.39 〇F2 95.0 0.9 0.7 1.36 〇F3 94.7 1.1 0.8 1.38 〇F4 96.0 0.4 1.0 1.38 ◎ F, 1 91.2 1.8 5.0 1.45 XF, 2 93.6 1.5 3.2 1.43 Δ R1 95.5 0.2 1.0 1.42 ◎ R2 96.7 0.2 0.6 1.40 ◎ R, 1 93.0 0.2 3.7 1.48 ◎ GO 92.0 0 .7 4.0 — G1 96.7 0.4 0.5 1.27 G2 96.0 0.5 0.1 1.32 G3 95.5 0.5 0.6 1.38 G4 96.2 0.3 0.2 1.35 G7 1 95.0 0.5 2.2 1.43 94.7 0.5 1.8 1.41 (Please read the precautions on the back before filling this page) The paper size Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -35- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 B7 V. Description of the invention (33) Example 7 [Preparation of nuclear particle dispersion] 27.4 g of methyltrimethoxysilane was mixed in 0.85 g of a sodium hydroxide aqueous solution of 0.65 wt%, and stirred at room temperature for 1 hour to obtain CH3S iO3 / 2 1 · 5. A colorless and transparent partial hydrolysate aqueous solution by weight. Next, a mixture of 20 g of silica sol with an average particle diameter of 5 nm and a concentration of Sio2 of 20% by weight and 380 g of pure water was heated at 80 ° C. The p 母 of the mother liquor of this reaction is 60 · 5, and in the same mother liquor, 900 g of a SiO 2 1 · 5% by weight aqueous sodium silicate solution and 900 g of an aqueous solution of the above partial hydrolysate, It was simultaneously added with 1 800 g of sodium aluminate aqueous solution having a concentration of 0.5% by weight in 0.58% over a period of 6 hours. Meanwhile, the temperature of the reaction solution was maintained at 80 ° C. The p Η of the reaction solution rose to 12.7 immediately after the addition, and there was almost no change thereafter. After the end of the addition, the reaction solution was cooled to room temperature, and washed with an ultrafiltration membrane to obtain a dispersion solution of S 1 02 · A 1 2 03-containing composite oxide containing methyl groups at a solid content concentration of 20% by weight ( A 1). [Formation of the first silica-based coating layer] Next, 550 grams of pure water was added to 250 grams of the dispersion (A 1) and heated at 9 8 t: while maintaining the temperature at the same time. A silicic acid solution (si 0 2 concentration of 3.5% by weight) obtained by debasing an aqueous sodium silicate solution with a cation exchange resin was added at 1,000 g over 5 hours to obtain a methyl group containing methyl sulphate coated with S 1〇2 · A 1 2 03 Particles of composite oxides The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -36- ------------- --------- Order --------- line ^^ (Please read the notes on the back before filling out this page) Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 495485 A7 B7 V. Description of the invention (34) Proton prosol (B 1). [Selective removal of elements] This sol (B 1) was washed with an ultrafiltration membrane, and 1.1 g of pure water was added to 500 g of sol having a solid content concentration of 13% by weight, and then dropped. Add concentrated hydrochloric acid (concentration: 35 · 5%) to pH l · 0, and perform demarking treatment. Next, while adding 10 liters of a hydrochloric acid aqueous solution of P Η 3 and 5 liters of pure water, while washing and removing the dissolved aluminum salt using an ultrafiltration membrane, and concentrating to obtain a solid content of 13% by weight silica A dispersed sol (C 1) of the coated S i02 · A 1 2 03 composite oxide particles containing a methyl group. Example 8 [Formation of a second silica coating layer] The washed dispersed sol (C 1) 1500 g obtained in Example 7 and 500 g of pure water, 1,750 g of ethanol, and 28% ammonia water After heating 6 2 6 g of the mixed solution at 3 5 t, 104 g of ethyl silicate (SiO 2 concentration 28% by weight) was added, and the aforementioned silica-coated S 1 02 · A 1 2 03 The surface of the composite oxide fine particles was coated with a hydrolyzate of ethyl silicate to obtain an open-type methyl-containing S 1 02 · A 1 2 03 composite oxide fine particles coated with silica. Sol (D 2). ^ The paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -37: I --- I I ---------------- Order ----- ---- Line ^^ (Please read the precautions on the back before filling this page) 495485 A7 B7 V. Description of the invention (35) Example 9 [Heat treatment] (Please read the precautions on the back before filling out this page ) The dispersion sol (D 2) ′ obtained in Example 8 was concentrated by an evaporator to a solid content concentration of 5% by weight, and then 1% ammonia water was added to bring the pH to 10, and the autoclave was heated at 180 ° C. After processing for 2 hours, a silica sol (E 3) was obtained in which the silica coating layer was a closed type S i02 · A 1 2 03 composite oxide fine particle containing no pores. Fenshi Example 10. Mix 50.6 g of vinyltrimethoxysilane in 1.3 wt% sodium hydroxide aqueous solution 8 4 9 4 g, and stir at room temperature for 1 hour to obtain CH2CHS i〇3 / 2 3 · 0% by weight of a colorless and transparent hydrolysate in water. The same treatment as in Example 7 is performed except that the colorless transparent partial hydrolysate solution obtained by hydrolyzing the vinyltrimethoxysilane is used instead of the colorless transparent partial hydrolyzate solution obtained by hydrolyzing the methyltrimethoxysilane in Example 7. A dispersion sol (C 4) containing Si i 2 o A 1 2 03 composite oxide fine particles coated with silica was obtained. Example 11 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 The dispersed sol (C 4) 1 500 g obtained in Example 10 and 500 g of pure water, 1,750 g of ethanol and 626 g of 28% ammonia water After the mixture was warmed at 35 ° C, 104 g of ethyl silicate (28% by weight of Si02) was added, and the aforementioned silica-coated Si02 · -38- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 495485 A7 B7 V. Description of the invention (36) (Please read the notes on the back before filling this page) A 1 2 03 Surface of composite oxide particles, Covered with a hydrolyzate of ethyl silicate to obtain an open-type dispersion of SiO 2 · A 1 2 0 3 composite oxide microparticles containing ethyl methacrylate with 2 layers of gravel (D 5 Example 1 2 The dispersion sol (D 5) obtained in Example 11 was concentrated by an evaporator to a solid content concentration of 5% by weight, then 15% ammonia water was added to make it P Η 1 0, and the autoclave was used at 180 Heat-treated at ° C for 2 hours to obtain a silica-coated closed-type vinyl-containing S i 〇2 · A 1 2 0 3 composite oxide particle without pores Disperse the sol (E 6). Example 13 The same treatment as in Example 7 was performed except that 1 800 g of an ammonium carbonate aqueous solution with a concentration of 0.5% by weight of ZrO2 was used instead of the aqueous sodium aluminate solution of Example 7. To obtain a dispersed sol (C 7) of S i02 · Z r 0 2 composite oxide particles containing vinyl coated with silica. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 1 4 Example After the washed disperse sol (C 7) 1 500 g obtained in 13 and the mixed solution of 50 g of pure water, 1,750 g of ethanol and 6 2 6 g of 28% ammonia water were heated at 3 5 ° C, 104 g of ethyl silicate (28% by weight of SiO2) was added, and the surface of the above-mentioned SiO 2 · A 1 2 03 composite oxide fine particles coated with silica was added to -39- paper Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 495485 A7 B7 V. Description of the invention (37) Hydrolysate coating of ethyl silicate to obtain an open type containing silica coated with 2 layers Based on the dispersed sol of S 1〇2 · Z r〇2 composite oxide particles (please read the precautions on the back before filling this page) (D 8). Example 1 5 The dispersion sol (D 8 V obtained in Example 14 was concentrated by an evaporator to a solid content concentration of 5% by weight, and then 15% ammonia water was added to bring the pH to 10, and then an autoclave was used at 180. Heat-treated at ° C for 2 hours to obtain a silica-coated dispersed sol (E 9), which is a closed-type methyl-containing Sio2 · Z r 0 2 composite oxide fine particle having no pores. Comparative Example 4 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, a mixture of 100 g of silica sol with an average particle size of 5 nm and a concentration of 20% by weight of S 100 and 1 900 g of pure water at 80 ° C Warming up. The pH of the mother liquor of this reaction was 10 · 5, and S i02. 1.5% by weight sodium oxalate aqueous solution of 90000 g and A 1 2003.5% by weight of aluminum were simultaneously added to the same mother liquor. 