JP2014136345A - Laminated coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated coating film, the outermost surface-layer coating film of which is formed as a hydrophilic coating film and which is excellent in warm water resistance, water permeation resistance and weather resistance on the whole and to provide a method for producing the laminated coating film.SOLUTION: The laminated coating film has at least three-layer coating films and is characterized in that the outermost surface-layer coating film thereof is the hydrophilic coating film and at least two-layer coating films, each of which contains a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure, are formed under the outermost surface-layer coating film. The method for producing the laminated coating film comprises the steps of: forming at least two-layer coating films, each of which contains the polymer obtained by polymerizing the monomer component containing the monomer having the alicyclic structure; and forming the hydrophilic coating film as the outermost surface-layer coating film.

Description

  The present invention relates to a laminated coating film. More specifically, the present invention relates to a multilayer coating film having a topmost layer coating film which is a hydrophilic coating film and which is comprehensively excellent in warm water resistance, water permeability resistance and weather resistance, and a method for producing the same. The laminated coating film of the present invention can be suitably used for a base material such as a building exterior or a ceramic building material.

  In recent years, in order to avoid environmental problems due to the release of volatile organic compounds into the atmosphere, water-based paints using water-dispersed resins such as water-soluble resins and emulsions have been used in place of solvent-based paints. . However, in contrast to organic solvent-based paints, water-based paints are generally inferior in the durability and appearance of paint films such as drying, water resistance, and weather resistance due to the use of water as a solvent. There is a technical problem that it is difficult to increase the coating film hardness.

  Accordingly, an aqueous coating composition containing two resin components having different glass transition temperatures in a specific ratio as an aqueous coating composition having enhanced coating film hardness and good coating film appearance and durability (for example, patent document) 1), an aqueous coating composition excellent in weather resistance, water resistance, discoloration resistance, crack resistance, polymerization stability, storage stability, warm water resistance, film-forming properties, temperature resistance resistance and coating film appearance. An aqueous coating composition in which multilayer structure particles having a core part and a shell part made of an acrylic polymer having a specific glass transition temperature are dispersed in water has been proposed (for example, see Patent Document 2).

  However, the water-based coating composition does not sufficiently satisfy the water resistance, water permeability, and weather resistance at the same time, while the outermost layer is excellent in hydrophilicity.

JP 2001-200181 A Japanese Patent Laid-Open No. 2002-12816

  The present invention has been made in view of the above prior art, and the outermost layer coating film is a hydrophilic coating film, and a laminated coating film that is comprehensively excellent in warm water resistance, water permeability resistance, and weather resistance, and its It is an object to provide a manufacturing method.

The present invention
(1) A multilayer coating film having at least three coating films, the outermost coating film being a hydrophilic coating film, and a monomer having an alicyclic structure in the lower layer of the outermost coating film A multilayer coating film comprising at least two coating films containing a polymer obtained by polymerizing a monomer component containing, and (2) a multilayer coating film having at least three coating films A method for producing a film, comprising: forming at least two coating films containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure; The present invention relates to a method for producing a laminated coating film characterized by forming a hydrophilic coating film.

  According to the present invention, the outermost-layer coating film is formed of a hydrophilic coating film, and a laminated coating film that is comprehensively excellent in hot water resistance, water permeability resistance, and weather resistance is provided.

  As described above, the multilayer coating film of the present invention is a multilayer coating film having at least three coating films, the outermost layer coating film is formed of a hydrophilic coating film, and the lowermost coating layer layer has a lower layer. The coating film containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure is formed in at least two layers. Moreover, the manufacturing method of the laminated coating film of this invention is a manufacturing method of the laminated coating film which has a coating film of at least 3 layers as mentioned above, and is a monomer component containing the monomer which has an alicyclic structure After forming at least two coating films containing a polymer obtained by polymerizing the above, a hydrophilic coating film is formed as the outermost coating film.

  The number of the coating film which the laminated coating film of this invention has is at least 3 layers. Among the three-layer coating film, the outermost-layer coating film is formed of a hydrophilic coating film, and a monomer containing a monomer having an alicyclic structure is formed under the outermost-layer coating film. At least two coating films containing a polymer obtained by polymerizing the components are formed. The coating film constituting the laminated coating film is formed of at least the three layers in order to achieve the desired object of the present invention. In addition, from the viewpoint of reducing the thickness of the entire laminated coating film, the total number of coating films constituting the laminated coating film is preferably 10 layers or less, more preferably 8 layers or less.

  A coating film containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure, for example, polymerizes a monomer component containing a monomer having an alicyclic structure It can form by apply | coating the aqueous coating material containing the polymer obtained by making it a base material.

  Suitable water-based paints include, for example, paints containing a resin emulsion obtained by emulsion polymerization of a monomer component containing a monomer having an alicyclic structure.

  The resin emulsion is obtained by emulsion polymerization of a monomer component containing a monomer having an alicyclic structure in the presence of an emulsifier.

  In the monomer having an alicyclic structure, the alicyclic structure is preferably a cycloalkyl group having 4 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of the monomer having an alicyclic structure include cycloalkyl (meth) acrylate and cycloalkylalkyl (meth) acrylate, but the present invention is not limited to such examples. These monomers having an alicyclic structure may be used alone or in combination of two or more. The monomer having an alicyclic structure may have a substituent as long as the object of the present invention is not impaired. Examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, and a tert-butyl group, a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, and a halogen atom. The present invention is not limited to such examples.

  In the present specification, “(meth) acrylate” means “acrylate” or “methacrylate”, and “(meth) acryl” means “acryl” or “methacryl”.

  As the cycloalkyl (meth) acrylate, for example, a cycloalkyl group such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate and the like preferably has 4 to 20 carbon atoms, more preferably 4 to 10 cycloalkyl (meth) acrylates. However, the present invention is not limited to such examples. These cycloalkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the cycloalkylalkyl (meth) acrylate include carbon numbers of cycloalkyl groups such as cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, and 4-methylcyclohexylmethyl (meth) acrylate. Is preferably 4 to 20, more preferably 4 to 10 cycloalkylalkyl (meth) acrylate, but the present invention is not limited to such examples. These cycloalkylalkyl (meth) acrylates may be used alone or in combination of two or more.

  Among the monomers having an alicyclic structure, the number of carbon atoms is 4 from the viewpoint of forming a laminated coating film having a hydrophilic outermost layer and simultaneously satisfying hot water resistance, water permeability resistance and weather resistance. Preferred are cycloalkyl (meth) acrylates having -20 cycloalkyl groups, more preferred are cycloalkyl (meth) acrylates having 4 to 10 carbon atoms cycloalkyl groups, isobornyl (meth) acrylates and cyclohexyl (meth) acrylates. Is more preferable.

