JP5633958B2 - Coating film manufacturing method and painted product - Google Patents

Description

  The present invention relates to a coating film, a method for producing the coating film, and a coated product having the coating film. Specifically, the surface of the coating is made hydrophilic immediately after the coating is formed to have good water wettability, and the function of washing rainwater and washing water into the interface between the coating and the contaminant to wash away the contaminant is developed. The present invention relates to a coating film that is excellent in stain resistance and sustains its effect, a method for producing the coating film, and a coated article having the coating film.

  Paint is applied to protect the building and enhance its appearance. Conventionally, organic solvent dilution type paints have been used extensively, but environmental problems such as the emission of organic solvents into the atmosphere, such as those found in sick house / sick school syndrome and volatile organic compound (VOC) regulations, have been raised. Conversion to water-based paint is progressing at an accelerated pace. On the other hand, consumer needs are increasing expectations for long-term durability and high functionality of the coating film of these products.

  If non-polar pollutants such as dust and oily substances in the atmosphere or carbon contained in exhaust gas adhere to and accumulate on the coating film of building materials, etc., they will accumulate without being washed away by rainwater or washing water. The state of is uneven and easily noticeable. Usually, in order to prevent this rain streak contamination, a technique is employed in which rainwater is intervened at the interface between the pollutant and the coating surface by increasing the hydrophilicity of the coating surface, and the pollutant is washed away. In solvent-based paints, a technique has been proposed in which alkoxysilane is coordinated on the surface of the coating film and hydrolyzed with time to make the surface of the coating film hydrophilic. The problem with this technology is that the degree of hydrolysis depends on the weather conditions for about one month immediately after the formation of the coating film. It is a point to end up.

  In water-based paints, a method of reducing the water contact angle of a coating film by adding a specific solvent to an aqueous emulsion has been proposed (Patent Document 1), but the effect is not sufficient, and over a long period of time. It was difficult to maintain the effect.

  Patent Document 2 proposes that a specific block copolymer cross-linking agent and dihydrazide compound cross-linking agent may be used together to reduce contamination by forming a cross-linked coating film with a polycarbonyl compound. However, water resistance is not sufficient. It was inferior in sustainability.

  Patent Document 3 proposes a method of overcoating a mixture of an acrylic resin and colloidal silica on a coating film of a colloidal silica aqueous dispersion inorganic coating containing an inorganic filler, but sufficient contamination is not obtained. It was.

  In patent document 4, although the method of hydrophilizing the coating-film surface by cold-blending colloidal silica to an emulsion is proposed, it is required with respect to 30-400 weight part of solid content of an acrylic resin emulsion. The amount of colloidal silica was as large as 100 parts by weight, and the durability of the effect was inferior.

  Patent Document 5 also proposes a method of forming a coating film having excellent decontamination property using fluorine-containing polymer particles, colloidal silica, and organoalkoxysilane, but the solid content of the fluorine-containing polymer particles is 100. A very large amount of colloidal silica of 50 to 300 parts by weight with respect to parts by weight was required.

  Patent Document 6 proposes a method of forming an emulsion in which colloidal silica is covered with a vinyl polymer to form a coating film having a high solid content concentration and excellent film formability. Since it was covered with a vinyl polymer, it was inferior in the ability to prevent contamination.

  Patent Document 7 proposes a coating film and a coated product excellent in stain resistance, transparency, weather resistance, and frost damage resistance in which a layer made of silica particles is formed on the coating film surface. Since the layer is composed only of silica particles, the silica particles are easily washed away by rainwater, and the maintenance of the stain resistance function is poor.

Japanese Patent Laid-Open No. 10-46099 Japanese Patent Laid-Open No. 10-298489 JP 54-139938 A Japanese Patent Application Laid-Open No. 11-116885 Japanese Patent Laid-Open No. 11-124534 JP 2000-290464 A JP 2007-31648 A

  The object of the present invention is to solve the above-mentioned problems, and when exposed to the outdoors, there is little contamination of the coating film surface due to adsorption of dust and oily substances in the atmosphere, especially from immediately after the coating film formation. It is an object of the present invention to provide a coating film capable of preventing contamination and maintaining stain resistance in which long-lasting traces of rain after rainfall can be maintained and a method for producing the coating film.

In accordance with the present invention,
(A) an aqueous resin dispersion and (B) an aqueous resin composition having an amphiphilic polymer having at least one functional group selected from an amide group, an amino group, a hydroxyl group or an oxyalkylene group, and (C) an aqueous dispersion A coating film characterized by applying a coating composition containing colloidal silica, and drying and curing the coating composition is provided.

  Moreover, according to this invention, the coating material characterized by having the said coating film is provided.

Furthermore, according to the present invention,
(A) an aqueous resin dispersion and (B) an aqueous resin composition having an amphiphilic polymer having at least one functional group selected from an amide group, an amino group, a hydroxyl group or an oxyalkylene group, and (C) an aqueous dispersion Applying a paint coating composition comprising colloidal silica;
And a step of drying and curing the applied paint coating composition.

Method for producing a coating film and the coating film of the present invention, in a single coating to form a coating film of 50-9 6% of the coating surface composition gradient in the thickness direction of the coating film colloidal silica occupies Since the surface of the coating film is hydrophilized, it is excellent in stain resistance and water resistance when applied to the outermost layer portion of the coating system. The paint easily wets and spreads on the coating film, and has high adhesion, so it has excellent recoatability.

  The coated article of the present invention has the coating film of the present invention and is excellent in stain resistance, water resistance and recoatability.

  Hereinafter, embodiments of the present invention will be described in detail.

  As a result of various studies conducted by the present inventors to achieve the above object, a paint containing (A) an aqueous resin dispersion, (B) an aqueous resin composition, and (C) an aqueous dispersion colloidal silica. It was found that a coating film having good stain resistance and excellent water resistance can be formed over a long period of time by applying the coating composition, drying and curing.