9 000 g of aqueous sodium solution. Meanwhile, the temperature of the reaction solution was maintained at 80 ° C. The p of the reaction solution rose to 1 2 · 5 immediately after the addition, and there was almost no change thereafter. After the end of the addition, the reaction solution was cooled to room temperature, washed with an ultrafiltration membrane, and concentrated to obtain a presol of 8 〇2 · A 1 203 composite oxide particles with a solid content concentration of 20% by weight ( S) ◦ Add 1.7 g of pure water to 500 g of plastisol (S) and warm to 98 ° C, and keep the silicate at this temperature while maintaining the temperature of -40- this paper standard Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 495485 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7___ V. Description of the invention (38) Silicic acid solution obtained by removing alkali with sodium cation exchange resin (S 1 〇2 concentration 3.5% by weight) 2,000 grams was added over 5 hours to obtain a SiO 2 · A 1 2 03 composite oxide particle presol (T) coated with flaxite. Here, the sol (T) was washed with an ultrafiltration membrane to 500 g of a sol having a solid content concentration of 13% by weight, and 1,125 g of pure water was added, and then cyclic hydrochloric acid (35.5%) was added dropwise. pHl · 0, and dealumination treatment. Next, while adding 10 liters of a hydrochloric acid aqueous solution of p Η 3 and 5 liters of pure water, the aluminum salts dissolved in the ultrafiltration membrane were separated to obtain a silica-coated S i02 · A 1 2 03 composite. Disperse sol (U) of oxide particles. Comparative Example 5 A mixture of 20 g of silica sol with an average particle diameter of 5 nm and a concentration of Si02 of 20% by weight and 380 g of pure water was heated at 80 ° C. The mother liquor of this reaction had a pH of 0.5. Simultaneous addition of SiO 2 1.5 wt% sodium silicate aqueous solution 1 800 g and A 1 230 0 5 wt% aluminate were added to the same mother liquor at the same time. 1 800 grams of aqueous sodium solution. During the addition at a rate of 5 ml / min, the temperature of the reaction solution was maintained at 80 ° C. The p Η of the reaction solution rose to 1 2 · 5 immediately after the addition, and there was almost no change after that. After the addition was completed, the reaction solution was cooled to room temperature to obtain a dispersion (0) of S i02 · A 1 2 03 composite oxide fine particles. Add 1.7 g of pure water to 500 g of this dispersion (〇). The paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -41------- employment — ^ -------- Order --------- line (please read the precautions on the back before filling this page) 495485 A7 B7 V. Description of the invention (39) and warm up to 9 8 ° C, and while maintaining at this temperature, the silicic acid solution obtained by debasing the sodium silicate aqueous solution with a cation exchange resin ((Please read the precautions on the back before filling in this page) S 10 2 concentration 3.5 3,000 grams of sol added to this sol, washed with ultrafiltration membrane to 500 grams of sol with a solid content concentration of 13% by weight, added 1,125 grams of pure water, and then dripped into the hydrochloric acid (3 5 · 5%) Let ρ. 1.0, and dealumination treatment. Secondly, while adding 10 liters of a hydrochloric acid aqueous solution of P 3 and 5 liters of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated to obtain a S i〇2 · A 1 2 03 composite oxidation that removes part of the aluminum. Dispersion of fine particles (P). This mixture (P) 1 500 grams, 500 grams of pure water 'ethanol 1, 7,500 grams and 28% ammonia water 6 2 6 grams of the mixture was heated at 3 5 ° C, and then added silicic acid Ethyl ester (Sio2 concentration: 28% by weight) was printed in 104 grams by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The surface of the composite oxide particles was coated with a hydrolyzed polycondensate of ethyl silicate. Next, after concentrating with an evaporator to a solid content concentration of 5% by weight, 15% ammonia water was added to ρΗ10, and then heat-treated at 180 ° C for 2 hours using an autoclave to obtain S i02 · A coated with silica. Dispersion (Q) of 1 2 03 complex oxide particles. Comparative Example 6 The methyl-containing SiO 2 · A 1 20 3 complex oxide dispersion (A 1) obtained in Example 