  The content of the monomer having an alicyclic structure in the monomer component is the viewpoint of forming a multilayer coating film that simultaneously satisfies the hot water resistance, water permeability resistance and weather resistance while having the outermost layer having hydrophilicity. Therefore, it is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, further preferably 10 to 100% by mass, and still more preferably 30 to 100% by mass. Therefore, the monomer component may be composed only of a monomer having an alicyclic structure. In addition, the monomer component preferably has 0 to 99% by mass from the viewpoint of forming a laminated coating film having a hydrophilic outermost layer and simultaneously satisfying hot water resistance, water permeability resistance and weather resistance. More preferably, the monomer is copolymerizable with a monomer having an alicyclic structure within the range of 0 to 95% by mass, more preferably 0 to 90% by mass, and still more preferably 0 to 70% by mass. It may be contained.

  Examples of the monomer copolymerizable with the monomer having an alicyclic structure include aromatic monomers and ethylenically unsaturated monomers, and these may be used alone. Two or more types may be used in combination. In addition, both the aromatic monomer and ethylenically unsaturated monomer referred to in the present specification mean a monomer having no alicyclic structure.

  Examples of aromatic monomers include styrene monomers and aralkyl (meth) acrylates, but the present invention is not limited to such examples.

  Examples of the styrenic monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, and the like, but the present invention is limited only to such examples. is not. These monomers may be used alone or in combination of two or more. Styrene monomers have functional groups such as alkyl groups such as methyl and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms in the benzene ring. May be. Among the styrene monomers, styrene is preferable from the viewpoint of increasing the water resistance of the coating film.

  Examples of the aralkyl (meth) acrylate include aralkyl having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate and the like. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These aralkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer include alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate, carboxyl group-containing monomer, oxo group-containing monomer, fluorine atom-containing monomer, and nitrogen atom-containing monomer. Examples include monomers, epoxy group-containing monomers, alkoxyalkyl (meth) acrylates, silane group-containing monomers, carbonyl group-containing monomers, aziridinyl group-containing monomers, and the present invention is only such examples. It is not limited to. These ethylenically unsaturated monomers may be used alone or in combination of two or more.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) Examples thereof include alkyl (meth) acrylates having 1 to 18 carbon atoms in ester groups such as acrylate and stearyl (meth) acrylate, but the present invention is not limited to such examples. These alkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy Examples include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group such as butyl (meth) acrylate, but the present invention is not limited to such examples. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, and itaconic acid monomethyl. Examples thereof include carboxyl group-containing aliphatic monomers such as esters, itaconic acid monobutyl ester, and vinyl benzoic acid, but the present invention is not limited to such examples. These carboxyl group-containing monomers may be used alone or in combination of two or more. Among these carboxyl group-containing monomers, acrylic acid, methacrylic acid and itaconic acid are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoint of improving the dispersion stability of the emulsion particles.

  Examples of the oxo group-containing monomer include (di) ethylene glycol (methoxy) (meta) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. ) Acrylate and the like, but the present invention is not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more.

  Examples of the fluorine atom-containing monomer include fluorine atom-containing alkyl having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These fluorine atom-containing monomers may be used alone or in combination of two or more.

  Examples of the nitrogen atom-containing monomer include (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and Nn-propyl (meth). Acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropylacrylamide, Acrylamide compounds such as diacetone acrylamide, nitrogen atom-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, ( Data) but and acrylonitrile, the present invention is not limited only to those exemplified. These nitrogen atom-containing monomers may be used alone or in combination of two or more.

  Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and glycidyl allyl ether. It is not limited to only. These epoxy group-containing monomers may be used alone or in combination of two or more.

  Examples of the alkoxyalkyl (meth) acrylate include methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, and trimethylolpropane tripropoxy (meth) acrylate. However, the present invention is not limited to such examples. These alkoxyalkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the silane group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltri Examples include chlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to such examples. These silane group-containing monomers may be used alone or in combination of two or more.

  Examples of the carbonyl group-containing monomer include acrolein, humylstyrene, vinyl ethyl ketone, (meth) acryloxyalkylpropenal, acetonyl (meth) acrylate, diacetone (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Examples include acetyl acetate, butanediol-1,4-acrylate acetyl acetate, and 2- (acetoacetoxy) ethyl (meth) acrylate, but the present invention is not limited to such examples. These carbonyl group-containing monomers may be used alone or in combination of two or more.

  Examples of aziridinyl group-containing monomers include (meth) acryloylaziridine and 2-aziridinylethyl (meth) acrylate, but the present invention is not limited to such examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

  Suitable monomers copolymerizable with a monomer having an alicyclic structure include, for example, aromatic monomers, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, carboxyl group-containing monomers, Examples thereof include ethylenically unsaturated monomers such as oxo group-containing monomers, fluorine atom-containing monomers, nitrogen atom-containing monomers, and epoxy group-containing monomers. Or two or more of them may be used in combination. Among monomers that can be copolymerized with monomers having an alicyclic structure, it forms a laminated coating film that has both a water resistance, water resistance and weather resistance at the same time while having a hydrophilic outermost layer. From the viewpoint of making it, an ethylenically unsaturated monomer is preferable, alkyl (meth) acrylate is more preferable, and tert-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are more preferable.

  Further, in the present invention, from the viewpoint of imparting ultraviolet stability and ultraviolet absorption to the emulsion particles, an ultraviolet stable monomer, an ultraviolet absorbing monomer, and the like are simply used within a range that does not impede the purpose of the present invention. You may make it contain in a mass component.

  Examples of UV-stable monomers include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine (4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano -4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- Crotonoylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-si No-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano Examples include -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like. However, these monomers may be used alone or in combination of two or more.

  Examples of the UV-absorbing monomer include benzotriazole-based UV-absorbing monomers and benzophenone-based UV-absorbing monomers, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the benzotriazole-based UV-absorbing monomer include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole and 2- [2′-hydroxy-5′-. (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2 ′ -Hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzo Triazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyhex Ruphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′ -Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acrylyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydride Xyl-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′- tert-butylphenyl] -4-tert-butyl-2H-benzotriazole, and the like, but the present invention is not limited to such examples. These benzotriazole-based UV-absorbing monomers may be used alone or in combination of two or more.

  Examples of the benzophenone-based UV-absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2- Hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- Examples include [2- (meth) acryloyloxy] butoxybenzophenone, but the present invention is not limited to such examples. These benzophenone-based ultraviolet absorbing monomers may be used alone or in combination of two or more.

  Examples of the method for emulsion polymerization of the monomer component include, for example, an aqueous medium containing a water-soluble organic solvent such as lower alcohol such as methanol and water, an emulsifier dissolved in a medium such as water, and the monomer under stirring. Examples of the method include dropping a component and a polymerization initiator, and a method of dropping a monomer component that has been pre-emulsified with an emulsifier and water into water or an aqueous medium. It is not limited. Note that the amount of the medium may be appropriately set in consideration of the nonvolatile content contained in the obtained aqueous resin composition. The medium may be charged in the reaction vessel in advance or used as a pre-emulsion. The medium may be used when a resin emulsion is produced by emulsion polymerization of monomer components as required.

