KR100254534B1 - Process for preparing dispersion of silicon oxide sol - Google Patents

Abstract

The present invention provides a coating composition containing a ceramic component, which is excellent in fouling resistance, decontamination, weathering (light) resistance, chemical resistance, moisture resistance, and appearance, and is used for a coating composition having high environmental conservation and safety. A method for producing a silicon sol dispersion, specifically, after azeotropic distillation of water contained in an aqueous silicon oxide sol with an azeotropic agent with water, the silicon oxide sol dispersion is surfaced with a silane coupling agent. It is characterized by processing.

Description

Process for producing dispersion of silicon oxide sol {PROCESS FOR PREPARING DISPERSION OF SILICON OXIDE SOL}

The present invention relates to a method for producing a dispersion of a specific silicon oxide sol, and more particularly, the present invention comprises a ceramic component, pollution resistance, decontamination resistance, weather resistance (photo) resistance, chemical resistance, chemical resistance The present invention relates to a method for producing a dispersion of silicon oxide sol, which provides a coating film having excellent wettability and appearance and is used for a paint composition having high environmental conservation and safety.

In recent years, with changes in the environment such as air pollution, oil droplets and dusts contained in the air increase, and as a result, coatings coated on dried products or automobiles are more likely to be contaminated than in the past, and the contamination is difficult to remove. There is a problem. Therefore, as the performance of the coating film, resistance to contamination, that is, contamination resistance, or removal ability of the contaminant from the contaminated coating film, that is, decontamination property, is desired. From these circumstances, it is desired to create a coating composition that is excellent in stain resistance, decontamination, weather resistance (light), and has excellent gloss, appearance, water resistance, and chemical resistance, as well as excellent environmental protection and safety. .

The stain-resistant paint conventionally used is a fluorine-containing resin as a main component, and its stain resistance is due to the high weather resistance of the fluorine-containing resin. The fluorine-containing resin has stability due to (1) the magnitude of the bonding energy between the fluorine atom and the carbon atom is greater than the bonding energy between the hydrogen atom and the carbon atom, (2) the atomic radius of the fluorine atom is larger than that of the hydrogen atom, and Since the polarization rate between fluorine atoms is low (0.68 x 10 ^-24 cc), its function is expressed by water repellency and oil repellency due to low surface free energy.

However, fluorine-containing resins have a high electronegativity of fluorine atoms, and have a different polymerizability from ordinary acrylic monomers, so that the range of resin design is limited, fluorine-containing resins are high, and fluorine-containing monomers There is a problem that the solubility in a solvent is limited, hydrofluoric acid is generated at the stage of disposal of the coating film using a fluorine-containing resin, which may cause adverse effects on the environment. Problems such as restrictions on use, adverse effect on environment at the time of disposal are getting close-up.

On the other hand, in recent years, the coating composition which provided weather resistance by the acryl polyol obtained by copolymerizing a polymeric ultraviolet stable monomer as an essential component as a highly weather-resistant coating composition is proposed (Japanese Patent Laid-Open No. 1-261409). However, in this publication, there is no description of resistance to contamination. Moreover, as a fouling-resistant composition, the coating composition which mix | blended the partial condensation product of an organosilicon compound with specific silica fine particles is proposed (Japanese Patent Laid-Open No. 2-3468). However, in this publication, no detailed description is given about the resin component used for the coating composition. Moreover, the coating composition containing an acryl polyol resin, a binder, an inorganic organic sol, and a solvent is proposed (Japanese Patent Laid-Open No. 4-173882). However, although this coating composition improves to some extent with respect to stain resistance and weather resistance (light), it has the drawback of insufficient decontamination.

Thus, the paint composition which gives the coating film excellent in all contamination resistance, decontamination property, and weather resistance (light) is not known yet.

The present invention is a coating composition which is such a practical material, has excellent pollution resistance, decontamination property and weather resistance (light), and has a good water resistance, chemical resistance, appearance, and the like, and which has high environmental conservation and safety. It aims at providing the manufacturing method of the dispersion of the silicon oxide sol used for the following.

The present invention provides a method for producing a dispersion of a solvent-dispersed silicon oxide sol, characterized in that the aqueous silicon oxide sol is subjected to azeotropic distillation and dehydration with an adjuvant, followed by surface treatment with a silane coupling agent.

Other objects, aspects and advantages of the present invention will become sufficient from the following description.

In the coating composition of one example in which the dispersion of the silicon oxide sol obtained by the method for producing the dispersion of the silicon oxide sol of the present invention can be used, the resin used as the component (A) has a glass transition temperature of 50 to 120 ° C. Range. If the glass transition temperature is less than 50 ° C., the resulting coating film is insufficient in hardness and hardly obtains high weather resistance. If it exceeds 120 ° C., the workability at the time of coating is deteriorated, and the resulting coating film has an appearance such as sensibility and gloss. This degrades. In addition, by adjusting the glass transition temperature in the above range, the low pollution removal property, which is a drawback of the coating composition proposed in Japanese Patent Laid-Open No. 4-173882, is improved. In view of hardness, appearance, decontamination property and workability of the coating film, the preferred glass transition temperature is in the range of 50 to 100 ° C.

The resin has a number average molecular weight in the range of 2,000 to 100,000. If the number average molecular weight is less than 2000, the weather resistance of the coating film obtained is insufficient, and if it exceeds 100,000, the workability at the time of coating will fall. In view of weather resistance and workability of the coating film, the number average molecular weight is preferably in the range of 2,200 to 70,000, and particularly preferably in the range of 2,200 to 40,000.

Moreover, the hydroxyl value of this resin is 50-150 mgKOH / g. If the hydroxyl value is less than 50 mgKOH / g, the resulting coating film is insufficient in crosslinking density, and it is difficult to obtain high stain resistance and high pollution removal property. If it exceeds 150 mgKOH / g, the structure of the coating film becomes too dense and the shrinkage stress at the time of film formation becomes large. It becomes impossible to alleviate, and it becomes easy to produce a crack etc. in a coating film. The hydroxyl value is preferably in the range of 50 to 130 mgKOH / g in view of contamination resistance, decontamination property and suppression of crack generation of the coating film.