7 was washed with an ultrafiltration membrane to obtain a solid content concentration of 13% by weight. A dispersion (R) of S i02 · A 1 2 03 composite oxide fine particles containing a methyl group. -42- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 495485 A7 ------- B7___ V. Description of the invention (40) Examples 7 to 15 above and comparative examples Table 3 shows the properties of the precursors and coatings of the nuclear particles prepared from 4 to 6, and Table 4 shows the properties, refractive index, and dispersion stability of the composite oxide fine particles. Regarding dispersion stability, 100 parts by weight of the above-mentioned dispersed sol (C 1, D 2, E 3, etc.) and acrylic resin latex (manufactured by ZENECA Co., Ltd .: A-6 1 4 and acrylic resin concentration 32% by weight) were used. , Water-dispersed media) 75 parts by weight of the mixed dispersion, left standing at 80 t for 1 day, visually observed, and evaluated according to the following criteria. The refractive index of the fine particles was measured according to the method described in Example 1. 〇: Dispersion state as good as when mixing △: Those with a tendency to separate the resin layer and the particle layer are observed x: Those with an increase in viscosity or gelation in the dispersion liquid ------ I ---- ----------- Order --------- line (Please read the note on the back? Matters before filling out this page} The paper size printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 495485 A7 _B7 V. Description of the invention (41) Table 3 Average particle diameter of pre-coating layer of nuclear particles M0x / Sl02 Thickness (nm) ( Molar / ratio (nm) Example 7 19.6 0.17 1.0 Example 8 19.6 0.17 7.3 Example 9 19.6 0.17 7.0 Example 10 27.2 0.12 1.4 Example 11 27.2 0.12 10.1 Example 12 27.2 0.12 9.7 Example 13 23.1 0.17 1.2 Example 14 23.1 0.17 8.6 Example 15 23.1 0.17 8.3 Comparative Example 4 20.2 0.17 3.5 Comparative Example 5 19.9 0.17 5.1 Comparative Example 6 19.6 0.17 — (Please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs The paper size printed by the cooperative is applicable to China National Standard (CNS) A4 (210 X 297 mm) -44- 495485 A7 B7 V. Description of the invention (42) Table 4 Composite oxide particles printed by the Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Mox / Sl02 Sr / St average dispersion index of fine pores Volume particle size stability (mol / r) (mol / r) (cc / g) (nm) Example 7 4.26 X 10'3 0.26 0.30 21.6 〇1.31 Example 8 3.69 X IO03 0.23 0.22 34.2 〇1.34 Example 9 3.60 X 10'3 0.23 0.00 33.6 Δ 1.36 Example 1 0 3. 12 X 10'3 0.36 0.50 30.0 〇1.26 Example 1 1 2.68 X 10'3 0.31 0.41 47.4 〇1.28 Example 1 2 2.6 6 X IO03 0.30 0.00 46.6 Δ 1.33 Example 1 3 6.66 X 10-3 0.24 0.22 25.5 〇1.34 Example 1 4 5.77 X 10'3 0.21 0.19 40.3 〇1.35 Example 1 5 5.69 X 10'3 0.21 0.00 39.7 Δ 1.38 Comparative Example 4 4.72 X ΙΟ3 0.00 0.17 27.2 X 1.36 Comparative Example 5 7.68 X ΙΟ3 0.00 0.00 30.1 Δ 1.42 Comparative Example 6 170 X 1〇 · 3 0.44 0.08 19.6 〇1.46 (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm)-45-

Claims (1)

495485 A8 B8 C8 D8 mT: Announce the scope of patent application of this application No. 8 8 1 2 2 3 〇 Patent Application No. 8 for Chinese Patent Application Amendment (please read the notes on the back before filling this page) Republic of China 90 years 1 2 Month correction 1 · A fine particle characterized by a porous composite oxide particle composed of silica and an inorganic oxide other than silica, and is oxidized by a porous silica-based inorganic oxide having a thickness of 0.5 to 2 0 nm The material layer is coated, and the maximum pore diameter of the silica-based inorganic oxide layer is 0.5 to 5 nm. Silica is represented by S i 〇2, and inorganic oxides other than silica are represented by μ ×. The ear ratio Mox / Sio2 is in the range of 0.001 to 0.2; the pore volume is 0 · 1 to 1 · 5cc / g. 2 · The fine particles according to item 1 of the scope of the patent application, wherein the inorganic oxide is Al2O3, B2O3. Ti02, Zr02, S η0 2 > C e 2 03, P2 Ο 5, S b 2 Ο 3 > Μ ο Ο 3, Zn η〇 One or two selected from the printed ZO 2 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. It also has No. 3 fine silica coating as in the first patent application. 