  When the monomer component is emulsion-polymerized, the monomer component, the emulsifier and the medium may be mixed and then emulsion polymerization may be performed. The emulsion polymerization may be carried out after preparing the emulsion, or the emulsion polymerization may be carried out by mixing at least one of the monomer component, the emulsifier and the medium and the remaining pre-emulsion. The monomer component, the emulsifier, and the medium may be added all at once, dividedly, or continuously dropped.

  When the outer layer is formed on the emulsion particles contained in the resin emulsion obtained above, the monomer component is emulsion-polymerized in the resin emulsion in the same manner as described above to form the outer layer on the emulsion particles. An outer layer can be formed. Moreover, when forming an outer layer further on the emulsion particle | grains in which the said outer layer was formed, an outer layer is further formed on the said emulsion particle | grain by carrying out the emulsion polymerization of the monomer component in a resin emulsion like the above. Can be made. Thus, a resin emulsion containing emulsion particles having a multilayer structure can be prepared by a multistage emulsion polymerization method.

  When preparing emulsion particles having a multilayer structure, one or more stages of emulsion polymerization may be performed before the emulsion polymerization for forming the inner layer. The emulsion polymerization for forming the inner layer and the intermediate layer may be performed. One-stage or multi-stage emulsion polymerization may be performed between the emulsion polymerization to be formed. Moreover, you may perform one step or multiple steps | paragraphs of emulsion polymerization between the emulsion polymerization which forms the said intermediate | middle layer, and the emulsion polymerization which forms the said outer layer. Furthermore, after the emulsion polymerization for forming the outer layer, one or more stages of emulsion polymerization may be performed.

  Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, and a polymer emulsifier. These emulsifiers may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate. Polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; ammonium laurate, sodium stearate, etc. Fatty acid salt; bis ( (Rioxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkylsulfosuccinate ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt, allyloxymethylalkyloxypoly Sulfuric acid ester having an allyl group, such as sulfonate salt of oxyethylene or a salt thereof; Sulfuric acid ester salt of allyloxymethylalkoxyethyl polyoxyethylene, polyoxyalkylene alkenyl ether ammonium sulfate, and the like. It is not limited to.

  Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Examples include condensation products with amines, allyloxymethylalkoxyethylhydroxypolyoxyethylene, and polyoxyalkylene alkenyl ethers, but the present invention is not limited to such examples.

  Examples of the cationic emulsifier include alkylammonium salts such as dodecylammonium chloride, but the present invention is not limited to such examples.

  Examples of amphoteric emulsifiers include betaine ester type emulsifiers, but the present invention is not limited to such examples.

  Examples of the polymer emulsifier include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinyl pyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; single polymers constituting these polymers. Although the copolymer etc. which use 1 or more types of a monomer as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  The emulsifier is preferably an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier from the viewpoint of improving weather resistance and frost damage resistance, and a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.

  As the reactive emulsifier, for example, propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, manufactured by Sanyo Chemical Industries, Ltd., Product name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, product name: Aqualon HS-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salt [for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, product name: ADEKA manufactured by ADEKA Corporation Rear soap SE-10 etc.), Ryloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (for example, manufactured by ADEKA, trade name: Adekaria soap SR-10, SR-30, etc.), bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate Salts (for example, Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene [eg, ADEKA Corporation, trade name: Adeka Soap ER-20, etc. ], Polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, Product Name: Adekaria Soap E-10, etc.) and the like, the present invention is not limited only to those exemplified.

  The amount of the emulsifier is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, particularly preferably from the viewpoint of improving the polymerization stability per 100 parts by mass of the monomer component. Is 3 parts by mass or more, and is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, still more preferably 5 parts by mass or less, particularly preferably from the viewpoint of improving weather resistance, blocking resistance and frost damage resistance. 4 parts by mass or less.

  Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; hydrogen peroxide , Benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, peroxides such as ammonium peroxide, and the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator is preferably 0.05 parts by mass or more, more preferably 0 from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component per 100 parts by mass of the monomer component. From the viewpoint of improving weather resistance and frost damage resistance, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.

  The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. From the viewpoint of advancing the completion time of the polymerization reaction, a part of the polymerization initiator may be added before or after the monomer component is added to the reaction system.

  In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.

  A chain transfer agent can be used to adjust the weight average molecular weight of the polymer constituting the emulsion particles. Examples of the chain transfer agent include 2-ethylhexyl thioglycolate, tert-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α-methyl. Although a styrene dimer etc. are mentioned, this invention is not limited only to this illustration. These chain transfer agents may be used alone or in combination of two or more. The amount of the chain transfer agent is preferably 0.01 to 10 parts by mass per 100 parts by mass of the monomer component from the viewpoint of adjusting the weight average molecular weight of the emulsion particles.

  Moreover, you may add additives, such as a pH buffer, a chelating agent, and a film-forming aid, in the reaction system as needed. Since the amount of the additive varies depending on the type, it cannot be determined unconditionally, but usually, it is preferably about 0.01 to 5 parts by weight, more preferably 0.1 to 100 parts by weight per 100 parts by weight of the monomer component. About 3 parts by mass.

  The atmosphere for emulsion polymerization of the monomer component is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of increasing the efficiency of the polymerization initiator.

  Although the polymerization temperature at the time of carrying out emulsion polymerization of a monomer component does not have limitation, Usually, Preferably it is 50-100 degreeC, More preferably, it is 60-95 degreeC. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for emulsion polymerization of the monomer component is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.

  In addition, when carrying out emulsion polymerization of a monomer component, you may make it neutralize part or all of the acidic group which the polymer obtained has with a neutralizing agent. The neutralizing agent may be used after the monomer component is added in the final stage. For example, the neutralizing agent may be used between the first stage polymerization reaction and the second stage polymerization reaction. It may be used at the end of the polymerization reaction.

  Examples of the neutralizing agent include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide; alkali metal and alkaline earth metal carbonates such as calcium carbonate; and organic amines such as ammonia and monomethylamine. Although an alkaline substance is mentioned, this invention is not limited only to this illustration. Among these neutralizing agents, an alkaline substance having volatility such as ammonia is preferable from the viewpoint of improving weather resistance and hot water whitening resistance.

  Further, when the monomer component is emulsion-polymerized, a silane coupling agent may be used in an appropriate amount from the viewpoint of improving weather resistance and hot water whitening resistance. Examples of the silane coupling agent include a silane coupling agent having a polymerizable unsaturated bond such as a (meth) acryloyl group, a vinyl group, an allyl group, and a propenyl group. It is not limited.