  Although the detailed mechanism of the present invention has not yet been elucidated, the present inventors consider as follows. (B) The aqueous resin composition interacts with (C) water-dispersed colloidal silica to form a colloidal silica domain. The ratio of colloidal silica gradually increases from the inside of the paint film to the paint film surface by the domain of the colloidal silica moving to the paint film surface by convection generated in the paint coating composition applied onto the substrate during the drying process. A composition gradient layer is formed in the film thickness direction of the coating film. Therefore, it becomes possible to express excellent stain resistance and water resistance. Furthermore, the outermost surface of the coating film is not composed only of (C) water-dispersed colloidal silica, and the interaction between (B) the aqueous resin composition and (C) water-dispersed colloidal silica is maintained even after the coating film is formed. Therefore, (C) water-dispersed colloidal silica is not washed away by rainwater, and the maintenance of the anti-contamination function is also excellent.

(A) The aqueous resin dispersion may be a resin composition using water as a medium, and preferably (1) an emulsion having a uniform structure obtained by polymerizing an α, β-ethylenically unsaturated monomer, An aqueous resin dispersion containing one or both of emulsions having a heterogeneous structure obtained by a multistage emulsion polymerization method,
(2) An aqueous resin composition obtained by phase-transforming and forcibly emulsifying an acrylic resin, alkyd resin, epoxy resin, polyester resin, polyurethane resin or the like polymerized and / or condensed in an organic solvent medium with water.

  In addition, when a water-soluble resin is used instead of the aqueous resin dispersion (A), the coating film is inferior in water resistance, hot water whitening resistance, elution rate, and the like.

  An emulsion having a uniform structure can form a dense coating film and can provide a coating film excellent in water permeability and clearness. Heterogeneous structure emulsions are formed by using these emulsions, such as by combining monomers having different glass transition temperatures to obtain a coating film having excellent film forming properties and excellent non-adhesiveness. The range of coating properties can be widened.

  Aqueous resin composition obtained by phase conversion and forced emulsification of acrylic resin, alkyd resin, epoxy resin, polyester resin, polyurethane resin, etc. polymerized and / or condensed in organic solvent medium with water It is possible to form a coating film having excellent properties and toughness.

(A) Examples of the α, β-ethylenically unsaturated monomer that can be used in the aqueous resin dispersion include the following monomers.
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl Acrylate, n-amyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl ( (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypropyl (Meth) acrylate monomers such as (meth) acrylate and ethoxypropyl (meth) acrylate;
Styrene derivatives such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene, methoxystyrene;
Carboxyl group-containing monomers such as (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and crotonic acid;
(Meth) acrylic acid, crotonic acid, itaconic acid,
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2 (3) -hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, allyl alcohol, and poly (mono) methacrylate of polyhydric alcohol;
Amide group-containing monomers such as (meth) acrylamide and maleamide;
Amino group-containing monomers such as 2-aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-butylaminoethyl (meth) acrylate, and vinylpyridine;
Epoxy group-containing monomers and oligomers obtained by reaction of glycidyl (meth) acrylate, allyl glycidyl ether, an epoxy compound having two or more glycidyl groups and an ethylenically unsaturated monomer having an active hydrogen atom;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- (meth) Acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryl Alcohols such as loxypropylmethyldipropoxysilane, 3- (meth) acryloxybutylphenyldimethoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, and 3- (meth) acryloxypropyldiethylmethoxysilane Shishiriru group-containing monomer;
Other representative examples include vinyl acetate, vinyl chloride, and ethylene, butadiene, acrylonitrile, dialkyl fumarate, and the like.

  Furthermore, in order to improve the function of the obtained coating film, it is also possible to introduce a crosslinked structure. In general, the crosslinked structure is roughly classified into two types: “intraparticle crosslinked structure” and “interparticle crosslinked structure”.

  By incorporating this “particle internal cross-linked structure” or “inter-particle cross-linked structure” into the emulsion particles, the coating film performance such as toughness, blocking resistance, non-adhesiveness, and solvent resistance of the coating film can be greatly improved. be able to. Examples of monomers for obtaining the internal / inter-crosslinked structure of the particles are listed as follows.

Particle internal cross-linking: A monomer having two or more polymerizable unsaturated double bonds in the molecule.
Method using divinylbenzene, ethylene glycol di (meth) acrylate, trimethylol lopantri (meth) acrylate, allyl (meth) acrylate, etc .; monomers having functional groups that react with each other at temperature during the emulsion polymerization reaction For example, a method of using a monomer mixture that selectively contains an ethylenically unsaturated monomer having a functional group in combination such as a carboxyl group and a glycidyl group or a hydroxyl group and an isocyanate group; hydrolysis condensation reaction (Meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, and the like, a method of using a monomer mixture containing a hydrolyzable silyl group-containing ethylenically unsaturated monomer, etc. It can be manufactured by a method.

  Interparticle cross-linking: The most typical example is a method in which an ethylenically unsaturated monomer having a carbonyl group is copolymerized and then a compound having two or more hydrazide groups is mixed in the molecule.

  Examples of the carbonyl group-containing ethylenically unsaturated monomer include acrolein, diacetone (meth) acrylamide, formylstyrene, (meth) acryloxyalkylpropanal, diacetone (meth) acrylate, acetonyl (meth) acrylate, acetoacetoxy Examples include ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate-acetyl acetate, butanediol-1,4-acrylate-acetyl acrylate, vinyl ethyl ketone, and vinyl isobutyl ketone. In particular, acrolein, diacetone acrylamide and vinyl methyl ketone are preferable.

  Examples of the compound having two or more hydrazide groups in the molecule as a pair of the carbonyl group include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, and sebacic acid. Examples include dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide, and thiocarbodihydrazide. Among these, carbohydrazide, adipic acid dihydrazide, and succinic acid dihydrazide are preferable from the viewpoint of dispersibility in the emulsion and water resistance.