In addition, the acid value of this resin is the range of 1-25 mgKOH / g. If the acid value is less than 1 mgKOH / g, the pigment dispersibility deteriorates in the enamel paint system, and inconveniences such as sedimentation and flocculation of the pigment occur at the time of coating storage, and if it exceeds 25 mgKOH / g, the pot life of the paint is extremely extreme. The tendency to fall can be seen. The acid value is preferably in the range of 2 to 20 mgKOH / g in terms of dispersibility of the pigment, storage stability of the paint, and pot life.

The resin of the component (A) comprises (a) an ester of (meth) acrylic acid of alkyl alcohol having 1 to 12 carbon atoms, (b) a hydroxy group-containing monomer having a polymerizable double bond, and (c) a polymerizable double bond. The obtained carboxyl group-containing monomer is obtained by copolymerizing (d) styrene, (e) acrylonitrile and (f) other monomers as necessary.

The ester of (meth) acrylic acid (hereinafter referred to as "acrylic ester") of alkyl alcohol having 1 to 12 carbon atoms of (a) component used as the essential monomer component is 10 to 90% by weight based on the weight of all monomers. Used as. Acrylic ester is an indispensable component for adjusting the glass transition temperature of a coating film, and when the carbon number of the alkyl group of the alcohol part exceeds 12, the glass transition temperature of resin obtained can be seen to become too low. Moreover, if the usage-amount of this acryl-type ester is less than 10 weight%, the glass transition temperature of resin obtained will not be 50 degreeC or more, unless another monomer with low polymerizability is used, For example, if a monomer with low polymerizability is used, a coating film will be used. The weather resistance of remarkably falls. On the contrary, when it exceeds 90% by weight, it is difficult to introduce a required hydroxyl group or carboxyl group into the resin, and it is difficult to obtain a coating film having high weather resistance, high pollution resistance, and high fouling resistance. In order to obtain the coating film which has desired preferable physical property, the preferable usage-amount of this acryl-type ester is the range of 35 to 80 weight%.

The alkyl alcohol having 1 to 12 carbon atoms forming the acrylic ester of the component (a) may be any alcohol as long as it has a linear, branched or cyclic alkyl group. As an example of the acrylic ester of (a) component, For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, meta T-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, adanthyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, acrylic acid Methyl, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 20 ethylhexyl acrylate, admantyl acrylate, dodecyl acrylate And isobornyl acrylate. These may be used 1 type or may be used in combination of 2 or more type.

Next, the hydroxy group-containing monomer having a polymerizable double bond of component (b) to be used as the essential monomer component is used in a proportion of 10 to 50% by weight based on the weight of all monomers. If this amount is less than 10% by weight, the crosslinking point necessary for the obtained resin cannot be introduced, and a coating film having high weather resistance, high pollution resistance, and high pollution removal property cannot be obtained. On the other hand, when it exceeds 50 weight%, the crosslinking density of a coating film becomes high too much, or at the time of the crosslinking reaction of resin and (B) component obtained, an unreacted hydroxyl group remains in resin, and also the water resistance and moisture resistance of a coating film It is a cause of reducing the weather resistance of a coating film. In order to introduce an appropriate number of crosslinking points into the resin and to obtain a coating film having desired desirable physical properties, the preferred amount of the monomer of this (b) component is in the range of 10 to 30% by weight.

The hydroxyl group-containing monomer having a polymerizable double bond of component (b) may be one having at least one polymerizable double bond and one hydroxyl group, but preferably one having a polymerizable double bond and one hydroxyl group.

Examples of the monomer of the component (b) include, for example, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 1,4-butanediol monomethacrylate, and hydroxyethyl methacrylate. ε-caprolactone adduct, ethylene oxide and propylene oxide adduct of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 1,4-butanediol monoacrylate And (epsilon) -caprolactone adducts of hydroxyethyl acrylate, ethylene oxide and propylene oxide adducts of hydroxyethyl acrylate, and the like. These may be used 1 type or may be used in combination of 2 or more type.

Moreover, the carboxyl group-containing monomer which has a polymerizable double bond of (c) component used as an essential monomer component is used in the ratio of 0.1 to 10 weight% based on the weight of all the monomers. If this amount is less than 0.1% by weight, the acid value of the resin obtained is too small, the pigment dispersibility deteriorates in the enamel paint system, causing inconveniences such as sedimentation and aggregation of the pigment during the storage of the paint, and when it exceeds 10% by weight, It can be seen that the storage stability of the paint, pot life, and the like are markedly lowered. From the standpoints of dispersibility of the paint, storage stability of the paint, pot life, and the like, the preferred amount of the component (c) is in the range of 1 to 5% by weight, particularly preferably in the range of 1 to 3% by weight.

The carboxyl group-containing monomer having a polymerizable double bond of component (c) may have one or more polymerizable double bonds and one or more carboxyl groups, but preferably has one polymerizable double bond and one or two carboxyl groups. .

As an example of the monomer of (c) component, methacrylic acid, acrylic acid, itaconic acid, mesaconic acid, maleic acid, fmaric acid, (omega)-carboxy- polycaprolactone (n = 2) monoacrylate (for example, Aronix M-5300 (manufactured by Toako Sekagaku Kogyo Co., Ltd.), phthalate monohydroxyethyl acrylate (e.g., Aronix M-5400 (manufactured by Toako Sekagaku Kogyo Co., Ltd.)), acrylic acid dimer And Aronix M-5600 (manufactured by Toko Sekagaku Kogyo Co., Ltd.). These may be used 1 type or may be used in combination of 2 or more type.

Moreover, the styrene of (d) component is not an essential component, It is used as needed for the purpose of improving the appearance, such as the selectivity of a coating film. When styrene is used, it is used in proportion of 20 weight% or less based on monomer total weight. When the usage-amount of styrene exceeds 20 weight%, the tendency for the weather resistance, stain resistance, and decontamination property of the coating film obtained can be seen to fall. In terms of the balance of the appearance, weather resistance, contamination resistance, decontamination property, etc. of the coating film, etc., the preferred amount of styrene used is in the range of 1 to 18% by weight.

