JP2015196314A - Laminated coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated coating film which has a hydrophilic coating film formed on a coating film of the outermost layer, and which is comprehensively excellent in warm water resistance, water permeation resistance, weatherability, and warm water freezing stability.SOLUTION: There is provided the laminated coating film which has a hydrophilic coating film formed as a coating film of the outermost layer, and in which a monomer component used as a raw material of a resin component forming a lower layer of the hydrophilic coating film is a monomer component containing a fluorine-containing monomer. There is also provided a method for producing a laminated coating film having a hydrophilic coating film formed as the outermost coating film, comprising: forming a coating film containing a resin component obtained by polymerizing the monomer component containing the fluorine-containing monomer; and subsequently forming on the coating film a hydrophilic coating film as the coating film of the outermost layer.

Description

  The present invention relates to a laminated coating film. More specifically, the present invention provides a laminated coating film in which a hydrophilic coating film is formed as the outermost coating film, and is excellent in warm water resistance, water permeability resistance, weather resistance and hot water freeze stability, and a method for producing the same. About. 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 fully satisfy simultaneously the hot water resistance, water permeability resistance, weather resistance, and hot water freezing stability 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 prior art, and a hydrophilic coating film is formed as the outermost coating film, which is comprehensively excellent in hot water resistance, water permeability resistance, weather resistance and hot water freezing stability. It is an object of the present invention to provide a laminated coating film and a method for producing the same.

The present invention
(1) A laminated coating film in which a hydrophilic coating film is formed as an outermost coating film, and a monomer component used as a raw material for a resin component of a coating film forming a lower layer of the hydrophilic coating film Laminated coating film characterized by being a monomer component containing a fluorine-containing monomer,
(2) The multilayer coating film according to (1), wherein the monomer component further contains a monomer having an alicyclic structure,
(3) A method for producing a laminated coating film in which a hydrophilic coating film is formed as the outermost coating film, which contains a resin component obtained by polymerizing a monomer component containing a fluorine-containing monomer. After forming the coating film, a hydrophilic coating film is formed as the outermost coating film on the coating film, and (4) The monomer component further comprises a fat. It is related with the manufacturing method of the laminated coating film as described in said (3) containing the monomer which has a ring structure.

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

  As described above, the multilayer coating film of the present invention is a multilayer coating film in which a hydrophilic coating film is formed as the outermost coating film, and is a raw material for the resin component of the coating film that forms the lower layer of the hydrophilic coating film. The monomer component used as is a monomer component containing a fluorine-containing monomer.

  Among the coating films of the laminated coating film of the present invention, the outermost layer is formed of a hydrophilic coating film, and a monomer component containing a fluorine-containing monomer in the coating film forming the lower layer of the hydrophilic coating film A resin obtained by polymerizing is used. Another coating film may be further formed under the coating film forming the lower layer. Moreover, the sealer may be apply | coated to the surface of the base material in which a laminated coating film is formed. 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 2 to 10 layers, more preferably 2 to 8 layers, and further preferably 3 to 8 layers.

  As a coating material used for the lower layer coating film of the hydrophilic coating film constituting the outermost layer of the laminated coating film of the present invention, an aqueous coating material is preferable from the viewpoint of improving the affinity with the hydrophilic coating film.

  Examples of suitable water-based paints include paints containing a resin emulsion obtained by emulsion polymerization of a monomer component containing a fluorine-containing monomer.

  The resin emulsion can be obtained by emulsion polymerization of a monomer component containing a fluorine-containing monomer in the presence of an emulsifier.

  Examples of the fluorine-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. Examples thereof include, but are not limited to such examples. These fluorine atom-containing monomers may be used alone or in combination of two or more.

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

  The content of the fluorine-containing monomer in the monomer component is a laminated coating that has an excellent outermost layer having hydrophilicity and is comprehensively excellent in hot water resistance, water permeability resistance, weather resistance and hot water freeze stability. From the viewpoint of forming a film, it is preferably 1 to 50% by mass, more preferably 3 to 45% by mass, and further preferably 5 to 40% by mass.

  As the monomer component, a monomer copolymerizable with a fluorine-containing monomer is used. Examples of the monomer copolymerizable with the fluorine-containing monomer include a monomer having an alicyclic structure, an aromatic monomer, an ethylenically unsaturated monomer, and the like. You may use independently and may use 2 or more types together. In the present invention, the aromatic monomer and the ethylenically unsaturated monomer both mean monomers having no alicyclic structure.

  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.

  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, from the viewpoint of forming a laminated coating film that has the outermost layer having hydrophilicity and simultaneously satisfies the resistance to warm water, water permeability, weather resistance and warm water freezing stability. Cycloalkyl (meth) acrylate having a cycloalkyl group having 4 to 20 carbon atoms is preferred, cycloalkyl (meth) acrylate having a cycloalkyl group having 4 to 10 carbon atoms is more preferred, isobornyl (meth) acrylate and More preferred is cyclohexyl (meth) acrylate.

