TW201139276A - Process for production of silica-alumina sol, silica-alumina sol, coating agent for formation of transparent coating film which comprises the sol, and substrate having transparent coating film attached thereto - Google Patents

Abstract

Disclosed are: a silica-alumina sol which is stable even when the sol is used at a high concentration and has good dispersibility in a matrix component; and a process for producing the sol. Silica-alumina particles are prepared by removing any cation (an alkali metal ion) that is derived from a production raw material from a silica-alumina sol, reducing the amount of any contaminant ion contained in the silica-alumina sol, and adjusting the amount of a negative charge present on the surface of the silica-alumina sol to a value falling within a predetermined range. The silica-alumina particles are used. An organosilicon compound is adsorbed on the surfaces of the particles in advance, and the compound is hydrolyzed, thereby treating the surfaces of the particles.

Description

[Technical Field] The present invention relates to a method for producing a cerium oxide-alumina sol which is stable at a high concentration, a cerium oxide-alumina sol containing a transparent film of the sol. The coating and the substrate of the transparent film are applied. More specifically, it is stable even at a high concentration, and the dispersibility of the matrix component is also good, whereby the coating for forming a transparent film can be made highly concentrated, and the coating property is excellent even at a high concentration. In addition to thick film formation, it can be applied to the production of a substrate coated with a transparent film excellent in adhesion to a substrate, scratch resistance, film hardness, film strength, transparency, haze, etc. A method for producing an aluminum sol, a cerium oxide, an alumina sol, a coating material for forming a transparent film containing the sol, and a substrate to which a transparent film is attached. [Prior Art] In order to improve the scratch resistance of a substrate such as a glass, a plastic sheet or a plastic lens, and a display device, it is known to form a transparent film having a hard coating function on the surface of the substrate. Specifically, the organic resin film or the inorganic film having transparency is formed on the surface of glass or plastic, a display device substrate or the like. In this case, inorganic fine particles such as resin particles or cerium oxide are added to the organic resin film or the inorganic film to further improve adhesion to the substrate, scratch resistance, and the like. Further, in order to suppress the dry texture, a high refractive index particle such as titanium oxide or an oxidation pin or a composite oxide particle having a high refractive index is added, and the refractive index difference from the substrate of -5 to 201139276 is reduced. Further, in order to impart electric prevention performance, conductive inorganic oxide particles such as antimony pentoxide, tin-doped indium oxide, or antimony-doped tin oxide may be added. When such inorganic oxide particles are used, it is desired to improve the dispersibility of the matrix component by surface treatment with a decane coupling agent. In order to improve the stability of the cerium oxide sol, it is known that the surface of the cerium oxide particles is modified with aluminum. For example, Patent Document 1 describes an acidic cerium oxide sol which is subjected to deionization treatment, and an acidity. After the aluminum salt aqueous solution is mixed, the obtained cerium oxide sol having a pH of 4 to 5 is heated. Further, Patent Document 2 describes that an aqueous solution of a cerium oxide sol having a pH of 6 or more is treated as an ammonia-type or amine-type cation exchange resin, and a metal salt of an aluminate is added, followed by heat treatment at 70 ° C or higher to produce an acidity. Or the neutral zone is a method of a stable cerium oxide sol. In the cerium oxide sol described in Patent Document 1 and Patent Document 2, the surface of the cerium oxide particles is coated with aluminum hydroxide or aluminum oxide to improve the stability. However, the cerium oxide particles have a positive electric charge on the surface of the particles. Therefore, when it is mixed with an organic compound containing a negatively charged organic group, aggregation tends to occur, and when it is a coating composition, there is a problem that transparency is lowered. Further, in the paint to which the past particles are added, there is a limit to the high concentration, and there is a problem that it is not suitable for the formation of a thick film. Even if the concentration is high, the stability is insufficient, and the adhesion to the substrate of the obtained transparent film, the film strength, the scratch resistance, and the like may be lowered. In addition, when the concentration is high, the viscosity is high, and the coating property is lowered. Therefore, the adhesion to the substrate, the film strength, the scratch resistance, and the like may be lowered. -6-201139276. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] US Patent No. 445 1 3 8 8 [Patent Document 2] Japanese Laid-Open Patent Publication No. Hei No. 5 8- 1 1 04 1 5 The inventors of the present invention have reviewed the results in detail in view of such a problem, and found that the cation (alkali metal ion) derived from the raw material is removed in the cerium oxide-alumina sol, and the surface negative charge amount is adjusted by reducing the inclusion ions. The cerium oxide-alumina particles in a predetermined range, after the organic cerium compound is adsorbed on the surface of the particles in advance, the particles which have been hydrolyzed and surface-treated have a stable dispersion and a higher concentration than the particles in the past, and the viscosity is high. It is also low, and the coating liquid using the same can be highly concentrated and excellent in stability, and the present invention has been completed. The present invention provides a high-concentration and stable dispersion, and is excellent in dispersibility for a matrix component. Therefore, the coating material for forming a transparent film can be formed with high concentration, and the coating property of the coating material is excellent and can be thickened. Cerium oxide, a method for producing an alumina sol, and a cerium oxide for producing a substrate coated with a transparent film excellent in adhesion to a substrate, scratch resistance, film hardness, film strength, transparency, haze, and the like An alumina sol, a coating material for forming a transparent film containing the sol, and a substrate to which a transparent film is attached. 201139276 Means for Solving the Problems The present invention relates to a method for producing a cerium oxide-alumina sol, which is characterized by the following steps (a) to (f). (a) the average particle diameter is in the range of 5 to 100 nm, and the alumina content in the particles is 0.01 to 5% by weight in terms of Al2〇3, and the solid content concentration is The aqueous dispersion which is dispersed in the range of 1 to 30% by weight is treated with an ion exchange resin until the concentration of ions (excluding H+ and 0H_) is less than or equal to 50 ppm in the cerium oxide alumina fine particles (b). Step (c) in which the cerium oxide-alumina fine particle aqueous dispersion is substituted with an alcohol, and the organic cerium compound represented by the following formula (1) is added to the Rn-SiO in the cerium oxide-alumina fine particle alcohol dispersion (4.n)/2 is a step R η S ΐ X 4 . η ( 1 ) in the range of 1 to 50% by weight of the silica sand alumina fine particles (however, in the formula, R is the carbon number I The non-substituted or substituted hydrocarbon groups of ～10 may be the same or different from each other. X: alkoxy group having a carbon number of 1 to 4, a hydroxyl group, a halogen, hydrogen, η: an integer of 1 to 3) (d) - stirring and oxidizing氧化铝. Alumina fine particle alcohol dispersion, while adsorbing the aforementioned organic cerium compound to cerium oxide. Alumina fine particles Step (e) Step of hydrolyzing the organic hydrazine compound by adding water and a catalyst for hydrolysis -8- 201139276

Cf) Step of aging at 40 to 120 ° C for 0.5 to 24 hours The above step (a) is preferably carried out by the following steps (al) and (a2). (al) a step of treating with a cation exchange resin to a pH of 1. 0 to 0.6 · (a2): treating with an anion exchange resin until the pH of the dispersion is higher than that of the dispersion in the above step (al) Step in which the pH is also higher in the range of 2.0 to 7.0 The above steps (g) and/or (h) may be preferably carried out for the above step (f). (g) Step of concentrating instead of organic solvent (h) Step of concentrating the cerium oxide obtained by the above step (a). The cerium oxide of the aqueous dispersion of alumina granules. The negative charge per unit surface area of the alumina granules Q The amount is preferably in the range of 0.1 to 1.5 pq/m 2 at a pH of 2.0 to 7.0. The Mohr ratio (MH20) / (Moc) of the water molar number (MH20) in the above step (e) and the molar number (Moc) of the organic ruthenium compound is preferably in the range of 1 to 300. The catalyst for hydrolysis in the above step (e) is ammonia, the molar number of ammonia (MNH3) and the molar ratio of molar number (Moc) of the organic cerium compound (Mnh3) / (Moc) is in the range of 0.1 to 12. Time is better. The negative charge amount per unit surface area of the ceria-alumina fine particles of the ceria-alumina fine particle aqueous dispersion obtained in the above step (f) is -9-201139276, and the solid content is 0.5% by weight, ΡΗ7. When the dispersion of 5±1·5 is measured, it is preferably in the range of 0.5 to 2.0 micro-coulombs/cm 2 . The organic solvent in the above step (g) is preferably one or more selected from the group consisting of ethers, esters, ketones and alcohols. When the solid content concentration is in the range of 20 to 70% by weight, the viscosity is preferably in the range of 1 to 10,000 cp. In the cerium oxide-alumina sol of the present invention, the average particle diameter is in the range of 5 to 100 nm, and the alumina content in the particles is in the range of 0.01 to 5% by weight in terms of a1203, and the following formula (1) a dispersion of cerium oxide. alumina fine particles surface-treated with an organic cerium compound, a surface-treated cerium oxide, a negative charge amount per unit surface area of the alumina fine particles (Qi), and surface treatment with an organic sand compound The ratio (Qi) / (Q2) of the negative charge amount (q2) per unit surface area of the prior art silica sand oxide target is 0.2 to 0.8. R η -S i X4 - η (1) (However, in the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, The base, the dentate, and the hydrogen, η: an integer of 1 to 3) The negative charge amount (Ql) is measured by a dispersion having a solid concentration of 〇·5 wt% and ρΗ7·5±1·5. - 5 to 2 Micro Micro-coulombs / cm2 The range is characterized by the -10- 201139276 cerium oxide alumina sol described in claim 9. The coating film for forming a transparent film of the present invention is formed from the ceria-alumina sol, the matrix-forming component and the dispersion medium described in any one of the above, and has a total solid content concentration of 30 to 70% by weight, and a matrix-forming component. The concentration is in the range of 6 to 63% by weight in terms of solid content, and the concentration of cerium oxide. The fine particles of alumina is characterized by a solid content of 3 to 56% by weight. The matrix forming component is a lanthanoid matrix forming component or an organic resin matrix forming component, and preferably a polyfunctional acrylate resin or a polyfunctional fluorene resin. Further, it is preferred that the solid component contains 0.003 to 0.7% by weight of an antimony-based antifouling agent. Further, it is preferred that the coating agent is contained in an amount of from 0.003 to 0.56 by weight per gram as a solid component. The dispersion medium is preferably one or more selected from the group consisting of ethers and esters, ketones and alcohols. The substrate to which the transparent film of the present invention is applied is formed of a base material and a transparent film formed on the substrate. The transparent film is formed by using the coating material for forming a transparent film described in any one of the above. The content of the cerium oxide. The alumina fine particles in the transparent film is in the range of 10 to 80% by weight in terms of solid content. The content of the matrix component is preferably in the range of 20 to 90% by weight in terms of solid content. . The film thickness of the transparent film is preferably in the range of 0.5 to 20 μm. -11 - 201139276 EFFECT OF THE INVENTION The present invention provides a cerium oxide alumina sol which is stable at a high concentration and excellent in dispersibility for matrix components, and a method for producing the same. In addition, a coating material for forming a transparent film which contains the above-mentioned ceria-alumina sol' and which has a low viscosity at a high concentration and which is excellent in applicability under stability can be obtained. Further, it is excellent in adhesion to the substrate, scratch resistance, film hardness, film strength, transparency, haze, etc., and excellent chemical resistance, water resistance, water repellency, and oil repellency can be maintained over a long period of time. A substrate that adheres to a transparent film that is resistant to fingerprint adhesion. MODE FOR CARRYING OUT THE INVENTION [Method for producing cerium oxide-alumina sol] The method for producing cerium oxide-alumina sol according to the present invention is characterized by the following steps (a) to (f). Step (a) (a) The average particle diameter is in the range of 5 to 100 nm, and the alumina content in the particles is in the range of 0.01 to 5% by weight in terms of Al 2 〇 3 of cerium oxide alumina fine particles. The aqueous dispersion which is dispersed in the range of 1 to 30% by weight of the component is treated with an ion exchange resin until the concentration of ions (other than H+, OH·) is 50 ppm or less in the cerium oxide. The alumina fine particles are -12. - 201139276 The cerium oxide-alumina fine particle dispersion liquid used in the present invention is not particularly limited as long as the average particle diameter of the cerium oxide-alumina fine particles and the alumina content are within the above range, and it is known in the past. The cerium oxide-alumina fine particle aqueous dispersion (hereinafter sometimes referred to as cerium oxide/alumina hydrosol). The pH of the cerium oxide-alumina fine particle aqueous dispersion which can be suitably used in the present invention is generally an alkaline region of 8 to 12%. The average particle diameter of the cerium oxide-alumina fine particles is from 5 to 100 nm, more preferably from 10 to 80 nm. When the average particle diameter is less than 5 nm, the stability of the obtained cerium oxide-alumina sol is insufficient, and it is difficult to obtain a high concentration of cerium oxide-alumina sol, so that it is difficult to obtain a transparent transparent at a high concentration. A coating liquid for forming a film. When the average particle diameter of the cerium oxide ♦ alumina fine particles exceeds 1 OOnrn, the particle diameter is increased, and the surface negative charge amount of the cerium oxide-alumina fine particles obtained in the step (b) described later is low, so in the step (d) The amount of the organic ruthenium compound adsorbed is insufficient, and it is difficult to obtain a cerium oxide-alumina fine particle dispersion liquid which is excellent in dispersibility and stability in an organic solvent, and it is difficult to obtain a high-concentration and stable transparent film-forming coating. Cloth liquid. Further, the alumina content of the cerium oxide. The alumina fine particles is preferably 0.01 to 5% by weight in terms of Al2?3, more preferably 0.05 to 3% by weight. When the amount of alumina in the cerium oxide-alumina fine particles is less than 〇·〇1% by weight in the case of Α12〇3, the surface negative charge of the cerium oxide obtained in the step (a)·oxidized-13-201139276 aluminum fine particles When the amount is low, the amount of adsorption of the organic hydrazine compound in the step (d) described below is insufficient, and it is difficult to obtain a cerium oxide-alumina fine particle dispersion liquid excellent in dispersibility of the organic solvent. The amount of alumina in the cerium oxide-alumina fine particles is more than 5% by weight in terms of ai2o3, and the surface negative charge amount of the cerium oxide-alumina fine particles obtained in the step (a) is not higher, only cerium oxide. - Reduction of alkali (Na) in alumina fine particles and removal of alumina The use of a cation exchange resin can reduce the efficiency of ion exchange resin treatment. Further, the cerium oxide-alumina aqueous sol is washed by a limiting filtration membrane method or an ion exchange resin method after production, and the alkali derived from the raw material remains in the particles and in the dispersion medium. The amount of alkali remaining in the cerium oxide-alumina fine particles is in the range of 1000 to 10, OOO ppm. Further, in addition to the base, there are other cations and anions derived from raw materials, equipment, and the like, and the total ion concentration is 1,200 to 12,000 ppm. The concentration of the cerium oxide-alumina fine particle aqueous dispersion is not particularly limited as long as the ion exchange resin is used to remove the alkali cation treatment and the inclusion ions, and the weight of the SiO 2 · Al 2 〇 3 is 1 to 30. % is preferably, more preferably in the range of 2 to 25% by weight. As the ion exchange resin, a cation exchange resin or a cation exchange resin and an anion exchange resin or a two ion exchange resin are used. The method of treating the ion exchange resin is a method of mixing the above resin with a cerium oxide/alumina fine particle aqueous dispersion, or passing the cerium oxide/alumina fine particle aqueous dispersion through a tube-14-filling the ion exchange resin. The method of the 201139276 column is general. The ion concentration in the cerium oxide-alumina solution treated with the ion exchange resin is present in the sand dioxide/oxidizing crystal 500 ppm or less, more preferably 250 ppm or less. Among them, as ions of ion concentration, Na + genus ions which are used for the production of cerium oxide/alumina sol for cations, genus ions as impurities in these alkali metal ions, and other cerium oxide alumina sols The metal ions and the like which are mixed and produced. The anion is mainly a chloride ion derived from the production of a raw material of an alumina sol, a raw material acid ion or the like.

