JPH10130576A - Coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating material composition capable of providing a coating membrane excellent in antifouling properties, stain-release properties and weather (light) resistance and having good water resistance, chemical resistance, processability, appearance, etc., and further having a superior environmental protection and safety. SOLUTION: This coating material composition comprises (A) at least one kind of resin selected from a polyester resin having a hydroxyl group and 3,000-50,000 number average molecular weight, and a silicone-modified polyester resin, (B) at least one kind of compound selected from a polyisocyanate compound containing one or more than two isocyanate group and/or blocked isocyanate group in a molecule, and an aminoplast resin, and (C) at least one kind of dispersion of an inorganic oxide sol selected from aluminum oxide sol, silicone oxide sol, zirconium oxide sol and antimony oxide sol so that the portion of the heating residue of component C may be 5-60wt.% based on the amount of the whole heating residue of components A, B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel coating composition. More specifically, the present invention provides a coating containing a ceramic component, which is excellent in stain resistance, stain removal properties, weather (light) resistance, chemical resistance, moisture resistance, workability, appearance, and environmental preservation. And a highly safe coating composition.

[0002]

2. Description of the Related Art In recent years, with environmental changes such as air pollution,
Oil droplets and dust contained in the air are increased, and as a result, there are problems such as that coatings applied to buildings and automobiles are more easily contaminated than before, and that dirt is difficult to remove. ing. Therefore, as the performance of the coating film, there has been a demand for resistance to contamination, that is, stain resistance, and the ability to remove contaminants from the contaminated coating film, that is, stain removal. Under these circumstances, a coating film that is excellent in stain resistance, stain removal properties, weather resistance (light), gloss, appearance, water resistance, and chemical resistance is excellent, and is excellent in environmental preservation and safety. There has been a demand for the creation of a coating composition that has been used. Conventionally used stain-resistant paints have a fluorine-containing resin as a main component, and the stain resistance is due to the high weather resistance of the fluorine-containing resin. Fluororesin,
(1) stability due to the fact that the binding energy between the fluorine atom and the carbon atom is larger than the binding 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. Its function is expressed by water repellency and oil repellency due to its large surface and low surface free energy due to low polarizability between fluorine molecules (0.68 × 10 ⁻²⁴ cc).

[0003] However, the fluorine-containing resin is restricted by the strong electronegativity of the fluorine atom, which limits the range of resin design, the price of the fluorine-containing resin is high, and some fluorine-containing monomers are soluble in solvents. There is a problem that there is a possibility that there is a limit to the property, and there is a concern about adverse effects on the environment due to the generation of hydrofluoric acid at the stage of disposal treatment of the coating film using the fluorine-containing resin. Functionality, but price, usage restrictions,
Issues such as the negative impact on the environment at the time of disposal have been highlighted. On the other hand, recently, as a stain-resistant composition, there has been proposed a coating composition comprising a partial condensate of an organosilicon compound and specific silica fine particles (Japanese Patent Laid-Open No. 2-3468). However, this publication does not provide a detailed description of the resin component used in the coating composition. Furthermore, there has been proposed a coating composition containing an acrylic polyol resin, a binder, an inorganic organosol and a solvent (Japanese Patent Laid-Open No. Hei 4 (1999) -104).
173882). However, this coating composition has the drawback that, although the stain resistance and weather (light) resistance are improved to some extent, the stain removal properties are insufficient. As described above, a coating composition that provides a coating film having excellent stain resistance, stain removal properties, and weather (light) resistance has not been found yet, and polyester resin is used as the binder resin. In fact, no coating composition using a resin has been found.

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention is excellent in stain resistance, stain removal properties and weather (light) resistance, and has good water resistance, chemical resistance and workability. The purpose of the present invention is to provide a coating composition having high environmental preservation and safety in addition to providing a coating film having an appearance and the like. The present inventors have conducted intensive studies to develop a coating composition having the above characteristics, and as a result, are selected from a polyester resin having a hydroxyl group and a number average molecular weight of 3,000 to 50,000 and a silicone-modified polyester resin. The present inventors have found that a coating composition containing at least one resin, a polyisocyanate compound or an aminoplast resin, and a specific ceramic component can be suitable for the purpose, and based on this finding, complete the present invention. Reached.

