KR100222502B1 - Coating composition and process for preparing the composition - Google Patents

Abstract

(A) As essential component (a) Carbon number 1 Ester of (meth) acrylic acid of alkyl alcohol of 12 90 wt%, (b) hydroxy group-containing monomer 10 with polymerizable double bonds 50% by weight, (c) carboxyl group-containing monomer 0.1 having a polymerizable double bond Glass transition temperature 50 obtained by copolymerizing 10 weight% 120 ℃, number average molecular weight 2000 100,000, 50 hydroxyl value 150 mgKOH / g, acid value 1 At least one compound selected from a polyisocyanate compound and an aminoplast resin containing two or more resins of 25 mgKOH / g, (B) isocyanate group and / or block isocyanate group in one molecule, and (C) aluminum oxide sol, silicon oxide It contains a dispersion of at least one inorganic oxide sol selected from sol, zirconium oxide sol and antimony oxide sol, and the non-volatile content of the above-mentioned (C) component is (A) component, (B) line segment and (C) component Based on the weight of the total non-volatile content of A paint composition of 60% by weight and a resin of the above-mentioned (A) component were prepared, and after completion of this copolymerization, a dispersion of the inorganic oxide sol of the above-mentioned (C) component was added to the polymerization solution to prepare an organic inorganic composite. Moreover, it is a manufacturing method of the coating composition which mixes this organic inorganic complex and the compound of the said (B) component. This coating composition has excellent characteristics, such as being excellent in weather resistance (light) resistance, stain resistance, and decontamination, giving a coating film having good appearance, water resistance, and chemical resistance, and having high environmental conservation and stability.

Description

[Name of invention]

Paint composition and manufacturing method of paint composition

[Technical Field]

The present invention relates to a novel paint composition, a more preferred paint composition containing a dispersion of an inorganic oxide sol obtained by a specific production method, a more preferred paint composition obtained by a specific production method, and a method of producing the specific paint composition. . More specifically, the present invention contains a ceramic component, gives a coating film excellent in fouling resistance, pollutant resistance, weather resistance (light), chemical resistance, moisture resistance and appearance, and also has high environmental conservation and safety A method for producing a composition and a paint composition thereof.

[Background]

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 preservation and stability. .

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, and (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 × 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, the coating composition has been improved to some extent with respect to fouling resistance and weather resistance, but has a drawback of insufficient pollutant removal.

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, etc., and also has high environmental conservation and stability. And a method for producing the coating composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to develop the coating composition which has the said characteristic, the coating composition containing a specific acrylic resin, a polyisocyanate compound or an aminoplast resin, and a specific ceramic component is suitable for the objective. To obtain better object properties by mixing a specific acrylic resin and a specific ceramic component in the final step of the polymerization process of the specific acrylic resin, and using a specific ceramic component treated with a specific silane coupling agent. It was found out to obtain more excellent object properties, and thus the present invention was completed based on this knowledge.

Detailed description of the invention

[Initiation of invention]

The present invention, (A) (a) carbon number 1 Ester of (meth) acrylic acid of alkyl alcohol of 12 90% by weight, (b) hydroxy group-containing monomer 10 having a polymerizable double bond 50% by weight, (c) carboxyl group-containing monomer 0.1 having a polymerizable double bond 10% by weight, (d) styrene 0 20 wt%, (e) acrylonitrile 0 20% by weight and (f) other monomers 0 Glass transition temperature 50 obtained by copolymerizing 10 weight% 120 ℃, number average molecular weight 2,000 100,000, 50 hydroxyl value 150 mgKOH / g, acid value 1 At least one selected from a compound consisting of a polyisocyanate compound and an aminoplast resin containing two or more resins (B) isocyanate groups and / or blocked isocyanate groups in one molecule and (C) aluminum oxide, 25 mgKOH / g, At least one selected from dispersions of sol of inorganic oxides of silicon oxide, zirconium oxide and antimony oxide, and the non-volatile content of the component (C) is 5 based on the weight of the total non-volatile content. It is to provide a paint composition, characterized in that 60% by weight.

Moreover, this invention is (a) carbon number 1 Ester of (meth) acrylic acid of alkyl alcohol of 12 90% by weight, (b) hydroxy group-containing monomer 10 having a polymerizable double bond 50% by weight, (c) carboxyl group-containing monomer 0.1 having a polymerizable double bond 10% by weight, (d) styrene 0 20 wt%, (e) acrylonitrile 0 20% by weight and (f) other monomers 0 Copolymerization of 10% by weight of glass transition temperature 50 120 ℃, number average molecular weight 2,000 100,000, 50 hydroxyl value 150 mgKOH / g, acid value 1 Resin (A) of 25 mgKOH / g was prepared, and then, at the end of the copolymerization, at least one selected from the dispersions of sol of inorganic oxides of aluminum oxide, silicon oxide, zirconium oxide and antimony oxide in the polymerization liquid ( C), the non-volatile content of the component (C) is 5 based on the weight of the total non-volatile content At least one member selected from polyisocyanate compounds and aminoplast resins containing an organic inorganic complex and at least two isocyanate groups and / or fluoroisocyanate groups in one molecule by adding 60% by weight. It is to provide a method for producing a coating composition, characterized in that the compound (B) is mixed.

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

Preferred Mode for Carrying Out the Invention

In the coating composition of the present invention, the resin used as the component (A) has a glass transition temperature of 50. It is the range of 120 degreeC. 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 terms of hardness, appearance, decontamination and workability of the coating film, the preferred glass transition temperature is 50 It is the range of 100 degreeC.

The resin has a number average molecular weight of 2,000. It is in the range of 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 terms of weatherability and workability of the coating film, the number average molecular weight is 2,200 A range of 70,000 is preferred, especially 2,200 A range of 40,000 is suitable.

In addition, 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 fouling resistance, and if it exceeds 150 mgKOH / g, the structure of the coating film becomes too dense, resulting in coating film formation. Shrinkage stress becomes large and it is impossible to relieve | stretch, and cracks etc. become easy to produce in a coating film. In terms of fouling resistance, decontamination and suppression of cracking of the coating film, the hydroxyl value is 50. The range of 130 mgKOH / g is preferred.