  By emulsion polymerization of the monomer component as described above, a resin emulsion containing emulsion particles can be obtained.

  The polymer constituting the emulsion particles may have a crosslinked structure. The weight average molecular weight of the polymer is such that the polymer has a cross-linked structure and a case where the polymer does not have a cross-linked structure. From the viewpoint of forming a laminated coating film that simultaneously satisfies the weather resistance, it is preferably 100,000 or more, more preferably 300,000 or more, still more preferably 550,000 or more, and particularly preferably 600,000 or more. The upper limit of the weight average molecular weight of the polymer is not particularly limited when it has a crosslinked structure, since it is difficult to measure the weight average molecular weight, but when it does not have a crosslinked structure, the flexibility of the coating film From the viewpoint of improving the viscosity, it is preferably 5 million or less.

In this specification, the weight average molecular weight is determined by gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel.
The weight average molecular weight (polystyrene conversion) measured using GMHXL-L in series] is meant.

  The glass transition temperature of the polymer is preferably −40 ° C. or more, from the viewpoint of forming a laminated coating film that simultaneously satisfies the hot water resistance, water permeability resistance and weather resistance while having the outermost layer having hydrophilicity. Preferably it is −25 ° C. or higher, more preferably −10 ° C. or higher. From the viewpoint of improving the flexibility of the coating film, it is preferably 70 ° C. or lower, more preferably 60 ° C. or lower, and even more preferably 50 ° C. or lower. . The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer used for the monomer component.

In the present specification, the glass transition temperature of the polymer is expressed by the following formula: the glass transition temperature of the homopolymer of the monomer used in the monomer component constituting the polymer.
1 / Tg = Σ (Wm / Tgm) / 100
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
The temperature calculated | required based on the Formula of Fox (Fox) represented by these.

  The glass transition temperature of the polymer is, for example, -70.degree. C. for 2-ethylhexyl acrylate homopolymer, -56.degree. C. for n-butyl acrylate homopolymer, 105.degree. C. for methyl methacrylate homopolymer, and cyclohexyl methacrylate homopolymer. 83 ° C for the polymer, 55 ° C for the homopolymer of hydroxyethyl methacrylate, 70 ° C for the homopolymer of γ-methacryloxypropyltrimethoxysilane (TMSMA), 95 ° C for the homopolymer of acrylic acid, tert-butyl methacrylate It is 107 ° C. for the homopolymer of 1), 180 ° C. for the homopolymer of isobornyl methacrylate, 130 ° C. for the homopolymer of methacrylic acid, and 16 ° C. for the homopolymer of cyclohexyl acrylate.

  In this specification, the glass transition temperature of a polymer means the glass transition temperature calculated | required based on the said formula, unless there is particular notice. For monomers with unknown glass transition temperature such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperature in the monomer component is 10% by mass. In the following cases, the glass transition temperature is determined using only monomers whose glass transition temperature is known. When the total amount of monomers whose glass transition temperature is unknown in the monomer component exceeds 10% by mass, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC), differential calorimetry (DTA), It is calculated | required by thermomechanical analysis (TMA) etc.

  The nonvolatile content in the resin emulsion is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of improving productivity, and preferably 70% by mass or less, more preferably from the viewpoint of improving handleability. 60% by mass or less.

In the present specification, the non-volatile content in the aqueous resin composition is determined by weighing 1 g of the aqueous resin composition and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Nonvolatile content in water-based resin composition (mass%)]
= ([Residue mass] ÷ [aqueous resin composition 1 g]) × 100
Means the value obtained based on

  From the viewpoint of improving the storage stability of the emulsion particles, the average particle diameter of the emulsion particles is preferably 30 nm or more, more preferably 50 nm or more, and further preferably 70 nm or more, from the viewpoint of improving weather resistance and frost damage resistance. , Preferably 250 nm or less, more preferably 200 nm or less.

In this specification, the average particle size of the emulsion particles is a particle size distribution measuring instrument [Particle Sizing Systems (Particle) by a dynamic light scattering method.
This means a volume average particle diameter measured using a product name (NICOMP Model 380) manufactured by Sizing Systems).

  The paint contains a resin emulsion obtained by emulsion polymerization of a monomer component containing a monomer having an alicyclic structure, and further imparts crosslinkability by containing a crosslinking agent. be able to. As a crosslinking agent, a crosslinking reaction may be started at room temperature, or a crosslinking reaction may be initiated by heat. By containing a crosslinking agent in the aqueous resin composition of the present invention, it is possible to improve warm water whitening resistance and blocking resistance.

  Suitable cross-linking agents include, for example, oxazoline group-containing compounds, isocyanate group-containing compounds, aminoplast resins, and the like. These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, an oxazoline group-containing compound is preferable from the viewpoint of improving hot water whitening resistance and blocking resistance.

  The oxazoline group-containing compound is a compound having in the molecule two or more oxazoline groups that can react with the carboxyl group that the carboxyl group-containing monomer used as the monomer component has as a functional group.

  Examples of the oxazoline group-containing compound include 2,2′-bis (2-oxazoline), 2,2′-methylene-bis (2-oxazoline), 2,2′-ethylene-bis (2-oxazoline), 2 , 2'-trimethylene-bis (2-oxazoline), 2,2'-tetramethylene-bis (2-oxazoline), 2,2'-hexamethylene-bis (2-oxazoline), 2,2'-octamethylene -Bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis (2-oxazoline), 2,2'- m-phenylene-bis (2-oxazoline), 2,2′-m-phenylene-bis (4,4′-dimethyl-2-oxazoline), bis (2-oxazolinylcyclohexane) sulfi , Bis (2-oxazolinyl sulfonyl norbornane) sulfide, but like oxazoline ring-containing polymer, the present invention is not limited only to those exemplified. These oxazoline group-containing compounds may be used alone or in combination of two or more. Among the oxazoline group-containing compounds, from the viewpoint of improving the reactivity, a water-soluble oxazoline group-containing compound is preferable, and a water-soluble oxazoline ring-containing polymer is more preferable.

  The oxazoline ring-containing polymer contains an addition-polymerizable oxazoline as an essential component, and can be easily prepared by polymerizing a monomer component containing a monomer copolymerizable with the addition-polymerizable oxazoline as necessary. Can do.

  Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. It is not limited to only. These addition polymerizable oxazolines may be used alone or in combination of two or more. Among these addition-polymerizable oxazolines, 2-isopropenyl-2-oxazoline is preferable because it is easily available.