[0005]

The present invention provides (A) at least one resin selected from the group consisting of a polyester resin having a hydroxyl group and a number average molecular weight of 3,000 to 50,000 and a silicone-modified polyester resin; A) polyisocyanate compounds containing two or more isocyanate groups and / or blocked isocyanate groups in one molecule, and at least one compound selected from aminoplast resins, and (C) aluminum oxide sol, silicon oxide sol And a dispersion of at least one inorganic oxide sol selected from the group consisting of zirconium oxide sol and antimony oxide sol, and wherein the heating residue of component (C) is component (A), component (B) And 5 to 60% by weight based on the total weight of the residual heating of the component (C). That.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the coating composition of the present invention,
The resin used as the component (A) is a polyester resin or a silicone-modified polyester resin, and the polyester resin and the silicone-modified polyester resin have a hydroxyl group and a number average molecular weight of 3,000 to 5,
0,000, preferably 5,000 to 50,000. When the number average molecular weight is less than 3,000, the cured coating film has too high a crosslink density, resulting in reduced flexibility and a problem in workability. On the other hand, when the number average molecular weight exceeds 50,000, the viscosity of the solution becomes high, handling becomes difficult, and there is a possibility that a problem may occur in coating workability when a coating material is used. The hydroxyl group of the polyester resin or the silicone-modified polyester resin is a functional group indispensable for a heat curing reaction with a polyisocyanate compound and / or a melamine resin. The hydroxyl value of the polyester resin or silicone-modified polyester resin is 1 to 100 m
A range of gKOH / g is preferred.

The polyester resin is directly esterified,
It can be produced using a known method such as a transesterification method and a ring-opening polymerization method. As a specific example of the direct esterification method, for example, there is a method of polycondensing a polyvalent carboxylic acid and a polyhydric alcohol. As the polyvalent carboxylic acid, for example,
Phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, maleic acid,
Dibasic acids such as maleic anhydride, fumaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and their anhydrides, trivalent or higher such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, etc. Polycarboxylic acids and their anhydrides. As polyhydric alcohols, ethylene glycol, propylene glycol, diethylene glycol,
Diols such as butanediol, neopentyl glycol, 1,4-hexanediol, 1,6-hexanediol, and cyclohexanedimethanol; trihydric or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol And the like. Further, the polyester resin can also be produced by polycondensation by transesterification between a lower alkyl ester of a polycarboxylic acid and a polyhydric alcohol. Further, the polyester resin can also be produced by ring-opening polymerization of lactones such as β-propiolactone, δ-valerolactone, and ε-caprolactone.
Such polyester resins that are commercially available include:
For example, Byron 56 (manufactured by Toyobo Co., Ltd., trade name),
Elitel UE-3250 (trade name, manufactured by Unitika Ltd.), Espel 1612 (trade name, manufactured by Hitachi Chemical Co., Ltd.) and the like can be mentioned. The polyester resin of the present invention also includes a high-molecular polyester resin having a linear structure, which is called a linear polyester resin.

The silicone-modified polyester resin which can be used in the present invention is obtained, for example, by adding a silicone intermediate such as a reactive silicone oligomer having hydroxyl groups at both ends to the polyhydric alcohol and polybasic acid used in the above polyester resin. And condensation polymerization at 220 to 280 ° C. The equivalent ratio between the hydroxyl group of the polyhydric alcohol and the silicone intermediate and the carboxyl group of the polybasic acid is preferably 1: 1 to 1.5: 1. Examples of the silicone intermediate include TSR-165 (trade name, manufactured by Toshiba Silicone Co., Ltd.), SH6018 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.), KR218
Commercial products such as (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. Alternatively, condensation polymerization can be performed by adding a silicone intermediate such as a reactive silicone oligomer having a carboxyl group at both terminals to a polyhydric alcohol and a polybasic acid. The equivalent ratio of the hydroxyl group of the polyhydric alcohol to the polybasic acid and the carboxyl group of the silicone intermediate is
It is preferable that the ratio be 1: 1 to 1.5: 1.

In the coating composition of the present invention, the curing agent of the component (B) is selected from polyisocyanate compounds containing two or more isocyanate groups and / or blocked isocyanate groups in one molecule, and aminoplast resins. At least one compound is used. Examples of polyisocyanate compounds containing two or more isocyanate groups in one molecule include, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexylmethane-
Compounds referred to as isocyanate monomers such as 4,4'-diisocyanate, and polyisocyanate derivatives such as biuret, isocyanurate, and adduct of trimethylolpropane are preferably exemplified. One of these polyisocyanate compounds may be used, or two or more may be used in combination.

Examples of the polyblock isocyanate compound include, for example, those prepared by blocking a part or all of the isocyanate groups of the above-mentioned polyisocyanate compound with a blocking agent. 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 phenol blocking agents such as phenol, cresol, catechol and nitrophenol. , Isopropanol, and trimethylolpropane; and active methylene-based blocking agents such as malonic esters and acetoacetic esters. These polyblock isocyanate compounds may be used alone or in combination of two or more. Preferable examples of the aminoplast resin include a melamine resin and a guanamine resin. One of these aminoplast resins may be used, or two or more thereof may be used in combination. More specifically, there is no particular limitation as long as two or more reactive groups are contained in one molecule, and one or more triazine rings are present in one molecule of melamine or guanamine resin. No problem. As the reactive group present in those resins, preferably, a methylol group, an imino group, or a group obtained by etherifying a methylol group with methanol, butanol, or the like is used.