On the other hand, the acid value of this resin is 1 25 mgKOH / g. If the acid value is less than 1 mgKOH / g, the pigment dispersibility deteriorates in the enamel paint system, and the discomfort such as sedimentation and coagulation of the pigment occurs at the time of coating storage, and if it exceeds 25 mgKOH / g, the pot life of the paint The back tends to be extremely deteriorated. In terms of dispersibility of pigment, storage stability of paint, pot life, etc., the acid value is 2 A range of 20 mgKOH / g is preferred.

In this invention, resin of (A) component is (a) carbon number 1 as an essential component. An ester of (meth) acrylic acid of alkyl alcohol of 12, b) a hydroxy group-containing monomer having a polymerizable double bond and (c) a carboxyl group-containing monomer having a polymerizable double bond, and optionally (d) styrene, (e) It is obtained by copolymerizing acrylonitrile and (f) other monomers.

Carbon number 1 of (a) component used as an essential monomer component The ester of (meth) acrylic acid of alkyl alcohol of 12 (hereinafter referred to as "acrylic ester") is 10 based on the weight of all monomers. It is used in the ratio of 90 weight%. 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 a coating film having desired desirable physical properties, the preferred amount of this acrylic ester is 35 It is 80% by weight.

Carbon number 1 which forms the acrylic ester of (a) component The alkyl alcohol of 12 may be any alcohol as long as it has a linear, branched or cyclic alkyl group. Examples of the acrylic ester of the component (a) include, for example, methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, and isobutyl methacrylate. , Methacrylic acid-t-butyl, pentyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, admanthyl methacrylate, dodecyl methacrylate, isopropyl methacrylate Neyl, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, cyclohexyl acrylate, 20 ethylhexyl acrylate, adder acrylate Mantyl, dodecyl acrylate, isobornyl acrylate and the like. These may be used 1 type or may be used in combination of 2 or more type.

Next, the hydroxyl group-containing monomer having a polymerizable double bond of component (b) used as the essential monomer component is 10 based on the weight of the total monomer. It is used in the ratio of 50 weight%. 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, if it exceeds 50% by weight, an unreacted hydroxy group remains in the resin at the time of the crosslinking reaction between the resulting resin and the component (B), further reducing the water resistance and moisture resistance of the coating film and reducing the weather resistance of the coating film. It becomes a cause and the crosslinking density of a coating film becomes high too much. 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 component (b) is 10 It is the range of 30 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 0.1 based on the weight of all the monomers. It is used in the ratio of 10 weight%. 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. In terms of dispersibility of the paint, storage stability of the paint, pot life, and the like, the preferred amount of the component (c) is 1 In the range of 5% by weight, in particular 1 The range of 3 weight% is preferable.

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 of the coating film and the like, weather resistance, pollution resistance, decontamination, etc., the preferred amount of styrene is preferably 1 It is the range of 18 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 view of the balance of adhesion, impact resistance, weather resistance, decontamination, etc. to the substrate of the coating film, the preferred amount of use of acrylonitrile is 1 It is the range of 18 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 preferred amount of use when using other monomers of the component (f) is 1 7% by weight.

The other monomer having a 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, malic acid esters such as programs. 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.

The polymerization temperature is generally 60 The range of 150 degreeC is preferable. 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 produce radicals, the growth reaction proceeds effectively. Difficult to do The polymerization time cannot be determined uniformly depending on the polymerization temperature or other conditions, but generally 2 6 hours is enough.

In the coating composition of the present invention, 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 a 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 ω-caprolactam, methyl ethyl ketoxime, methyl isoamyl ketoxime and methyl isobutyl ketoxime, 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 coating composition of the present invention, when the blending ratio of the component (A) and the component (B) is a polyisocyanate compound containing two or more isocyanate groups and / or block isocyanate groups in one molecule, The molar ratio of the isocyanate group and / or the blocked isocyanate group in the component (B) to the hydroxyl group of the component (A) is 0.6. It is preferably in the range of 1.6, particularly preferably 0.8 It is in the range of 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 by some unreacted reaction, and the water resistance and deterioration of the coating film obtained may deteriorate. It may be the cause. 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, the non-volatile content weight ratio of (A) component and (B) component is 97: 3 It is preferably in the range of 60:40, and 95: 5 More preferably in the range 65:35, in particular 91: 9 It is preferably in the range of 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 coating composition of the present invention, as the ceramic component of component (C), a dispersion of at least one inorganic oxide sol selected from among dispersions of sol of inorganic oxides of aluminum oxide, silicon oxide, zirconium oxide and antimony oxide is used. . The inorganic oxide sol is preferably a silicon oxide sol.

These inorganic oxide sols are generally supplied as an aqueous dispersion, and in the case of an aqueous dispersion, if the coating composition is water-based, it can be used as it is, but if it is an organic solvent, it is a method of phase switching in a desired organic solvent. Can be used. Preferred among the organic solvents used 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 the inorganic oxide sol is surface-treated with a silane coupling agent, and it is particularly preferable that the dispersion of the silicon oxide sol is surface-treated with a silane coupling agent. The surface-treated inorganic oxide sol dispersion can introduce various functional groups on its surface, and when used in the coating composition of the present invention, it is organic in resins, polyisocyanate compounds or aminoplast resins. It is easy to chemically bond with the powder. 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, dimethyl dimethoxysilane 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, the compounding quantity to a silane coupling agent is 1 with respect to the non volatile matter of an inorganic oxide sol. 40 wt% is preferred and 5 30 weight% is more preferable.

As the dispersion of the inorganic oxide sol treated with the silane coupling agent, after azeotropic distillation of water contained in the aqueous inorganic oxide sol with an azeotropic agent with water, the dispersion of the inorganic oxide sol is surfaced with the silane coupling agent. It is preferable to use the dispersion of the non-conjugated dispersed inorganic oxide sol obtained by treatment. It is particularly preferable that the dispersion of the inorganic oxide sol is a dispersion of the silicon oxide sol. Dispersion of the inorganic oxide sol obtained by this production method improves pollution resistance, decontamination resistance, weather resistance, etc., and also enables high concentration of the inorganic oxide sol. 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-solvent include water-soluble (ie, water-soluble) alcohols, carboxylic acid esters, steriles in the cyclic form, 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 does not interfere even 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 which does not aggregate the sol, and also varies depending on the solvent, but usually 1 The range of 10 weight% is preferable.