  (A) The aqueous resin dispersion can use together 1 type, or 2 or more types of aqueous resin dispersion. For example, the combined use of an aqueous resin dispersion obtained by polymerizing an α, β-ethylenically unsaturated monomer and an aqueous resin dispersion such as urethane dispersion improves the water resistance and blocking properties of the coating film. Therefore, the maintenance of the stain resistance after forming the coating film becomes better.

  Furthermore, in order to improve the weather resistance and light resistance of the resulting coating film, it is possible to incorporate a polymerizable light-stable monomer or a polymerizable UV-absorbing monomer. It is also possible to use a non-reactive light stabilizer or ultraviolet absorber together during the polymerization.

  Examples of the polymerizable light-stable monomer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetra. Methylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6 , 6-Tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl -4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like It is done.

  Examples of the polymerizable ultraviolet absorbing monomer include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyl). Oxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyhexyl) ) Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-t-butyl-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′ -T-butyl-3 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazol 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5 Methoxy-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) ) Phenyl] -5-t-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like.

  As the polymerization initiator used when polymerizing the α, β-ethylenically unsaturated monomer in the composition of the present invention, those conventionally used for radical polymerization can be used. . For example, persulfates such as potassium persulfate and ammonium persulfate; 2,2′-azobis (2-aminodipropane) hydrochloride, 4,4′-azobis-cyanovaleric acid, 2,2′-azobis ( 2-methylbutanamide oxime) azo compounds such as dihydrochloride tetrahydrate; peroxides such as hydrogen peroxide and t-butyl hydroperoxide. Furthermore, a redox system in which a reducing agent such as L-ascorbic acid or sodium thiosulfate is combined with ferrous sulfate or the like can also be used.

  Alkyl mercaptans such as lauryl mercaptan, n-butyl mercaptan, t-butyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, thioglycolic acid-2-ethylhexyl, 2-methyl-t-butylthiophenol, carbon tetrabromide , And chain transfer agents such as α-methylstyrene dimer can also be used. By appropriately using these, the gloss, film formability, and non-adhesiveness of the coating film can be controlled.

(A) When the aqueous resin dispersion is obtained by emulsion polymerization, a surfactant generally used in emulsion polymerization can be used as an emulsifier. For example,
Alkyl sulfate such as sodium lauryl sulfate, higher alcohol sulfate, alkyl benzene sulfonate such as sodium dodecylbenzene sulfonate, polyethylene oxide alkyl ether sulfate, polyoxynonyl phenyl ether sulfonate, polyethylene oxide-polypropylene oxide glycol ether Anionic surfactants such as so-called reactive emulsifiers, which have a sulfate, sulfonic acid group or sulfate ester group and a polymerizable carbon-carbon unsaturated double bond in the molecule;
Polyethylene oxide alkyl ether, polyethylene oxide nonyl phenyl ether, sorbitan fatty acid ester, polyethylene oxide fatty acid ester, or reactive nonionic surfactant having a skeleton and a polymerizable carbon-carbon unsaturated double bond in the molecule Of nonionic surfactants;
Examples thereof include cationic surfactants such as alkylamine salts and quaternary ammonium salts. Of these, one or more surfactants may be used in combination.

  As the pH adjuster, various nitrogen-containing basic compounds conventionally known as neutralizers can be used without particular limitation. Specifically, for example, trimethylamine, alkylamines such as triethylamine, tributylamine, triethanolamine, dimethylethanolamine, diethanolamine, monoethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, ethylpropanolamine Representative examples include alcohol amines such as volatile nitrogen-containing basic compounds such as morpholine and ammonia. Of these, one or more pH adjusting agents may be used in combination.

  Further, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltriethoxysilane, 3- ( Amino group-containing alkoxysilanes such as 2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropylmethyldimethoxysilane, and 3-anilinopropyltrimethoxysilane are also part of the neutralizing agent. Can be used together.

  The aqueous resin composition comprising an amphiphilic polymer having at least one functional group selected from (B) an amide group, amino group, hydroxyl group or oxyalkylene group used in the present invention is (C) water-dispersed colloidal silica. The colloidal silica domain is formed by interacting with the coating surface, and the colloidal silica is moved to the coating surface during the drying process of the coating film. It is contained to facilitate the formation of a hydrophilic composition gradient layer.

  Furthermore, by using the aqueous resin composition (B), it is possible to obtain a coating film excellent in stain resistance by designing a coating material excellent in coating workability and forming a coating film having higher hydrophilicity.

  (B) As an amphiphilic polymer of the aqueous resin composition, for example, poly N-isopropylacrylamide, poly N-vinyl-2-pyrrolidone, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylic acid, polychlorate, And polyacrylic acid ester copolymers, among which poly N-isopropylacrylamide, polyvinyl alcohol and hydroxypropyl cellulose are preferred. As these (B) aqueous resin compositions, those synthesized by general bulk polymerization or solution polymerization or commercially available products can be used. Moreover, you may use together 1 type, or 2 or more types of aqueous resin composition among these.

  These (B) water-soluble resin compositions preferably have a weight average molecular weight of 5,000 to 100,000 g / mol. When the weight average molecular weight is less than 5,000 g / mol, the toughness and weather resistance of the coating film It tends to be inferior. On the other hand, when the weight average molecular weight exceeds 100,000 g / mol, the viscosity becomes high and the coating workability is deteriorated.

  (B) The aqueous resin composition is preferably an aqueous resin composition having a polyoxyethylene-polyoxyalkylene-polyoxyethylene (the alkylene chain has 3 or more carbon atoms) as a basic skeleton. In this case, the molecular weight is preferably 1000 to 10000 g / mol, and more preferably 1500 to 8000 g / mol.