  Examples of monomers copolymerizable with the addition polymerizable oxazoline include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate. , Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, monoesterified product of (meth) acrylic acid and polyethylene glycol, 2-aminoethyl (meth) acrylate and its salt, caprolactone modified product of (meth) acrylic acid, (meth) acrylic -(2,2,6,6-tetramethylpiperidine, (meth) acrylic acid-1, methacrylic acid esters such as 1,2,2,6,6-pentamethylpiperidine; sodium (meth) acrylate, (meta ) (Meth) acrylates such as potassium acrylate and ammonium (meth) acrylate; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) ) Unsaturated amides such as (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; Vinyl chloride, vinylidene chloride, vinyl fluoride, etc. Halogen-containing α, β-unsaturated fat Hydrocarbon compounds; styrene, alpha-methyl styrene, alpha such as sodium styrene sulfonate, beta-although such unsaturated aromatic hydrocarbon compounds, the present invention is not limited only to those exemplified. These monomers copolymerizable with the addition-polymerizable oxazoline may be used alone or in combination of two or more.

  Oxazoline group-containing compounds are easily commercially available as, for example, Nippon Shokubai Co., Ltd., trade names: Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K-2020, Epocross K-2030, etc. can do. Among these, from the viewpoint of improving reactivity, water-soluble oxazoline group-containing compounds such as Nippon Shokubai Co., Ltd., trade names: Epocross WS-500 and Epocross WS-700 are preferable.

  The isocyanate group-containing compound is a compound containing an isocyanate group that can react with a hydroxyl group that the hydroxyl group-containing monomer used as the monomer component has as a functional group.

  Examples of the isocyanate group-containing compound include water-dispersed (block) polyisocyanate. In addition, (block) polyisocyanate means polyisocyanate and / or block polyisocyanate.

  Examples of the water-dispersed polyisocyanate include those obtained by dispersing a polyisocyanate imparted with hydrophilicity by a polyethylene oxide chain in water with an anionic dispersant or a nonionic dispersant.

  Examples of the polyisocyanate include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and polyisocyanate derivatives (modified products) of these diisocyanates such as trimethylolpropane adduct, burette, and isocyanurate. The present invention is not limited to such examples. These polyisocyanates may be used alone or in combination of two or more.

  Water-dispersed polyisocyanates are, for example, made by Nippon Polyurethane Industry Co., Ltd., trade names: Aquanate 100, Aquanate 110, Aquanate 200, Aquanate 210, etc .; manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Baihijur TPLS-2032, SUB-isocyanate L801, etc .; manufactured by Mitsui Takeda Chemical Co., Ltd., trade names: Takenate WD-720, Takenate WD-725, Takenate WD-220, etc .; manufactured by Dainichi Seika Kogyo, trade name: Resamine It can be easily obtained commercially as D-56 or the like.

  The water-dispersed block polyisocyanate is obtained by blocking the isocyanate group of the water-dispersed polyisocyanate with a blocking agent. Examples of the blocking agent include diethyl malonate, ethyl acetoacetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, dimethyl-1,2,4-triazole, and 3,5-dimethylpyrazole. , Imidazole and the like can be mentioned, but the present invention is not limited to such examples. These blocking agents may be used alone or in combination of two or more. Among these blocking agents, those that cleave at a temperature of 160 ° C. or lower, preferably 150 ° C. or lower are desirable. Suitable blocking agents include, for example, butanone oxime, cyclohexanone oxime, 3,5-dimethylpyrazole and the like. Of these, butanone oxime is more preferred.

  Examples of the water-dispersed block polyisocyanate include Mitsui Takeda Chemical Co., Ltd., trade names: Takenate WB-720, Takenate WB-730, Takenate WB-920, etc .; Sumika Bayer Urethane Co., Ltd., trade name: Bihijur BL116, Bihijoule BL5140, Bihijoule BL5235, Bihijoule TPLS2186, Death Module VPLS2310, etc. can be easily obtained commercially.

  The aminoplast resin is an addition condensate of a compound having an amino group such as melamine or guanamine with formaldehyde, and is also called an amino resin.

  Examples of aminoplast resins include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkyl methylated melamine, fully alkyl butylated melamine, fully alkyl isobutylated melamine, completely Melamine resins such as alkyl mixed etherified melamine, methylol group methylated melamine, imino group methylated melamine, methylol group mixed etherified melamine, imino group mixed etherified melamine; butylated benzoguanamine, methyl / ethyl mixed alkyl Benzoguanamine, methyl / butyl mixed alkylated benzoguanamine, guanamine resins such as butylated glycoluril, and the like, but the present invention is limited only to such examples. Not to. These aminoplast resins may be used alone or in combination of two or more.

  Aminoplast resin is, for example, made by Mitsui Cytec Co., Ltd., trade names: My Coat 506, My Coat 1128, Cymel 232, Cymel 235, Cymel 254, Cymel 303, Cymel 325, Cymel 370, Cymel 771, Cymel 1170, etc. It can be easily obtained commercially.

  The amount of aminoplast resin is usually such that the weight ratio of the solid content of the polymer contained in the emulsion particles to the solid content of the aminoplast resin (solid content of polymer / solid content of aminoplast resin) is 60/40. It is preferable to adjust so that it may be set to -99/1.

  In the present invention, in addition to the crosslinking agent described above, for example, a carbodiimide compound; a crosslinking agent such as a polyvalent metal compound represented by a zirconium compound, a zinc compound, a titanium compound, an aluminum compound, etc. It can be used as long as it is not inhibited.

  If necessary, the paint can contain a pigment. Examples of the pigment include organic pigments and inorganic pigments, and these may be used alone or in combination of two or more.

  Examples of organic pigments include azo pigments such as benzidine and hansa yellow, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, and iminoisoindoline. Pigments, iminoisoindolinone pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavantron pigments, indanthrone pigments, anthrapyrimidine pigments, carbazole pigments, monoarylide yellow, diaryride yellow, benzimidazolone yellow, tolyl orange , Naphthol orange, quinophthalone pigment, and the like, but the present invention is not limited to such examples. These organic pigments may be used alone or in combination of two or more.

  Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc white, lithopone, lead white, red iron oxide, black iron oxide, iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferrocyanide Pigment with flat shape such as ferric (Prussian blue), ultramarine, lead chromate, mica, clay, aluminum powder, talc, aluminum silicate, calcium carbonate, magnesium hydroxide, aluminum hydroxide And extender pigments such as barium sulfate and magnesium carbonate, but the present invention is not limited to such examples. These inorganic pigments may be used alone or in combination of two or more.

  The amount of the pigment per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, from the viewpoint of improving weather resistance and blocking resistance, and the flexibility of the coating film. From the viewpoint of improving the ratio, it is preferably 190 parts by mass or less.

  In addition, the said coating material may contain other resin emulsions other than the said resin emulsion within the range which does not inhibit the objective of this invention.

  In addition, the paint includes, for example, an ultraviolet absorber, an ultraviolet stabilizer, a filler, a leveling agent, a pH adjuster, a dispersant, a thickener, a wetting agent, and a plasticizer within a range that does not impair the object of the present invention. Additives such as stabilizers, antifoaming agents, preservatives, dyes and antioxidants may be contained in appropriate amounts.