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

Public distillation dehydration is 30 It is preferable to carry out in 100 degreeC, and especially 40 It is preferable to carry out in 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.

It is preferable that the water content in the azeotropic agent dispersed inorganic oxide sol after azeotropic distillation dehydration is usually 2% by weight or less, and particularly preferably 1% by weight or less.

The concentration of the dispersion of the azeotropic agent dispersed mugging oxide sol after azeotropic distillation dehydration is preferably 55% by weight or less, particularly 25 It is preferable that it is 55 weight%.

The surface treatment with a silane coupling agent can be performed by mixing a silane coupling agent with the dispersion of an azeotropic agent dispersion inorganic oxide sol after azeotropic distillation and dehydration. Although the surface treatment temperature by a silane coupling agent is not specifically limited, Usually 20 It is preferable to carry out in 100 degreeC, and it is 30 It is more preferable to carry out in the range of 90 degreeC, Especially 40 It is preferable to carry out in 80 degreeC.

It is preferable that the water content in the solvent-dispersed inorganic 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.

Moreover, the solvent of an unanticipated dispersion inorganic 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 on the kind of solvent used when replacing, 30 It is preferable to carry out in 120 degreeC, and especially 40 It is preferable to carry out in 110 degreeC.

In the coating composition of the present invention, one kind of dispersion of the inorganic oxide sol may be used, or two or more kinds thereof may be used in combination, and the blending amount of the nonvolatile matter of the dispersion of the inorganic oxide sol is (A 5) for the total nonvolatile matter of the component, (B) component and (C) component. It is selected to be 60% by weight. If the non-volatile content of the inorganic oxide sol dispersion is less than 5% by weight relative to the total non-volatile content, the effect of adding the dispersion of the inorganic 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 terms of balance of fouling resistance, decontamination property, weather resistance, and flexibility of the coating film, the nonvolatile content of the dispersion of the inorganic oxide sol is 5% of the total nonvolatile content. A 40 weight percent range is preferred.

The dispersion of the inorganic 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 stain resistance and decontamination property of the coating film are lowered.

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

In the coating composition of the present invention, 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, tin compounds or zinc The compound 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. The curing reaction catalyst is 0.01 to the total nonvolatile matter in the paint composition. It is preferable to use it in the ratio of 5 weight%. 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 curing rate and coating film properties, a more preferable compounding amount of this curing reaction catalyst is 0.01 to the total nonvolatile matter in the composition. It is the range of 2 weight%.

In the coating composition of the present invention, when the aminoplast resin is used 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 was 0.01% of the total nonvolatile matter of the paint. The range of 2 weight% is preferable. 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, when producing the coating composition of the present invention, an appropriate amount of an appropriate pigment, dye, or brightening agent is added to enamel, so that the original function is not lost. 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 coating composition of the present invention, when a pigment is included, the blending ratio of the pigment is usually 0.1 40% by weight is preferred, in particular 0.5 35% by weight is preferred.

There is no restriction | limiting in particular in the preparation method of the coating composition of this invention, 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) carbon number 1 Ester of (meth) acrylic acid of alkyl alcohol of 12 90 wt%, (b) hydroxy group-containing monomer 10 with polymerizable double bonds 50% by weight, (c) carboxyl group-containing monomer 0.1 having a polymerizable double bond 10% by weight, (d) styrene 0 20 wt%, (e) acrylonitrile 0 20% by weight and (f) other monomers with polymerizable double bonds 0 Copolymerization of 10% by weight of glass transition temperature 50 120 ℃, number average molecular weight 2,000 100,000, 50 hydroxyl value 150 mgKOH / g, acid value 1 A resin (A) of 25 mgKOH / g was prepared, and then, after the completion of the copolymerization, the polymer solution was subjected to at least one inorganic oxide sol selected from aluminum oxide sol, silicon oxide sol, zirconium oxide sol, and antimony oxide sol. In the dispersion (C), the non-volatile content of the component (C) is 5 based on the weight of the total non-volatile content of the component (A), the component (B) and the component (C). A method of preparing an organic inorganic composite obtained by adding 60% by weight or dispersion stabilized component (C) in the monomer, followed by copolymerization of the monomer to prepare a resin (A) to prepare an organic inorganic composite obtained. The method is preferred.

In particular, the dispersion of the inorganic oxide sol of component (C) is obtained by heating or dispersing the dispersion of the inorganic oxide sol to the polymerization liquid after the completion 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 inorganic oxide sol of (C) component replaces addition of a diluent. .

By adding the dispersion of the inorganic 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 inorganic oxide sol is unlikely to occur and dispersion of the inorganic oxide sol in a subsequent step. Addition of a sieve also makes it difficult to cause aggregation. 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 paint composition of this invention is suitable also as a paint which can reduce environmental pollution.

Addition of the dispersion of the inorganic 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 glass transition temperature is 50 120 ℃, number average molecular weight 2,000 100,000, 50 hydroxyl values 150 mgKOH / g and acid number 1 It means that after resin of (A) component which has 25 mgKOH / g is manufactured, the polymerization liquid may contain the unreacted monomer.

The addition of the dispersion of the inorganic oxide sol of the component (C) is preferably performed at a temperature below the boiling point of the dispersion medium of the inorganic oxide sol of the component (C), more particularly than the boiling point of the dispersion medium of the inorganic oxide sol of the component (C). 10 A low temperature of 50 ° C. is preferred.

As for the polymerization liquid before adding the dispersion of the inorganic oxide sol of (C) component, resin content is 40 It is preferable to exist in the range of 80 weight%, especially 50 It is preferable to exist in the range of 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 the inorganic oxide sol of component (C) in a polymerization solvent, the monomer of (A) component is prepared in the same manner as the polymerization conditions described above. The organic-inorganic composite solution in which the inorganic oxide sol is dispersed and stabilized is prepared by polymerization and production, or by polymerizing the resin of component (A) and dispersing and stabilizing the dispersion of the inorganic oxide sol in a resin solution under heating or non-heating. The method of preparing the coating composition of this invention 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. have.

Moreover, in the case of an enamel paint system, the coating composition of this invention can be prepared by disperse | distributing resin of (A) component, a pigment dispersant, etc. and a desired pigment by a disperser, and mix | blending it with said 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 to cure the coating composition of the present invention thus obtained depend on the type of each component and the reaction catalyst to be used, but it is generally about 30 seconds to about 10 hours at a temperature ranging from room temperature to 220 ° C. to be.