  The proportion of polyethylene oxide in the aqueous resin composition having polyoxyethylene-polyoxyalkylene-polyoxyethylene as a basic skeleton is preferably 5 to 80% by weight, more preferably 5 to 50% by weight. When the proportion of polyoxyethylene is less than 5% by weight, the hydrophobicity is high, and the chain length of polyoxyethylene is shortened or the cloud point is lowered to near room temperature, so that it is not practical. Moreover, when the ratio of polyoxyethylene exceeds 80 weight%, hydrophilicity will become high and the water resistance of a coating film will fall.

  In addition, when an aqueous resin composition having polyoxyethylene-polyoxyalkylene-polyoxyethylene as a basic skeleton is heated, bonded water molecules are gradually desorbed and the hydrophilicity gradually decreases, so that it can eventually dissolve in water. Without precipitation. The temperature at this time is called a cloud point. In the present invention, the cloud point of (B) the aqueous resin composition is preferably 20 ° C to 90 ° C, more preferably 20 ° C to 50 ° C. When the cloud point is less than 20 ° C., it is difficult to use at room temperature, and the polyoxyethylene chain is shortened and the stability after coating tends to be lacking. When the cloud point exceeds 90 ° C., the proportion of polyoxyethylene is high, and the chain length becomes long, so that the water resistance when the coating film is formed tends to decrease.

As an aqueous resin composition having polyoxyethylene-polyoxyalkylene-polyoxyethylene as a basic skeleton, for example,
ADEKA Corporation Pluronic L-31, F-38, L-42, L-43, L-44, L-61, L-62, L-63, L-64, P-65, F-68 , L-72, P-75, F-77, L-81, P-84, P-85, F-87, F-88, L-92, P-94, F-98, L-101, P -103, P-104, P-105, F-108, L-121, L-122, P-123, F-127,
New Pole PE-61 and PE-62 manufactured by Sanyo Chemical Industries, Ltd. PE-64, PE-68, PE-71, PE-74, PE-75, PE-78, PE-108, PE-128,
Evan 410, 420, 450, 485, 610, 680, 710, 720, 740, 750, 785, U-103, U-105, U-108 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.,
Pronon # 102, # 104, # 201, # 202B, # 204, # 208 manufactured by NOF Corporation, Unilube 70DP-600B, 70DP-950B
Commercial products such as these can be used. Of these, one or more (B) aqueous resin compositions may be used in combination.

  Furthermore, as the water-soluble resin composition (B), an aqueous resin composition having a polyorganosiloxane having a polyoxyalkylene group (an alkylene group having 2 or more carbon atoms) as a basic skeleton is preferable. An aqueous resin composition having a polyorganosiloxane having a polyoxyalkylene group (an alkylene group having 2 or more carbon atoms) as a basic skeleton is excellent in surface-active ability, so that the composition is inclined in the film thickness direction of the coating film with a small amount of addition. A coating film can be obtained.

As an aqueous resin composition having a polyorganosiloxane having a polyoxyalkylene group (an alkylene group having 2 or more carbon atoms) as a basic skeleton, for example,
L-7001, L-7002, L-7604, FZ-2105, FZ-2110, FZ-2123, FZ-2191, 8029 ADDITIVE, 8032 ADDITIVE, 57 ADDITIVE, 67 ADDITIVE, 8616, manufactured by Toray Dow Corning Co., Ltd. ADDITIVE,
X-22-3939A, X-22-4741, X-22-4492, X-22-4272, X-22-4515, X-22-6266, X-22-6191, KF manufactured by Shin-Etsu Chemical Co., Ltd. -351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, KF-6011, KF-6012 , KF-6015, KF-6017, KF-6004,
COATOSIL 1211, COATOSIL 2400, COATOSIL 2812, COATOSIL 3500, COATOSIL 3501, COATOSIL 3505, COATOSIL 3573, COATOSIL 7500, COATOSIL 7510, COATOSIL 7604, OSATOSIL 7604, COATOSIL 7604, COATOSIL 7604 77, COATOSIL 2810,
Commercial products such as these can be used. Of these, one or more (B) aqueous resin compositions may be used in combination.

  The proportion of the (B) aqueous resin composition is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight based on the solid content of the (A) aqueous resin dispersion. (A) When it is less than 0.1% by weight on the basis of the solid content with respect to the aqueous resin dispersion, it is not sufficient for (C) water-dispersed colloidal silica to float on the surface of the coating film during the film formation process. When the contamination effect is inferior and (A) the water-based resin dispersion is more than 15% by weight based on the solid content, the water resistance of the coating film is lowered.

  As the shape of the (C) water-dispersed colloidal silica used in the present invention, a spherical shape, a chain shape, a rod shape, a pearl like shape or a different shape can also be used. The shape and average particle diameter of the water-dispersed colloidal silica can be confirmed by observation with an electron microscope. Moreover, the average particle diameter of the water-dispersed colloidal silica is not particularly limited, but is preferably 0.1 to 100 nm, and more preferably 4 to 30 nm. When the average particle size of the water-dispersed colloidal silica is larger than 100 nm, the particles are easily settled, so that the storage stability is lowered. On the other hand, the lower limit of the average particle diameter was set to 0.1 nm because it indicates an average particle diameter that can be easily obtained at present. When the average particle diameter is less than 0.1 nm, it becomes very expensive and difficult to obtain, and the usage is narrowed. End up.

  The pH of (C) water-dispersed colloidal silica is preferably 8.4 to 11.5. When the pH of the water-dispersed colloidal silica is less than 8.4, the system becomes unstable with an alkaline coating composition. Moreover, when pH exceeds 11.5, the dispersion stability of the water dispersion colloidal silica in a coating composition is inferior.