In the coating composition of the present invention, the mixing ratio of the component (A) and the component (B) is such that the component (B) contains at least two isocyanate groups and / or blocked isocyanate groups in one molecule. When the compound is an isocyanate compound, the molar ratio of the isocyanate group and / or the blocked isocyanate group in the component (B) to the hydroxyl group in the component (A) is preferably in the range of 0.6 to 1.6, and in particular, Preferably it is in the range of 0.8 to 1.2.
When the molar ratio is less than 0.6, a hydroxyl group in the resin may remain partially unreacted during the crosslinking reaction between the polyisocyanate compound of the component (B) and the resin of the component (A), Water resistance and moisture resistance of the obtained coating film are reduced,
As a result, the weather resistance of the coating film may be deteriorated. On the other hand, if the molar ratio exceeds 1.6, the isocyanate group and / or the blocked isocyanate group may remain unreacted, and also in this case, the water resistance and moisture resistance of the coating film are reduced, and the weather resistance of the coating film is further reduced. It may cause deterioration of sex. When the component (B) is an aminoplast resin, the heating residue weight ratio of the component (A) to the component (B) is 9%.
It is preferably in the range of 7: 3 to 60:40, and 9
More preferably, it is in the range of 5: 5 to 65:35,
In particular, the ratio is preferably in the range of 91: 9 to 70:30. This is because if the aminoplast resin is less than the 97: 3 compounding ratio, the crosslink density of the coating film may be low and physical properties such as solvent resistance may not be satisfied, and the aminoplast resin may be less than the 60:40 compounding ratio. If the amount of the resin is too large, problems such as deterioration in workability of the coating film may occur, which is not preferable.

In the coating composition of the present invention, as the ceramic component (C), at least one selected from the group consisting of dispersions of sols of inorganic oxides of aluminum oxide, silicon oxide, zirconium oxide and antimony oxide. A dispersion of an inorganic oxide sol is used. Preferred of these inorganic oxide sols are silicon oxide sols. These inorganic oxide sols are often supplied as an aqueous dispersion in general, and in the case of an aqueous dispersion, if the coating composition is aqueous, it can be used as it is, but if it is an organic solvent, A method of phase inversion in a desired organic solvent can be used. Preferred organic solvents to be used are ketone solvents such as methyl isobutyl ketone and cyclohexanone. As a method of this phase inversion, for example, a method of adding a water-soluble organic solvent in an aqueous dispersion and repeating the operation of distilling off water to perform phase inversion in a desired organic solvent is used. Can be.

The dispersion of the silicon oxide sol can be obtained by adding silicon tetrahalide to water, adding an acid to an aqueous solution of sodium silicate, or the like. As a commercially available product, for example, as a water-based dispersion, Snowtex-O
[Nissan Chemical Industry Co., Ltd. product name] and Snowtex
N [manufactured by Nissan Chemical Industries, Ltd., trade name] and the like, and examples of the organic solvent dispersion include Snowtex MIBK-ST [manufactured by Nissan Chemical Industry, trade name]. The dispersion of the inorganic oxide sol is preferably a surface-treated with a silane coupling agent, and particularly preferably the surface of a dispersion of a silicon oxide sol with a silane coupling agent.
Since the dispersion of the surface-treated inorganic oxide sol can introduce various functional groups into the particle surface, when used in the coating composition of the present invention, a resin or a polyisocyanate compound or an aminoplast resin It becomes easy to chemically bond with organic components such as. When the ceramic component and the organic component are chemically bonded as described above,
Crosslinking of the coating film becomes stronger as compared with the case where it is not chemically bonded, and stain resistance, stain removal property, weather resistance, and the like are improved.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane,
γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane and the like, preferably methyltrimethoxysilane, dimethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyl Oxypropyltrimethoxysilane, particularly preferably methyltrimethoxysilane and dimethyldimethoxysilane. As commercial products, A-162, A
-163 and AZ-6122 (both are trade names, manufactured by Nippon Unicar Co., Ltd.) and the like. These silane coupling agents can be used alone or in combination of two or more. When the surface treatment is performed with a silane coupling agent, the amount of the silane coupling agent is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, based on the heating residue of the inorganic oxide sol.