Moreover, acrylonitrile of (e) component is not an essential component, It is used as needed in order to improve adhesiveness, impact resistance, etc. with respect to the base material of a coating film. When acrylonitrile is used, it is used in the ratio of 20 weight% or less based on monomer total weight. When the amount of acrylonitrile used exceeds 20% by weight, the weathering resistance, stain resistance and decontamination property of the coating film may be deteriorated. In terms of balance of adhesion, impact resistance, weather resistance, decontamination, etc. to the substrate of the coating film, the preferred amount of acrylonitrile is preferably in the range of 1 to 18% by weight.

Next, the other monomer of (f) component is not an essential component, and when designing a coating film, it selects suitably as needed according to a base material, a purpose of use, etc. as needed. When using another monomer, it uses at the ratio of 10 weight% or less based on monomer total weight. If this amount is more than 10% by weight, it is difficult to obtain a coating film having desired physical properties. The preferable usage-amount in the case of using the other monomer of (f) component is 1-7 weight%.

The other monomer having the polymerizable double bond of the component (f) may be one having at least one polymerizable double bond, but preferably has one polymerizable double bond.

As an example of the other monomer of (f) component, for example, a hosmer (product made from a chemical), glycidyl methacrylate, glycidyl acrylate, aryl methacrylate, aryl acrylate, 3,4-epoxycyclohexylmethyl Methacrylate, 3,4-epoxycyclohexylmethyl acrylate, phenyl methacrylate, phenyl acrylate, α-methylstyrene, p-vinyltoluene, methacrylamide, acrylamide, N, N-dimethylmethacrylamide, N , N-dimethylacrylamide, methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl, acrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl, meta 2,2,6,6-tetramethyl-4-piperidyl, acrylic acid 2,2,6,6-tetramethyl-4-piperidyl, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl Aliphatic vinyl ether compounds such as ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and also 2,3-dihydrofuran, 3,4-dihydrate -2H- may include pyran, trimethoxysilyl propyl methacrylate, maleic anhydride, itaconic anhydride, maleic acid esters, fumaric acid esters. These may be used 1 type or may be used in combination of 2 or more type.

By copolymerizing these monomers in the said ratio, resin of (A) component can be obtained. There is no restriction | limiting in particular about the polymerization method at this time, A well-known method, for example, solution polymerization, suspension polymerization, emulsion polymerization, block polymerization, precipitation polymerization, etc. in an organic solvent can be used. Moreover, there is no restriction | limiting in particular also about a polymerization type, For example, although any of radical polymerization, cation polymerization, and anionic polymerization can be used, among these, radical polymerization is suitable from an industrial viewpoint. As a polymerization initiator used in radical polymerization, for example, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy neodecanate, t-butyl peroxy pivalate, t-hexyl peroxy Organic peroxides such as 2-ethylhexanoate and methyl ethyl ketone peroxide, or 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropio Azo initiators such as nitrile) (AIBN) and 2,2'-azobis (2-methylbutyronitrile). Of course, it is not limited to these. These radical polymerization initiators may be used 1 type, or may be used in combination of 2 or more type.

In general, the polymerization temperature is preferably in the range of 60 to 150 ° C. If the temperature is less than 60 ° C., the radical polymerization initiator is difficult to disperse, and the reaction is difficult to proceed. If the temperature is higher than 150 ° C., even if the radical polymerization initiator is dispersed by heat to generate radicals, its life is short. it's difficult. The polymerization time cannot be determined uniformly depending on the polymerization temperature or other conditions, but generally 2 to 6 hours is sufficient.

In the coating composition, at least one compound selected from polyisocyanate compounds and aminoporous resins containing two or more isocyanate groups and / or blocked isocyanate groups in one molecule is used as the curing agent for component (B).

Examples of the polyisocyanate compound having two or more isocyanate groups in one molecule include, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl methane-4, Compounds called isocyanate monomers such as 4'-diisocyanate, polyisocyanate derivatives such as biuret bodies, isocyanurate bodies and adducts of trimethylolpropane and the like are preferably mentioned. These polyisocyanate compounds may be used 1 type, or may be used in combination of 2 or more type.

As an example of a polyblock isocyanate compound, the thing manufactured by blocking one part or all part of the isocyanate group of the said polyisocyanate compound with a blocking agent, for example is manufactured. Examples of this blocking agent include, for example, ketoxime blocking agents such as ε-caprolactam, methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, and phenols such as phenol, cresol, catechol and nitrophenol. Alcohol blocking agents, such as a system block agent, isopropanol, and a trimethylol propane, active methylene type blocking agents, such as malonic acid ester and acetoacetic acid ester, etc. are mentioned. 1 type of these polyblock isocyanate compounds may be used, and may be used in combination of 2 or more type.

As an example of an aminoplast resin, a melamine resin, guanamine resin, etc. are mentioned preferably. 1 type of these aminoplast resins may be used, and may be used in combination of 2 or more type. More specifically, as long as it contains two or more reactive groups in one molecule, there is no restriction | limiting at all, and one or more triadin rings which exist in one molecule of melamine or guanamine resin do not interfere. As reactive groups which exist in these resin, Preferably, the etherification of the methylol group, the imino group, and the methylol group by methanol, butanol, etc. is mentioned.

In the above coating composition, the blending ratio of the component (A) and the component (B) is (A) when the component is a polyisocyanate compound containing two or more isocyanate groups and / or blocked isocyanate groups in one molecule. The molar ratio of the isocyanate group and / or the blocked isocyanate group in the component (B) to the hydroxy group of the component is preferably in the range of 0.6 to 1.6, particularly preferably in the range of 0.8 to 1.2. When this molar ratio is less than 0.6, at the time of crosslinking reaction of the polyisocyanate compound of (B) component and the resin of (A) component, the hydroxyl group in resin may remain in unreacted part, and the water resistance and moisture resistance of the coating film obtained are This decreases, and may further cause deterioration of weather resistance of the coating film. On the other hand, when the molar ratio exceeds 1.6, the isocyanate group and / or the blocked isocyanate group may remain unreacted, and in this case, the water resistance and the moisture resistance of the coating film may be lowered, and furthermore, the weather resistance of the coating film may be a cause of deterioration. have.