Examples of water-dispersed colloidal silica include:
Snowtex ST-20, ST-O, ST-C, ST-S, ST-N, ST-20L, ST-AK, ST-UP, ST-ZL manufactured by Nissan Chemical Industries,
Adelite AT-20, AT-30, AT-20N, AT-30N, AT-20A, AT-20S, AT-20Q, AT-30A, AT-30S, AT-40, AT-50 manufactured by ADEKA Corporation , AT-300,
Cataloid S-20H, Cataloid S-30, Cataloid S-30H, Cataloid SI-500, Cataloid SN, Cataloid SA, manufactured by Catalytic Chemical Industry Co., Ltd.
Silica Doll 30, Silica Doll 20, Silica Doll 20A, Silica Doll 20B manufactured by Nippon Chemical Industry Co., Ltd.
Clevosol 30R9, Clevosol 30R50, Clevosol 50R50 manufactured by Clariant Japan Co., Ltd.
DuPont Ludox HS-40, Ludox HS-30, Ludox LS, Ludox SM-30, Ludox AS, Ludox AM
Etc. Of these, one or more water-dispersed colloidal silicas may be used in combination.

  (C) The ratio containing the water-dispersed colloidal silica is preferably 0.5 to 20% by weight, particularly preferably 3 to 15% by weight, based on the solid content with respect to the (A) aqueous resin dispersion. (A) When the amount is less than 0.5% by weight based on the solid content with respect to the aqueous resin dispersion, the effect of stain resistance is inferior, and (A) exceeds 20% by weight based on the solid content with respect to the aqueous resin dispersion. In this case, the coating film becomes hard and brittle, and the inside of the coating film tends to be porous, and the water resistance tends to be inferior. Further, the proportion of (C) the water-dispersed colloidal silica is preferably 0.5 to 200% by weight based on the solid content of (B) the aqueous resin composition, and (B) the solid content of the aqueous resin composition. When the amount is less than 0.5% by weight, the effect of stain resistance is inferior. When the amount exceeds (B) 200% by weight based on the solid content of the aqueous resin composition, the coating becomes stiff and the water resistance is low. Inferior.

  Further, when a hydrolyzable silane represented by the following general formula (a) is further contained, the outflow of (C) water-dispersed colloidal silica after the formation of the coating film due to rainwater is suppressed, so that the stain resistance is maintained. It becomes better, and the coating film strength is further improved, and the durability, hardness and heat resistance are improved.

_{(R 1) n -Si- (R} 2) 4-n (a)

In the formula (a), n is an integer of 0 to 3, R ₁ is a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, It is selected from a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms. The n R ₁ may be the same or different. R ₂ is selected from an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, or a hydroxyl group. (4-n) pieces of R ₂ may be the same or different.

  Examples of the hydrolyzable silane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  The proportion containing the hydrolyzable silane is preferably 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight, based on the solid content with respect to the (A) aqueous resin dispersion. (A) When it is less than 0.05% by weight based on the solid content with respect to the aqueous resin dispersion, the effect of maintaining the stain resistance obtained by including hydrolyzable silane is reduced, and (A) the aqueous resin dispersion On the other hand, when the solid content exceeds 5% by weight, the storage stability of the coating is lowered.

An aqueous resin composition comprising (A) an aqueous resin dispersion obtained as described above and (B) an amphiphilic polymer having at least one functional group selected from an amide group, amino group, hydroxyl group or oxyalkylene group And (C) a paint coating composition containing water-dispersed colloidal silica is applied onto a substrate, dried and cured to obtain a coating film. To the resultant coating film expressing good stain resistance, upon elemental analysis coating the outermost surface, of water-dispersed colloidal silica of the coating film surface area calculated as Si accounts for 50% to 9 6% it is preferable, even more preferably 80-9 6%. Moreover, since the contact angle with the pure water of the coating-film surface measured by static surface contact angle meter CA-X type (made by Kyowa Interface Science Co., Ltd.) is 75 degrees or less, it is excellent in the stain resistance of a coating film. More preferably, it is more preferably 60 ° or less.

  The coating film of the present invention is preferably used for building interior materials and exterior materials. As the paint coating composition, both clear paint and enamel paint can be used. Colored pigments such as commonly used bengara, carbon black, titanium oxide, calcium carbonate, barium carbonate, talc, clay, Mica, alumina, alum, white clay, magnesium hydroxide, magnesium oxide, diatomaceous earth and other extender pigments, as well as titanium oxide with photocatalytic activity, frying Pontite with anti-smudge / adsorption function, activated zinc white, magnesium silicate, etc. Paint coating compositions containing functional pigments can also be used. Moreover, you may add a thickener, a dispersing agent, an antisettling agent, an antifungal agent, an antiseptic | preservative, a ultraviolet absorber, a light stabilizer, etc. suitably.

  During film formation, an organic solvent such as ethylene glycol monobutyl ether or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (film forming aid) is used in the coating composition for the purpose of lowering the film formation temperature. Agent) can be optionally added.

  Examples of the method for applying the coating composition on a substrate include various coating methods such as spray coating, roll coating, flow coating, bar coating, brush coating, and dipping.

  A coating film is obtained by drying and curing the coating coating composition applied to the substrate surface in the range of 0 ° C. to 150 ° C., and more preferably, the coating film performance is obtained by forced drying at 40 ° C. to 100 ° C. It becomes easy to obtain. When the drying temperature is less than 0 ° C., the water-based paint coating composition is not only frozen, but also the evaporation of moisture is slow, so that it takes a long time to completely dry and harden the coating film, which is not practical. When the drying temperature is higher than 150 ° C., the resin component is thermally decomposed and the coating film is easily yellowed. Moreover, after forming a coating film at 0 degreeC-60 degreeC, it can heat further and can make a coating film more tough.

  Examples of the substrate include slate plate, gypsum board, cement mortar, concrete, metal, glass, earthen tile, asphalt, wood, waterproof rubber, plastic, and calcium silicate substrate. Further, these base materials may be subjected to treatment such as undercoating and intermediate coating in advance.