4. As for the fine particles in the scope of the patent application, the fine particles in the " ^ " contain organic groups directly bonded to silicon. 5 · As for the fine particles in the scope of patent application No. 4, in which the mole number (SR) of organic silicon and the mole number (S τ) of all silicon are directly combined. The paper size applies the Chinese National Standard (CNS) A4 specification ( 210X297 mm) 495485 A8 B8 C8 D8 Six, the ratio of the scope of patent application Sr / St is in the range of 〇〇〇〇1〜 0.9. (Please read the precautions on the back before filling out this page.) 6 — A kind of sol, which is obtained by dispersing the fine particles in the scope of the patent application in items 1 to 5 in a dispersed medium. 7. A method for manufacturing a fine particle dispersed sol, which is characterized by the following processes (a) to (c); (a) an aqueous solution of silicate and / or an acidic oxalic acid solution and a chemical formula ( 1) The hydrolysate of the organic silicon compound shown, and the aqueous solution of the inorganic compound that is soluble in the test, in the alkaline aqueous solution of ρ Η 10 or more, or the test aqueous solution of P Η 10 or more where the seed particles are dispersed as necessary, (B) adding an aqueous solution of a silica source or a gravel source and an inorganic compound salt other than silica to the aforementioned nuclear particle precursor dispersion, and in front of the nuclear particles; A process of forming a first silica-based coating layer in the material; (c) a process of adding an acid to the dispersion liquid and selecting to remove at least a part of elements other than silicon and oxygen from the elements constituting the precursor of the core particle; R n S i X (4-η) ......... (1) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [However, R: non-substituted or substituted hydrocarbon group with 1 to 10 carbons, X: alkoxy, silanol, halogen or hydrogen having 1 to 4 carbon atoms, n: 1 ~ 3]. 8. A method for producing a microparticle-dispersed sol, which is obtained by adding an alkaline aqueous solution and an organic silicon compound represented by the chemical formula (2) to the microparticle-dispersed sol obtained in the process (c) of the patent application item 7. Or its partial hydrolysate, and forming a second silica coating on the particles, the paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 495485 A8 B8 C8 D8 patent application scope (4-2 X 〇 [But 'R: Unsubstituted or substituted hydrocarbon group with 1 to 10 carbon atoms, alkoxy group, silanol group, halogen or hydrogen with 1 to 4 carbon atoms, Preparation 9. A method for manufacturing a fine particle dispersing sol, which is a dispersing sol of the fine particles obtained in item 8 of the scope of patent application, and is heat-treated at 500 ° C to 350 ° C, so that the second silica coating layer The pores disappeared. 1 〇—A low-reflection coating base material containing fine particles in the scope of patent applications No. 1 to No. 5, which is characterized in that the surface of the base material containing No. 1 patent scope No. 1 ~ Any of item 5 Microparticles and film-coated substrates. 1 1. The film substrate described in item 10 of the patent application scope, where the refractive index of the substrate is 1 _ 60 or more. The low-reflection coating substrate of fine particles 1 to 5 is characterized in that it has an intermediate coating having a refractive index of 1.6 or more on the surface of the substrate having a refractive index of 1.6 or less, and is formed on the coating. Films containing fine particles and substrates for film formation as described in any one of claims 1 to 5 of the scope of patent application. 1 3. The film substrate as described in claim 12 of the scope of patent application, wherein the intermediate film is Contains 30 to 95% by weight of metal oxide fine particles with an average particle size of 5 to 100 nm. 1 4 ♦ If the film substrate of the 10th or 12th of the scope of patent application, the substrate is selected From glass, polycarbonate, acrylic resin, PET, TAC and other plastic sheets, plastic films, plastic panels. This paper size applies to China National Standard (CNS) A4 specifications (210X297 mm) 3- (Please read the note on the back first (Please fill in this page)