When (B) component is an aminoplast resin, it is preferable that the non-volatile content weight ratio of (A) component and (B) component is the range of 97: 3-60: 40, and is 95: 5-65: 35. It is more preferable that it is a range, and it is especially preferable that it is the range of 91: 9-70: 30. If the amount of aminoplast resin is less than the compounding ratio of 97: 3, the crosslinking density of the coating film may be low, and physical properties such as solvent resistance may not be satisfied. If the amount of aminoplast resin is higher than the compounding ratio of 60:40, the flexibility of the coating film may be reduced. It is not preferable because this may cause inconvenience such as deterioration.

In the said coating composition, the dispersion of a silicon oxide sol is used as a ceramic component of (C) component.

In general, the silicon oxide sol is often supplied as an aqueous dispersion, and in the case of the aqueous dispersion, if the coating composition is water-based, it can be used as it is, but if it is an organic solvent, a method of phase inversion in a desired organic solvent, etc. Can be used. Preferable organic solvents are ketone solvents such as methyl isobutyl ketone and cyclohexanone.

As the method of phase inversion, for example, a method of phase inversion in a desired organic solvent by adding an aqueous solvent, i.e., an organic solvent soluble in water, to remove residual water in the aqueous dispersion, and the like are repeated. Can be used.

The dispersion of silicon oxide sol can be obtained by adding silicon tetrahalide in water and adding an acid to an aqueous sodium silicate solution. As a commercially available product, for example, an aqueous solvent dispersion includes snortex-0 [manufactured by Nissan Kagaku Kogyo Co., Ltd., product name], Snotex-N [manufactured by Nissan Kagaku Co., Ltd., product name], etc. Examples thereof include Snowtex MIBK-ST (manufactured by Nissan Kagaku Co., Ltd., trade name).

It is preferable that the dispersion of silicon oxide sol was surface-treated with the silane coupling agent. The surface-treated silicon oxide sol dispersion can introduce various functional groups on the particle surface thereof, and therefore, when used in the coating composition, it can be used for organic components such as resins, polyisocyanate compounds or aminoplast resins, and chemicals. It is easy to combine. In this way, when the ceramic component and the organic component are chemically bonded, the crosslinking of the coating film is stronger as compared with the case where the ceramic component and the organic component are not chemically bonded, and the stain resistance, decontamination property, weather resistance, and the like are improved.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltrimethoxy. Methoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and the like, and preferably, methyltrimethoxysilane, dimethyldimethoxysilane and γ-glycidoxypropyltrimethoxysilane , γ-methacryloyloxypropyltrimethoxysilane, and particularly preferably methyltrimethoxysilane and dimethyldimethoxysilane. Moreover, as a commercial item, A-162, A-163, AZ-6122 (all are brand names, the Japan Uniker Corporation make), etc. are mentioned. These silane coupling agents can be used 1 type or in combination of 2 or more types. When surface-treating with a silane coupling agent, 1-40 weight% is preferable with respect to the non volatile matter of a silicon oxide sol, and, as for the compounding quantity to a silane coupling agent, 5-30 weight% is more preferable.

As the dispersion of the silicon oxide sol treated with the silane coupling agent, after the azeotropic distillation of the dispersion of the silicon oxide sol obtained according to the present invention, that is, the water contained in the aqueous silicon oxide sol, by an azeotropic agent with water, It is preferable to use the dispersion of the non-conjugated disperse silicon oxide sol obtained by surface-treating the dispersion of silicon oxide sol with a silane coupling agent. In the dispersion of the silicon oxide sol obtained by the production method of the present invention, the contamination resistance, decontamination property, weather resistance, and the like are improved, and the silicon oxide sol can be highly concentrated. Therefore, the width | variety which selects the viscosity adjusting thinner at the time of coating is wide, and it is also possible to make a coating film into a thick film.

Examples of the co-agent include water-soluble (ie, soluble in water) alcohols, carboxylic acid esters, cyclic esters, and the like.

As the water-soluble alcohol, for example, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, methyl cellosolve, ethyl cellosolve , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 3- Methyl-3-methoxy butanol, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, etc. are mentioned.

As water-soluble carboxylic acid ester, methyl acetate, ethyl acetate, etc. are mentioned, for example. 1,4-dioxane etc. are mentioned as a water-soluble cyclic ether.

These utilities can be used 1 type or in combination of 2 or more types.

Moreover, even if it is a solvent which does not mix with water, it is good also if it uses for the purpose of improving azeotropic distillation dehydration efficiency by making into a solvent which mixes with water. As this solvent, benzene, xylene, toluene, cyclohexanone, diphenyl ether, dibutyl ether, etc. are mentioned, for example. These solvents can be used 1 type or in combination or 2 or more types. However, the amount of use thereof is limited to the range in which the sol is not aggregated, and also varies depending on the solvent, but is usually in the range of 1 to 10% by weight.

It is preferable to perform azeotropic distillation dehydration, dropping an azeotropic system.

It is preferable that azeotropic distillation dehydration is performed in 30-100 degreeC, and it is especially preferable to carry out in 40-80 degreeC.

In addition, although azeotropic distillation dehydration is possible under reduced pressure or normal pressure, it is preferable to carry out under reduced pressure.

The water content in the azeotropic agent-dispersed silicon oxide sol after azeotropic distillation dehydration is preferably 2% by weight or less, and particularly preferably 1% by weight or less.

It is preferable that non-volatile content is 55 weight% or less, and, as for the density | concentration of the dispersion of azeotropic agent dispersion silicon oxide sol after azeotropic distillation dehydration, it is especially preferable that it is 25 to 55 weight%.

Surface treatment with a silane coupling agent can be performed by mixing a silane coupling agent with the dispersion of azeotropic agent dispersion silicon oxide sol after azeotropic distillation and dehydration. Although the surface treatment temperature by a silane coupling agent does not have a restriction | limiting in particular, Usually, it is preferable to carry out in 20-100 degreeC, It is more preferable to carry out in the range of 30-90 degreeC, Especially it is performed in the range of 40-80 degreeC. Is preferred.