The coating composition of the present invention can be used for either a single layer coating film or a composite coating film.

As an example of a composite coating film, for example, a coating composition for a colored film is formed on a substrate to form a base coating film, and then a transparent upper coating film is formed on the base coating film by applying a clear film forming composition as a coating composition of the present invention. There is a composite coating obtained by the coating finishing method.

The colored film forming composition of the base coating film contains a resin binder and a pigment.

Examples of the resin binder include various binders such as known acrylic resins, polyester resins (including alkyd resins), polyurethane resins, and melamine resins.

In addition, to the colored film-forming composition of the base coating film, various additives commonly used, for example, at least one of a surfactant, a leveling agent, a thixotropic agent, a filler, an antifoaming agent, an organic solvent, a catalyst and the like can be added. .

In the colored film-forming composition, the pigment is 1 It is preferable to mix | blend 80 weight%, especially 3 It is preferable to mix | blend 60 weight%.

As the pigment, various pigments such as organic pigments and inorganic pigments are used. For example, aluminum, copper, brass, bronze, stainless steel, or mica iron oxide, scaly-shaped methyl powder, titanium oxide, which have been subjected to respective surface treatments. And metal pigments such as mica pieces coated with iron oxide. In addition, inorganic pigments such as titanium dioxide, iron oxide, yellow iron oxide, carbon black, organic pigments such as phthalocyanine blow, phthalocyanine green, and quinacridone red pigments, and extender pigments such as precipitated barium sulfate, gray, silica, talc, and the like. Can be mentioned.

In the coating and finishing method of the composite coating film, the colored film-forming composition of the base coating film is heated as necessary or adjusted to a desired viscosity by adding an organic solvent or a reactive diluent, and then air spray, electrostatic air spray, roll coater. Coating after drying using a commonly used painter such as a paint coater, a flow coater or a deflator, or a brush, a bar coater, or an applicator. Apply to 300㎛, usually 50 5 seconds at a temperature of 300 ° C In the case of performing heat curing for 24 hours and carrying out two coat 1 bake coating, the colored film-forming composition is diluted to a desired viscosity with an appropriate diluent such as, for example, an organic solvent, and then dried using the above method. Later film thickness is usually 5 40 μm, preferably 7 Apply | coated to 35 micrometers, and room temperature 1 at a temperature of 100 ℃ It was left to stand for 20 minutes, and then the film thickness after drying the clear film forming composition of a clear coating film using the said method is 10. 100 μm, preferably 10 Apply to 60㎛, 50 5 seconds at a temperature of 300 ° C The method of heat-hardening for 24 hours etc. are mentioned. Moreover, as for a coating method, spray coating is preferable among the above-mentioned methods.

As another example of the composite coating film, for example, a coating method of coating a colored base coating paint on a substrate, applying a clear coating paint in an uncrosslinked state, baking it, and then coating and baking the overclear coating paint. In the present invention, there is a composite coating film obtained by a coating and finishing method comprising using an acrylic resin / aminoplast resin paint as the clear coating paint and using the paint composition of the present invention as the overclear coating paint.

As the colored base coating material, those similar to the composite coating film can be used.

As the clear coating paint in which the copper coating is applied in an uncrosslinked state on the colored base coating film, an acrylic resin / aminoplast resin is used.

As the acrylic resin, for example, (a) carbon number 1 An ester of (meth) acrylic acid of an alkyl alcohol of 12, (b) a hydroxy group-containing monomer having a polymerizable double bond and (c) a carboxyl group-containing monomer having a polymerizable double bond, as necessary, and (d) styrene and copolymerization of (e) acrylonitrile and (f) other monomers.

Moreover, as an example of an aminoplast resin, a melamine resin, guanamine resin, etc. are mentioned preferably, for example. One kind of these aminoplast resins may be used or two or more kinds thereof may be used in combination. In addition, as long as two or more reactive groups are contained in one molecule, there is no restriction | limiting at all other than this, Specifically, even if one or more triadin rings exist in one molecule of melamine or guanamine resin, it does not interfere. As a reactive group which exists 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 acrylic resin / aminoplast resin, the blending ratio of the acrylic resin and the aminoplast resin is not particularly limited, but the weight ratio of the acrylic resin and the aminoplast resin is 90:10. The range of 50:50 is preferable, especially 80:20 The range of 60:40 is preferable.

In acrylic resin / aminoplast resin, you may mix | blend the curing reaction catalyst of aminoplast resin. As an example of the hardening reaction catalyst of an aminoplast resin, sulfonic-acid hardening catalysts, such as a phosphate hardening catalyst, toluenesulfonic acid, and dodecylbenzenesulfonic acid, or those amine block bodies, are preferable, for example. These compounds may be used alone or in combination of two or more thereof, and may be used at all, and the curing time may be adjusted in combination with other compounds. In addition, the amount of these compounds added was 0.01% of the total nonvolatile matter in the acrylic resin / aminoplast resin. The range of 2 weight% is preferable.

In addition, it is possible to mix | blend additives, such as a flow regulator, a leveling agent, an antigelling agent, antioxidant, a ultraviolet absorber, and a radical trapping agent, with the clear coating paint in the coating film finishing method of the said composite coating film as needed.

Preferable examples of the coating and finishing method for the composite coating include heating the colored base coating as needed or adjusting the viscosity to a desired viscosity by adding an organic solvent or a reactive diluent, followed by air spray, electrostatic air spray, roll coater, and flow. The film thickness of the coating film after drying using a coater commonly used, such as a coater or a dipping machine, or a brush, a bar coater, an applicator, or the like is usually 5 40 μm, preferably 7 Apply | coated to 35 micrometers, and room temperature 1 at a temperature of 100 ℃ The film thickness of the coating film after drying for 20 minutes and then drying the clear coating paint using the above method is 10. 100 μm, preferably 10 Apply to 60㎛, 50 5 seconds at a temperature of 300 ° C Heat curing for 24 hours.

Next, the film thickness of the coating film after drying the overclear coating paint using the said method is 5 50 μm, preferably 5 Apply to 20㎛, 50 5 seconds at a temperature of 300 ° C Heat curing for 24 hours.