  In the present invention, first, at least two layers of a coating film containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure are formed.

  The said coating film can be formed on the surface of the base material represented by building materials, such as ceramics type building materials, for example. Examples of ceramic building materials include tiles and outer wall materials. Ceramic building materials are obtained by adding inorganic fillers, fibrous materials, etc. to hydraulic glue that is the raw material of inorganic hardened bodies, molding the resulting mixture, curing the resulting molded body, and curing it. can get. As an inorganic building material which comprises the exterior of a building, a flexible board, a calcium silicate board, a gypsum slag perlite board, a piece of wood cement board, a precast concrete board, an ALC board, a gypsum board etc. are mentioned, for example. A top coating material (water-based paint) is usually applied to the surface of these building materials in order to impart a desired design. The said coating material can be used as this top coat material (water-based coating material).

  Examples of the method for forming the coating material on the surface of the substrate include a coating method using a brush, a trowel, a bar coater, an applicator, an air spray, an airless spray, a roll coater, a flow coater, and the like. Is not limited to such examples. The surface of the base material may be subjected to, for example, primer treatment or sealer treatment as necessary.

The amount of coating applied to the substrate is such that even if the outermost coating layer is formed of a hydrophilic coating layer, a laminated coating film that is comprehensively excellent in hot water resistance, water permeability resistance and weather resistance is formed. From the viewpoint, it is usually preferable that the nonvolatile content is about ²⁰ to 200 g / m ² .

  The drying conditions of the formed coating film need only be able to sufficiently evaporate the solvent used in the coating material, and vary depending on the type and amount of the solvent used in the coating material. Usually, the coating film may be dried by heating to a temperature of preferably 50 to 150 ° C, more preferably 60 to 120 ° C. The drying time is not particularly limited as long as the coating film is sufficiently dried.

  Next, on a coating film (hereinafter also referred to as coating film A for convenience) containing a polymer obtained by polymerizing the monomer component containing the monomer having an alicyclic structure formed above. Furthermore, a coating film containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure (hereinafter also referred to as coating film B for convenience) is formed. On the coating film A, another coating film may be formed before forming the coating film B, but even if the outermost coating film is formed with a hydrophilic coating film, it is resistant to warm water and water. From the viewpoint of forming a laminated coating film that is comprehensively excellent in properties and weather resistance, it is preferable to form the coating film B directly on the coating film A.

  The coating film B further formed on the coating film A may be one layer or two or more layers. However, even if the outermost coating film is formed of a hydrophilic coating film, From the viewpoint of forming a laminated coating film that is comprehensively excellent in properties, water resistance and weather resistance, it is preferably one layer or two layers. When two or more coating films B are formed on the coating film A, the composition of the two or more coating films B to be formed may be the same or different.

  The coating film B formed on the coating film A can be formed using, for example, the same coating material as that used when forming the coating film A. Therefore, the coating material used when forming the coating film A and the coating material used when forming the coating film B may be the same or different. The method for forming the coating film B may be the same as that for the coating film A. In the present invention, since the coating film B is formed on the coating film A, the outermost coating film is formed of a hydrophilic coating film as compared with the case where the coating film A is formed of only one layer. In spite of this, it is possible to form a laminated coating film that is comprehensively excellent in hot water resistance, water permeability resistance and weather resistance.

  Next, a hydrophilic coating film is formed on the coating film B as the outermost coating film. Here, the hydrophilic coating film means a coating film having a contact angle with water of 50 ° or less. The contact angle of the hydrophilic coating film with water can be measured using, for example, a contact angle measuring device [manufactured by Kyowa Interface Science Co., Ltd., trade name: FACE contact angle meter CA-X type]. The contact angle of the hydrophilic coating film with water is preferably 40 ° or less from the viewpoint of sufficiently imparting hydrophilicity to the base material typified by building materials such as ceramic building materials.

  When forming the hydrophilic coating film, a hydrophilic coating can be used. The hydrophilic paint is not particularly limited as long as it forms a hydrophilic paint film as the outermost paint film. Examples of the hydrophilic paint include acrylic hydrophilic paint, cellulose hydrophilic paint, polyurethane hydrophilic paint, polyester hydrophilic paint, polyether polyol hydrophilic paint, polyamide hydrophilic paint, and epoxy resin hydrophilic. Examples thereof include an inorganic paint and an inorganic hydrophilic paint, but the present invention is not limited to such examples. Among these hydrophilic paints, an inorganic hydrophilic paint containing a surfactant, a colloidal solution such as colloidal silica, alumina sol and the like is preferable from the viewpoint of efficiently imparting hydrophilicity in a small amount.

The coating amount of the hydrophilic paint is usually from the viewpoint of forming a laminated coating film that is excellent in warm water resistance, water permeability resistance and weather resistance even when the outermost coating film is formed of a hydrophilic coating film. The non-volatile content is preferably about 0.2 to 20 g / m ² .

  The drying condition of the formed outermost layer coating film only needs to be able to sufficiently evaporate the solvent used in the hydrophilic paint, and varies depending on the type and amount of the solvent used in the hydrophilic paint, so it is generally Can not be determined. Usually, the coating film may be dried by heating to a temperature of preferably 50 to 150 ° C, more preferably 60 to 120 ° C. The drying time is not particularly limited as long as the coating film is sufficiently dried.

  After forming at least two coating films containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure as described above, the outermost coating film A laminated coating film can be produced by forming a hydrophilic coating film. This laminated coating film is comprehensively excellent in hot water resistance, water permeability resistance and weather resistance, although a hydrophilic coating film is formed as the outermost layer coating film. Therefore, the laminated coating film of this invention can be used conveniently for the base material represented by building materials, such as ceramics building materials, for example.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. In the following Examples, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Preparation Example 210 parts deionized water, 60 parts dispersant (trade name: Demol EP, manufactured by Kao Corporation), 50 parts dispersant (trade name: DISCOAT N-14, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Wetting agent [manufactured by Kao Corporation, trade name: Emulgen LS-106] 10 parts, propylene glycol 60 parts, titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., product number: CR-95] and glass beads (diameter: 1 mm) ) A white paste was prepared by dispersing 200 parts with a homodisper at a rotational speed of 3000 min ^{−1 for} 60 minutes.

Production Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. To the dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 270 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A pre-emulsion for dropping consisting of 100 parts of methyl methacrylate, 500 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and 10 parts of acrylic acid is prepared, of which the total amount of all monomer components 77 parts corresponding to 5% was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 19 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts were added, and further 21.5 parts of water and 0.5 parts of 25% ammonia water were added, and the mixture was stirred with a homodisper at a rotational speed of 1500 min ^{-1 for} 30 minutes, and then obtained in Preparation Example. 30 parts of white paste and 0.5 part of an antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) are added, and 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. By adding a thickener [made by Nippon Shokubai Co., Ltd., trade name: Acre Reset WR-503A] so that the viscosity when measured at KU is 61 KU, and stirring in that state for 30 minutes, The fee A was prepared.