It is preferable that the water content in the solvent-dispersed silicon oxide sol after the surface treatment with the silane coupling agent is usually 1% by weight or less, and particularly preferably 0.5% by weight or less.

In addition, the solvent of an unconjugated dispersing silicon oxide sol can be substituted by a desired solvent as needed.

As a solvent which can be used for this solvent substitution, the above-mentioned alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylacetoamide, dimethylformamide, etc. are mentioned, for example.

Although solvent substitution depends also on the kind of solvent used at the time of substitution, it is preferable to carry out in 30-120 degreeC, and it is especially preferable to carry out in 40-110 degreeC.

In the said coating composition, the dispersion of a silicon oxide sol may be used 1 type, may be used in combination of 2 or more type, and the compounding quantity of the non-volatile content of the dispersion of a silicon oxide sol is (A) component It is chosen so that it may become 5 to 60 weight% with respect to the total non volatile matter of (B) component and (C) component. If the non-volatile content of the silicon oxide sol dispersion is less than 5% by weight relative to the total non-volatile content, the effect of adding the dispersion of the silicon oxide sol is not sufficiently exhibited, thereby improving the stain resistance, decontamination resistance, and weather resistance of the coating film. When it is not confirmed very much and exceeds 60 weight%, the tendency for the flexibility of a coating film to fall can be seen. In view of the balance of contamination resistance, decontamination property, weather resistance and flexibility of the coating film, the non-volatile content of the dispersion of the silicon oxide sol is preferably in the range of 5 to 40% by weight based on the total non-volatile content.

In addition, the dispersion of the silicon oxide sol preferably has an average particle diameter of 100 nm or less, and particularly preferably an average particle diameter of 50 nm or less. When the average particle diameter is larger than 100 nm, the transparency in the clear film is impaired, and the fouling resistance and decontamination property of the coating film are lowered.

In the coating composition, a curing reaction catalyst may be used.

In the coating composition, in the case of using a polyisocyanate compound containing two or more isocyanate groups and / or block isocyanate groups in one molecule as the component (B), for example, a tin compound or a zinc compound is used as the curing reaction catalyst. Can be mentioned. Examples of the tin compound include organic tin compounds such as tin halides such as tin chloride and tin bromide, dibutyltin diacetate and dibutyltin dilaurate, and the like, and examples of zinc compounds include zinc chloride and zinc bromide. Zinc salts of organic acids, such as zinc halide, an octylic acid zinc, and zinc laurate, etc. are mentioned. 1 type of tin compounds and zinc compounds as a curing reaction catalyst may be used, may be used in combination of 2 or more type, and may be used together with another curing reaction catalyst. It is preferable to use a curing reaction catalyst in the ratio of 0.01-5 weight% with respect to the total non volatile matter in a coating composition. If the amount is less than 0.01% by weight, the promoting effect of the curing reaction may not be sufficiently exhibited. If the amount exceeds 5% by weight, the water resistance and moisture resistance of the coating film are lowered, and further, the fouling resistance and decontamination property of the coating film are reduced. , Weather resistance and the like may be a cause of deterioration. In view of the balance of the curing rate and the coating film properties, a more preferable compounding amount of this curing reaction catalyst is in the range of 0.01 to 2% by weight based on the total nonvolatile content in the composition.

In the coating composition, when using an aminoplast resin as the component (B), a curing reaction catalyst of the aminoplast resin may be used. As an example of the hardening reaction catalyst of an aminoplast resin, sulfonic-acid hardening catalysts, such as a phosphate hardening catalyst, toluene sulfonic acid, and dodecylbenzene sulfonic acid, or those amine block bodies, are preferable, for example. One kind of these compounds may be used, or two or more kinds thereof may be used in combination, and the curing time may be adjusted in combination with other compounds.

The amount of the curing reaction catalyst of the aminoplast resin is preferably in the range of 0.01 to 2% by weight in the total nonvolatile matter of the paint. The reason for this is that when the paint is cured at less than 0.01% by weight, the effect of the curing reaction catalyst of the aminoplast resin may not be expressed. If the content exceeds 2% by weight, the effect of the curing reaction catalyst of the aminoplast resin is formed after the coating film is formed. This adversely affects the performance of the coating film, such as water resistance and moisture resistance, and furthermore, the contamination resistance, decontamination property, and weather resistance of the coating film may be lowered.

In addition, an appropriate amount of pigments, dyes, and brighteners may be blended in the production of the paint composition to produce enamels, without losing its original function. Therefore, not only a clear paint but also a coloring pigment can be mix | blended and can provide designability, such as coloring a to-be-painted object. It is also possible to mix the extender pigment to adjust the physical properties of the coating film. Specific examples thereof include coloring pigments such as titanium oxide, carbon black, organic pigments and red oxide, colorants such as glass flakes, aluminum flakes and miker flakes, fillers such as actives, and extender pigments such as strontium chromium and barium sulfate. Can be.

In the said coating composition, when a pigment is included, 0.1-40 weight% is preferable normally, and, as for the compounding ratio of a pigment, 0.5-35 weight% is especially preferable.

There is no restriction | limiting in particular in the preparation method of the said coating composition, The method of mixing each essential component and desired various additives in arbitrary order, or other various methods can be used, The method shown next is suitable.

That is, (a) 10 to 90% by weight ester of (meth) acrylic acid of alkyl alcohol having 1 to 12 carbon atoms, (b) 10 to 50% by weight of hydroxy group-containing monomer having a polymerizable double bond, (c) polymerizable double 0.1-10% by weight of carboxyl group-containing monomer having a bond, 0-20% by weight of (d) styrene, 0-20% by weight of (e) acrylonitrile and (f) 0-10% of other monomers having a polymerizable double bond % Was copolymerized to prepare a resin (A) having a glass transition temperature of 50 to 120 DEG C, a number average molecular weight of 2,000 to 100,000, a hydroxyl value of 50 to 150 mgKOH / g, and an acid value of 1 to 25 mgKOH / g. Later, in the polymerization solution, the dispersion (C) of the silicon oxide sol was 5 to 5 parts based on the weight of the total nonvolatile matter of the component (A), the component (B) and the component (C). After dispersion-stabilization of the method or (C) component prepared by using the organic-inorganic composite obtained by adding so that it may become 60 weight% in a monomer, copolymerizing a monomer and resin (A) is carried out. The method of preparing using the organic-inorganic composite obtained by manufacture is preferable.