The base material to which the coating composition of the present invention 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, plaster And organic materials such as boards 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 composition obtained by applying the thermosetting composition of the present invention or the coating composition obtained by applying the above alternative coating composition, for example, a building, a structure, a wooden product, a metal product, a plastic product, a rubber product, a processed paper, a ceramic product, a glass product, etc. Can be mentioned. More specifically, metal plates such as automobiles, automobile parts (for example, bodies, bumpers, spoilers, mirrors, wheels (for example, aluminum wheels, etc.), interior materials and the like, and various materials), steel plates, etc.) , Motorcycles, parts for motorcycles, road materials (e.g. guard rails, traffic signs, etc.), tunnel materials (e.g. sidewall plates, etc.), ships, railway vehicles, aircraft, printing equipment, printing machine parts, furniture , Musical instruments, home appliances, building materials, containers, office supplies, sporting goods, toys and the like.

Moreover, the coating composition of this invention can be used also for an ink, an adhesive agent, a molded article, etc. besides a coating material.

EXAMPLE

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) Manufacture of Clear Coating Trial

Baking epoxy resin [Epico Primer No.] on abrasive steel sheet (JIS G-3141) 1000 BF2, manufactured by Nihon Yushi Co., Ltd.] was coated so as to have a thickness of 20 μm, and then 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 at 80 degreeC for 30 minutes, and the test plate was produced by preventing overnight.

(2) Production of enamel coating test plate

The test plate is coated on a polishing steel sheet (JIS G-3141) by coating baking epoxy resin (Epico Primer No. 1000BF2, manufactured by Nihon Yushi Co., Ltd.) to a thickness of 20 µm and baking at 160 ° C. for 20 minutes. Made.

(3) Evaluation of coating film 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) Sun Young 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 determined by a test by the Sunshine Carbon Arc Equation weathering 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 the condition of 40 ± 1 ° C., the surface state of the test piece was taken out and 2 hours later was 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 made the surface of the test piece penetrate 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 JIS K-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: An adhesion test was conducted in accordance with JIS K-5400 (1990) 8.5.1, and 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 thickness 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: A value obtained by subtracting the L value after exposure from the initial L value before exposure (3) by performing an outdoor exposure test on the specimen for 3 months and using SM color computer SM-4-MCH (manufactured by Suga Test Equipment Co., Ltd.) L) evaluated the contamination of the coating film surface.

(4) workability

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

◎ very good

○: good

△: not all good

×: not good overall

(n) Deposition efficiency: It refers to the efficiency that the sprayed paint adheres to the coating. The spread of the mist and the arrival rate of the mist to the coating at the time of coating are comprehensively observed and evaluated 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.

[Production Example 1]

In a reaction vessel equipped with a stirring device, a thermometer, a reflux tube, and a dropping funnel, 50 parts by weight of xylene and 50 parts by weight of isobutyl acetate were prepared, 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-methylbutyronitrile ) A mixture of 2 parts by weight was added dropwise over 2 hours while maintaining the same temperature from the dropping funnel. After completion of the dropwise addition, the mixture was kept at the same temperature for 1 hour, and the mixture was mixed with 0.2 parts by weight of 2,2'-azobis (2-methylbutyronitrile) and 2 parts by weight of isobutyl acetate, and further 1 hour. Stirring was continued. After the end of the polymerization, a resin solution having a nonvolatile content of 50.2% by weight was obtained.

The glass transition temperature of the obtained resin was 50 degreeC, the number average molecular weight 4,800, the hydroxyl value was 80 mgKOH / g, and the acid value was 7 mgKOH / g.

Production Example 2 14]

Table 1 A resin solution was prepared in the same manner as in Production Example 1 using the solvent, monomer and polymerization initiator of the kind and amount shown in 4.

Physical properties of the obtained resin Table 1 Mark on 4.

[Production Example 15]

In reaction vessel equipped with a stirring device, thermometer, reflux tube with Dean and Stark trap, and dropping funnel, Snowtex MIBK-ST (manufactured by Nissan Kagaku Kogyo Co., Ltd., dispersion of silicon oxide (average particle diameter: 30 nm), fire Volatile content: 30% by weight, Solvent: 1000 parts by weight of methyl isobutyl ketone and 40 parts by weight of A-163 (manufactured by Nihon Uniker, Co., Ltd., Silane Coupling Agent) were prepared, and the resulting mixture was heated and kept at 80 ° C for 8 hours. 1020 parts by weight of silacazole (average particle diameter: 32 nm) surface-treated with

[Production Example 16]

A resin solution was prepared in the same manner as in Production Example 1 using the solvent, monomer and polymerization initiator of the kind and amount shown in Table 5.

The physical properties of the obtained resin are shown in Table 5.

Example 1

45.0 parts by weight of the resin solution obtained in Production Example 1, 4.5 parts by weight of cyclohexanone, 41.2 parts by weight of the surface-treated silicazol obtained in Production Example 15, 0.8 parts by weight of Tinuvin 900 (manufactured by Chiba-Geigi Co., Ltd., UV absorber), Tinubin 292 0.2 parts by weight of [Ciba-Geigi Co., Ltd., a hindered amine-type antioxidant], 1.0 part by weight of BYK-358 [manufactured by BICKEM Co., Ltd., leveling agent], 1 of SCAT-8 [manufactured by Mitsutomo Yukikase Co., Ltd., tin-based curing catalyst] A paint composition was prepared by stirring and mixing 1.0 parts by weight of the solution by weight and 6.3 parts by weight of duranate THA-10 (Asahi Kasei Co., Ltd., polymer of hexamethylene diisocyanate).

Subsequently, the paint composition is diluted with a Solveso # 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, and is then air. By spraying (spray atomization pressure of 5 kg / cm 2), the film was coated on the clear test plate so that the dry film thickness was 30 μm, and forced drying was performed at 80 ° C. for 30 minutes. Moreover, after leaving at room temperature for 3 days, the coating film performance was evaluated.

Table 6 shows the mixing ratio of each component in the paint composition and the conditions for baking, and Table 9 shows the coating performance.