Further, when the ion concentration in the SiO 2 and the oxidized gold lanthanum solution in which the ion concentration is not contained in the ion concentration ion is more than 50 ppm, the reason is that the organic hydrazine in the step (d) described later is used. When the amount of sorption of the compound is reduced, the concentration of the cerium oxide-alumina sol is increased to a high concentration, and the stability of the alumina sol tends to be insufficient. The above ion concentration in the present invention can be measured by ICP luminescence. The above step (a) is preferably carried out in the following steps (a 1 ) and (in the case of dispersing the particles in the microparticles, it is possible to dissolve the alkaline gold-based gold device such as K + > cerium oxide - The dispersion of sulfur-containing microparticles is not necessarily clear, and is weak or weak at the same time. Therefore, even if it can be optically analyzed, it is -15-201139276. Step (a 1 ) First, treatment with cation exchange resin to cerium oxide. The pH of the alumina fine particle dispersion is 1.0 to 6.0', preferably 1.5 to 4.0. The pH of the ceria-alumina fine particle dispersion after the cation exchange resin treatment is less than 1.0, the ceria. The amount of alumina in the step (a) will be excessively reduced, and the amount of negative charge per unit surface area of the particles obtained in the step (a) will be low, and the amount of adsorption of the organic hydrazine compound in the step (d) may be insufficient. A cerium oxide alumina sol which is stabilized at a high concentration is obtained. When the pH of the ceria-alumina fine particle dispersion after the cation exchange resin treatment exceeds 6.0, the concentration of the cation (Na ion) or the intercalated cation in the ceria-alumina fine particles may not be as low as the above range. The sorption amount of the organic ruthenium compound in the step (d) described later may be reduced, or at the same time, the sorption of the surface of the oxidized granules may be weakened, and the cerium oxide alumina sol may be finally obtained. The concentration is not sufficient, and even if the concentration is high, the stability tends to be insufficient. The step (a2) is continued, and the pH of the dispersion is higher than the pH of the dispersion in the above step (al), and it is preferably treated with an anion exchange resin to 2.0 to 7.0, more preferably in the range of 2.5 to 6.0. The cerium oxide-alumina fine particles after the anion exchange resin treatment -16-201139276 When the pH of the dispersion liquid is less than 2.0, the removal of the anion may be insufficient, or the amount of surface negative charge described later may be insufficient. The anion exchange resin-treated cerium oxide-alumina fine particle dispersion may be treated as described in the above step (a1), and the pH does not exceed 7 · 〇, and the anion concentration is not further reduced. The negative charge per unit surface area of the ceria-alumina fine particles of the ceria-alumina fine particle aqueous dispersion obtained in the above step (a) is preferably 0.1 to 1.5 pq/m 2 in the pH of 2.0 to 7.0. More preferably, it is in the range of 0.2 to 1.5 pq/m2. In the case where the amount of negative charge per unit surface area of the cerium oxide-alumina fine particles is less than 0.1 μεq/m 2 , the amount of adsorption of the organic cerium compound in the step (d ) described later is small, and the absorbing power is also weak. There is a possibility that it is difficult to obtain a cerium oxide-alumina fine particle dispersion liquid which is excellent in dispersibility and stability to an organic solvent. When it is difficult to obtain a large amount of negative charge per unit surface area of the cerium oxide-alumina fine particles exceeding 1.5 pq/m 2 , even if obtained, the amount of adsorption of the organic sand compound does not further increase, and it is difficult to obtain dispersibility for the organic solvent. A high-concentration, high-concentration cerium oxide-alumina fine particle dispersion. In the present invention, the specific surface area (m2/g) of the particles is measured by the BET method, and the negative charge amount (μ eq / g ) is a particle charge meter (Spectris: PCD_03), and the solid content concentration is 1 Determination of cerium oxide % alumina fine particle aqueous dispersion. The amount of negative charge per unit surface area (Peq/m2) is obtained by dividing the above negative charge amount -17-201139276 (μεq/g) by the surface area. Step (b) The aqueous dispersion of cerium oxide-alumina fine particles is replaced with an alcohol solvent. The purpose of solvent substitution here is to dissolve in the step (c) without hydrolyzing the organic ruthenium compound, and to adsorb the organic ruthenium compound on the cerium oxide-alumina microparticles in the step (d). The solvent substitution method may be changed by the kind of the alcohol, but the concentration of the ceria-alumina fine-particle alcohol dispersion after the solvent substitution is preferably 1 to 30% by weight, more preferably 2 When the range is ~20% by weight. In addition, the amount of water remaining in the alcohol dispersion of the cerium oxide-alumina fine particles may vary depending on the type of the organic hydrazine compound, the hydrolyzability, etc., but it is 5% by weight or less in the dispersion liquid, and more preferably 1% by weight or less. good. When the residual amount of water in the cerium oxide-alumina fine particle alcohol dispersion exceeds 5% by weight, the liquid is hydrolyzed in the step (c), or the adsorption is inhibited in the step (d), and the condensation is formed in the step (e). Glue, or agglomerate the particles in step (f). The measurement of the amount of water at this time was measured by a trace moisture analyzer. Step (c) continues, in the alcohol dispersion of cerium oxide. Alumina fine particles, the organic cerium compound represented by the following formula (1) is obtained, even though it is based on the particle diameter of the cerium oxide-oxidized -18-201139276 aluminum fine particles. The difference is in the range of 1 to 50% by weight, more preferably 5, % by weight of Rn_SiC)(4_n)/2 cerium oxide. R η ' S ΐ X 4 . η ( 1 ) (However, in the formula, the unsubstituted or substituted R having a carbon number of 1 to 10 may be the same or different from each other. X: the number of the alkyl group having a carbon number of 1 to 4, and the diameter The hydrogen, η: an integer of 1 to 3) The organic sand compound represented by the formula (1) may, for example, be methoxydecane, dimethyldimethoxydecane or phenyltrimethoxydiphenyl. Methoxy decane, methyl triethoxy decane, dimethyl decane, phenyl triethoxy decane 'diphenyl diethoxy sand trimethyl decane, vinyl trimethoxy decane, B Dilute trioxane, vinyl ginseng (β-methoxyethoxy) decane, 3,3,3-yltrimethoxydecane, methyl-3,3,3-trifluoropropyldimethoxyanthracene ( 3,4-Epoxycyclohexyl)ethyltrimethoxydecane, γ-epoxymethyltrimethoxydecane, γ-glycidoxymethyltriethoxyphosphoniumoxypropyloxyethyltrimethyl Oxydecane, γ-glycidoxyethyl decane, γ-glycidoxypropyltrimethoxydecane, γ-epoxypropyltrimethoxydecane, γ-glycidoxypropyl Triethoxy oxime glycidoxypropyl triethoxy oxime 'γ-(β-glycidoxy)propyltrimethoxydecane, γ-(meth)acryloxymethyltrioxane, γ-(meth)acryloxymethyltriethoxydecane, Γ- In terms of bis-hemihydrocarbyl, benzyl, halomethyltrioxane, diethoxy, isobutylethoxytrifluoropropane, β-propoxy, γ-triethoxypropoxy γ- Ethoxymethoxy (methyl-19-201139276) propyleneoxyethyltrimethoxydecane, γ-(meth)acryloxyethyltriethoxydecane, γ-(meth)acryloxy Propyltrimethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane, γ-(meth)acryloxypropyltriethoxylate, γ-(methyl)propane Propyl triethoxy decane, butyl trimethoxy decane, isobutyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, butyl Diethoxy hospital, isobutyl triethoxy sand, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, 3-ureido isopropyl propyl Ethoxy decane, perfluorooctylethyl Methoxy decane, perfluorooctylethyl triethoxy decane, perfluorooctylethyl triisopropoxy decane, trifluoropropyl trimethoxy sand, Ν-β (aminoethyl) γ - Aminopropyl methyl dimethoxy decane, Ν-β (aminoethyl) γ-aminopropyl trimethoxy decane, Ν-phenyl-γ-aminopropyltrimethoxy decane, γ - Hydrogenthiopropyltrimethoxydecane, trimethylstanol, methyltrichlorodecane, and the like. In addition, the organic ruthenium compound having an alkoxy group having a carbon number of 1 to 4 in the above formula (1), and the residual amount of water in the cerium oxide-alumina fine particle alcohol dispersion liquid are in a large amount in the above range. In this case, there is a tendency that it is not easily hydrolyzed and adsorbed, and surface treatment for improving dispersibility can be efficiently performed, which is preferable. The organic germanium compound is added in an amount of Rn-SiO(4-n)/2, and the high concentration stability of the surface-treated cerium oxide-alumina fine particles obtained is less than 1% by weight of the cerium oxide-alumina fine particles. The dispersibility of the matrix components may be insufficient. When the amount of the organic ruthenium compound added is more than 50% by weight of the oxidized alumina fine particles of the dioxane-20-201139276 Rn_SiO(4.n)/2, the average particle diameter is different, but the adsorption is difficult. The excess organic cerium compound may form a gel in step (e) or may cause agglomeration of the particles in step (f), and even if sorbed, the hydrolyzed organic cerium compound on the surface of the cerium oxide-alumina fine particles may be laminated. However, only the amount is increased, or the dispersibility cannot be further improved, and the concentration cannot be increased. In the step (d), the organic ruthenium compound is adsorbed to the cerium oxide-alumina fine particles while the cerium oxide-alumina fine-particle alcohol dispersion is stirred, and the temperature of the dispersion at this time is not particularly limited, but is normal temperature. (large 槪 20 ° C) ~ below the boiling point of the alcohol solvent. Step (e) Continuing, adding water and a catalyst for hydrolysis to hydrolyze the organic hydrazine compound. At this time, the molar ratio of the molar number of the added water (Μη2〇) to the mole number of the organic hydrazine compound (Moc) ( ΜΗ2〇) / (Moc) is 1 to 300, more preferably 5 to 200. When the molar ratio (MH2〇) / (Moc) is less than 1, the hydrolysis is not sufficient. The unhydrolyzed organic ruthenium compound must be removed. Even if it is removed, it is difficult to obtain a cerium oxide alumina sol having excellent high stability and stability. When Mohr ratio (MH20) / (Moc) exceeds 30,000 hrs, it is necessary to remove from -21 to 201139276, but this removal is difficult, and when it is used for a coating liquid for forming a transparent film using an organic solvent to be described later, stability is improved. The change was insufficient, and a stable and high concentration coating liquid could not be obtained. Further, ammonia is preferred as the catalyst for hydrolysis. When ammonia is used, it can be easily removed even if it remains in the coating liquid, and if it remains in a small amount, it does not cause too much damage to the stability of the coating liquid, and the performance of the transparent film formed by using the coating liquid does not occur. got damage. The molar ratio of the molar number of the added ammonia (μΝΗ3) to the molar number of the organic cerium compound (M〇c) (Mnh3) / (M〇c) is 〇·1 to 12, more preferably 0.2 to 10 The scope. When the molar ratio (MNH3) / (Moc) is less than 0.1, the hydrolysis becomes insufficient, and the unhydrolyzed organic ruthenium compound must be removed. Even if it is removed, it is difficult to obtain a cerium oxide alumina sol having excellent high stability and stability. When the molar ratio (MNH3) / (M〇c) exceeds 12, the unhydrolyzed material does not remain, but a large amount of ammonia remains, so that the stability of the coating liquid and the performance of the transparent film (scratch resistance, transparency) , appearance, etc.) does not charge #, so the residual ammonia must be removed. The addition method of water and ammonia may be added separately, but it is preferably added by ammonia. Step (f) continues, at 4 〇 ° C ~ 1 2 ° ° C, especially for the boiling point of the solvent in y g line: 0.5 ~ 24 hours of ripening. By the aging of the above conditions, the hydrolysis of the organic ruthenium compound adsorbed on the surface of the cerium oxide·oxidized granules-22- 201139276 will be completely completed, and the binding reaction between the surface of the particles and the hydrolyzate is promoted, and the high concentration can be obtained. Stabilized cerium oxide alumina sol with excellent dispersibility. The amount of negative charge per unit surface area of the ceria-alumina fine particles of the cerium oxide-alumina fine particles obtained in the above step (f) is 固体·5 wt% in the solid content concentration. The dispersion of 117.5 ± 1.5 is preferably measured in the range of 55 to 2.0 micro-coulombs/cm2. It is difficult to obtain surface treated cerium oxide. The negative charge amount per unit surface area of the alumina fine particles (Q!) is less than 0.5 microcoulombs/cm2, and more than 2.0 microcoulombs/cm2. The method of the present invention can be obtained by a conventionally known method by a sand pot pot mixture treatment, and the dispersibility and stability of the organic solvent may be insufficient. The measurement method of the negative charge amount per unit surface area will be described later. In the present invention, following the above step (f), the following steps (g) and/or (h) are preferred. Step (g) replaces the organic solvent. As the organic solvent, an organic solvent used in a coating material described later is preferred. Specifically, it is preferably one or more selected from the group consisting of ethers, esters, ketones, and alcohols. If it is such an organic solvent, a high concentration and stable cerium oxide can be obtained. -23- 201139276 • Oxidation of the sol. Further use of such a cerium oxide. Alumina sol can obtain a highly concentrated and stable coating. The method of substituting the organic solvent is not particularly limited as long as it can be substituted. The general limit filtration membrane method and the distillation method are preferred. Concentration can also be carried out at this time. By substituting the organic solvent to remove residual impurities such as moisture or a hydrolysis catalyst such as ammonia, unreacted materials, etc., it is possible to obtain an odorizable and stable silica sand which can be used in the coating of the present invention. Jin sol. Step (h) continues and concentrates as necessary. As the concentration method, the same ultimate filtration membrane method and distillation method as in the step (g) can be employed. Further, in the present invention, only steps (g) and (h) may be carried out, and both may be implemented, and the order may be changed. The cerium oxide-alumina sol thus obtained has a solid content concentration of 20 to 70% by weight, more preferably 30 to 70% by weight. When the solid content concentration of the cerium oxide ♦ alumina sol is less than 20% by weight, the stable sol is not limited to the present invention, and even if it is added to the coating liquid for forming a transparent film, a high-concentration coating liquid cannot be obtained. When it is difficult to obtain a solid content concentration of the cerium oxide-alumina sol of more than 70% by weight, even if it is obtained, the stability is insufficient and it is not suitable for the formation of a transparent film. Further, although the viscosity of the cerium oxide-alumina sol differs depending on the concentration, -24-201139276 is preferably 1 to 10 Torr, and 〇〇〇 cp is more preferably in the range of 2 to 5,000 cp. When the viscosity of the alumina sol is less than 1 CP, it is difficult to obtain the above-mentioned concentration range of cerium oxide. The alumina sol, when it exceeds 1 〇, when 〇〇〇Cp, the long-term stability will be lowered and the coating property will also be It is difficult to reduce the formation of a transparent film which is excellent in uniform film thickness, scratch resistance, transparency, and appearance. Further, in the viscosity measurement of the present invention, it can be measured by a viscometer (manufactured by Toki Sangyo Co., Ltd.: B L type viscometer). [Silica dioxide/oxidized sol] The cerium oxide-alumina sol of the present invention has an average particle diameter of 5 to 1 〇〇 nm, and the alumina content in the particles is 0.01 by Al 2 〇 3 a dispersion of cerium oxide-alumina fine particles surface-treated with an organic cerium compound represented by the following formula (1) in a range of 5% by weight, characterized by a surface area per unit surface of the surface-treated cerium oxide-alumina fine particles The ratio (Qi) / (Q2) of the negative charge amount (Qi) to the negative charge amount per unit surface area (Q2) of the cerium oxide-alumina fine particles before the surface treatment with the organic cerium compound is 〇_2 to 0.8. The scope. R η _ S i X 4 - η (1) (However, in the formula, R is an unsubstituted or substituted hydrocarbon group having a carbon number of 1 to 1 ,, which may be the same or different from each other. X: a hospital oxygen having a carbon number of 1 to 4 Base, radial basis, g, hydrogen, η: an integer of 1 to 3) -25- 201139276 Surface treatment of ceria · Alumina fine particles In the present invention, surface treatment of ceria. Alumina fine particles, alumina content It is 0.01 to 5 wt%, more preferably 0.05 to 3 wt%, in terms of Al2〇3. When the amount of alumina in the surface-treated cerium oxide-alumina fine particles is less than 0.01% by weight in terms of Al2〇3, the cerium oxide fine particles in the conventional cerium oxide sol or the surface of the conventional decane coupling agent The amount of the cerium oxide microparticles to be treated is as large as the amount of negative charge (Qi) per unit surface area described later, and it is difficult to obtain a cerium oxide-alumina fine particle dispersion liquid excellent in dispersibility and stability to an organic solvent. The amount of alumina in the surface-treated cerium oxide-alumina fine particles is not more than 5% by weight in terms of Al2〇3, and the amount of negative charge (Q,) per unit surface area is not less, and the organic content is not improved. Solvent dispersibility and stability. The surface-treated cerium oxide-alumina fine particles have an average particle diameter of 5 to 100 nm, more preferably in the range of 10 to 80 nm. When the average particle diameter is less than 5 nm, the stability of the surface-treated cerium oxide-alumina fine particle dispersion is insufficient, and it is difficult to obtain a high-concentration cerium oxide-alumina sol, so that it is difficult to obtain a high-concentration and stable transparent film formation. Use a coating solution. When the average particle diameter of the surface-treated ceria-alumina fine particles exceeds 1 ΟΟηηι, the surface of the ceria-alumina fine particles obtained in the above step (b) has a small amount of surface charge, so the step ( d) The amount of adsorption of the organic ruthenium compound is insufficient, and it is difficult to obtain a surface-treated cerium oxide-alumina fine dispersion having excellent dispersibility and stability of the solvent of -26-201139276. And a stable coating liquid for forming a transparent film. Surface treatment of cerium oxide. The ratio of the negative charge amount per unit surface area (Qi) of the alumina fine particles to the negative charge amount per unit surface area (Q2) of the front cerium oxide alumina fine particles surface-treated with the organic cerium compound (Qi) / (Q2) is 0-2 to 0.8, more preferably 0.2 to 0.6. It is difficult to obtain that the above ratio (Q1) / (Q 2 ) is less than 〇. 2, when the above ratio (Qi) / (Q2) exceeds 0.8, the method of the present invention is not required to be carried out, and a known method can be used to carry out decane coupling agent treatment. In addition, the dispersibility and stability of the organic solvent are insufficient. The negative charge amount (Q!) per unit surface area of the surface-treated ceria-alumina fine particles is 0.5 to 2.0 microcoulombs when measured as a dispersion having a solid concentration of 0.5% by weight and a pH of 7.5±1.5 (Microcoulombs) Preferably, /cm2 is more preferably in the range of 0.5 to 1.6 microcoulombs/cm2. It is difficult to obtain surface treatment of cerium oxide-alumina microparticles. The amount of negative charge per unit surface area (Qi) is less than 微·5 micro-coulombs/cm2, and more than 2.0 micro-coulombs. A larger number of /cm2 does not need to be subjected to the above-described method of the present invention, and a conventionally known method can be obtained by treatment with a decane coupling agent, and the dispersibility and stability of the organic solvent are insufficient. The negative charge amount per unit surface area (Q ^) of the surface-treated ceria-alumina microparticles of the present invention, and the surface area per unit surface area of the ceria-alumina microparticles before the surface treatment of the organic antimony compound -27-201139276 The amount of charge (q2) is measured by surface-treating the ceria-alumina fine particle dispersion or by adding water to the ceria-alumina fine particle dispersion before surface treatment with an organic antimony compound to adjust the solid content concentration to 〇. 5 wt%, the pH was adjusted to pH 7.5 ± 1.5, using a particle charge meter (Spectris: PCD-03), using a 0.001 N polydipropenyldimethylammonium chloride as a titrant to determine the surface negative The amount of charge (peq/g) was obtained by dividing the specific surface area into Microcoulombs/cm2. Also, the conversion uses the following relationship. 1 Micro-coulombs /c m2 = 0 · 0 6 2 8 c har ges/n m2 ( RALPH K.ILER, THE CHEMISTRY OF SILICA : John & Sons .Inc : 1 979 ) [For transparent film formation Coating Material The coating film for forming a transparent film of the present invention is formed of the above-mentioned ceria alumina alumina sol and matrix forming component and a dispersing medium, and the total solid content concentration is in the range of 30 to 70% by weight, and the concentration of the matrix forming component is The solid content is in the range of 6 to 63% by weight, and the concentration of the ceria-alumina fine particles is in the range of 3 to 56% by weight. As the ceria, the alumina sol, a ceria-alumina sol obtained by the above-described ceria-alumina sol and the above-described ceria-alumina sol production method can be used. -28- 201139276 Matrix Forming Component As the matrix forming component used in the present invention, an organic resin matrix forming component or a lanthanide (solly gel) matrix forming component can be used. As the organic resin matrix forming component, a conventionally known organic resin can be used. Specifically, as the resin for coating, any of a known thermosetting resin or a thermoplastic resin can be used. For example, a poly resin, a polycarbonate resin, a polyamide resin, a polyoxymethylene resin, a thermoplastic acryl-based resin, a chlorinated vinyl resin, a fluororesin, an ethyl acetate-based resin, and a poly-polymer used in the past may be mentioned. Thermoplastic resin such as silicone resin, urethane resin, melamine resin, enamel resin, butyral resin, reactive polyoxyl resin, phenol resin, epoxy resin, unsaturated polyester resin, thermosetting propylene-based resin, etc. Thermosetting resin, etc. Further, two or more kinds of copolymers or modified bodies of these resins may be used. These resins may be an emulsion resin, a water-soluble resin, or a hydrophilic resin. Further, it may be a thermosetting resin, an ultraviolet curing type, or an electron beam curing type, and may also contain a thermosetting resin and a curing catalyst. In the present invention, it is also preferred to use a polyfunctional acrylate resin or a multi-functional enamel resin. The functional group at this time may, for example, be a (meth) propylene group or an epoxy group. The polyfunctional acrylate resin may, for example, be (1) an acrylate resin having a functional group having three or more functional groups, (2) a bifunctional acrylate resin, and/or a bifunctional oxime resin. Specific examples of the acrylate resin having a functional group having three or more functional groups include trifunctional acrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate. a trifunctional urethane acrylate resin such as a tetrafunctional acrylate resin such as a resin or pentaerythritol tetraacrylate, or a hexafunctional urethane resin such as dipentaerythritol hexaacrylate or a pentaerythritol hexamethyl acetonate urethane prepolymer or pentaerythritol. The epoxy group such as polyepoxypropyl ether acrylate contains a tetrafunctional acrylate resin, a methyl phenolic epoxy acrylate, a bisphenol A diglycidyl ether acrylic acid addition product, and the like, and the epoxy group contains a polyfunctional acrylic acid. As the ester resin or the like, a mixture thereof may also be used. As the acrylate resin having a functional group having three or more functional groups, a monomer may be used, and an oligomer or a polymer having a volume of two or more may be used. Examples of the (2) bifunctional acrylate resin include polyethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate 'polypropylene glycol diacrylate, and polyethylene glycol dimethyl. Acrylate, neopentyl glycol dimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate A glycol acrylate such as polypropylene glycol dimethacrylate. Further, examples include 1.4-butylene glycol dimethacrylate, 1.6-hexanediol dimethacrylate, 1.9-nonanediol dimethacrylate, 1.10-nonanediol dimethacrylate, and glycerin. Dimethacrylate, 2-hydroxy-3-propylene methoxypropyl methacrylate, hexanediol diacrylate, i.9-nonanediol diacrylate, dimethylol-tricyclodecane II Non-glycol-based acrylic acid-30-201139276 esters such as acrylate and 2_hydroxy-3-propenyloxypropyl methacrylate may also be used. As the bifunctional oxime resin, the following chemical formula can be used (in the formula (1), Ri, R~3 to Rs are unsubstituted, and the unsubstituted fluorenyl group having 1 to 6 carbon atoms, X!' X2 represents an acryl group, a methyl propyl group, or a propylene group, and may be the same or different. η is a positive number of 1 to 10. [Chemical 1]