In particular, the dispersion of the silicon oxide sol of component (C) is heated to the polymerization liquid after the end of the polymerization in the copolymerization of the monomer for obtaining the resin of the component (A). It is preferred to add at and stabilize the dispersion.

Usually, after obtaining by polymerizing resin of (A) component, in order to adjust the density | concentration of this resin liquid, a diluent is added, but addition of the dispersion of the silicon oxide sol of (C) component replaces addition of a diluent. .

By adding the dispersion of the silicon oxide sol of component (C) to the polymerization liquid after the completion of the polymerization of the resin of the component (A), aggregation of the dispersion of the silicon oxide sol hardly occurs, and the dispersion of the silicon oxide sol in a subsequent step Even if a sieve is added again, aggregation becomes less likely to occur. In addition, in coating the paint, electrostatic coating workability, arrival efficiency, atomization, and adhesion are very good. Therefore, in a painting work line, workability is very good and the appearance obtained is also excellent. Moreover, even if the density | concentration of the organic-inorganic composite solution which the obtained (C) component is disperse | distributing stabilized is made high, the viscosity rise is comparatively small and it becomes possible to attain high non volatile matter differentiation easily. Therefore, the said coating composition is suitable also as a coating material which can reduce environmental pollution.

Addition of the dispersion of the silicon oxide sol of the component (C) is after the completion of the polymerization of the resin of the component (A). After completion of the polymerization, the copolymerization of the monomers results in a glass transition temperature of 50 to 120 ° C. and a number average molecular weight of 2,000. It means that after resin of (A) component which has -100,000, a hydroxyl value of 50-150 mgKOH / g, and an acid value of 1-25 mgKOH / g is manufactured, the polymerization liquid may contain the unreacted monomer.

The addition of the dispersion of the silicon oxide sol of the component (C) is preferably carried out at a temperature below the boiling point of the dispersion medium of the silicon oxide sol of the component (C), particularly than the boiling point of the dispersion medium of the silicon oxide sol of the component (C) Low temperatures of 10 to 50 ° C. are preferred.

It is preferable that resin content exists in the range of 40 to 80 weight%, and, as for the polymerization liquid before adding the dispersion of the silicon oxide sol of (C) component, it is especially preferable to exist in the range which is 50 to 70 weight%.

As a method for preparing a preferred paint composition in the case of a clear paint system, after dispersing and stabilizing a dispersion of silicon oxide sol of component (C) in a polymerization solvent, the monomer of component (A) is prepared in the same manner as the polymerization conditions described above. The organic-inorganic composite solution in which the silicon oxide sol is dispersed and stabilized is prepared by polymerization and production, or after polymerization of the resin of component (A), dispersion dispersion stabilization of the silicon oxide sol in a resin solution under heating or non-heating. The method of preparing the said coating composition is produced by homogeneously mixing this and resin of (A) component, the hardening | curing agent of (B) component, and various additives used as needed as needed.

In the case of an enamel paint system, the paint composition can be prepared by dispersing a resin of the component (A), a pigment dispersant, or the like with a disperser, and blending it in the above-mentioned clear paint. In addition, as various additives used as desired, for example, dyes, glass flakes, aluminum flakes, mica flakes and other coloring agents, fillers, solvents, pigment dispersants, flow regulators, leveling agents, antigelling agents, antioxidants, ultraviolet rays Absorbers, ultraviolet stabilizers, radical trapping agents and the like.

The temperature and time required for curing the coating composition obtained in this way depend on the type of each component and the reaction catalyst to be used, but are usually about 30 seconds to about 10 hours at a temperature ranging from room temperature to 220 ° C.

The base material to which the coating composition is applied is not particularly limited, and various base materials can be used. For example, wood, glass, metal, cloth, plastic, foam, elastomer, paper, ceramic, concrete, gypsum board, etc. Organic materials and inorganic materials. These base materials may be surface-treated in advance, or the coating film may be previously formed in the surface.

As a coating article obtained by apply | coating the said coating composition, a building, a structure, a wooden article, a metal article, a plastic article, a rubber article, a processed paper, a ceramic article, a glass article, etc. are mentioned, for example. More specifically, metal plates such as automobiles and steel plates, motorcycles, ships, railway vehicles, aircrafts, furniture, musical instruments, home appliances, building materials, tunnel interior plates, coating materials, containers, office supplies, sporting goods, toys, etc. have.

In addition to the paint, the paint composition can also be used for inks, adhesives, molded articles, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited at all by these Examples.

In addition, preparation of a test plate and evaluation of coating-film performance were performed as follows.

(1) production of clear coating test plates

Baking epoxy resin (Epico Primer No. 1000 BF2, manufactured by Nihon Yushi Co., Ltd.) was coated on an abrasive steel sheet (JIS G-3141) so as to have a thickness of 20 µm, and baked at 160 ° C for 20 minutes. Subsequently, the urethane resin No. 5000 (white) [registered trademark, manufactured by Nihon Yushi Co., Ltd.] and the urethane curing agent HA [registered trademark, manufactured by Nihon Yushi Co., Ltd.] of a curing agent were mixed thereon in a ratio of 6: 1 by weight. After coating so that it might become a dry film thickness of 25 micrometers, it was forced to dry for 30 minutes at 80 degreeC, and the test plate was produced by leaving it overnight.

(2) Production of enamel coated test plates

A test plate was coated on a polishing steel sheet (JIS G-3141) with a baking epoxy resin (Epico Primer No. 1000 BF2, manufactured by Nihon Yushi Co., Ltd.) at 20 占 퐉 as a dry film thickness, and then baked at 160 ° C for 20 minutes. Made.