Production Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. To a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 310 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A pre-emulsion for dropping consisting of 560 parts of methyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and 10 parts of acrylic acid was prepared, of which 77 parts corresponding to 5% of the total amount of all monomer components Was added to the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 18 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts were added, and further 21.5 parts of water and 0.5 parts of 25% ammonia water were added, and the mixture was stirred with a homodisper at a rotational speed of 1500 min ^{-1 for} 30 minutes, and then obtained in Preparation Example. 30 parts of white paste and 0.5 part of an antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) are added, and 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. By adding a thickener [made by Nippon Shokubai Co., Ltd., trade name: Acre Reset WR-503A] so that the viscosity when measured at KU is 61 KU, and stirring in that state for 30 minutes, The fee B was prepared.

Production Example 3
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. In a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 300 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A pre-emulsion for dropping consisting of 60 parts of methyl methacrylate, 500 parts of styrene, 20 parts of hydroxyethyl methacrylate and 10 parts of acrylic acid was prepared, and 77 parts corresponding to 5% of the total amount of all monomer components were added to the flask. The temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 18 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts were added, and further 21.5 parts of water and 0.5 parts of 25% ammonia water were added, and the mixture was stirred with a homodisper at a rotational speed of 1500 min ^{-1 for} 30 minutes, and then obtained in Preparation Example. 30 parts of white paste and 0.5 part of an antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) are added, and 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. By adding a thickener [made by Nippon Shokubai Co., Ltd., trade name: Acre Reset WR-503A] so that the viscosity when measured at KU is 61 KU, and stirring in that state for 30 minutes, The fee C was prepared.

Production Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. To a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 310 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A drop pre-emulsion comprising 60 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 150 parts of tert-butyl methacrylate, 150 parts of isobornyl methacrylate, 20 parts of hydroxyethyl methacrylate and 10 parts of acrylic acid is prepared. 77 parts corresponding to 5% of the total amount of was added to the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of 5% ammonium persulfate aqueous solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 21 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts were added, and further 21.5 parts of water and 0.5 parts of 25% ammonia water were added, and the mixture was stirred with a homodisper at a rotational speed of 1500 min ^{-1 for} 30 minutes, and then obtained in Preparation Example. 30 parts of white paste and 0.5 part of an antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) are added, and 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. By adding a thickener [made by Nippon Shokubai Co., Ltd., trade name: Acre Reset WR-503A] so that the viscosity when measured at KU is 61 KU, and stirring in that state for 30 minutes, The fee D was prepared.

Production Example 5
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. To the dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 270 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A pre-emulsion for dropping consisting of 100 parts of methyl methacrylate, 500 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and 10 parts of acrylic acid is prepared, of which the total amount of all monomer components 77 parts corresponding to 5% was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 19 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts are added, and further 21.5 parts of water, 0.5 parts of 25% aqueous ammonia and 5 parts of resin beads [made by Nippon Shokubai Co., Ltd., trade name: Eposta MA1010] are added, and the Crabs unit viscosity is added. Thickener [made by Nippon Shokubai Co., Ltd., trade name: ACR Reset WR-503A] so that the viscosity is 61 KU when measured at 25 ° C. using a total [manufactured by Brookfield, product number: KU-1] In this state, paint P was prepared by stirring with a homodisper at a rotational speed of 1500 min ^{−1 for} 30 minutes.

Production Example 6
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. To a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 310 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A pre-emulsion for dropping consisting of 560 parts of methyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and 10 parts of acrylic acid was prepared, of which 77 parts corresponding to 5% of the total amount of all monomer components Was added to the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 18 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts are added, and further 21.5 parts of water, 0.5 parts of 25% aqueous ammonia and 5 parts of resin beads [made by Nippon Shokubai Co., Ltd., trade name: Eposta MA1010] are added, and the Crabs unit viscosity Thickener [made by Nippon Shokubai Co., Ltd., trade name: ACR Reset WR-503A] so that the viscosity is 61 KU when measured at 25 ° C. using a total [manufactured by Brookfield, product number: KU-1] In this state, paint Q was prepared by stirring with a homodisper at a rotational speed of 1500 min ^{−1 for} 30 minutes.

Production Example 7
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 796 parts of deionized water was charged. To a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], 310 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, A drop pre-emulsion comprising 60 parts of methyl methacrylate, 200 parts of cyclohexyl methacrylate, 150 parts of tert-butyl methacrylate, 150 parts of isobornyl methacrylate, 20 parts of hydroxyethyl methacrylate and 10 parts of acrylic acid is prepared. 77 parts corresponding to 5% of the total amount of was added to the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of 5% ammonium persulfate aqueous solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 8 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in this resin emulsion was 43%, and the glass transition temperature of the resin constituting the emulsion particles contained in the resin emulsion was 21 ° C.

Next, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS as a film forming aid to 100 parts of the resin emulsion obtained above. -12] 5 parts are added, and further 21.5 parts of water, 0.5 parts of 25% aqueous ammonia and 5 parts of resin beads [made by Nippon Shokubai Co., Ltd., trade name: Eposta MA1010] are added, and the Crabs unit viscosity is added. Thickener [made by Nippon Shokubai Co., Ltd., trade name: ACR Reset WR-503A] so that the viscosity is 61 KU when measured at 25 ° C. using a total [manufactured by Brookfield, product number: KU-1] In this state, paint R was prepared by stirring with a homodisper at a rotational speed of 1500 min ^{−1 for} 30 minutes.

Production Example 8
780 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. In a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10), 400 parts of n-butyl acrylate, 530 parts of methyl methacrylate, hydroxyethyl A pre-emulsion for dripping consisting of 30 parts of methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and 30 parts of acrylic acid was prepared, and 154 parts corresponding to 10% of the total amount of all monomer components were added to the flask, The temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion, 30 parts of 5% aqueous ammonium persulfate solution and 20 parts of 5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise into the flask over 240 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, and the pH was adjusted to 7 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The content of nonvolatile components in this resin emulsion was 43%.

Next, 2.5 parts of butyl cellosolve was added to 5 parts of the resin emulsion obtained above as a film-forming aid, and further 1000 parts of water, an anionic surfactant [trade name: ADEKA COAL EC- manufactured by ADEKA Corporation] 8600] 1 part and 100 parts of colloidal solution [Nissan Chemical Industry Co., Ltd., trade name: Snowtex C] are added, and a paint X is prepared by stirring with a homodisper at a rotational speed of 1000 min ^{-1 for} 30 minutes. did.