R 4 — R Γ

X

S-R S I ο

5 •R

X specifically includes a diacrylate modified polyoxyalkylene, a dimethyl allene modified polysiloxane, a diepoxypropyl group, a polyoxan, and a dimerized vinegar modified polyoxyl Alkane, diether modified polyoxyalkylene, and the like, and mixtures thereof. In this case, a bifunctional acrylate resin or a bifunctional oxime resin is preferably used. When a monomer is used, the acrylate resin having the above-mentioned trifunctional or higher functional group and the above-mentioned monofunctional oxime resin (sand antifouling agent) can be promoted to combine water repellency, oil repellency, and fingerprint resistance. Excellent in properties and chemical resistance, it can suppress the detachment of one tube of enamel resin (hereinafter sometimes referred to as leakage), and can maintain water repellency, oil repellency, fingerprint adhesion resistance, and chemical resistance for a long period of time. Further, in the coating material for forming a transparent film, it is preferred to use one tube of an anthraquinone resin as the antimony-based antifouling agent by using (3) represented by the following chemical formula (2). In the formula (2), '1^~5" represents a substituted or unsubstituted group having 1 to 3 carbon atoms, and X represents a propenyl group, a methacryl group or a glycidyl group. n is a positive number of ι~2〇 -31 - 201139276. [Chemical 2]