  The coated article of the present invention has the coating film of the present invention. Examples of the coated material of the present invention include building materials, building interior and exterior, window frames, window glass, structural members, plate materials, vehicle exteriors, exteriors of machinery and articles, dustproof covers, reflectors for road signs, and line-of-sight guidance. Indicators, road markings, road mirrors, various display devices, advertising towers, road sound insulation walls, railway sound insulation walls, road decorative boards, light source covers for traffic lights, outdoor display boards, bridges, guardrails, tunnel interiors, lighting equipment in tunnels, the sun Battery cover, solar water heater collector cover greenhouse, vehicle lamp cover, vehicle mirror, motorcycle weighing cover, glass lens, plastic lens, goggles, helmet shield, house, window glass for automobiles and railway vehicles, vehicle windshield Glass, showcase, membrane structure material, heat exchange fins, glass surface in various places, blinds, tire wheels, roofing materials, roofing gutters, antennas, Electric wire, housing equipment, toilet, bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, tableware storage, dishwasher, tableware dryer, sink, cooking range, kitchen hood, ventilating fan, aquarium material for viewing, Surface materials in contact with circulating water at facilities that use circulating water, antithrombogenic materials, antiprotein adhesion materials, lipid adhesion prevention materials, contact lenses, urinary catheters, transdermal devices, artificial organs, blood packs, blood collection packs, lungs Examples include drainage, ship bottoms, tent canvases, slides, functional fibers, televisions, display displays such as personal computers, and films to be attached to these articles.

  In these coated objects, good hydrophilicity is imparted from the initial stage of coating film formation, so that a self-cleaning action by rainwater is expressed and excellent stain resistance is exhibited.

  Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, “parts” and “%” are shown on a mass basis unless otherwise specified.

(Production example of aqueous resin dispersion A1)
In a reactor equipped with a stirrer, a thermometer, a cooling pipe and a dropping device, 250 parts of ion exchange water, polyoxyethylene polycyclic phenyl ether sulfate ammonium salt (trade name: New Coal 707SF, non-reactive anionic emulsifier, 10 parts of Nippon Emulsifier Co., Ltd. were charged, respectively, and the temperature was raised to 80 ° C. while replacing the inside of the reactor with nitrogen.

  Next, 1.2 parts of potassium persulfate (polymerization initiator) was added, and 180 parts of methyl methacrylate, 120 parts of butyl acrylate, 92 parts of cyclohexyl methacrylate, 8 parts of methacrylic acid, 16 parts of New Coal 707SF, and 300 parts of water were dispersed. The emulsified mixture obtained by emulsifying and stirring was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was aged while continuing stirring at 80 ° C. for 1 hour, cooled to 40 ° C., adjusted to pH 9.0 with 25% aqueous ammonia solution, and having a solid content of 42% in which emulsion particles having a uniform structure were dispersed. An aqueous resin dispersion A1 was obtained.

(Production example of aqueous resin dispersion A2)
In a reactor equipped with a stirrer, a thermometer, a cooling pipe and a dropping device, 250 parts of ion-exchanged water and 10 parts of New Coal 707SF were charged, respectively, and the temperature was raised to 80 ° C. while replacing the inside of the reactor with nitrogen.

  Next, 1.2 parts of potassium persulfate (polymerization initiator) is added, and an emulsified mixed solution composed of 172 parts of methyl methacrylate, 90 parts of 2-ethylhexyl acrylate, 8 parts of methacrylic acid, 10 parts of New Coal 707SF, and 140 parts of water is prepared. It was dripped over 2 hours. Next, 50 parts of methyl methacrylate, 90 parts of 2-ethylhexyl methacrylate, 50 parts of cyclohexyl methacrylate, 10 parts of 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts of Newcor 707SF The emulsion mixture consisting of 140 parts of deionized water was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was aged with stirring at 80 ° C. for 2 hours, cooled to 40 ° C., adjusted to pH 9.0 with 25% aqueous ammonia solution, and the solid content in which the heterophasic emulsion particles were dispersed by the multistage emulsion polymerization method. A 42% aqueous resin dispersion A2 was obtained.

(Production example of water-soluble resin composition B1)
In a reactor equipped with a stirrer, a thermometer, and a condenser tube, 75 parts of polyethylene glycol monomethacrylate (trade name: Blemmer PE-350, manufactured by NOF Corporation), 15 parts of 2-hydroxyethyl acrylate, 10 decyl methacrylate Part, 2,2'-azobisisobutyronitrile 0.1 part, after substituting with nitrogen, it heated with the water bath of 65 degreeC, superposed | polymerized for 4 hours, and obtained water-soluble resin composition B1 .

(Examples 1-13 and Comparative Examples 1-5)
Test paints of Examples 1 to 13 and Comparative Examples 1 to 5 were prepared as shown in Tables 1 and 2. Deionized water, titanium oxide (trade name: Taipei CR-90, manufactured by Ishihara Sangyo Co., Ltd.) as a pigment, and nonionic surfactant (trade name: Disperbyk-190, manufactured by Big Chemie Japan Co., Ltd.) as an additive. In addition to mixing, (A) aqueous resin dispersion, (B) aqueous resin composition aqueous solution previously diluted with ion-exchanged water to a concentration of 20% by weight, (C) water-dispersed colloidal silica, urethane type Each paint by adding a sticky agent (trade name: Primal RM-8W, manufactured by Rohm and Haas Co., Ltd.), a silicone-based antifoaming agent (trade name: SN deformer 1312, manufactured by San Nopco Co., Ltd.), and ethylene glycol And various performance evaluations were performed as follows. The results are shown in Tables 1 and 2.

<Contact angle>
Each test paint to which an appropriate amount of film forming aid was added was applied to a glass plate with a 6 mil applicator, dried and cured at a predetermined temperature for 2 hours, and then cured at room temperature for 1 day. A static contact angle with pure water was measured using a FACE contact angle meter CA-X manufactured by Kyowa Interface Science.