As a dispersion of the inorganic oxide sol treated with the silane coupling agent, water contained in the aqueous inorganic oxide sol is azeotropically distilled and dehydrated with an azeotropic solvent with water, and then the inorganic oxide sol is dispersed. It is preferable to use a dispersion of an azeotropic solvent-dispersed inorganic oxide sol obtained by subjecting the dispersion to a surface treatment with a silane coupling agent. In particular, the dispersion of the inorganic oxide sol is preferably a dispersion of a silicon oxide sol. Dispersion of the inorganic oxide sol obtained by this manufacturing method is improved in stain resistance, stain removal property, weather resistance, etc., and furthermore, it is possible to increase the concentration of the inorganic oxide sol, so that it is made into a paint. Is also easily heated and differentiated. Therefore, the range of selecting the viscosity adjusting thinner at the time of coating is wide, and the coating film can be made thick. Examples of the azeotropic solvent include water-soluble alcohols, carboxylic esters, and cyclic ethers. Examples of the water-soluble alcohol include ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, methyl cellosolve, ethyl cellosolve, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monobutyl ether,
Examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, propylene glycol monomethyl ether, ethylene glycol, and propylene glycol. Examples of the water-soluble carboxylate include methyl acetate, ethyl acetate and the like. Examples of the water-soluble cyclic ether include 1,4-dioxane.

These azeotropic solvents can be used alone or in combination of two or more. In addition, a solvent that is immiscible with water may be used for the purpose of increasing the azeotropic distillation dehydration efficiency by using a solvent that is miscible with water. Examples of the solvent include benzene, xylene, toluene, cyclohexanone, diphenyl ether, dibutyl ether and the like. These solvents can be used alone or in combination of two or more. However, the amount used is limited to a range that does not cause aggregation of the sol, and varies depending on the solvent. The azeotropic distillation dehydration is preferably performed while dropping an azeotropic solvent. The azeotropic distillation dehydration is preferably performed in the range of 30 to 100 ° C, and particularly preferably in the range of 40 to 80 ° C. The azeotropic distillation dehydration can be performed under reduced pressure or normal pressure, but is preferably performed under reduced pressure. The water content in the azeotropic solvent-dispersed inorganic oxide sol after azeotropic distillation dehydration is usually preferably 2% by weight or less, and particularly preferably 1% by weight or less.
It is preferable that the content be not more than weight%. The concentration of the dispersion of the azeotropic solvent-dispersed inorganic oxide sol after the azeotropic distillation dehydration is preferably such that the heating residue is 55% by weight or less, particularly 25 to 5%.
Preferably it is 5% by weight.

The surface treatment with the silane coupling agent is as follows.
It can be performed by mixing a silane coupling agent with a dispersion of an azeotropic solvent-dispersed inorganic oxide sol after azeotropic distillation and dehydration. The surface treatment temperature with the silane coupling agent is not particularly limited, but is usually preferably performed in the range of 20 to 100 ° C, more preferably in the range of 30 to 90 ° C, and particularly preferably in the range of 40 to 80 ° C. It is preferred to be performed. The time of the surface treatment with the silane coupling agent is not particularly limited, but it can be usually carried out by reacting for 30 minutes to 48 hours. The water content in the solvent-dispersed inorganic oxide sol after the surface treatment with the silane coupling agent is usually preferably 1% by weight or less, particularly preferably 0.5% by weight or less. Further, the azeotropic solvent-dispersed inorganic oxide sol can be replaced with a desired solvent as needed. Examples of the solvent that can be used for this solvent replacement include the above-mentioned alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylacetamide, dimethylformamide and the like. The solvent substitution is preferably performed in the range of 30 to 120 ° C, particularly preferably in the range of 40 to 110 ° C, depending on the type of the solvent used in the substitution.

In the coating composition of the present invention, one dispersion of the inorganic oxide sol may be used, or two or more dispersions of the inorganic oxide sol may be used in combination. Is 5 to 60% by weight based on the total heating residue of the components (A), (B) and (C).
Choose to be. When the heating residue of the dispersion of the inorganic oxide sol is less than 5% by weight based on the total heating residue, the effect of adding the dispersion of the inorganic oxide sol is not sufficiently exhibited, and the coating film is resistant to contamination. The effect of improving the properties, stain removal properties, weather resistance, and acid resistance is not appreciably observed, and if it exceeds 60% by weight, the processability, gloss, moisture resistance, chemical resistance, and the like of the coating film tend to decrease. From the viewpoint of the balance of the stain resistance, stain removal property, weather resistance, workability, etc. of the coating film, the heating residue of the dispersion of the inorganic oxide sol is in the range of 5 to 40% by weight based on the total heating residue. Is preferred. The dispersion of the inorganic oxide sol preferably has an average particle size of 100 nm or less, and has an average particle size of 50 nm.
The following are particularly preferred. When the average particle size is larger than 100 nm, the transparency of the clear film is impaired, and the stain resistance and stain removal of the coating film are reduced. The lower limit of the average particle size is not particularly limited, but is preferably 1 nm or more, and particularly preferably 5 nm or more.