Ri I R 2 a S i I r3

(2) Specifically, a propylene-based modified polyoxyalkylene, a methacrylic acid modified polyoxyalkylene-epoxypropyl group becomes a polyoxyalkylene, a polyester modified polyoxane, and a polyether modified Polyoxane, etc. and mixtures thereof. For example, a single-end (meth) acryl base sand oil, a single-end epoxy propyl sand oil, etc. are mentioned. Further, it is also preferable that the acrylic acid-based oxime resin monomer or its polymer (anthracene oil), the epoxy-based oxime resin monomer or its polymer (an oil), a polyester-based resin monomer or a polymer (an oil). Further, it is preferred that the coating material for forming a transparent film contains a coating agent. Examples of the coating agent include polyethylene oxide tridecyl ether, polyethylene oxide lauryl ether, polyoxyalkylene lauryl ether, polyethylene isodecyl ether, and polyethylene polypropylene oxide. Block polymer, polyethylene oxide oleate, polyethylene oxide distearate, polyethylene oxide castor oil, other as a special coating or special acrylic coating agent or defoamer Give known materials. When such a leveling agent is contained, a transparent film excellent in appearance can be obtained. Dispersion medium The dispersion medium to be used in the invention is preferably one or more selected from the group consisting of ethers, esters, ketones and alcohols. Specific examples thereof include alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), buty-32-201139276 alcohol, diacetone alcohol, mercapto alcohol, and tetrahydrofurfuryl alcohol, ethylene glycol, and hexanediol. Polyols; methyl acetate 'ethyl acetate' isopropyl acetate, propyl acetate, isobutyl acetate 'butyl butyl acetate, isoamyl acetate, amyl acetate, 3-methoxybutyl acetate, acetic acid 2_ethylbutyl ester, cyclohexyl acetate, ethylene glycol monoacetate and other esters; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ethers such as ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; acetone, methyl ethyl ketone a ketone such as methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methylcyclohexanone, dipropyl ketone, methyl amyl ketone or diisobutyl ketone. These can be used alone or in combination of two or more. Polymerization initiator In the present invention, a matrix-forming component, cerium oxide, alumina microparticles, and a polymerization initiator may be contained. As the polymerization, a known one can be used without particular limitation, and examples thereof include bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and bis(2,6-dimethoxybenzophenone). Mercapto) 2,4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propan-1-one, 2, 2-dimethoxy-1 , 2-diphenylethane ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-l-[4-(methylthio)phenyl-2-oxamorphpropan-1-one, and the like. Coating composition The coating material for forming a transparent film has a total solid concentration of 30 to 7% by weight, more preferably 4 to 65% by weight. -33-201139276 When the total solid content concentration of the coating material for forming a transparent film is not less than that of the present invention, it is also possible to easily obtain a transparent coating which is difficult to obtain a film thickness of 0.5 μm or more by one application. When it is dried, the hardness or resistance of the obtained transparent film is insufficient, the haze or appearance is deteriorated, or the productivity and the production are lowered. When the total solid content concentration of the coating material for forming a transparent film exceeds %, the viscosity of the coating material is lowered until the time of use, and the haze of the obtained transparent film is increased, or the scratch resistance is insufficient. The cerium oxide in the coating material for forming a transparent film has an oxidation concentration of 3 to 56% by weight in terms of solid content, and more preferably 6 to 39 Å. When the cerium oxide and the oxidizing concentration in the coating material for forming a transparent film are less than 3% by weight in terms of solid content, the effect of adding dioxide, such as adhesion, film strength, and scratch resistance, cannot be obtained. When the cerium oxide in the coating material for forming a transparent film has an oxidizing concentration of more than 56% by weight in terms of a solid content, the adhesion to the substrate, the film strength, and the scratch resistance are continued, and the transparent film is formed. The matrix in the coating is formed in a solid content of 6 to 63% by weight, more preferably 16 to 0.001. In addition, the matrix-forming component indicates that the above-mentioned polyfunctionality is 30% by weight, and even if the film is available, the scratch resistance is changed to 70% by weight, or the thickness of the coated surface is increased by the weight of the fine particles. The composition of the microparticles to the substrate is less than that of the microparticles of the microparticles. Concentration of the component 5% by weight of acrylate tree -34- 201139276 Fat, polyfunctional oxime resin, and antimony-based antifouling agent and coating agent described later. When the concentration of the matrix-forming component in the coating material for forming a transparent film is less than 6% by weight in terms of the solid content, the adhesion to the substrate, the film strength, and the scratch resistance are insufficient due to the small matrix component. When the concentration of the matrix-forming component in the coating material for forming a transparent film exceeds 63% by weight in terms of the solid content, the adhesion to the substrate, the film strength, the scratch resistance, and the like may become insufficient. In the coating material for forming a transparent film, the acrylate resin having a functional group having three or more functional groups (1) has a solid content of 6 to 63% by weight, more preferably 16 to 5% by weight. When the concentration of the acrylate resin having a functional group having three or more functional groups in the coating material for forming a transparent film is less than 6% by weight based on the solid content, adhesion to the substrate of the transparent film, strength, and scratch resistance may occur. Not fully changed. When the concentration of the acrylate resin having a trifunctional or higher functional group in the coating material for a transparent film formation is more than 63% by weight, the adhesion to the substrate, the film strength, the scratch resistance, and the like may become insufficient. (2) and/or (3) have fewer matrix components, and cracks are formed in the transparent film, or sufficient water repellency, oil repellency, and fingerprint adhesion resistance cannot be obtained. The concentration of the (2) bifunctional acrylate resin and/or the bifunctional oxime resin in the coating material for forming a transparent film is 2.6 to 6.3 wt%, preferably 1.6 to 5.5 wt%. . When the concentration of the bifunctional acrylate resin and/or the bifunctional sand in the coating material for forming a transparent film is less than 0.6% by weight, cracks may occur in the film of the transparent-35-201139276, or a tube can be produced as described later. Insufficient bonding of the resin will be insufficient 'water repellency, oil repellency, fingerprint adhesion, chemical resistance, etc.' will cause the detachment of one tube of resin (also known as leakage) 'to make water repellency' The oil repellency, fingerprint adhesion resistance, chemical resistance, and the like are lowered with time. When the concentration of the bifunctional acrylate resin and/or the bifunctional ruthenium in the coating material for forming a transparent film is more than 6.3 by weight, the bonding with the one tube of the enamel resin does not increase, and thus the water repellency is not improved. , oil repellency, fingerprint adhesion resistance, chemical resistance, etc., does not inhibit the detachment (leakage) of one tube of resin. Further, the adhesion to the substrate, the film strength, and the like may be insufficient. The concentration of the antimony-based antifouling agent in the coating material for forming a transparent film is 0.003 to 0.7% by weight, more preferably 0.008 to 0.52% by weight, based on the solid content. When the concentration of the antimony-based antifouling agent in the coating material for forming a transparent film is less than 0.003 wt% in terms of solid content, it differs depending on the film thickness of the obtained transparent film, and water repellency, oil repellency, fingerprint adhesion resistance, and resistance There may be insufficient conditions such as pharmaceuticals. The concentration of the antimony-based antifouling agent in the coating material for forming a transparent film does not further increase the water repellency, oil repellency, fingerprint adhesion resistance, chemical resistance, etc., even when the solid content exceeds 7% by weight. The adhesion, film strength, etc. may be insufficient. Further, the coating material for forming a transparent film preferably contains 0.003 to 0_56% by weight, more preferably 0.008 to 0.33 by weight, based on the solid content. /〇 -36- 201139276 The leveling agent is better. When the concentration of the leveling agent in the coating material for forming a transparent film is less than 0.003 wt% in terms of a solid content, defects or the like occur, and the appearance of the obtained transparent film is deteriorated, and sufficient scratch resistance cannot be obtained. When the concentration of the coating agent in the coating material for forming a transparent film is more than 0.56% by weight in terms of a solid content, the appearance is not further improved, and the film strength is insufficient. A method for forming a transparent film using such a transparent film-forming coating material is a known method such as a dipping method, a spray method, a spin method, a roll coating method, a bar coating method, a gravure printing method, or a microgravure printing method. The material is subjected to coating, drying, ultraviolet irradiation, heat treatment, etc., and is cured to form a transparent film. It is preferable that the film thickness of the transparent film of the base material to which the transparent film is attached is in the range of 0.5 to 20 μm. [Substrate to which a transparent film is attached] The substrate to which the transparent film of the present invention is applied is formed of a substrate and a transparent film formed on the substrate, and the transparent film is formed by using the coating liquid for forming a transparent film. feature. The substrate to be used in the present invention is not particularly limited, and may be, for example, a plastic sheet such as glass, polycarbonate, acrylic resin, PET or TAC, a plastic film or the like, or a plastic plate. It is also preferred to use a resin-37-201139276 substrate. Transparent film The transparent film is made of cerium oxide-alumina fine particles and a matrix component. In the cerium oxide-alumina fine particles, the content of the cerium oxide-alumina fine particles in the transparent film is preferably from 1 〇 to 80% by weight, more preferably from 1 5 to 60% by weight, based on the solid content. When the content of the cerium oxide-alumina fine particles in the transparent film is less than 10% by weight in terms of the solid content, the adhesion to the substrate, the film strength, the scratch resistance, and the like may be insufficient. When the content of the cerium oxide-alumina fine particles in the transparent film is more than 80% by weight in terms of the solid content, the matrix component is small, and the adhesion to the substrate, the film strength, and the scratch resistance may be insufficient. The situation. Matrix component As the matrix component, the above-described lanthanide matrix component and organic resin matrix component are used. Further, the organic resin matrix forming component in the transparent film is hardened. The organic resin matrix component may preferably contain the aforementioned polyfunctional acrylate. As the polyfunctional acrylate, the aforementioned polyfunctional acrylate can be used. The polyfunctional acrylate resin may, for example, be an acrylate resin having a functional group of (1) 3 or more, (2) a bifunctional acrylic-38-201139276 ester resin, and/or a bifunctional oxime resin. The content of the matrix component in the transparent film is 20 to 90% by weight as a solid component. /〇 is better' better than the range of 40 to 85% by weight. When the content of the matrix component in the transparent film is not in the above range in terms of the solid content, the adhesion to the substrate, the film strength, and the scratch resistance may be insufficient. The content of the organic resin having a functional group of three or more functional groups (1) in the transparent film is from 20 to 90% by weight, more preferably from 40 to 80% by weight, based on the solid content. When the content of the organic resin having a functional group having three or more functional groups in the transparent film is less than 20% by weight in terms of the solid content, the adhesion to the base material of the transparent film and the scratch resistance may be There are insufficient circumstances. When the content of the organic resin having a trifunctional or higher functional group in (1) in the transparent film is more than 90% by weight in terms of a solid content, the matrix component of (2) and/or (3) described later is small, and thus It is fully water-repellent, oil-repellent, and fingerprint-resistant. Further, the content of the (2) bifunctional organic resin and/or the two functional enamel resin in the transparent film is in the range of 2 to 9 wt%', more preferably 4 to 8.5% by weight, based on the solid content. When the content of the (2) bifunctional organic resin and/or the bifunctional oxime resin in the transparent film is less than 2% by weight in terms of the solid content, the combination of the later (3) and the one tube resin can be insufficient. 'Water repellency, oil repellency, fingerprint adhesion, chemical resistance, etc. will become insufficient' and contain 1 tube energy -39- 201139276 矽 resin, it will cause a tube to detach the resin (sometimes called leakage) ) 'Reducing the water repellency' oil-repellent property, fingerprint-resistant adhesion, and chemical resistance are reduced with time. The content of the (2) bifunctional organic resin and/or the bifunctional oxime resin in the transparent film is not more than 9% by weight in terms of solid content, and (3) does not increase the bonding with the one tube resin, thereby not The water repellency, oil repellency, fingerprint adhesion resistance, chemical resistance, etc. will be further improved, and the detachment (leakage) of the enamel resin will not be inhibited. Further, the adhesion to the substrate, the film strength, and the like may be insufficient. In the transparent film, it is preferred to use the (3) 1 tube-based resin as the antimony-based antifouling agent. The content of the (3) 1 tube enamel resin (ruthenium-based antifouling agent) in the transparent film is 固体1 to 1% by weight, more preferably 〇2 to 0.8% by weight, based on the solid content. When the content of the ruthenium resin in the transparent film is less than 0.01% by weight in terms of solid content, it varies depending on the film thickness of the transparent film, and water repellency, oil repellency, fingerprint adhesion resistance, chemical resistance, etc. There are insufficient circumstances. When the content of the monofunctional oxime resin in the transparent film is more than 1% by weight in terms of the solid content, the water repellency, the oil repellency, the fingerprint adhesion resistance, the chemical resistance, and the like are not further improved, and the adhesion to the substrate is improved. There is a case where the film strength or the like is insufficient. Further, the above-mentioned leveling agent can be used for the transparent film. The content of the leveling agent in the transparent film is preferably 0.001 to 0.8% by weight, more preferably 0.02 to 0.5% by weight, based on the solid content. -40- 201139276 When the content of the coating agent in the transparent film is less than 0 _ 0 1% by weight of the solid content, the film thickness of the transparent film is different, and the appearance of the transparent film is deteriorated. Or can not get full scratch resistance. When the content of the coating agent in the transparent film exceeds 0.8% by weight in terms of the solid content, the film strength may not be further improved. The film thickness of the transparent film is preferably in the range of 〇·5 to 2 〇Km. When the film thickness of the transparent film is less than 0.5 μm, sufficient scratch resistance cannot be obtained. When the film thickness of the transparent film exceeds 20 μm, the film shrinks due to shrinkage of the film, or the adhesion to the substrate may be insufficient. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited by the scope of the examples. [Example 1] Cerium oxide. Alumina sol (1) was prepared by adding a pure sodium hydroxide aqueous solution (Si〇2/Na2〇 molar ratio 3.1) having a concentration of Si〇2 of 24% by weight to prepare pure Si. The concentration of 〇2 was 1.2% by weight of a diluted aqueous solution of sodium citrate. In addition, a sodium citrate aqueous solution (SiO 2 /Na20 molar ratio 3.1) having a concentration of S i 0 2 of 5 wt% was subjected to de-testing with a cation exchange resin, and then adjusted to -41 - 201139276 to produce an acidic tannic acid solution (3丨02 The concentration was 4.8% by weight, ?112.8). Continuing, in a concentration of 1.2% by weight of a diluted sodium citrate aqueous solution of 60 1 kg, an acidic citric acid solution (concentration of Si 〇 2 is 4.8 wt%, pH 2.8) 166 kg, and aging at 79 t for 30 minutes to prepare seed particle dispersion. liquid. Continuing, while stirring the seed particle dispersion, the acid tannic acid solution (concentration of SiO 2 was 4.8% by weight, pH 2.8) was continuously added thereto at the same time and for 15 hours, and 5135 kg of aluminate having a concentration of Al2〇3 of 0.6% by weight was used. Aqueous sodium solution 185kg. Subsequently, the film was washed with a limiting filtration membrane, and after concentration, an aqueous dispersion of cerium oxide-alumina fine particles (1) having a concentration of SiO 2 ·Al 2 〇 3 of 30% by weight was prepared. The pH of the cerium oxide-alumina fine particle (1) aqueous dispersion was 9.1. Further, in the cerium oxide. The alumina fine particles (1) had an average particle diameter of 12 nm, an Al2?3 content of 0.10% by weight, and a Na20 content of 〇.5% by weight. Further, the ion concentration was present in the silica sand. The alumina fine particles (1) was 1,500 ppm, and the surface negative charge was 2.2 pq/m2. Continuing, the concentration of SiO 2 · Al 2 〇 3 is 30% by weight of cerium oxide. Alumina granules (1) 600 kg of an aqueous dispersion, and a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) is added to the dispersion. The pH was 2.0 and the separation of the ion exchange resin was continued. (Step (al)) Continuing, an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20A) was added until the pH of the dispersion was 5.0', and the ion exchange resin was further separated to prepare a SiO2 concentration of 27% by weight of SiOrAhO3.氧化铝. Alumina microparticles (1) aqueous dispersion. (Step (a2)) -42- 201139276 The silica sand alumina fine particle (1) obtained herein has a specific surface area of 260 m 2 /g 'the surface negative charge amount is 0.3 ^ ecl / m 2 'Al 2 〇 3 content is 0.07 The weight %, Na2〇 content is 〇.〇2% by weight. Further, the ion concentration is 10 〇 ppm in the silica sand and oxidized fine particles (i). Continue, dilute to S i Ο2 ♦ A12 Ο 3 concentration is 20% by weight, then cerium oxide. Alumina fine particles (1) aqueous dispersion 2000g by solvent filtration method by methanol The concentration of Si02_Al203 was 20% by weight of cerium oxide-alumina fine particle (1) alcohol dispersion. (Step (b)) The content of water in the cerium oxide-alumina fine particle (1) alcohol dispersion liquid was 0.5% by weight. Measurement of the amount of negative charge of cerium oxide-alumina fine particles The 20% by weight of the cerium oxide-alumina fine particle (1) alcohol dispersion was diluted to a solid concentration of 0.5% by weight (in this case, pH 6.5). The surface negative charge amount of the cerium oxide-alumina fine particle (1) is shown in the table. Continuing, the cerium oxide-alumina fine particle (I) alcohol dispersion 200 00 g was adjusted to 25 t, and γ-(meth)acryloxypropyltrimethoxy decane as an organic hydrazine compound was added thereto (Shin-Etsu Chemical ( Stock system · KBM-5 03 ) 60g ( ( Moc ) =0_24 Moer : υίΟ (3) / 2 is 3 wt % )). (Step (c)) Subsequently, the cerium oxide-alumina fine particle (1) alcohol dispersion was stirred at 25 ° C for 0.5 hours to adsorb the organic hydrazine compound. (Step (d -43- 201139276 continued, in the cerium oxide. Alumina granules (1) alcohol dispersion" 1.5 g of ammonia water having a concentration of ammonia of 28% by weight and 7.8 g of pure water (8.78 g of water) Ear number (Mh2〇) = 〇.49, molar ratio (Mh2〇) / (M〇c) = 1.96): ammonia 0.42g (mole number (MNH3) = 0.025, molar ratio (MNH3) / (M 〇c) =〇·1). (Step (e)) Continue, adjust the dispersion to 50 °C for 19 hours of aging. (Step (f)) Surface treatment of the negative charge of cerium oxide and alumina fine particles The measurement was carried out by adding water to the alcohol dispersion of the ceria-alumina fine particle (1) obtained by the aging, and diluting to a solid content concentration of 0.5% by weight. The pH of the dispersion at this time was 7.0. The surface was measured using the dispersion. The surface negative charge amount of the cerium oxide-alumina fine particle (1) was measured, and the results are shown in the table. Further, the obtained dispersion liquid was concentrated by a distillation method while being subjected to solvent substitution with methyl isobutyl ketone. A cerium oxide-alumina sol (1) having a solid concentration of 40% by weight is prepared (step (g)) (step (h)) The cerium oxide-alumina sol (1) has a viscosity of 5 cp and a stability of 5 Å. Moreover, the stability of the sol can be measured by the following accelerated test method. The cerium oxide alumina sol is placed at 90°. C, the time to reach a viscosity of more than 10,000 cp was measured by a viscometer (Toki Industries Co., Ltd.: BL type). -44- 201139276 The coating of the transparent film forming coating (1) will be organic as a trifunctional or more. 6-functional acrylate resin dipentaerythritol hexaacrylate (manufactured by Kyoei Chemical Co., Ltd. LIGHT ACRYLATE DPE-6A) 53 g, 1, 6-hexanediol diacrylate as a bifunctional organic resin (Japan) Pharmaceutical (stock) system: KAYARAD KS-HDDA) 5.9g, a monofunctional polyoxyl resin sheet end methacrylic acid eucalyptus oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X-22-1 74DX) 〇.4g, propylene glycol single 75.5 g of methyl ether and a photopolymerization initiator 2·4·6-trimethylbenzhydryldiphenylphosphine oxide (manufactured by BAS JAPAN: Lucirin TPO) 3.5 g were mixed to prepare a solid component. A matrix of 44% by weight is formed into a component solution (1). 30.0 g of the matrix-forming component solution (1) having a body component concentration of 44% by weight and 30.0 g of a ceria-alumina sol (1) surface-treated with an organic cerium compound having a solid concentration of 40% by weight to prepare a solid The coating liquid for forming a transparent film having a component concentration of 42% by weight (1) » The viscosity of the coating liquid for forming a transparent film (1) was 3 cp. Further, the stability of the coating liquid for forming a transparent film (1) was 5 days. And the stability of the coating liquid was measured by the following accelerated test method. The coating liquid was allowed to stand at 90 ° C, and the viscosity reached a time exceeding 5,000 cp by a viscometer (manufactured by Toki Sangyo Co., Ltd.: BL type). Production of the base film (1) to which the transparent film is applied. The coating liquid for forming a transparent film (1) is easily adhered to a PET film (-45-201139276: Toyobo: Cosmoshine A-4300, thickness 188 μm, total light transmittance 9 2 · 0) %, haze 0.7%) was applied by a bar coating method (rod #1 2 ), and dried at 8 CTC for 1 minute, and then an ultraviolet irradiation device equipped with a high-pressure mercury lamp (120 W/cm) (manufactured by Japanese battery: UV irradiation) The device CS30L21-3) was irradiated with 600 mJ/cm 2 to be cured, and a substrate (1) to which a transparent film was attached was prepared. The thickness of the transparent film at this time was 5 μm. The total light transmittance and haze of the obtained transparent film were measured by a haze tester (manufactured by Nippon Denshoku Co., Ltd.: NDH-2000), and the results are shown in the table. Further, the pencil hardness, the scratch resistance, and the adhesion were evaluated by the following methods and evaluation criteria, and the results are shown in the table. Measurement of pencil hardness The measurement was carried out by a pencil hardness tester in accordance with JIS-K-5400. Further, since the coating material for forming a transparent film of the present invention is a coating liquid which is not stable even at a high concentration, the formed coating film can be prevented from being unstable during exposure to a high temperature, and a dense transparent film can be formed. Thereby, a transparent film having a high pencil hardness can be obtained. That is, the pencil hardness can be used as an indicator of the stability of the paint. The scratch resistance was measured by using #0000steelwool at a load of 500 g/cm2 for 50 times, and the surface of the film was visually observed and evaluated under the following criteria. The results are shown in the table. -46- 201139276 No streaks were confirmed: ◎ Scars were confirmed only on the stripes: 多数 Most of the scars were confirmed on the stripes: △