<Occupancy of colloidal silica on the outermost surface of the coating>
The coating film obtained as described above was subjected to elemental analysis using a HITACHI SU-70 scanning electron microscope equipped with INCA X-Sight elemental analyzer manufactured by OXFORD Instruments, and colloidal silica having a surface area on the outermost surface of the coating film in terms of Si. Occupancy was calculated.

<Rain-stain stain resistance>
A slate plate coated with a white paint (dimensions 10 cm × 30 cm × thickness 5 mm) is spray-coated with appropriate additions of film forming aids to the paints of Examples 1 to 13 and Comparative Examples 1 to 5, and a predetermined temperature is applied. And dried for 2 hours. After this was cured for 10 days, the rain that fell on the roof was covered with a coating film that had a roof inclined at 10 degrees with respect to the horizontal plane and having a groove with a length of 30 mm and a depth of 3 mm carved at a pitch of 3 mm. Mounted vertically to the south so as to flow down on the surface, and exposed for 1 month, 6 months, or 12 months in that state, the appearance of the coating film was compared with an untested coating film, and the contamination state was visually observed. .
[Evaluation criteria]
(Double-circle): Dirt has not adhered at all and is maintaining the state equivalent to the time of a test start.
○: Although there is slight dirt, almost no rain streak is confirmed.
(Triangle | delta): There exists a local stain | pollution | contamination and a rain stripe is confirmed slightly.
X: There is considerable dirt on the entire surface, and rain streaks are confirmed firmly.

<Water resistance>
Each test paint to which an appropriate amount of film forming aid was added was coated on a glass plate with a 6 mil applicator, dried and cured at a predetermined temperature for 2 hours, and then cured at room temperature for one day. Thereafter, the test plate was immersed in water at 23 ° C. for 1 week, and the degree of whitening of the coating film after drying was visually determined.
[Evaluation criteria]
A: There is no discoloration of the coating film.
○: The coating film has almost no discoloration or is slightly bluish and transparent.
Δ: The coating film is locally whitened.
X: The coating film is whitened as a whole.

<Hot water whitening resistance>
After preparing a clear paint from which the pigment was removed from each of the above test paints, applying each test paint to which a suitable amount of film-forming aid was added with a 6 mil applicator, drying and curing at a predetermined temperature for 2 hours, Cured for one day at room temperature. Thereafter, the test plate was immersed in warm water at 60 ° C. for 24 hours, and the degree of whitening of the coating film after drying was visually determined.
[Evaluation criteria]
A: There is no discoloration of the coating film.
○: The coating film has no discoloration or is slightly bluish and transparent.
Δ: The coating film is locally whitened.
X: The coating film is whitened as a whole.

<Elution properties>
Each test paint was applied to a polytetrafluoroethylene (PTFE) plate with a 6 mil applicator, dried and cured at a predetermined temperature for 2 hours, and then cured at room temperature for 1 day. The produced film was peeled off, cut into a 10 cm × 10 cm square and the film weight was measured, and then immersed in ion exchange water at 23 ° C. for 24 hours. The taken-out membrane was dried under reduced pressure at 23 ° C., and the elution rate of the coating film into water was calculated according to the following general formula;
Elution rate (%) = {1− (absolute dry weight after immersion) / (absolute dry weight before immersion)} × 100
[Evaluation criteria]
A: Less than 1% elution rate (There is no deterioration of the coating film and the state at the start of the test is maintained)
○: Elution rate of 1% or more and less than 2% (the coating film is hardly deteriorated and the gloss is maintained)
Δ: Elution rate of 2% or more and less than 5% (the surface of the coating film is washed away slightly and the gloss is partially reduced)
X: Elution rate of 5% or more (the surface of the coating film becomes brittle and the gloss decreases overall)

<Storage stability>
Each coating material of Examples 1 to 13 and Comparative Examples 1 to 5 was put into a 100 ml glass sample bottle, stored in a 50 ° C. constant temperature room for one month in a sealed state, and the state was evaluated as follows.
[Evaluation criteria]
○: Same state as before the test, no change.
(Triangle | delta): Although deposit is not confirmed visually, a difference arises in the external appearance when it paints.
X: Precipitate was confirmed visually.

<Recoatability>
Each test paint to which an appropriate amount of film forming aid was added was applied to a glass plate with a 6 mil applicator, dried and cured at a predetermined temperature for 2 hours, and then cured at room temperature for 1 day. The same process was performed again on the prepared coating film.

Next, according to JIS-K-5600-5-6 (1999) adhesion (cross-cut method), 25 squares of 2 mm × 2 mm were prepared on the coating surface of the test coating plate, and the cross-cut portion of the coating film Adhesive tape was stuck on the surface, and the state of the coating film on the grid after being peeled off was visually evaluated.
[Evaluation criteria]
(Double-circle): Peeling is not recognized at all.
○: Less than 10% peeling is observed.
Δ: Peeling of 10% or more and less than 20% is observed.
X: Peeling of 20% or more is recognized.

＊１ 三井武田ケミカル（株）製ウレタンディスパージョン、ＮＶ３５％
＊２ ＢＡＳＦジャパン（株）製水溶性樹脂、ＮＶ７７％
＊３ 日本触媒製ポリビニルピロリドン，平均分子量８００００〜１２００００
＊４ （株）ＡＤＥＫＡ製（ポリエチレンオキサイド−ポリプロピレンオキサイド−ポリエチレンオキサイド），平均分子量２９００，ＥＯ４０％、曇点５８℃
＊５ 信越化学工業（株）製ポリエーテル変性シリコーンオイル
＊６ 日油（株）製ポリエチレングリコール、平均分子量３００
＊７ 球状コロイダルシリカ、日産化学工業（株）製、固形分ＳｉＯ_２：２０％、粒子径：１０〜２０ｎｍ、ｐＨ９．５〜１０．０、Ｎａ安定型
＊８ 酸化チタン、石原産業（株）製
＊９ノニオン性界面活性剤、ビックケミージャパン（株）製
＊１０ ウレタン系増粘剤、ローム・アンド・ハース（株）製
＊１１ シリコーン系消泡剤、サンノプコ（株）製