Example 2-15

After the coating composition was prepared in the same manner as in Example 1 at the blending ratio shown in Table 6-8, a coating film was formed on the test plate. Table 6 shows the conditions of baking or forced drying during film formation 8, Table 9 shows the coating performance. Mark 11

Example 16

52.5 parts by weight of titanium oxide [Dupontitanium R-960, manufactured by DuPont], 35.0 parts by weight of the resin solution obtained in Production Example 1, and 12.5 parts by weight of cyclohexanone were mixed and dispersed at 3000 rpm for 40 minutes by a motor mill (manufactured by Iger Japan Co., Ltd.), A pigment dispersion resin solution was prepared.

Next, 46.9 parts by weight of this pigment dispersion resin solution, 22.0 parts by weight of the resin solution obtained in Production Example 1, 3.0 parts by weight of cyclohexanone, 20.5 parts by weight of the surface-treated silicaazole obtained in Production Example 15, and 0.2 parts by weight of tinubin 292. The coating composition was prepared by stirring and mixing 1.0 parts by weight of BYK-358, 1.0 parts by weight of a 1% by weight solution of SCAT-8, and 5.4 parts by weight of duranate THA-100.

Next, this coating composition is diluted with the Solvesso # 100 [Eso company] / cyclohexanone mixture solvent (weight ratio 50/50) so that the viscosity at 20 degrees C of pod cup No. 4 may be set to 15 second, By air spray (spraying pressure 5 kg / cm <2>), the test plate was coated so that a dry film thickness might be set to 30 micrometers, and it forced-dried at 80 degreeC for 30 minutes. Moreover, after leaving for three days at room temperature, the coating film performance was evaluated. Coating performance is shown in Table 12.

Dismodule BL-3175: Polymer of block type hexamethylene diisocyanate made by Sumitomo Bayer Urethane Co., Ltd.

Reference Example 1 3]

A resin solution was prepared in the same manner as in Production Example 1 using the solvent, the monomer and the polymer initiator of the kinds and amounts shown in Table 13. The physical properties of the obtained resin are shown in Table 13.

Comparative Example 1

49.6 parts by weight of the resin solution obtained in Reference Example 1, 5.0 parts by weight of cyclohexanone, 29.0 parts by weight of the surface-treated silicazol obtained in Production Example 15, 0.8 parts by weight of Tinuvin 900 [supra], 0.2 parts by weight of Tinuvin 292, BYK A paint composition was prepared by stirring and mixing 1.0 parts by weight of -358, 1.0 parts by weight of a 10% by weight solution of SCAT-8, and 13.4 parts by weight of DIS module BL-3175.

Next, the paint composition is diluted with a Solveso # 100 (manufactured by Etso Co., Ltd.) / Cyclohexanone mixture solution (weight ratio 50/50) so that the viscosity at 20 ° C. of the pod cup No. 4 is 15 seconds, and the air is By spraying (spraying pressure 5 kg / cm <2>), it coated on the clear test board so that a dry film thickness might be set to 30 micrometers, and baked at 140 degreeC for 30 minutes. Moreover, after leaving for three days at room temperature, the coating film performance was evaluated.

Table 14 shows the mixing ratio and the baking or forced drying conditions of each component in the paint composition and Table 16 shows the coating properties.

Comparative Example 2 7]

After the coating composition was prepared in the same manner as in Comparative Example 1, the coating film on the test plate is shown in Table 17.

Allotan UW2818: Nihon Shokubaikagaku Co., Ltd., acrylic polyol resin, non-volatile content 60% by weight

Coronate 2515: Nihon Polyurethane Co., Ltd., isocyanate, nonvolatile content 80% by weight

Organosilica sol: 30% by weight of non volatile matter

Organo titania sol: 30% by weight of non volatile matter

Example 17

45.0 parts by weight of the resin solution obtained in Production Example 1, 4.5 parts by weight of cyclohexanone, 41.2 parts by weight of the surface-treated silicaazole obtained in Production Example 15, 0.8 parts by weight of Tinuvin 900 (manufactured by Chiba Chemical Co., Ltd., UV absorber) 0.2 parts by weight of Nuvin 292 [manufactured by Chiba Co., Ltd., hindered amine-based antioxidant], 1.0 part by weight of BYK-358 [manufactured by BICKEM Co., Ltd., leveling agent], banbu 220 [Mitsuito Arts Co., Ltd., melamine resin] 7.3 parts by weight The coating composition was prepared by mixing.

Subsequently, the paint composition is diluted with a Solveso # 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, and is then air. By spraying (spraying pressure 5 kg / cm <2>), it coated on the clear test board so that a dry film thickness might be set to 30 micrometers, and baked at 140 degreeC for 30 minutes. Moreover, after leaving at room temperature for 3 days, the coating film performance was evaluated.

Table 18 shows the compounding ratio of each component in the paint composition and the conditions for baking or forced drying, and Table 21 shows the coating performance.

Example 18 30 and 32]

Table 18 After the coating composition was prepared in the same manner as in Example 17 at the blending ratio shown in 20, a coating film was formed on the test plate. Table 18 shows the baking and forced drying conditions for forming the film. 20, the film performance is shown in Table 21 Mark on 23.

Example 31

52.5 parts by weight of titanium oxide [Dupontitanium R-960, manufactured by DuPont], 35.0 parts by weight of the resin solution obtained in Production Example 1, and 12.5 parts by weight of cyclohexanone were mixed and dispersed at 3000 rpm for 40 minutes by a motor mill (manufactured by Iger Japan Co., Ltd.), A pigment dispersion resin solution was prepared.

Next, 46.9 parts by weight of this pigment dispersion resin solution, 22.0 parts by weight of the resin solution obtained in Production Example 1, 3.0 parts by weight of cyclohexanone, 20.5 parts by weight of the surface-treated silicaazole obtained in Production 15, 0.2 parts by weight of Tinuvin 292, A coating composition was prepared by stirring and mixing 1.0 parts by weight of BYK-358 and 6.4 parts by weight of milk board 220 (manufactured by Mitsui Art Co., Ltd., melamine resin).

Next, this paint composition is diluted with the Solvesso # 100 [product of Eso company] / cyclohexanone mixture (weight ratio 50/50) so that the viscosity at 20 degrees C of pod cup No. 4 may be set to 15 second, By air spray (spraying pressure 5 kg / cm <2>), it coated on the test plate for enamel coating so that a dry film thickness might be set to 30 micrometers, and baked at 140 degreeC for 30 minutes. Moreover, after leaving for three days at room temperature, the coating film performance was evaluated. Coating performance is shown in Table 23.