The surface is fully exploited: X is adhered to the surface of the substrate (1) to which the transparent film is attached, and is cut into 1 格子 grid of 1 parallel flaws at intervals of 1 mm in the longitudinal direction and the transverse direction. (registered trademark) is adhered, and when the tape (registered trademark) is peeled off, the number of cells remaining without peeling off the film is classified into the following four steps to evaluate the adhesion. The results are shown in the table. The number of remaining grids is more than 9 5: ◎ The number of remaining grids is 90 to 94: 〇 The number of remaining grids is 85 to 89: △

The number of remaining lattices was 84 or less. _ X Appearance The substrate (1) to which the transparent film was attached was visually observed for pop-up and film spots, and evaluated according to the following criteria. Pop-up and film spots are not confirmed: ◎ Only a slight pop-up and film spot are confirmed: 〇 Confirmed pop-up and film spots: △

A large number of ejections and film spots were confirmed: X-47-201139276 [Example 2] Preparation of cerium oxide ♦ Alumina sol (2) A seed particle dispersion was prepared in the same manner as in Example 1. While continuing to stir the seed particle dispersion, it was continuously added to the acidic citric acid solution (concentration of SiO 2 of 4.8 wt. / 〇, pH 2.8) of 5042.5 kg and aluminum of 0.6 wt% of Al2〇3 at the same time for 15 hours. The sodium acid aqueous solution was continued at 924.3 kg, and was washed with a limiting filtration membrane and concentrated to prepare a silica dispersion of oxidized sand and oxidized fine particles (2) having a concentration of Si 02 · Al 2 〇 3 of 30% by weight. The pH of the cerium oxide-alumina fine particle (2) aqueous dispersion was 9.1. Further, the average particle diameter of the cerium oxide-alumina fine particles (2) was 12 nm, the content of Al2?3 was 0.50% by weight, and the content of Na20 was 0.5% by weight. Further, when the ion concentration was further added to the cerium oxide-alumina fine particles (2), it was 1,5 50 ppm, and the surface negative charge amount was 2.8 pq/m 2 . Continuing to add cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) to 600 kg of a concentration of 30% by weight of cerium oxide-alumina fine particles (2) in a dispersion of Si02.Al203 until the pH of the dispersion reaches 2.0. , and then separate the ion exchange resin. (Step (al)) Next, an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20A) is added until the pH of the dispersion reaches 5.0' and the ion exchange resin is separated to prepare a concentration of S i 0 2 · A12 〇3. It is a water dispersion of 27% by weight of silica sand·alumina fine particles (2). (Step (a2)) The obtained cerium oxide. The alumina fine particle (1) has a specific surface area of -48 to 201139276 269 m2 / g. The surface negative charge amount is 〇.6 peq/m 2 and the Al 2 〇 3 content is 0.41 by weight. The %' NazO content was 0.04% by weight. Further, the ion concentration was 1200 ppm in the cerium oxide-alumina fine particles (1). Then, after diluting to a concentration of Si〇2·Al2〇3 of 20% by weight, 2000 g of an aqueous dispersion of cerium oxide. Alumina fine particles (2) was subjected to solvent substitution by methanol to prepare SiO 2 by a limiting filtration membrane method. The concentration of Al2〇3 is 20% by weight of a ceria-alumina fine particle (2) alcohol dispersion. (Step (b)) The content of water in the cerium oxide-alumina fine particle (2) alcohol dispersion is 0.5% by weight. /〇. The surface negative charge amount of the cerium oxide. Alumina fine particles (2) was measured in the same manner as in Example 1. The results are shown in the table. Continuing, the cerium oxide. Alumina granule (2) alcohol dispersion 2 〇〇〇g was adjusted at 25 ° C. Here, (meth) propylene oxypropyl trimethoxy decane was added as an organic hydrazine compound (Shin-Etsu Chemical (stock) system: KBM-503) 60g ((Moc) =0.24 Mohr: υίΟ(3)/2 is 3 wt%)). (Step (c)) Next, the ceria-alumina fine particle (2) alcohol dispersion was stirred at 25 ° C for 0.5 hours to adsorb the organic ruthenium compound. (Step (d)) Next, 1.5 g of ammonia water having a concentration of ammonia of 28% by weight and 7.8 g of pure water (7.88 g of water (molar number) were added to the cerium oxide-alumina fine particle (2) alcohol dispersion. MH2〇) = 0.49, Mo Er ratio (MH20) / (Moc) -1_96) • Air enthalpy _42g (Mole number (Mnh3) = 0.025 ' Mohr ratio (Mnh3) / (M〇c) = 0.1). (Step (e)) -49 - 201139276 Next, the dispersion was adjusted to 5 Torr, and aging was carried out for 19 hours. (Step (f)) Next, as in Example 1, surface-treated cerium oxide-alumina fine particles were measured ( 2) The surface negative charge amount' results are shown in the table. Next, the methyl isobutyl ketone is subjected to solvent substitution by distillation to concentrate the silica sand oxide alumina sol having a solid concentration of 40% by weight. (2) » (Step (g)) (Step (h)) The viscosity of the cerium oxide-alumina sol (2) is 5 cp 'The stability is 6 Å. The preparation example of the coating film (2) for transparent film formation In the same manner, a solid content concentration of 42% by weight was prepared in the same manner as in the case of the alumina sol (2) having a solid concentration of 40% by weight. The coating liquid for forming a transparent film (2). The coating liquid for forming a transparent film (2) has a viscosity of 5 cp and a stability of 5 Å. In the production example 1 of the substrate (2) to which the transparent film is attached, In the same manner as the coating liquid (2) for forming a transparent film, the substrate (2) to which the transparent film was applied was prepared in the same manner. The thickness of the transparent film at this time was 5 μm. The total light transmittance and haze of the obtained transparent film were measured. The pencil hardness, the scratch resistance, and the adhesion are shown in the table. -50-201139276 [Example 3] Preparation of cerium oxide* alumina sol (3) In the same manner as in Example 1, seed particles were prepared. Next, while stirring the seed particle dispersion, the acid citric acid solution (the concentration of SiO 2 was 4.8 wt%, pH 2.8) was continuously added thereto for 15 hours. The concentration of 458 kg and Al 2 〇 3 was 0.6 wt. 4621.7 kg of a sodium aluminate aqueous solution. Then, it was washed with a limiting filtration membrane and concentrated to prepare an aqueous dispersion of cerium oxide alumina fine particles (3) having a concentration of SiO 2 .Al 203 of 30% by weight. .Alumina Microparticles (3) Aqueous Dispersion The pH was 9.1. Further, the average particle diameter of the cerium oxide-alumina fine particles (3) was 13 nm, the content of Al2〇3 was 2.50% by weight, and the content of Na20 was 0.6% by weight. Further, the ion concentration was in cerium oxide. The alumina fine particles (3) are 1700 ppm, and the surface negative charge is 3.1 μq/m 2 . Then, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added to 600 kg of a concentration of 30% by weight of cerium oxide alumina fine particles (3) in a concentration of SiO 2 .Al 2 〇 3 to reach the pH of the dispersion. 2.0, Separating the ion exchange resin. (Step (al)) Next, an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20 A) was added until the pH of the dispersion reached 5.0, and the ion exchange resin was separated to prepare a concentration of S i 0 2 · A12 0 3 It is a water dispersion of 27% by weight of cerium oxide-alumina fine particles (3). (Step (a2)) The specific surface area -51 - 201139276 of the cerium oxide-alumina fine particles (3) obtained herein is 282 m 2 /g 'the surface negative charge amount is 〇.8 peq/m 2 , A 】 2 〇 3 content The content of 1.9 wt% 'Na20 is 〇.05 wt%. Further, the ion concentration was 115 ppm in the cerium oxide-alumina fine particles (3). Then, after diluting to a concentration of SiO 2 . Al 2 〇 3 of 20% by weight, 2000 g of an aqueous dispersion of cerium oxide alumina fine particles (3) was subjected to solvent substitution by methanol to prepare SiO 2 · Al 2 藉 by a limiting filtration membrane method. The concentration of 3 is 20% by weight of cerium oxide-alumina fine particle (3) alcohol dispersion. (Step (b)) The content of water in the cerium oxide-alumina fine particle (3) alcohol dispersion liquid is 0.5% by weight. The surface of the cerium oxide-alumina fine particle (3) is measured in the same manner as in the first embodiment. The charge amount' results are shown in the table. Continue to 'adjust the cerium oxide. Alumina granule (3) alcohol dispersion 2000g to 25 ° C' here to add γ_(methyl) propyl propyl propyl dimethoxy sand as an organic bismuth compound (Xin Yue Chemical (stock) system: KBM-5 03 ) 60g ( ( Moc) = 〇 · 24 Moule: υίΟ (3) / 2 is 3 wt%)). (Step (c)) Next, the cerium oxide. Alumina fine particle (3) alcohol dispersion was stirred at 25 ° C for 5 hours to adsorb the organic hydrazine compound. (Step (d)) Next, 1.5 g of ammonia water having a concentration of ammonia of 28% by weight and 7.8 g of pure water (8.78 g of water (molar number of MH20) were added to the cerium oxide-alumina fine particle (3) alcohol dispersion. =0.49, molar ratio (MH20) / (Moc) = 1.96): ammonia 0.42 g (mole number (mnh3) = 0.025, molar ratio (

Mnh3) /(M〇c) =〇·1). (Step (e)) -52- 201139276 The dispersion was then adjusted to 5 Torr for 19 hours of ripening. v (f)) Next, the surface negative charge amount of the surface-treated cerium oxide microparticles (3) was measured in the same manner as in Example 1. The results are shown in the table. Subsequently, the mixture was concentrated by a solvent distillation with methyl isobutyl ketone to prepare a cerium oxide-alumina sol (3) having a solid concentration of 4% by weight. (Step (g)) (Step (h)) Ceria. The viscosity of the alumina sol (3) was 7 cP' stability was 6.5 days. Preparation of the coating film (3) for transparent film formation In Example 1, the solid content concentration was 4 〇. In the same manner as the alumina sol (3), the coating liquid (3) for forming a transparent film having a solid concentration of 42% by weight was prepared in the same manner. The viscosity of the coating liquid (3) for forming a transparent film was 8 cp' stability for 6 days. Production of the base material (3) to which the transparent film is applied. In the first embodiment, the base material (3) to which the transparent film is attached is prepared in the same manner as the coating liquid (3) for forming a transparent film. The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness, scratch resistance, and adhesion of the obtained transparent film were measured, and the results are shown in the table. -53-201139276 [Example 4] Preparation of cerium oxide-alumina sol (4) A seed particle dispersion liquid was prepared in the same manner as in Example 1. Next, while stirring the seed particle dispersion, the acidic citric acid solution (the concentration of SiO 2 was 4.8% by weight, pH 2.8) was continuously added thereto at 15 hours, and the concentration of 6512〇3 and Α12〇3 was 0.6% by weight. The sodium aluminate solution was 919 kg. Subsequently, it was washed with a limiting filtration membrane and concentrated to prepare a water-dispersed silica sand alumina fine particle (4) having a concentration of SiO 2 ·Al 2 〇 3 of 30% by weight. The pH of the cerium oxide-alumina fine particle (4) aqueous dispersion was 9.1. Further, the average particle diameter of the cerium oxide-alumina fine particles (4) was 25 nm, the content of Al2〇3 was 0.10% by weight, and the content of Na20 was 0.9% by weight. Further, when the ion concentration was present in the ceria-alumina fine particles (4), it was 2,400 ppm, and the surface negative charge was 3.3 pq/m2. Then, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added to 600 kg of an aqueous dispersion of cerium oxide alumina fine particles (4) having a concentration of 30% by weight of SiO 2 . Al 203 to reach a pH of the dispersion to 2·· 0 'Separate ion exchange resin. (Step (al)) Next, an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20A) was added until the pH of the dispersion reached 5.0, and the ion exchange resin was separated to prepare SiO 2 . The concentration of Al 2 〇 3 was 27% by weight. An aqueous dispersion of cerium oxide-alumina fine particles (4). (Step (a2)) wherein the obtained cerium oxide. The alumina fine particles (4) have a specific surface area of -54 to 201139276 of 120 m2/g, a surface negative charge of 〇.2peq/m2, and an Al2〇3 content of 0.07 by weight. The % 'Na20 content is 〇.