* 1 Urethane dispersion manufactured by Mitsui Takeda Chemical Co., Ltd., NV 35%
* 2 Water-soluble resin manufactured by BASF Japan, NV77%
* 3 Polyvinylpyrrolidone made by Nippon Shokubai, average molecular weight 80000-120000
* 4 Made by ADEKA (polyethylene oxide-polypropylene oxide-polyethylene oxide), average molecular weight 2900, EO 40%, cloud point 58 ° C
* 5 Polyether-modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. * 6 Polyethylene glycol manufactured by NOF Corporation, average molecular weight 300
* 7 Spherical colloidal silica, manufactured by Nissan Chemical Industries, Ltd., solid content SiO ₂ : 20%, particle size: 10 to 20 nm, pH 9.5 to 10.0, Na stable type * 8 Titanium oxide, Ishihara Sangyo Co., Ltd. * 9 Nonionic surfactant, manufactured by Big Chemie Japan Co., Ltd. * 10 Urethane thickener, manufactured by Rohm & Haas Co., Ltd. * 11 Silicone antifoam, manufactured by San Nopco Co., Ltd.

  As is apparent from Tables 1 and 2, the coating film obtained by the coating film manufacturing method of the present invention was excellent in stain resistance and its maintainability, and was also excellent in water resistance, hot water whitening resistance and recoatability. . On the other hand, the coating film of only the general acrylic emulsion of Comparative Example 1 had a high contact angle and poor wettability, so that contamination was likely to adhere to it, and it was inferior in rain line contamination and recoatability. In the case of not containing (C) water-dispersed colloidal silica of Comparative Example 2, the rain-stain stain resistance, hot water whitening resistance, and elution were inferior. In the case of not containing the (B) aqueous resin composition of Comparative Example 3 or in Comparative Example 4 having a polyoxyethylene group but containing a low molecular weight substance instead of the (B) aqueous resin composition, Since the ratio of the colloidal silica to occupy was low, wettability did not improve, and rain-stain pollution property was inferior. In the case of using a water-soluble resin instead of the aqueous resin dispersion (A) of Comparative Example 5, the maintenance of rain-stain contamination, water resistance, hot water whitening resistance, and elution were inferior.

Claims (10)

(A) an aqueous resin dispersion,
(B) An aqueous resin composition having an amphiphilic polymer having at least one functional group selected from an amide group, an amino group, a hydroxyl group or an oxyalkylene group , wherein the amphiphilic polymer is polyoxyethylene -Polyoxyalkylene-Polyoxyethylene (the alkylene chain has 3 or more carbon atoms) as the basic skeleton, polyoxyalkylene group (the alkylene group has 2 or more carbon atoms) as the basic skeleton, polyvinyl A coating film formed by applying an aqueous resin composition that is pyrrolidone, poly-N-isopropylacrylamide, or hydroxypropylcellulose, and (C) a paint coating composition containing water-dispersed colloidal silica, followed by drying and curing, When elemental analysis was performed on the outermost surface of the coating film, the surface area of the coating film in terms of Si The 0 to 96% (C) a coating film, characterized in that occupied by the water-dispersed colloidal silica. The coating film according to claim 1, wherein the aqueous resin dispersion (A) is an emulsion obtained by polymerizing an α, β-ethylenically unsaturated monomer. The coating film of Claim 1 or 2 which formed the composition inclination layer in the film thickness direction of the said coating film. In the paint coating composition, the ratio of (B) the aqueous resin composition is 0.1 to 15% by weight based on the solid content with respect to the (A) aqueous resin dispersion, and (C) the water-dispersed colloidal silica is The content ratio is (A) 0.5 to 20% by weight based on the solid content with respect to the aqueous resin dispersion, and (B) 0.5 to 200% by weight based on the solid content with respect to the aqueous resin composition. The coating film according to any one of claims 1 to 3 . Coated article characterized by having a coated film according to any one of claims 1-4. (A) an aqueous resin dispersion,
(B) An aqueous resin composition having an amphiphilic polymer having at least one functional group selected from an amide group, an amino group, a hydroxyl group or an oxyalkylene group , wherein the amphiphilic polymer is polyoxyethylene -Polyoxyalkylene-Polyoxyethylene (the alkylene chain has 3 or more carbon atoms) as the basic skeleton, polyoxyalkylene group (the alkylene group has 2 or more carbon atoms) as the basic skeleton, polyvinyl Applying an aqueous resin composition that is pyrrolidone, poly N-isopropylacrylamide or hydroxypropyl cellulose and (C) a paint coating composition comprising water-dispersed colloidal silica;
It is a step of forming a coating film by drying and curing the applied coating composition, and when the outermost surface of the coating film is subjected to elemental analysis, 50 to 96% of the coating surface area in terms of Si ( C) The manufacturing method of the coating film characterized by having the process for which water dispersion | distribution colloidal silica occupies. The method for producing a coating film according to claim 6 , wherein the (A) aqueous resin dispersion is an emulsion obtained by polymerizing an α, β-ethylenically unsaturated monomer. The manufacturing method of the coating film of Claim 6 or 7 which forms a composition inclination layer in the film thickness direction of the said coating film. In the paint coating composition, the ratio of (B) the aqueous resin composition is 0.1 to 15% by weight based on the solid content with respect to the (A) aqueous resin dispersion, and (C) the water-dispersed colloidal silica is The content ratio is (A) 0.5 to 20% by weight based on the solid content with respect to the aqueous resin dispersion, and (B) 0.5 to 200% by weight based on the solid content with respect to the aqueous resin composition. method for producing a coating according to one any of claims 6-8. The method for producing a coating film according to any one of claims 6 to 9 , wherein a temperature for drying and curing the coating composition is 0 to 150 ° C.