Comparative Example 8

49.6 parts by weight of the resin solution obtained in Reference Example 1, 5.0 parts by weight of cyclohexanone, 29.0 parts by weight of the surface-treated silicazol obtained in Production Example 15, 0.8 parts by weight of Tinuvin 900 [supra], 0.2 parts by weight of Tinuvin 292, BYK A paint composition was prepared by stirring and mixing 1.0 parts by weight of -358 and 14.4 parts by weight of the lactose 220 (above).

Next, this paint composition is diluted with the Solvesso # 110 [product of Eso company] / cyclohexanone mixture (weight ratio 50/50) so that the viscosity at 20 degrees C of pod cup No. 4 may be set to 15 second, By air spray (spraying pressure 5 kg / cm <2>), it coated on a clear test board so that a dry film thickness might be set to 30 micrometers, and baked at 140 degreeC for 30 minutes. Moreover, after leaving for three days at room temperature, the coating film performance was evaluated.

Table 24 shows the compounding ratios and baking or forced drying conditions of the components in the paint composition and Table 25 shows the coating performance.

Comparative Example 9 12]

After the coating composition was prepared in the same manner as in Comparative Example 1, the coating film was formed on the test plate. Table 24 shows the baking or forced drying conditions in forming the film and Table 25 shows the coating performance.

[Production Example 17]

Snortex-0 (trade name, manufactured by Nissan Kagaku Co., Ltd., water-based silicon oxide sol, average particle diameter: 20 nm) 180.2 parts by weight, 63.1 parts by weight of isopropyl alcohol, dropping funnel, stirring device, The reaction vessel was equipped with a thermometer and a decompression device. 150 When heating at reduced pressure to 170 mmHg and internal temperature became 42 degreeC, 1216.2 weight part of isopropyl alcohol was dripped continuously at the dropping funnel, and azeotropic distillation dehydration was performed for 10 hours, and 234.2 weight part of silicon oxide dispersions disperse | distributed to isopropyl alcohol were obtained. . The water content (ie, 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. Deisopropyl alcohol was added dropwise with dropping 360.4 parts by weight of cyclohexanone from the dropping funnel under a reduced pressure of 170 mmHg, followed by internal temperature 50 By decyclohexanone at 55 degreeC, 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.

[Manufacture example 18 20]

Using the components and amounts shown in Table 26, a dispersion of silicon oxide sol was obtained in the same manner as in Production Example 17. The average particle diameters of the dispersion of the silicon oxide sol of Production Examples 18, 19, and 20 were 28 nm, 31 nm, and 28 nm, respectively.

[Production Example 21]

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 are 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-methylbutyronitrile ) Mixing 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, and 1 The stirring was continued for hours. After the completion of the polymerization, 36.9 parts by weight of silicon oxide sol dispersed in cyclohexanone obtained in Preparation Example 17 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.

[Production Example 22 27]

Using the components and amounts shown in Tables 27 and 28, an organic-inorganic composite solution was obtained in the same manner as in Preparation Example 21.

Example 33 40]

After the coating composition was prepared in the same manner as in Example 1 at the compounding ratios shown in Tables 29 and 30, a coating film was formed on the test plate. The baking or forced drying conditions in forming the coating film are shown in Tables 29 and 30, and the coating performance is shown in Tables 31 and 32.

Example 41

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 Production Example 21, and 7.1 parts by weight of cyclohexanone were prepared using zircon beads as a medium by a motor mill (manufactured by Iger Japan). 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.

Example 42 45]

After the coating composition was prepared in the same manner as in Example 38 at the compounding ratio shown in Table 33, a coating film was formed on the test plate. Table 33 shows the baking or forced drying conditions in forming the film and Table 34 shows the coating performance.

Example 46 48]

After the coating composition was prepared in the same manner as in Example 17 at the compounding ratio shown in Table 35, a coating film was formed on the test plate. Table 35 shows the baking or forced drying conditions in forming the film and Table 36 shows the coating performance.

Example 49 51]

After the coating composition was prepared in the same manner as in Example 41 at the compounding ratio shown in Table 37, a coating film was formed on the test plate. Table 37 shows the baking or forced drying conditions in forming the film and Table 38 shows the coating performance.

Production Example 28

In Production Example 17, a dispersion of solvent-dispersed silicon oxide sol was prepared in the same manner as in Production Example 17 except that the treatment with the silane coupling agent was not performed. Table 39 shows the kind and amount of the component used.

[Comparison of Storage Stability]

Preparation Example 17 The storage stability was compared with respect to the dispersion of the silicon oxide sol obtained in 20 and the dispersion of the silicon oxide sol obtained in Production Example 28. The results are shown in Table 40.

Example 52

Cationic electrodeposition paint Aqua No. 4200 (registered trademark, manufactured by Nihon Yushi Co., Ltd.) was electrodeposited and coated at 175 ° C for 25 minutes on a zinc phosphate treated steel sheet, and the intermediate coating epico No. 1500CP was used. The sealer (registered trademark, manufactured by Nihon Yushi Co., Ltd.) was air sprayed to have a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes. Subsequently, the bell coat No. 6000 silver metallic base coat paint (registered trademark, manufactured by Nihon Yushi Co., Ltd.) was coated with an air spray so as to have a dry film thickness of 15 μm at 1 minute and 30 seconds at intervals of 2 stages, followed by 3 minutes at 20 ° C. What was set was made into a trial version. In addition, the coating composition of Example 33 was diluted with thinner (xylene) to a coating viscosity (Pod Cup No. 4, 25 seconds at 20 ° C), and then air was dried on the test plate prepared by the above-described method so as to have a dry film thickness of 40 µm. It coated by spray, baked at 80 degreeC for 30 minutes, and created the test piece of a composite coating film. The mixing ratio, baking or forced drying condition of the paint is shown in Table 41 and the coating performance is shown in Table 42.

Example 53

In Example 52, the test piece was produced like Example 52 except having used the coating composition of Example 46 instead of the coating composition of Example 33. The mixing ratio of the paint, baking or forced drying conditions is shown in Table 41 and the coating performance is shown in Table 42.