〇2% by weight. Further, the ion concentration was 230 ppm in the cerium oxide-alumina fine particles (4). After diluting to a concentration of si 〇 2 · ai 2 〇 3 of 20% by weight, the cerium oxide. Alumina granule (4) aqueous dispersion 2 00 g was replaced by a solvent by a limiting filtration membrane method. A cerium oxide-alumina fine particle (4) alcohol dispersion having a concentration of si 〇 2 · ai 2 o 3 of 20% by weight was prepared. (Step (b)) The content of water in the cerium oxide ♦ alumina fine particle (4) alcohol dispersion was 0.5% by weight. The surface negative charge amount of the ceria-alumina fine particles (4) was measured in the same manner as in Example 1. The results are shown in the table. Continuing to adjust the cerium oxide-alumina microparticle (4) alcohol dispersion 200 g to 2 5 ° C, and add γ-(meth) propyleneoxypropyl trimethoxy decane as an organic hydrazine compound. (Shin-Etsu Chemical Co., Ltd.: 1^81^-503) 60g ((M〇c) = 〇·24 Mo Er: Ri-SiOo) / 〗 〖3 wt%)). (Step (c)) Next, the cerium oxide-alumina fine particle (4) alcohol dispersion was stirred at 25 ° C for 0.5 hour to adsorb the organic ruthenium compound. (Step (d)) Next, an ammonia water having a concentration of 28% by weight of ammonia was added to the alcohol dispersion of cerium oxide-alumina fine particles (4), and 7.8 g of pure water (8.78 g of water (molar number) (Mh2〇) = 〇.49, Moh ratio (Mh2〇) / (Moc) = 1.96): gas 〇 _42g (number of ears (Μνη3) = 〇 · 〇 25, molar ratio (MNH3) / (M 〇c) = 0.1) ° (Step (e)) -55- 201139276 Next, the dispersion was adjusted to 5 (TC, and aging was carried out for 19 hours. (Step (f)) Next, the surface treatment was measured in the same manner as in Example 1. The surface negative charge amount of the cerium oxide-alumina fine particles (4) is shown in the table. The solvent is then subjected to solvent distillation with methyl isobutyl ketone by distillation to prepare a solid concentration of 40% by weight. Cerium oxide. Alumina sol (4). (Step (g)) (Step (h)) The viscosity of cerium oxide-alumina sol (4) is 丨7 cp, and the stability is 4 days. Coating for transparent film formation In the preparation example 1 of (4), the solid content concentration was 42% by weight, except that the cerium oxide alumina sol (4) having a solid concentration of 40% by weight was used. The coating liquid for forming a transparent film (4). The coating liquid for forming a transparent film (4) has a viscosity of 20 cp and a stability of 5 Å. In the production example 1 of the substrate (4) to which the transparent film is attached, In the same manner as the coating liquid for forming a transparent film (4), the substrate (4) to which the transparent film was applied was prepared in the same manner. The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, and transparency of the obtained transparent film were measured. The pencil hardness, the scratch resistance, and the adhesion were as follows. -56-201139276 [Example 5] Preparation of cerium oxide. Alumina sol (5) The seed particle dispersion was prepared in the same manner as in Example 1. Next, while stirring the seed particle dispersion, the acidic citric acid solution (the concentration of s i0 2 was 4.8% by weight, pH 2.8) was continuously added thereto at 15 hours, and the concentration of 200 kg and Al 2 〇 3 was 0.6% by weight. The aqueous solution of sodium aluminate was 7,354 kg, and then washed with a limiting filtration membrane and concentrated to prepare an aqueous dispersion of cerium oxide-alumina fine particles (5) having a concentration of S i Ο 2 · Al 2 〇 3 of 30% by weight. Cerium oxide·alumina fine particles (5) water dispersion The pH of the cerium oxide-alumina fine particles (5) is 45 nm > the content of Al203 is 0.10% by weight, and the content of Na20 is 1.2% by weight. The ion concentration was 3,600 ppm in the ceria-alumina fine particles (5), and the surface negative charge was 3.4 pq/m2. Then, a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added to 600 kg of a concentration of 30% by weight of cerium oxide alumina fine particles (5) in a concentration of 30% by weight of Al2〇3 to reach the pH of the dispersion. 2.0' Separate ion exchange resin. (Step (a 1 )) Next, an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20A) was added until the pH of the dispersion reached 5.0, and then the ion exchange resin was separated to prepare SiO 2 . The concentration of Al 2 〇 3 was 27% by weight. The cerium oxide. Alumina granules (5) aqueous dispersion. (Step (a2)) The specific surface area of the cerium oxide-alumina fine particles (5) obtained herein is -57-201139276 is 68 m2/g. The surface negative charge amount is 〇.lpeq/m2, and the Al2〇3 content is 0.09. The % by weight 'Na20 content was 0.23% by weight. Further, the ion concentration was 380 ppm in the cerium oxide-alumina fine particles (5). After diluting to a concentration of SiO 2 —Al 203 of 20% by weight, 2000 g of cerium oxide. Alumina granules (5 ) aqueous dispersion was replaced by a solvent by a limiting filtration membrane method to prepare si 〇 2. The concentration of ai 2 o 3 was 20% by weight of cerium oxide-alumina fine particle (5) alcohol dispersion. (Step (b)) The content of water in the cerium oxide-alumina fine particle (5) alcohol dispersion liquid is 0 · 5 wt% » The cerium oxide. The alumina fine particle (5) is measured in the same manner as in the first embodiment. The surface has a negative charge and the results are shown in the table. Continuing, the cerium oxide-alumina fine particle (5) alcohol dispersion 200 00 g was adjusted to 25 ° C, and γ-(meth)acryloxypropyltrimethoxy decane as an organic hydrazine compound was added thereto (Shin-Etsu Chemical (stock). System: KBM-503) 60g ((Moc) = 0.24 Mohr: Ri-SiOo). 3 weight %)). (Step (c)) Next, the cerium oxide-alumina fine particle (5) alcohol dispersion was stirred at 25 ° C for 0.5 hours, and then the organic hydrazine compound was adsorbed. (Step (d)) Next to the cerium oxide-alumina fine particle (5) alcohol dispersion, as an ammonia addition concentration of 28% by weight of ammonia water 1. 5 g and pure water 7.8 g (water 8.7 8 g (mole number) (MH2〇) = 〇_49, molar ratio (MH20) / (Moc) = 1.96): ammonia 0.42g (mole number (MNH3) = 0.025, molar ratio (MnH3) / (M〇c) = 0.1 (Step (e)) -58- 201139276 Next, the dispersion was adjusted to 5 ° C for 19 hours of aging. (v (1)) Next, the surface treated silica sand * oxygen 1 was measured in the same manner as in Example 1. The surface of the aluminum microparticles (5) has a negative charge amount, and the results are shown in the table. Next, the solvent is substituted by methyl isobutyl ketone by distillation to prepare a silica sand having a solid concentration of 40% by weight. Alumina sol (5). (Step (g)) (Step (h)) Ceria. The viscosity of the alumina sol (5) is 2 5 cp 'The stability is 3 days. The coating for transparent film formation (5) In the same manner as in the preparation example 1, a transparent film having a solid concentration of 42% by weight was prepared in the same manner as in the case of the ceria-alumina sol (5) having a solid concentration of 40% by weight. The coating liquid (5) for forming the coating film (5) for transparent film formation has a viscosity of 3 2 cp, and the stability is 5 days. In the production example 1 of the substrate (5) to which the transparent film is attached, a transparent film is used. The base material (5) to which the transparent film was attached was prepared in the same manner as in the coating liquid (5). The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness of the obtained transparent film were measured. The results are shown in the table. -59-201139276 [Example 6] Preparation of cerium oxide-alumina sol (6) In Example 1, methyl isobutyl group was distilled by distillation. The ketone was concentrated while being solvent-substituted, and a cerium oxide-alumina sol (6) having a solid concentration of 60% by weight was prepared (step (g)) (step (h)) cerium oxide-alumina sol (6) The viscosity is 12 Ocp, and the stability is 3 days. Preparation and mixing of the coating film for transparent film formation (6) The tetrafunctional acrylate resin pentaerythritol tetraacrylate which is a trifunctional or higher organic resin (manufactured by Kyoei Chemical Co., Ltd.) :LIGHT ACRYLATE PE-4 A ) 53g, as 1,6-hexanediol diacrylate (Nippon Chemical Co., Ltd. HDDA) of a bifunctional organic resin, 5.9 g, and a terminal methacrylic acid eucalyptus oil as a monofunctional polyoxyl resin (Shin-Etsu Chemical Co., Ltd.) · X-22- 1 74DX) 〇.4g, propylene glycol monomethyl ether 33.4g, and photopolymerization initiator 2·4.6-trimethylbenzhydryldiphenylphosphine oxide (BAS JAPAN) : Lucirin TPO ) 3. 5 g, a matrix-forming component solution (2 ) having a solid concentration of 64% by weight was prepared. Next, a matrix-forming component solution (2) having a solid content concentration of 64% by weight (2) and a solid solution of cerium oxide (6) 30.0 g of a surface treatment of 60% by weight of an organic cerium compound were mixed to prepare a solid. The coating liquid for forming a transparent film having a composition concentration of 62% by weight (6-60-201139276 The coating liquid for forming a transparent film (6) has a viscosity of 1 1 〇 cp 'the stability is 3 days. The substrate to which the transparent film is attached ( (6) The coating liquid for forming a transparent film (6) was applied to a PET film (manufactured by Toyo-be: Cosmoshine A-4300, thickness 188 μm, total light transmittance: 92.0%, haze 0.7%) by bar coating method ( Bar #1 〇) Coating was performed at 80 ° C for 1 minute, and then subjected to a high-pressure mercury lamp (12 〇 W/cm) ultraviolet irradiation device (manufactured by Nippon Battery: UV irradiation device CS30L2 1-3) for 600 mJ/ The substrate (6) to which the transparent film was attached was prepared by irradiation with cm2, and the thickness of the transparent film at this time was 5 μm. [Example 7] Preparation of cerium oxide-alumina sol (7) In Example 1, By distillation with methyl isobutyl ketone Concentration with a solvent was carried out to prepare a ceria-alumina sol (7) having a solid concentration of 70% by weight. (Step (g)) (Step (h)) Ceria. Alumina sol (7) The viscosity is 78 Ocp, and the stability is 2 days. Preparation and mixing of the coating film for transparent film formation (7) The 6-functional acrylate resin dipentaerythritol hexaacrylate which is a trifunctional or higher organic resin (manufactured by Kyoritsu Chemical Co., Ltd.): LIGHT ACRYLATE DPE-6A ) 53g, as a 2-functional organic tree-61 - 201139276 Lipid 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd.: KAYARAD KS-HDDA) 5.9g, as a 1-functional poly Molybdenum resin end-end methacrylic acid eucalyptus oil (Shin-Etsu Chemical Co., Ltd.: X-22· 174DX) 0.4 g, propylene glycol monomethyl ether 25.4 g, and photopolymerization initiator 2.4.6-trimethylbenzene Methyl decyl diphenylphosphine oxide (manufactured by BAS JAPAN Co., Ltd.: LucirinTPO) 3.5 g, and a matrix-forming component solution (3) at a solid concentration of 74% by weight was prepared. Then, a matrix of 74% by weight of the solid component concentration was formed. Ingredient solution (3) 30.0g and concentrated with solid ingredients 30.0 g of a cerium oxide-alumina sol (7) which was surface-treated with a 70% by weight organic cerium compound, and a coating liquid for forming a transparent film (72) having a solid concentration of 72% by weight was prepared. The liquid (7) has a viscosity of 960 cp and the stability is 1 day. Manufacture of a substrate (7) to which a transparent film is applied. The coating liquid for forming a transparent film (7) is easily adhered to a PET film (Toyobo: Cosmoshine A-4300) , thickness Ι88μπι, total light transmittance 92.0%, haze 0.7%) was applied by bar coating method (rod #9), dried at 80 ° C for 1 minute, and then equipped with high-pressure mercury lamp (1 2 0 W) /mm) The ultraviolet irradiation device (Japanese battery system·UV irradiation device CS30L21-3) is irradiated and cured by 600 m J / c m2 to prepare a substrate (9) to which a transparent film is attached. The thickness of the transparent film at this time was 5 μm. -62-201139276 [Example 8] Preparation of coating film (8) for transparent film formation In Example 1, 'further as a coating agent, a special lanthanide coating agent (made by Nanben Chemical Co., Ltd.: Disparlon #1711) 〇. In the same manner as in Example 1, a matrix-forming component solution (4) having a solid concentration of 44% by weight was prepared in the same manner. Then, 30.0 g of a matrix-forming component solution (4) having a solid concentration of 44% by weight was mixed and prepared in the same manner as in Example 1. The solid content concentration was 40% by weight. /. The cerium oxide-alumina sol (1) 30. 〇g of the organic cerium compound was surface-treated to prepare a coating liquid (8) for forming a transparent film having a solid concentration of 42% by weight. The viscosity of the coating liquid (8) for forming a transparent film was 3 cp. Further, the stability of the coating liquid (8) for forming a transparent film was 5 Å. Production of the base material (8) to which the transparent film is applied. In the first embodiment, the base material (8) to which the transparent film is attached is prepared in the same manner as the coating liquid (8) for forming a transparent film. The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness, scratch resistance, and adhesion of the obtained transparent film were measured, and the results are shown in the table. [Comparative Example 1] Preparation of cerium oxide-alumina sol (R 1 ) In the same manner as in Example 1, SiO 2 .Al 203 which was used as a raw material for washing -63-201139276 net 'concentration with a limit filtration membrane was prepared. An aqueous dispersion of cerium oxide-alumina fine particles (1) having a concentration of 30% by weight. Then, after diluting to a concentration of Si〇2*Al2〇3 of 20% by weight, 2000 g of the aqueous dispersion of cerium oxide 'alumina fine particles (1) was subjected to solvent substitution by methanol to prepare SiO 2 by a limiting filtration membrane method. The concentration of Al203 is 10% by weight of cerium oxide-alumina fine particles (R alcohol dispersion. (Comparative step (b)) The content of water in the cerium oxide-alumina fine particle (R 1 ) alcohol dispersion is 〇·8 wt%. The surface negative charge amount of the cerium oxide-alumina fine particles (R 1 ) was measured in the same manner as in the examples, and the results are shown in the table. Continue to 'put the cerium oxide·alumina fine particles (r丨) The alcohol dispersion was adjusted to 25 ° C. The γ-(meth)acryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503) was added as an organic ruthenium compound 60 g ( (M 〇c) = 〇.24 Mohr: RrSiOp)" is 3 wt%)) (Step (c) is equivalent) Next, the cerium oxide. Alumina granule (R 1 ) alcohol dispersion is carried out at 25 ° C. · 5 hours of stirring, adsorption of organic cerium compounds. (Step d) is equivalent) followed by cerium oxide Microparticle (R 1 ) alcohol dispersion, as ammonia added concentration of 28% by weight of ammonia water 1 · 5 g and pure water 7.8 g (water 8.78g (mole number (Mh2〇) = 0.49, molar ratio (MH20) / (m〇c) = 1.96) '·Ammonia. 42g (mole number (mNH3) = 0.025, Mo ratio (