In the coating composition of the present invention, a curing reaction catalyst may be used. In the coating composition of the present invention,
When a polyisocyanate compound containing two or more isocyanate groups and / or blocked isocyanate groups in one molecule is used as the component (B), examples of the curing reaction catalyst include a tin compound and a zinc compound.
Examples of the tin compound include tin halides such as tin chloride and tin bromide, and organic tin compounds such as dibutyltin diacetate and dibutyltin dilaurate.Examples of the zinc compound include zinc halides such as zinc chloride and zinc bromide. And zinc salts of organic acids such as zinc octylate and zinc laurate. One of the tin compound and the zinc compound as the curing reaction catalyst may be used alone, two or more of them may be used in combination, or may be used in combination with another curing reaction catalyst. The curing reaction catalyst is preferably used in a proportion of 0.01 to 5% by weight based on the total heating residue in the coating composition. When this amount is less than 0.01% by weight,
The effect of accelerating the curing reaction may not be sufficiently exhibited, and if it exceeds 5% by weight, the water resistance and moisture resistance of the coating film are reduced, and thus the stain resistance, stain removal property, weather resistance, etc. of the coating film are reduced. May be reduced. From the viewpoint of the balance between the curing speed and the physical properties of the coating film, a more preferable compounding amount of the curing reaction catalyst is 0.00% based on the total heating residue in the composition.
It is in the range of 1-2% by weight.

In the coating composition of the present invention, when an aminoplast resin is used as the component (B), a curing reaction catalyst for the aminoplast resin may be used. Preferred examples of the curing reaction catalyst for the aminoplast resin include, for example, phosphoric acid-based curing catalysts, sulfonic acid-based curing catalysts such as toluenesulfonic acid and dodecylbenzenesulfonic acid, and amine block bodies thereof. These compounds may be used alone or in combination of two or more, and the curing time can be adjusted in combination with other compounds. The amount of the curing reaction catalyst for the aminoplast resin is preferably in the range of 0.01 to 2% by weight based on the total heating residue of the paint. The reason is that if the amount is less than 0.01% by weight, the effect of the curing reaction catalyst of the aminoplast resin may not be exhibited due to the curing of the coating material, and if the amount exceeds 2% by weight, the curing reaction of the aminoplast resin after forming the coating film. The effect of the catalyst may adversely affect the performance of the coating film such as water resistance and moisture resistance, and thus may reduce the stain resistance, stain removal properties, and weather resistance of the coating film.

In addition, when the coating composition of the present invention is prepared, an appropriate amount of a pigment, a dye, and a luminous agent may be blended in an appropriate amount to prevent the enamel from losing its original function. For this reason, not only the clear paint, but also a coloring pigment may be blended to impart a design property such as coloring an object to be coated. It is also possible to adjust the physical properties of the coating film by adding an extender pigment. Specific examples thereof include titanium oxide, carbon black, organic pigments, coloring pigments such as red iron oxide, glass flakes, aluminum flakes,
Examples include coloring agents such as mica flakes, fillers such as talc, silica, and alumina, and extenders such as strontium chromate and barium sulfate. In the coating composition of the present invention, when a pigment is contained, the compounding ratio of the pigment is usually preferably 0.1 to 40% by weight, particularly preferably 0.5 to 40% by weight.
35% by weight is preferred. The method for preparing the coating composition of the present invention is not particularly limited, and a method of mixing each essential component and various desired additives in an arbitrary order and various other methods can be used.

The temperature and time required for curing the thus obtained coating composition of the present invention depend on the type of each component and the reaction catalyst to be used. The time is generally about 10 seconds to 10 hours. The coating composition of the present invention can be used for both single-layer coating films and composite coating films. The thickness of the coating film obtained by applying the coating composition of the present invention is not particularly limited,
Usually, the thickness of the coating film after drying is preferably 8 to 100 μm,
More preferably, it is 8 to 60 μm. The substrate on which the coating composition of the present invention is applied is not particularly limited, and various substrates can be used, for example, wood, glass, metal, cloth, plastic, foam, elastic, Organic materials and inorganic materials such as paper, ceramic, concrete, and gypsum board are included. These substrates may be those which have been subjected to a surface treatment in advance, or those having a coating film formed on the surface in advance.

The coated articles obtained by applying the coating composition of the present invention include, for example, buildings, structures, wood products, metal products, plastic products, rubber products, processed paper, ceramic products, glass products and the like. Can be More specifically, automobiles, automobile parts (for example, parts such as bodies, bumpers, spoilers, mirrors, wheels, interior materials and the like, of various materials), metal plates such as steel plates, motorcycles, and motorcycles Parts, road materials (for example,
Guardrails, traffic signs, etc.), materials for tunnels (for example, side walls), ships, railway vehicles, aircraft, printing equipment, parts for printing equipment, furniture, musical instruments, home appliances, building materials, containers, office supplies, sporting goods , Toys, precoated steel sheets and the like. Incidentally, the coating composition of the present invention,
In addition to paints, it can be used for inks, adhesives, molded articles, and the like.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, the evaluation of the coating film performance of the test piece was performed as follows. (1) Evaluation of coating film performance (a) 60 ° gloss: JIS K-5400 (1990)
According to 7.6, 60 degree specular gloss of coating film (Gs60 °)
I asked. (B) Sharpness: Evaluated by visual observation according to the following criteria. ；: When a fluorescent light is projected on the coating film, the fluorescent light is clearly reflected. Δ: When a fluorescent lamp is projected on the coating film, the periphery (outline) of the fluorescent lamp is slightly blurred. ×: When a fluorescent lamp is projected on the coating film, the periphery (outline) of the fluorescent lamp is significantly blurred. (C) Accelerated weathering test: JIS D 0205 5.4
According to a test using a sunshine carbon arc lamp type weather resistance tester, a 60% gloss retention (%) (JIS K
-5400 (1990) 7.6).