Example 54

Cationic electrodeposition paint Aqua No. 4200 (registered trademark, manufactured by Nihon Yushi Co., Ltd.) was electrodeposited and coated at 175 ° C for 25 minutes on a zinc phosphate treated steel sheet, and the intermediate coating epico No. 1500CP was used. The sealer (registered trademark, manufactured by Nihon Yushi Co., Ltd.) was air sprayed to have a dry film thickness of 40 μm, and baked at 140 ° C. for 30 minutes. Subsequently, the bell coat No. 6000 silver metallic base coat paint (registered trademark, manufactured by Nihon Yushi Co., Ltd.) was coated with an air spray so as to have a dry film thickness of 15 μm at 1 minute and 30 seconds at intervals of 2 stages, followed by 3 minutes at 20 ° C. After setting, the bell coat No.6000 clear paint (registered trademark, manufactured by Nihon Yushi Co., Ltd., weight ratio of acrylic resin / aminoplast resin: 70/30), which is a clear coat paint made of acrylic resin / aminoplast resin, is dried. Air spray coating was carried out so that the film thickness might be 30 µm, and baking was carried out at 140 ° C for 30 minutes under curing conditions.

In addition, after diluting the paint of Example 35 as an overclear coat paint with a coating viscosity (Pod Cup No. 4, 25 seconds at 20 ° C.) by thinner (xylene), a dry film thickness of 10 It coated by air spray so that it might become micrometer, and baked at 80 degreeC for 30 minutes of hardening conditions, and created the test piece of the composite coating film. The mixing ratio, baking or forced drying condition of the paint is shown in Table 41 and the coating performance is shown in Table 42.

Example 55

In Example 54, the test piece was produced like Example 54 except having used the coating composition of Example 48 instead of the coating composition of Example 35. The mixing ratio of the paint, baking or forced drying conditions is shown in Table 41 and the coating performance is shown in Table 42.

The coating composition of the present invention, which has a ceramic component, is excellent in weather resistance (light), contamination resistance and decontamination, and gives a coating film having good appearance, water resistance, and chemical resistance, and also has high environmental conservation and stability. It has an outstanding characteristic.

Claims (12)

(A) (a) carbon number 1 Ester of (meth) acrylic acid of alkyl alcohol of 12 90 wt%, (b) hydroxy group-containing monomer 10 with polymerizable double bonds 50% by weight, (c) carboxyl group-containing monomer 0.1 having a polymerizable double bond 10% by weight. (D) Styrene 0 20 wt%, (e) acrylonitrile 0 20% by weight and (f) other monomers with polymerizable double bonds 0 Glass transition temperature 50 obtained by copolymerizing 10 weight% 120 ℃, number average molecular weight 2000 100,000, 50 hydroxyl value 150 mgKOH / g, acid value 1 At least one compound selected from a polyisocyanate compound and an aminoplast resin containing two or more resins of 25 mgKOH / g, (B) isocyanate group and / or block isocyanate group in one molecule, and (C) aluminum oxide sol , A dispersion of at least one inorganic oxide sol selected from silicon oxide sol, zirconium oxide sol, and antimony oxide sol, and the non-volatile content of the above-mentioned (C) component is (A) component, (B) component and ( C) 5 based on the total weight of nonvolatile components A paint composition, characterized in that 60% by weight. The coating composition according to claim 1, wherein the dispersion of the inorganic oxide sol is surface treated with a silane coupling agent. The dispersion of the inorganic oxide sol according to claim 1, wherein after the azeotropic distillation of water contained in the aqueous inorganic oxide sol with an azeotropic agent with water, the dispersion of the inorganic oxide sol is surface treated with a silane coupling agent. A paint composition, which is obtained. The inorganic oxide sol dispersion of (C) component was added to the polymerization liquid in any one of Claims 1-3 after completion | finish of superposition | polymerization in copolymerization of the monomer for obtaining resin of (A) component. Paint composition, characterized in that. (B) A component is a polyisocyanate compound which contains two or more isocyanate groups and / or a block isocyanate group in 1 molecule, The (B) component is a (B) with respect to the hydroxyl group of (A) component. Molar ratio of isocyanate group and / or blocked isocyanate group in component is 0.6 Paint composition, characterized in that the range of 1.6. The component (B) is an aminoplast resin, and the nonvolatile content weight ratio between the component (A) and the component (B) is 97/3. Paint composition, characterized in that the range of 60/40. The coating composition according to any one of claims 1 to 3, wherein the dispersion of the inorganic oxide sol of component (C) is a dispersion of silicon oxide sol. The coating composition according to any one of claims 1 to 3, wherein the average particle diameter of the dispersion of the inorganic oxide sol is 100 nm or less. The coating composition according to any one of claims 1 to 3, comprising a curing reaction catalyst. The paint composition according to any one of claims 1 to 3, which comprises a pigment. (a) carbon number 1 Ester of (meth) acrylic acid of alkyl alcohol of 12 90 wt%, (b) hydroxy group-containing monomer 10 with polymerizable double bonds 50% by weight, (c) carboxyl group-containing monomer 0.1 having a polymerizable double bond 10% by weight, (d) styrene 0 20 wt%, (e) acrylonitrile 0 20% by weight and (f) other monomers with polymerizable double bonds 0 Copolymerization of 10% by weight, glass transition temperature 50 120 ℃, number average molecular weight 2000 10,000, 50 hydroxyl value 150 mgKOH / g, acid value 1 Resin (A) of 25 mgKOH / g was prepared, and after the completion of this copolymerization, a dispersion of at least one inorganic oxide sol selected from aluminum oxide sol, silicon oxide sol, zirconium oxide sol, and antimony oxide sol in the polymerization liquid. (C), the non-volatile content of the component (C) is 5 based on the weight of the total non-volatile content of the component (A), (B) and (C) 60 wt% is added to prepare an organic inorganic composite, and the organic inorganic composite is selected from polyisocyanate compounds and aminoplast resins containing two or more isocyanate groups and / or block isocyanate groups in one molecule. A method for producing a coating composition, characterized by mixing at least one copper (B). The participation of the dispersion of the inorganic oxide sol of the component (C) in the polymerization liquid containing the resin of the component (A) is carried out at a temperature below the boiling point of the dispersion medium of the component (C). Process for producing a coating composition.