Mnh3) / (Moc) = 0.1). (Step (e) is equivalent) -64- 201139276 Next, the dispersion was adjusted to 50 °c' for 19 hours of aging. (Step (f) is equivalent) Next, the surface negative charge amount of the surface-treated silica sand·aluminum oxide fine particles (R1) was measured in the same manner as in Example 1. The results are shown in the table. Subsequently, the mixture was concentrated by a solvent distillation with methyl isobutyl ketone to prepare a silica sand oxidized aluminum sol (R1) having a solid concentration of 40% by weight. (Step (g) is equivalent) (Step (h) is equivalent) Ceria. The alumina sol (R1) has a viscosity of 240 cp and a stability of 〇. In the preparation example 1 of the coating material for forming a transparent film (R1), a transparent film having a solid concentration of 42% by weight was prepared in the same manner as in the case of using a cerium oxide alumina sol (R1) having a solid concentration of 20% by weight. Coating liquid (R1). The viscosity of the coating liquid for forming a transparent film (R1) was 360 cp' and the stability was 0.5 day. In the first embodiment, the substrate (R 1 ) to which the transparent film is attached is prepared in the same manner as in the first embodiment except that the coating liquid for forming a transparent film (R1 ) is used. The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness, scratch resistance, and adhesion of the obtained transparent film were measured, and the results are shown in the table. -65-201139276 [Comparative Example 2] Preparation of cerium oxide. Alumina sol (R2) In Comparative Example 1, 'γ-(meth)acryloxypropyltrimethoxydecane was added as an organic ruthenium compound (Shin-Etsu Chemical ( Stock system: ΚΒΜ-503) 120g ((Moc) =0.48 Mohr: Rl-Si〇(3)/2 is 6 wt%)). (Step (c) is equivalent) The work is to add ammonia concentration of 28% by weight of ammonia water to 7.5 g and pure water of 7.8 g (water 8.78 g (mole number (mh20) = 0.49, molar ratio (Mh2 〇) / ( M〇c ) = 1.00): 0.42 g of ammonia (molar number (Mnh3) = 〇.〇25, molar ratio (MNH3) / (Moc) = 〇·〇5) (step (e)), similarly A cerium oxide alumina sol (R2) having a solid concentration of 40% by weight was prepared. (Step (g)) (corresponding to step (h)) The viscosity of the cerium oxide alumina sol (R2) was 120 cp, and the stability was obtained. Further, after the above step (f), the surface negative charge amount of the surface-treated cerium oxide-alumina fine particles (R2) was measured in the same manner as in Example 1. The results are shown in the table. In the preparation example 1 of (R2), a coating liquid for forming a transparent film (R2) having a solid concentration of 42% by weight was prepared in the same manner as in the case of using a cerium oxide alumina sol (R2) having a solid concentration of 40% by weight. The viscosity of the coating liquid for forming a transparent film (R2) is 23 〇 cp 'The stability is 1 曰. -66- 201139276 The substrate (R2) to which the transparent film is attached In the same manner as in the first embodiment, the substrate (R2) to which the transparent film was applied was prepared in the same manner as in the case of using the coating liquid for forming a transparent film (R 2 ). The thickness of the transparent film at this time was 5 μm. The obtained transparent film was measured. The total light transmittance, the haze, the pen hardness, the scratch resistance, and the adhesion were as shown in the table. [Comparative Example 3] Preparation of cerium oxide-alumina sol (R3) In Example 1, in the step (c) Immediately after the adhesion (step (e)), the cerium oxide alumina sol (R3) having a solid concentration of 40% by weight was prepared in the same manner. The viscosity of the cerium oxide alumina sol (R3) The stability was 4 days, and after the above step (f), the surface negative charge amount of the surface-treated ceria-alumina fine particles (R3) was measured in the same manner as in Example 1. The results are shown in the table. In the preparation example 1 of the coating material for forming a transparent film (R3), a transparent film having a solid concentration of 42% by weight was prepared in the same manner as in the case of using a cerium oxide alumina sol (R3) having a solid concentration of 40% by weight. Coating solution (R3) The coating liquid for forming a transparent film (R3) has a viscosity of 5 cp and a stability of 3 Å. -67 - 201139276 Production of a substrate (R3) to which a transparent film is attached. In the first embodiment, a coating liquid for forming a transparent film is used. In the same manner as in R3, the base material (R3) to which the transparent film was applied was prepared in the same manner. The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness, scratch resistance, and density of the obtained transparent film were measured. The results are shown in the table. [Comparative Example 4] Preparation of cerium oxide organosol (R4): cerium oxide sol (made by day-to-smooth formation): CATALOID SI-30, average particle diameter: 12 nm, SiO 2 concentration: 30% by weight, Al2 in the particles 〇3 content 〇% by weight, ^2〇 content is 0.4% by weight, ρΗ9·3, ion concentration: 1300 ppm in cerium oxide microparticles, surface negative charge 1.9 peq/m2) diluted to SiO 2 concentration After being 20% by weight, the cerium oxide microparticle dispersion 2000 g was subjected to solvent substitution by a limiting filtration membrane method to prepare a cerium oxide microparticle (R4) having a SiO 2 concentration of 20% by weight. Alcohol dispersion. (Step (b) is equivalent) The content of water in the cerium oxide microparticle (R4) alcohol dispersion is 0.5% by weight. The surface negative charge amount of the cerium oxide microparticles (R4) was measured in the same manner as in Example 1. The results are shown in the table. Continuing, the cerium oxide microparticle (R4) alcohol dispersion 2000 g was adjusted to 25 ° C, and γ-(meth) propylene-68-201139276 oxypropyltrimethoxy decane (Xin Yue Chemical) as an organic ruthenium compound was added thereto. (Stock) system: ΚΒΜ-503) 6〇g ((Moc) = 0.24 Mohr: Ri-SiOn). 3.% by weight)). (Step (c) is equivalent) Next, the cerium oxide microparticle (R4) alcohol dispersion was stirred at 25 ° C for 0.5 hours to adsorb the organic hydrazine compound. (Step (d) is equivalent) Next, in the cerium oxide microparticle (R4) alcohol dispersion, 1.5 g of ammonia water having a concentration of ammonia of 28% by weight and 7.8 g of pure water (7.88 g of water (MH20) = 0.49, molar ratio (MH20) / (Moc) = 1·96): 0.42 g of ammonia (mole number (MNH3) = 0.025, molar ratio (ΜΝΗ3) / (Moc) = 0.1). (Step (e) Then, the dispersion was adjusted to 50 ° C, and aging was carried out for 19 hours. (Step (f) was equivalent.) Next, the surface negative charge amount of the surface-treated silica sand fine particles (R4 ) was measured in the same manner as in Example 1. As shown in the table, the silica oxide sol (R4) having a solid concentration of 40% by weight is prepared by a solvent distillation with methyl isobutyl ketone by distillation to prepare a solution (step (g)) (step ( h) equivalent) The viscosity of the cerium oxide sol (R4) is 3 60 cP 'the stability is 0.5 曰. Preparation of the coating film for transparent film formation (R4) In Example 1, a solid concentration of 40% by weight is used. In addition to the alumina sol (R4), a transparent film having a solid concentration of 42% by weight was prepared in the same manner. Cloth liquid (R4) ° -69- 201139276 The coating liquid for forming a transparent film (R4) has a viscosity of 450 cp and a stability of 0.5 Å. In the production example 1 of the substrate (R4) to which a transparent film is attached, a transparent film is used. The base material (R4) to which the transparent film was attached was prepared in the same manner as in the coating liquid (R4). The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness of the obtained transparent film were measured. The results are shown in the table. [Comparative Example 5] Preparation of cerium oxide organosol (R5): cerium oxide sol (made by day-to-smooth formation: CATALOID SI-30, The average particle diameter is 12 nm, the SiO 2 concentration is 30% by weight, the Al2〇3 content in the particles is 0% by weight, the Na20 content is 0.4% by weight, ρΗ9·3, and the ion concentration is 1300 ppm in the cerium oxide microparticles, and the surface is negative. After the amount of charge is 1.9 pq/m 2 ), the concentration of SiO 2 is diluted to 20% by weight, and then cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) is added to 600 kg of the aqueous dispersion of cerium oxide microparticles (R5) to reach dispersion. The pH of the solution is 2.0, and then separated Sub-exchange resin. (Step (a 1 ) is equivalent) Next, an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SA-20 A) is added until the pH of the dispersion reaches 5.0, and the ion exchange resin is separated to prepare S i 0 2 The concentration is 27% by weight of cerium oxide microparticles (R 5 ) water-70-201139276 dispersion. (Step (a2) is equivalent) The specific surface area of the cerium oxide microparticles (R5) obtained herein is 251 m2/g', the surface negative charge amount is 〇beq/m2, and the Al2〇3 content is 〇% by weight' NhO content is 〇.〇 2% by weight. Further, the ion concentration was converted to 11 ppm in the cerium oxide fine particles (R5). After diluting to a concentration of SiO 2 of 20% by weight, 2000 g of an aqueous dispersion of cerium oxide microparticles (R5) was substituted with methanol by a limiting filtration membrane method to prepare cerium oxide having a SiO 2 concentration of 20% by weight. Microparticle (R5) alcohol dispersion. (Step (b) is equivalent) The content of water in the cerium oxide microparticle (R5) alcohol dispersion is 〇. 5 wt%. The surface negative charge amount of the cerium oxide microparticles (R5) was measured in the same manner as in Example 1. The results are shown in the table. Continue to 'adjust the cerium oxide microparticle (R5) alcohol dispersion 2000g to 25 °C' here to add γ-(meth) propyleneoxypropyl trimethoxy chopper as an organic bismuth compound (Xin Yue Chemical Co., Ltd.) System: ΚΒΜ-503) 60g ((Moc) = 0.24 Mohr: R^SiOo) /;; is 3% by weight)). (Step (c) is equivalent) Next, the cerium oxide microparticle (R5) alcohol dispersion was stirred at 25 ° C for 5 hours to adsorb the organic hydrazine compound. (Step (d) is equivalent) Next, 1.5 g of gas water having a concentration of ammonia of 28% by weight and 7.8 g of pure water (8.78 g of water (Mh2〇) = 0 ml of ammonia concentration is added to the alcohol dispersion of cerium oxide microparticles (R5). 0.49, molar ratio (MH20) / (Moc) = 1.96): ammonia 0.42 g (moles (Mnh3) = 0.025, molar ratio (MNH3) / (Moc - 71 - 201139276) = 〇.l). Step (e) is equivalent. Next, the dispersion is adjusted to 50 ° C, and aging is carried out for 19 hours. (Step (f) is equivalent.) Next, the surface negative charge amount of the surface-treated silica sand fine particles (R5) is measured in the same manner as in Example 1. The results are shown in the table. Next, the solvent is substituted with methyl isobutyl ketone by distillation to concentrate, and a cerium oxide sol (R5) having a solid concentration of 40% by weight is prepared (step (g)) (step (g)) Step (h) is equivalent. The viscosity of the cerium oxide sol (R5) is 8 cp, and the stability is 4 Å. Preparation of the coating film for transparent film formation (R5) In Example 1, a cerium oxide having a solid concentration of 40% by weight is used. In the same manner as in the case of the alumina sol (R5), a coating liquid for forming a transparent film having a solid concentration of 42% by weight was prepared ( R5) The viscosity of the coating liquid (R5) for forming a transparent film is 12 cp, and the stability is 4 days. In the production example 1 of the base film (R5) to which the transparent film is attached, a coating liquid for forming a transparent film (R5) is used. In the same manner, the base material (R5) to which the transparent film was attached was prepared in the same manner. The thickness of the transparent film at this time was 5 μm. The total light transmittance, haze, pencil hardness, scratch resistance, and adhesion of the obtained transparent film were measured. 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Claims (1)