(D) Moisture resistance: After exposing the test piece at a relative humidity of 95% or more at 40 ± 1 ° C. for 240 hours,
Two hours after removal, the surface condition of the test piece was visually observed and evaluated according to the following criteria. ；: There is no change in the gloss and the surface condition of the test specimen as compared with the original test specimen. Δ: There is a slight change in gloss and blistering of the test specimen as compared to the original test specimen. ×: The test specimen has a noticeable change in gloss and blisters as compared to the original test specimen. (E) Xylene rubbing resistance: The surface of the test piece was rubbed 100 times with a flannel impregnated with xylene, and the change in the surface state was visually observed, and the xylene rubbing resistance was evaluated according to the following criteria. ；: There is no change in the gloss of the test specimen as compared to the original test specimen. Δ: There is a slight change in the gloss of the test piece as compared to the original test piece. ×: The gloss of the test piece is remarkably changed as compared with the original test piece. (F) Acid resistance: JIS K-5400 (1990)
An acid resistance test was performed in accordance with No. 22, and the acid resistance was evaluated according to the following criteria. ；: There is no change or discoloration in the gloss of the test specimen as compared to the original test specimen. Δ: There is little change or discoloration of the gloss of the test piece as compared to the original test piece. X: The gloss and the color tone of the test piece are significantly different from those of the original test piece.

(G) Alkali resistance: JIS K-540
0 (1990) 8.21, an alkali resistance test was performed, and the alkali resistance was evaluated according to the following criteria. ；: There is no change or discoloration in the gloss of the test specimen as compared to the original test specimen. Δ: There is little change or discoloration of the gloss of the test piece as compared to the original test piece. X: The gloss and the color tone of the test piece are significantly different from those of the original test piece. (H) Oil-resistant marker stainability: A line is drawn on the coating film of the test piece with an oil-based marker, heated at 80 ° C. for 5 hours, and then the surface state is changed after the line is wiped off with a flannel impregnated with xylene. Was visually observed, and the staining property of the oily marker was evaluated according to the following criteria. ；: The line of the oily marker on the test piece was completely wiped off, and no trace was left. Δ: A trace of the oil marker line on the test piece is slightly left. ×: Traces of the line of the oily marker on the test piece clearly remain. (I) Pencil hardness: JIS K-5400 (1990)
It was determined in accordance with 8.4.2.

(J) Adhesion: JIS K-5400 (1
990) An adhesion test was performed in accordance with 8.5.1. The adhesion was evaluated according to the following criteria. ；: 10 points. Δ: 8 points. ×: 6 points or less. (K) Outdoor exposure contamination: The test piece was subjected to an outdoor exposure test for 3 months, and a SM color computer SM-4-MCH was used.
(Suga Test Instruments Co., Ltd.) was used to evaluate the contamination of the coating film surface by the difference (ΔL) between the measured L value and the initial L value before exposure. [ΔL = (Initial L value before exposure) − (L value after exposure)] (1) Dirt after decontamination: The exposed surface is soaked with ion-exchanged water in clean gauze and reciprocated 10 times, then The gauze was exchanged, and dirt was removed by reciprocating 10 times in the same manner. Then, the gauze was wiped off with dry gauze, and the L value was measured with a color computer. ) Was used to evaluate the contamination of the coating film surface. [ΔL = (Initial L value before exposure) − (L value after exposure)] (m) Workability: After placing in a room at 20 ° C. or 5 ° C. for 1 hour, the test piece was placed with the painted surface outside. After bending by 180 degrees, the T number at which no cracks occurred was displayed by viewing the bent portion with a 30-fold scope. The T number is defined as 0 T when 180 ° bending is performed without sandwiching anything inside the bent portion, and 1 T or 2 T when bending one plate having the same thickness as the test plate.
2T, 3T, 4
T.