(3) Evaluation of coating performance

(a) 60 degree gloss: Based on JIS K-5400 (1990) 7.6, 60 degree mirror gloss (Gs60 degree) of the coating film was calculated | required.

(b) Sunyoung Sung: The evaluation was made by visual observation according to the following criteria.

(Circle): When a fluorescent lamp shines on a coating film, a fluorescent lamp shines wisely.

(Triangle | delta): When the fluorescent lamp shines on a coating film, the periphery (outline) of a fluorescent lamp will be slightly blurred.

X: When a fluorescent lamp shines on a coating film, the periphery (outline) of a fluorescent lamp becomes cloudy significantly.

(c) Accelerated weathering test: 60% gloss retention (%) (JIS K-5400 (1990) 7.6) was obtained by a test by the Sunshine Carbon Arc Equation weather resistance tester of JIS D 0205 5.4.

(d) Moisture resistance: After exposing the test piece to a relative humidity of 95% or more for 240 hours under conditions of 40 ± 1 ° C., the surface state of the test piece was taken out for 2 hours and visually observed, and evaluated according to the following criteria.

(Circle): There is no change in the gloss and surface state of a test piece compared with an original test piece.

(Triangle | delta): The glossiness and swelling (blister) of a test piece are slightly compared with the original test piece.

X: Compared with the original state test piece, there is a remarkable change in shine and swelling (blister) of the test piece.

(e) Xylene rubbing resistance: The change of the surface state at the time of reciprocating rubbing 100 times by the flannel which infiltrated the xylene with the xylene was visually observed, and the xylene rubbing resistance was evaluated according to the following criteria.

(Circle): There is no change in the glossiness of a test piece compared with an original test piece.

(Triangle | delta): The glossiness of a test piece has a little change compared with an original test piece.

X: The glossiness of the test piece was remarkably changed as compared with the original test piece.

(f) Acid resistance: The acid resistance test was done based on JISK-5400 (1990) 8.22, and acid resistance was evaluated according to the following criteria.

(Circle): There is no change or discoloration of the glossiness of a test piece compared with an original test piece.

(Triangle | delta): Compared with an intact test piece, there exists a slight change of the gloss of a test piece, and a change of color.

X: The change of the glossiness and the hue of a test piece have changed large compared with the original test piece.

(g) Alkali resistance: The alkali resistance test was done based on JISK-5400 (1990) 8.21, and the alkali resistance was evaluated according to the following criteria.

(Circle): There is no change or discoloration of the glossiness of a test piece compared with an original test piece.

(Triangle | delta): Compared with an intact test piece, there exists a slight change of the gloss of a test piece, and a change of color.

X: The change of the glossiness and the hue of a test piece have changed large compared with the original test piece.

(h) Oil-resistant marker fouling: Draw a line on the coating film of the test piece with an oil-based marker, heat it at 80 ° C for 5 hours, and visually observe the change in the surface state after wiping the line with a flannel impregnated with xylene. Oiliness marker contamination was evaluated according to the following criteria.

(Circle): The line of the oily marker of a test piece is wiped off completely, and a trace does not remain.

(Triangle | delta): The trace of the line of the oily marker of a test piece remains slightly.

X: The trace of the line of the oil-based marker of a test piece remains firmly.

(i) Pencil hardness: It calculated | required based on JISK-5400 (1990) 8.4.2.

(j) Adhesion: The adhesion test was conducted in accordance with JIS K-5400 (1990) 8.5.1, and the adhesion was evaluated according to the following criteria.

○: 10 points

△: 8 points

× 6 points or less

(k) Appearance at the time of thick-film coating: The film state of the test piece was visually observed with the film thickness of an average dry coating film being 60 micrometers, and it evaluated in accordance with the following criteria.

○: good

△: some defoaming traces

×: debris in the whole

(l) Outdoor Exposure Pollution: The outdoor exposure test of the test specimens was carried out for 3 months, and the L value measured by SM Color Computer SM-4-MCH (manufactured by Suga Test Equipment Co., Ltd.) was subtracted from the initial L value before exposure (△ L ), The contamination of the coating surface was evaluated.

(4) workability

(m) Atomization: The state of the mist at the time of coating of paint was observed and evaluated according to the following criteria.

◎ very good

○: good

△: not all good

×: not good overall

(n) Coating efficiency: The efficiency which sprayed paint adheres to a to-be-painted object, comprehensively observed the spread of mist and the arrival rate of the mist to the to-be-painted object at the time of coating, and evaluated it according to the following criteria. .

◎ very good

○: good

△: not all good

×: not good overall

(o) dirt after decontamination

After removing the dirt by injecting ion-exchanged water into the clean gauze and reciprocating it 10 times vertically, and then replacing the gauze and reciprocating it 10 times horizontally in the same manner, wipe off the moisture with a dry gauze The L value was measured, and the contamination of the coating film surface was evaluated by the value (ΔL) obtained by subtracting the L value after exposure from the initial L value.

Example

Example 1

Snortex-0 (trade name, product of Nissan Kagaku Co., Ltd., water dispersion type silicon oxide sol,

Average particle diameter: 20 nm) 180.2 parts by weight and 63.1 parts by weight of isopropyl alcohol were prepared in a reaction vessel equipped with a reflux tube with a Dean-Stark trap, a dropping funnel, a stirring device, a thermometer, and a pressure reduction device. When heating with reduced pressure to 150-170 mmHg and internal temperature became 42 degreeC, 1216.2 weight part of isopropyl alcohol was dripped continuously from the dropping funnel, carrying out azeotropic distillation dehydration for 10 hours, and obtaining 234.2 weight part of silicon oxide sol dispersed in isopropyl alcohol. The water content of the silicon oxide sol dispersed in this isopropyl alcohol was 0.8% by weight by Karl Fischer moisture titration. Next, 9 parts by weight of methyltrimethoxysilane was added to the silicon oxide sol dispersed in isopropyl alcohol under normal pressure, and reacted at 40 ° C. for 24 hours, followed by 360.4 parts by weight of cyclohexanone from the dropping funnel under a reduced pressure of 150 to 170 mmHg. The deisopropyl alcohol was dripped, and decyclohexanone was performed at 50-55 degreeC of internal temperature, and the silicon oxide sol (average particle diameter: 30 nm) disperse | distributed to 100 weight part of pale yellow transparent cyclohexanone was obtained. The nonvolatile content of the silicon oxide sol dispersed in the obtained cyclohexanone was 45% by weight and the water content was 0.1% by weight.