201139276 VII. Patent application scope: 1. A method for producing cerium oxide-alumina sol, which is characterized by the following steps (a) to (f), (a) having an average particle diameter of 5 to 100 nm. In the range, the alumina content in the particles is 〇1 to 5 by weight in terms of Al2〇3. /. The range of cerium oxide. Alumina granules 'dispersed in an aqueous dispersion having a solid concentration of 1 to 3 〇% by weight' is treated with an ion exchange resin to a concentration of ions (except H+, OH·). a step of 50 ppm or less in the alumina fine particles; (b) a step of substituting the aqueous dispersion of the ceria-alumina fine particles with an alcohol; (c) a ceria-alumina fine particle dispersion a step of adding an organic cerium compound represented by the following formula (1) to a range of from 1 to 50% by weight of the cerium oxide-alumina fine particles of Rn-Si〇(4-n)/2; Rn-SiX4 -n ( 1 ) (However, in the formula, R represents an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different from each other; X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, and a nitrogen; η: an integer of 1 to 3) (d) - a step of adsorbing the above-mentioned organic cerium compound to the ceria-alumina fine particles while stirring the ceria-alumina fine-particle alcohol dispersion; (e) adding water and hydrolyzing Using a catalyst to hydrolyze organic hydrazine compounds -75- 201139276; (f ) at 40~120. (: a step of aging for 0.5 to 24 hours. 2. A method for producing a cerium oxide-alumina sol according to claim 1, wherein the aforementioned step (a) is carried out by the following steps (al) and (a2) As a result, (al) is treated with a cation exchange resin to a pH of 丨·0 to 6.0; (a2) treatment with an anion exchange resin until the pH of the dispersion is higher than that of the above step (al) The high pH ' becomes a range of 2.0 to 7.0. 3. The method for producing a cerium oxide sol according to the first or second aspect of the patent application, wherein the step (f) is followed by the following step (g) And/or (h), (g) a step of substituting an organic solvent; (h) a concentration step. 4. Manufacture of cerium oxide or alumina sol according to any one of claims 3 to 3. The method, wherein the amount of negative charge per unit surface area of the cerium oxide. alumina fine particles of the cerium oxide-alumina fine particle aqueous dispersion obtained in the above step (a) is 〇·1~1 in ρΗ2.0~7.0. Range of 5peq/m2. 5 · If you apply for any of items 1 to 4 of the patent scope A method for producing an alumina sol, wherein the molar ratio of the molar number of the water in the step (e) (MH2〇) to the molar number of the organic germanium compound (M〇c) (Mh2〇) / (Moc) is a range of from 1 to 300. -76-201139276. The method for producing a cerium oxide-alumina sol according to any one of claims 1 to 5, wherein the aforementioned step (e) The catalyst for hydrolysis is ammonia, the molar number of ammonia (MNH3) and the molar ratio of moles (Moc) of organic bismuth compounds (MNH3) / (M〇c) are in the range of 〇·1 to 12〇 7. The method for producing a cerium oxide-alumina sol according to any one of the items 1 to 6, wherein the cerium oxide-alumina fine particle aqueous dispersion obtained in the above step (f) is oxidized. The negative charge per unit surface area of the cerium alumina fine particles is 0.5 to 2.0 micro-coulombs/cm2 when the solid concentration is 〇·5 wt% and the dispersion of pH 7.5±1.5 is measured. Scope of the invention. 8. The method for producing an alumina sol according to any one of claims 1 to 7 The organic solvent in the step (g) is one or more selected from the group consisting of ethers, esters, ketones, and alcohols. 9. The method of any one of claims 1 to 8 A method for producing an alumina sol, wherein the solid content concentration is in the range of 20 to 7 % by weight, and the viscosity is in the range of 1 to 1 Torr, 〇〇〇 cp. 1 0. - Kind of cerium oxide · Alumina The sol is in the range of 5 to 100 nm in average particle diameter, and the amount of alumina in the particles is in the range of 0.01 to 5% by weight in terms of Al 2 〇 3 'surface treatment with an organic cerium compound represented by the following formula (1) a dispersion of silica sand and alumina fine particles characterized by a negative charge amount per unit surface area (Q,) of the surface treated silica sand and oxidized fine particles and a cerium oxide before surface treatment with an organic cerium compound. The ratio of the negative charge per unit surface area of the alumina fine particles (Q2) -77 to 201139276 (Qi) / (Q2) is in the range of 0.2 to 0.8; Rn-SiX4.n (1) (but 'in the formula' R is The unsubstituted or substituted hydrocarbon groups having a carbon number of 1 to 0 may be the same or different from each other; X: Number ~ 4 alkoxy, hydroxy, halogen, hydrogen, n: integer of l~3). 1 1 · As in the patent application, item 10 of the cerium oxide. Alumina sol, wherein the aforementioned negative charge amount (Q1) is measured at a dispersion having a solid concentration of 0.5% by weight 'ρΗ7·5±1·5 It is a range of .5 to 2.0 micro-coulombs / cm2. 12. A coating material for forming a transparent film, which is characterized in that it is formed from a cerium oxide, an alumina forming sol, a matrix forming component and a dispersing medium according to any one of claims 1 to 11. The concentration of the component is in the range of 30 to 70% by weight/〇. The concentration of the matrix-forming component is in the range of 6 to 63% by weight in terms of solid content. The concentration of the alumina fine particles is 3 to 56 in terms of solid content. The range of % by weight. The coating material for forming a transparent film according to the second aspect of the invention, wherein the matrix forming component is a fluorene matrix forming component or an organic resin matrix forming component ‘containing a polyfunctional acrylate resin or a polyfunctional fluorene resin. In the case of the coating material for transparent film formation of the first or second aspect of the invention, the bismuth-based antifouling agent is further contained as a solid component of 003.003 to 〇.7 wt%. 1 5 - The coating film for forming a film according to any one of the above-mentioned items of the present invention, wherein the coating film further comprises as a solid component 〇.0〇3~〇.56% by weight The leveling agent. The coating material for forming a transparent film according to any one of the items 1 to 5, wherein the dispersion medium is one or two selected from the group consisting of ethers, esters, ketones, and alcohols. More than one species. 17. A substrate to which a transparent film is attached is characterized in that it is formed of a substrate and a transparent film formed on the substrate, and the transparent film is used as in the first to sixth items of the patent application scope. A person formed by a coating for forming a transparent film. 1 8 The base material of the transparent film to which the transparent film is applied, wherein the content of the cerium oxide and the aluminum oxide fine particles in the transparent film is in the range of 10 to 80% by weight in terms of solid content, and the matrix The content of the component is in the range of 20 to 90% by weight in terms of the solid content. 1 9 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ -79- 201139276 IV Designated representative map: (1) The representative representative of the case is: None. (II) Simple description of the symbol of the representative figure: None 201139276 V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none