Production Example 1 A reaction vessel equipped with a stirrer, a thermometer, a reflux tube equipped with a Dean-Stark trap, and a dropping funnel was charged with a Snowtex MIBK-ST [a dispersion of silicon oxide sol, manufactured by Nissan Chemical Industries, Ltd.]. (Average particle size: 30 nm), heating residue:
30% by weight, solvent: methyl isobutyl ketone] 1000
Parts by weight and 40 parts by weight of A-163 [manufactured by Nippon Unicar Co., Ltd., silane coupling agent], and heated to 80 ° C.
For 8 hours, the silica sol surface-treated with a silane coupling agent (average particle diameter of the dispersion: 32 n
m) 1020 parts by weight were obtained.

Production Example 2 Snowtex-O (trade name, manufactured by Nissan Chemical Industries, Ltd., water-dispersed silicon oxide sol, average particle size: 20 nm) 180.2
Parts by weight, 63.1 parts by weight of isopropyl alcohol were charged into a reaction vessel equipped with a reflux tube equipped with a Dean-Stark trap, a dropping funnel, a stirrer, a thermometer, and a decompression device. When heated to a temperature of 42 ° C. while reducing the pressure to 150 to 170 mmHg, isopropyl alcohol 121 is used.
While continuously dropping 6.2 parts by weight from the dropping funnel,
An azeotropic distillation dehydration was performed for 10 hours to obtain 234.2 parts by weight of a silicon oxide sol dispersed in isopropyl alcohol. The water content of the silicon oxide sol dispersed in the isopropyl alcohol was 0.8% by weight by Karl Fischer titration.
Met. 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.
360. from the dropping funnel under reduced pressure of 0 to 170 mmHg.
Silicon oxide sol dispersed in 100 parts by weight of light yellow transparent cyclohexanone by dissolving isopropyl alcohol while dropping 4 parts by weight of cyclohexanone and then decyclohexanone at an internal temperature of 50 to 55 ° C. (average particle diameter of dispersion) : 30 nm). The heating residue of the silicon oxide sol dispersed in the obtained cyclohexanone was 45% by weight, and the water content was 0.1% by weight.

Production Examples 3 to 5 Production Examples 2 to 5 were conducted using the components and amounts described in Table 1.
In the same manner as in the above, a dispersion of a silicon oxide sol was obtained. The average particle size of the dispersions of the silicon oxide sols of Production Examples 3, 4 and 5 was
They were 28 nm, 31 nm and 28 nm, respectively.

[0031]

[Table 1]

Production Example 6 25.4 parts by weight of isophthalic acid and 22.3 adipic acid were placed in a reaction vessel equipped with a stainless steel filler equipped with a Dean-Stark trap, a thermometer, and a stirrer.
Parts by weight, 14.5 parts by weight of neopentyl glycol, 1,
16.5 parts by weight of 6-hexanediol, 1.3 parts by weight of trimethylolpropane, silicone diol X-22-
20 parts by weight of 160AS (Mn = 1,000, α, ω-hydroxyethoxypropyldimethylpolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.05 part by weight of dibutyltin dioxide were charged, and the temperature was raised to 150 ° C. After that, the temperature was raised to 200 ° C. over 6 hours,
The temperature was raised over 0 hours, a dehydration condensation reaction was performed until the heating residue acid value reached 5, and then the reaction temperature was lowered to 100 ° C.
Xylol 30 parts by weight, methyl isobutyl ketone 150
By weight, a silicone-modified polyester resin solution having a transparent appearance was obtained. The properties of the obtained resin solution are as follows:
The heating residue was 67.7% by weight, and the Gardner viscosity at 25 ° C. was Y. Further, the molecular weight in terms of polystyrene by GPC was 8,000 in number average molecular weight, and the hydroxyl value was 15 mgKOH / g.

Examples 1 to 8 In accordance with the paint formulations shown in Table 2, Examples 1 to 8 were prepared in the following manner.
8 paints were prepared. Using the obtained paint, a paint was applied to a steel plate by the following method and baked to prepare a test piece. First, the pigment is dispersed together with a part of the polyester resin and a solvent using a paint shaker until the particle size becomes 10 μm or less. Next, the remaining polyester resin and melamine resin and / or (block) isocyanate compound are added. The obtained paint is designated as Paint A. Next, to the mixture of the organosilica sol and the solvent previously weighed in a container, the above-mentioned coating material A is added little by little with stirring, and after all the addition is completed, the mixture is further sufficiently stirred. The obtained paint is referred to as Paint B. A 0.4 mm-thick zinc phosphate-treated electrogalvanized steel sheet is coated with a pre-color primer P-44A (registered trademark, manufactured by NOF CORPORATION) as a primer coating for a pre-coated steel sheet to a dry film thickness of 5 μm. And baked to reach a material reaching temperature of 220 ° C. to obtain a primer-coated steel sheet. Each primer (paint B) obtained as described above was applied on this primer-coated steel sheet by a bar coater so that the dry film thickness became about 20 μm.
It was baked at 0 ° C to obtain each top-coated steel sheet, which was used as a test piece. Perform various tests on the obtained test piece,
The test results are shown in Table 4.