Examples 2-4

Using the components and amounts shown in Table 1, a dispersion of silicon oxide sol was obtained in the same manner as in Example 1. The average particle diameter of the dispersion of the silicon oxide sol of Examples 2, 3, and 4 was 28 nm, 31 nm, and 28 nm, respectively.

Application example 1

Into a reaction vessel equipped with a reflux tube, a dropping funnel, a stirring device, and a thermometer, 33.3 parts by weight of xylene and 33.3 parts by weight of isobutyl acetate were injected, heated, and maintained at 110 ° C. There, 61 parts by weight of methyl methacrylate, 19 parts by weight of butyl acrylate, 19 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid, and 2,2'-azobis (2-methylbutyro Nitrile) The mixture of 1.7 parts by weight was added dropwise over 2 hours while maintaining the temperature from the dropping funnel. After completion of the dropwise addition, the mixture was kept at the same temperature and continued stirring for 1 hour, and a mixture of 0.2 parts by weight of 2,2'-azobis (2-methylbutyronitrile) and 2 parts by weight of isobutyl acetate was added. The stirring was continued for hours. After the completion of the polymerization, 36.9 parts by weight of the silicon oxide sol dispersed in the cyclohexanone obtained in Example 1 was added dropwise over 10 minutes from the dropping funnel while maintaining the same temperature, followed by stirring for 30 minutes, followed by organic non-volatile content of 57% by weight. An inorganic composite solution was obtained. The obtained organic inorganic composite had a glass transition temperature of 54 ° C., a number average molecular weight of 5200, a hydroxyl value of 70 mmKOH / g, and an acid value of 6 mmKOH / g.

Application Examples 2-7

Using the components and amounts shown in Tables 2 and 3, an organic-inorganic composite solution was obtained in the same manner as in Application Preparation Example 1.

Application Examples 1 to 8

A paint composition was prepared at the blending ratios shown in Tables 4 and 5. Subsequently, the paint composition is diluted with a Solvetso # 100 [manufactured by Etso Co.] / Cyclohexanone mixture (weight ratio 50/50) so that the viscosity at 20 ° C. of the pod cup No. 4 is 15 seconds, followed by air. By spraying (spray atomization pressure of 5 kg / cm 2), the film was coated on a clear test plate so as to have a dry film thickness of 30 μm, and forced drying at 80 ° C. for 30 minutes. Moreover, after leaving at room temperature for 3 days, the coating film performance was evaluated. The baking or forced drying conditions at the time of coating formation are shown in Tables 4 and 5, and the coating performance is shown in Tables 6 and 7.

Application Example 9

58.3 parts by weight of titanium oxide (Dupontitanium R-960, manufactured by DuPont), 34.6 parts by weight of the organic-inorganic composite solution obtained in Application Preparation Example 1, and 7.1 parts by weight of cyclohexanone were used as a medium by using a zircon bead as a medium. Then, the mixture was dispersed and dispersed at 3000 rpm for 40 minutes to prepare a pigment dispersion resin solution.

Next, 45.3 parts by weight of the pigment dispersion resin solution, 35.3 parts by weight of the organic-inorganic composite solution obtained in Production Example 21, 13.0 parts by weight of the silica sol obtained in Production Example 17, 0.2 parts by weight of Tinuvin 292 and 1.0 of BYK-358. The coating composition was prepared by stirring and mixing the weight part, 1.0 weight part of 1 weight% solution of SCAT-8, and 6.9 weight part of duranate THA-100.

Application Examples 10-13

At the compounding ratio shown in Table 8, the coating composition was prepared in the same manner as in Application Example 6, and then a coating film was formed on the test plate. Table 8 shows the baking or forced drying conditions in forming the film and Table 9 shows the coating performance.

Application Examples 14-16

At the compounding ratio shown in Table 10, the coating composition was prepared in the same manner as in Application Example 1, and then a coating film was formed on the test plate. Table 10 shows the baking or forced drying conditions for forming the film and Table 11 shows the coating performance.

Application Examples 17-19

At the compounding ratio shown in Table 12, the coating composition was prepared similarly to the application example 9, and the coating film was formed on the test board. Table 12 shows the baking or forced drying conditions in forming the film and Table 13 shows the coating performance.

Comparative Example 1

In Example 1, the dispersion of the solvent-dispersed silicon oxide sol was produced in the same manner as in Example, except that the treatment with the silane coupling agent was not performed. Table 14 shows the kind and amount of the component used.

Comparison of Storage Stability

The storage stability was compared with respect to the dispersion of the silicon oxide sol obtained in Examples 1 to 4 and the dispersion of the silicon oxide sol obtained in the comparative example. The results are shown in Table 15.

As described above, according to the present invention, a silicon oxide to be used for a coating composition having excellent pollution resistance, decontamination resistance, weather resistance (light resistance), chemical resistance, moisture resistance, and appearance and which is used for high environmental conservation and safety It is possible to provide a method for preparing a dispersion of the sol.

Claims (3)

(correction) After the azeotropic distillation of water contained in the aqueous silicon oxide sol with an azeotropic agent with water, the dispersion of the silicon oxide sol is surface-treated with a silane coupling agent. Manufacturing method. (correction) The method for producing a dispersion of solvent-dispersed silicon oxide sol according to claim 1, wherein the dispersion of solvent-dispersed silicon oxide sol is replaced with another solvent. (correction) The silane coupling agent according to claim 1 or 2 is methyltrimethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ-methacryloyloxypropyltrimethoxysilane. Method for producing a dispersion of solvent-dispersed silicon oxide sol, characterized in that at least one selected from the compound consisting of.