Example 1
Paint B is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and 10 minutes at 100 ° C. By drying, a first-layer coating film was formed. Thereafter, the coating A is uniformly applied by air spray at a coating amount of 150 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 10 minutes, whereby the second-layer coating is applied. A film was formed. Further, the coating P is uniformly applied by air spray at a coating amount of 100 g / m ² on the second-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes, whereby the third-layer coating is applied. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined based on the following method. The results are shown in Table 1.

[Contact angle of water]
The contact angle of water on the coating film surface of the test plate was measured with a contact angle measuring device [Kyowa Interface Science Co., Ltd., trade name: FACE contact angle meter CA-X type].

[Hot water resistance]
After immersing the test plate in warm water maintained at a water temperature of 50 ° C. for 240 hours, the test plate is taken out from the warm water, thoroughly wiped off the water, and within 1 minute a color difference meter [Spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. SE-2000], ΔL was calculated from the L value measured before and after the test, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: ΔL is less than 5 Δ: ΔL is 5 or more and less than 10 x: ΔL is 10 or more

[Water permeability resistance]
The back and side surfaces of the test plate are sealed using bath bond [trade name: Bath bond Q] manufactured by Konishi Co., Ltd., immersed in water at room temperature (about: 25 ° C.) for 24 hours, and then immersed in water. The test piece was wiped off sufficiently, the difference in mass of the test piece before and after being submerged was measured, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: Mass difference before and after submersion of test specimen is less than 2 g Δ: Mass difference before and after submersion of test specimen is 2 g or more and less than 5 g ×: Mass difference before and after submersion of test specimen is 5 g or more

〔Weatherability〕
The test piece is cut into a size of 5 cm × 5 cm, the back and side surfaces thereof are sealed with aluminum tape, a weather resistance test is performed for 1000 hours under the following conditions, and a color difference meter [Nippon Denshoku Industries Co., Ltd., spectroscopic type is used. L, a and b are measured with a color difference meter SE-2000], and an _equation is obtained from measured values of L ₀ , a ₀ and b ₀ before the test and measured values of L ₁ , a ₁ and b ₁ after the test:
ΔE = [(L ₀ −L ₁ ) ² + (a ₀ −a ₁ ) ² + (b ₀ −b ₁ ) ² ] ^1/2
ΔE was calculated based on the following evaluation criteria.

(Weather resistance measurement conditions)
Test machine: Metal weather [Daipura Wintes Co., Ltd., product number: KU-R4]
Irradiation: Irradiation for 4 hours in an atmosphere of air temperature: 65 ° C. and humidity 70% (irradiation intensity: 80 mW / cm ² )
-Wet: Wet for 4 hours in an atmosphere of 35 ° C and 98% humidity-Shower: Shower for 60 seconds before and after wetting (Evaluation criteria)
○: ΔE is less than 2 Δ: ΔE is 2 or more and less than 4 ×: ΔE is 4 or more

〔Comprehensive evaluation〕
In each evaluation of hot water resistance, water permeability resistance, and weather resistance, the evaluation of ○ was 30 points, the evaluation of Δ was 15 points, and the evaluation of X was 0 points, and the total points were obtained. In addition, the highest score of comprehensive evaluation is 90 points, and the lowest score is 0 points.

Example 2
Paint A is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and at 100 ° C. for 10 minutes. By drying, a first-layer coating film was formed. Thereafter, paint B is uniformly applied by air spray at a coating amount of 150 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 10 minutes. A film was formed. Further, the coating P is uniformly applied by air spray at a coating amount of 100 g / m ² on the second-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes, whereby the third-layer coating is applied. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 3
Paint A is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and at 100 ° C. for 10 minutes. By drying, a first-layer coating film was formed. Thereafter, the coating A is uniformly applied by air spray at a coating amount of 150 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 10 minutes, whereby the second-layer coating is applied. A film was formed. Further, the coating Q is uniformly applied at a coating amount of 100 g / m ² by air spray on the coating film of the second layer formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Example 4
Paint C is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and then at 100 ° C. for 10 minutes. By drying, a first-layer coating film was formed. Thereafter, the coating D is uniformly applied at a coating amount of 150 g / m ² by air spray on the coating film of the first layer formed as described above, and dried at 100 ° C. for 10 minutes. A film was formed. Further, the coating layer R is uniformly applied at a coating amount of 100 g / m ² by air spray on the coating layer of the second layer formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
Paint B is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and 10 minutes at 100 ° C. By drying, a first-layer coating film was formed. Thereafter, paint B is uniformly applied by air spray at a coating amount of 150 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 10 minutes. A film was formed. Further, the coating Q is uniformly applied at a coating amount of 100 g / m ² by air spray on the coating film of the second layer formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
Paint B is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and 10 minutes at 100 ° C. By drying, a first-layer coating film was formed. Thereafter, the coating C is uniformly applied by air spray at a coating amount of 150 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 10 minutes. A film was formed. Further, the coating P is uniformly applied by air spray at a coating amount of 100 g / m ² on the second-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes, whereby the third-layer coating is applied. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3
Paint C is uniformly applied by air spray at a coating amount of 150 g / m ^{2 on} a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm), and then at 100 ° C. for 10 minutes. By drying, a first-layer coating film was formed. Thereafter, the coating A is uniformly applied by air spray at a coating amount of 150 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 10 minutes, whereby the second-layer coating is applied. A film was formed. Further, the coating Q is uniformly applied at a coating amount of 100 g / m ² by air spray on the coating film of the second layer formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed.

Next, paint X is uniformly applied by air spray at a coating amount of 30 g / m ² on the third-layer coating film formed as described above, and dried at 100 ° C. for 1 minute. By making it, the test board in which the laminated coating film was formed was produced.

  The physical properties of the laminated coating film formed on the test plate obtained above were examined in the same manner as in Example 1. The results are shown in Table 1.

  From the results shown in Table 1, not only are the laminated coating films obtained in each example excellent in hydrophilicity because a hydrophilic coating film is formed as the outermost coating film, Furthermore, since at least two coating films containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure are formed in the lower layer of the hydrophilic coating film, the outermost layer It can be seen that the water-resistant, water-permeable, and weather-resistant properties are excellent overall despite the formation of a hydrophilic coating film.

Claims (2)

  A laminated coating film having at least three coating films, wherein the outermost coating film is a hydrophilic coating film, and a single layer containing a monomer having an alicyclic structure in the lower layer of the outermost coating film. A laminated coating film comprising at least two coating films containing a polymer obtained by polymerizing a monomer component.   A method for producing a laminated coating film having at least three layers, wherein at least two layers of a coating film containing a polymer obtained by polymerizing a monomer component containing a monomer having an alicyclic structure are formed Then, a hydrophilic coating film is formed as the outermost layer coating film.