[0034]

[Table 2]

Note) Subscripts in Tables 2 and 3 indicate the following. 1) S-1612: manufactured by Hitachi Chemical Co., Ltd., trade name "Espel 1612", polyester resin, number average molecular weight: about 20,000, heating residue: 40% by weight, hydroxyl value: 7 to 102) UE-3250: Unitika Co., Ltd., trade name "Elitel UE-3250", polyester resin, number average molecular weight of about 17,500, heating residue 40% by weight, hydroxyl value 43) RV-56: manufactured by Toyobo Co., Ltd. Product name "Vylon 56CS", linear polyester resin, number average molecular weight about 20,000, heating residue 40% by weight, hydroxyl value 5
8 4) Cymel 303: manufactured by Mitsui Cyanamid Co., Ltd., trade name, methylated melamine resin, heating residue 100% by weight 5) Cymel 712: manufactured by Mitsui Cyanamid Co., Ltd., trade name, methylated melamine resin, heating residue 80% by weight 6) TPLS-2957: manufactured by Sumitomo Bayer Urethane, trade name, ε-caprolactam block of isocyanurate of hexamethylene diisocyanate, heating residue 75
7) R-960: manufactured by DuPont, trade name, titanium dioxide 8) MIBK-ST: manufactured by Nissan Chemical Industries, Ltd., trade name "organosilica sol MIBK-ST", organosilica sol, heating residue 30% by weight 9) NACURE 5225: manufactured by King Industry Co., USA, trade name, amine block of dodecylbenzenesulfonic acid

Comparative Examples 1-2 According to the paint formulations shown in Table 3, coatings were prepared in the same manner as in Examples 1-8 to obtain paints of Comparative Examples 1-2. Further, test pieces were prepared in the same manner as in Examples 1 to 8. A coating film performance test was performed on these test pieces, and the test results are shown in Table 4.

[0037]

[Table 3]

[0038]

[Table 4]

The pencil hardness of each of the coating films of Examples 1 to 8 is H or 2H, and the coating films have sufficient hardness. The workability tests were performed at 20 ° C. and 5 ° C.
T or less, and all of these coated steel sheets have excellent workability both at room temperature and at low temperature. With respect to the oil-resistant marker stainability, traces of the oil-based ink were not observed in any of the paint systems, and were extremely good. Also, in the outdoor exposure contamination test, the ΔL value is extremely excellent, 3 or less.
Further, even in the soil after decontamination, the ΔL value is 1.0 or less, and the contaminant is removed. On the contrary,
In Comparative Example 1 in which the heating residue of the dispersion of the inorganic oxide sol as the component (C) was less than 5% by weight, acid resistance, oil resistance marker staining, pencil hardness, outdoor exposure staining, and contamination after removal of contamination were obtained. Comparative Example 2, which is inferior to 60% by weight, has 60 ° gloss,
Poor clarity, moisture resistance, alkali resistance, workability, etc.

[0040]

The coating composition of the present invention has a ceramic component and is excellent in weather (light) resistance, stain resistance, and stain removal properties, and has good appearance, moisture resistance, and chemical resistance. It has excellent features such as giving a coating film having processability, pencil hardness, and high environmental preservation and safety.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 161/20 C09D 161/20 167/00 167/00 183/10 183/10 // C08G 18/42 C08G 18/42 Z 18 / 61 18/61 18/80 18/80 (C09D 167/00 161: 20) (C09D 183/10 161: 20) (72) Inventor Yoshifumi Ohama 6-22-32 Sasashita, Konan-ku, Yokohama, Kanagawa Prefecture

Claims (4)

[Claims] (A) a hydroxyl group-containing number average molecular weight of 3.0
(B) a polyisocyanate compound containing two or more isocyanate groups and / or blocked isocyanate groups in one molecule, and at least one resin selected from 00 to 50,000 polyester resins and silicone-modified polyester resins; Dispersion of at least one compound selected from aminoplast resins and (C) at least one inorganic oxide sol selected from aluminum oxide sol, silicon oxide sol, zirconium oxide sol and antimony oxide sol Wherein the heating residue of the component (C) is 5 to 60% by weight based on the weight of the total heating residue of the components (A), (B) and (C). Paint composition. 2. The coating composition according to claim 1, wherein the dispersion of the inorganic oxide sol is surface-treated with a silane coupling agent. 3. A dispersion of an inorganic oxide sol is obtained by subjecting water contained in an aqueous inorganic oxide sol to azeotropic distillation and dehydration with an azeotropic solvent with water, and then subjecting the dispersion of the inorganic oxide sol to a silane coupling agent. The coating composition according to claim 1, which is obtained by performing a surface treatment with the composition. 4. A dispersion of a component (C) inorganic oxide sol,
The coating composition according to any one of claims 1 to 3, which is a dispersion of a silicon oxide sol.