  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 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.

  The content of the monomer copolymerizable with the fluorine-containing monomer in the monomer component has a water resistance, water permeability, weather resistance and hot water freezing stability while having a hydrophilic outermost layer. From the viewpoint of forming a generally excellent laminated coating film, it is preferably 50 to 99% by mass, more preferably 55 to 97% by mass, and still more preferably 60 to 95% by mass.

  Of the monomers copolymerizable with the fluorine-containing monomer, monomers having an alicyclic structure are preferable. By using in combination with a fluorine-containing monomer and a monomer having an alicyclic structure, it is possible to form a laminated coating film that is excellent in hot water resistance, water permeability resistance, weather resistance and hot water freeze stability at the same time.

  When used in combination with a fluorine-containing monomer and a monomer having an alicyclic structure, the combined use of both has a water resistant outer layer, water resistance, weather resistance, and hot water freezing stability. Ratio of fluorine-containing monomer and monomer having alicyclic structure (fluorine-containing monomer / monomer having alicyclic structure: mass ratio) from the viewpoint of forming a multilayer coating film that simultaneously satisfies the properties Is preferably 1/99 to 50/50, more preferably 3/97 to 45/55, and even more preferably 5/95 to 40/60.

  Further, the monomer component may contain a monomer other than the fluorine-containing monomer and the monomer having an alicyclic structure within a range not impairing the object of the present invention. In this case, the content of the other monomer in the monomer component is a layer that has the outermost layer having hydrophilicity and simultaneously satisfies hot water resistance, water permeability resistance, weather resistance, and hot water freezing stability. From the viewpoint of forming a coating film, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

  Among the monomer components other than fluorine-containing monomers and monomers having an alicyclic structure, aromatic monomers, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, carboxyls Ethylenically unsaturated monomers such as group-containing monomers, oxo group-containing monomers, nitrogen atom-containing monomers, and epoxy group-containing monomers are preferred. These monomers may be used alone or in combination of two or more.

  Among the monomers other than the fluorine-containing monomer and the monomer having an alicyclic structure in the monomer component, while having the outermost layer having hydrophilicity, the water resistance, water resistance, weather resistance and Alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are more preferable from the viewpoint of forming a laminated coating film that simultaneously satisfies hot water freezing stability, and alkyl (meth) acrylate having an alkyl group with 1 to 8 carbon atoms and More preferred are hydroxyalkyl (meth) acrylates having 1 to 4 carbon atoms in the alkyl group.

  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 the UV-stable monomer include 2,2,6,6-tetramethylpiperidyl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidyl (meth) acrylate, and 2,2,6. , 6-tetramethylpiperidyl-4-cyano-4- (meth) acrylate, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyl-1-methoxy-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-cyano-4- (meth) acryloylua No-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino -2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the like, but the present invention is limited to such examples only. It is not something. 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, from the viewpoint of improving polymerization stability per 100 parts by mass of the monomer component. From the viewpoint of improving weather resistance, blocking resistance and frost damage resistance, it is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, and further preferably 5 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 weather resistance and hot water freezing stability, it is preferably 100,000 or more, more preferably 300,000 or more, further 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 addition, in this specification, the weight average molecular weight uses gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L used in series]. The weight average molecular weight (in terms of polystyrene) measured by

  The glass transition temperature of the polymer is preferably-from the viewpoint of forming a laminated coating film having the outermost layer having hydrophilicity and simultaneously satisfying the hot water resistance, water permeability resistance, weather resistance and hot water freeze stability. 40 ° C. or higher, more preferably −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 still more preferably. It is 50 degrees C or less. 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 ° C. for 2-ethylhexyl acrylate homopolymer, -56 ° C. for n-butyl acrylate homopolymer, 20 ° C. for n-butyl methacrylate homopolymer, methyl methacrylate 105 ° C., 55 ° C. for hydroxyethyl methacrylate homopolymer, 70 ° C. for homopolymer of γ-methacryloxypropyltrimethoxysilane (TMSMA), 82 ° C. for trifluoroethyl methacrylate homopolymer, 95 ° C for acrylic acid homopolymer, 83 ° C for cyclohexyl methacrylate homopolymer, 107 ° C for tert-butyl methacrylate homopolymer, 180 ° C for isobornyl methacrylate homopolymer, cyclohexyl acrylate homopolymer Then 16 ℃ 1,2,2,6,6 130 ° C. is a homopolymer of pentamethylpiperidyl methacrylate, 130 ° C. is a homopolymer of methacrylic acid.

  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 40 nm or more, and further preferably 50 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 the present specification, the average particle size of the emulsion particles is measured using a particle size distribution measuring instrument (manufactured by Particle Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. It means the volume average particle diameter.

  By incorporating a crosslinking agent into the water-based paint, cross-linking property may be imparted to the water-based paint. 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 salts thereof, caprolactone modified product of (meth) acrylic acid, 2, 2, 6, 6 − (Meth) acrylate esters such as tramethylpiperidyl (meth) acrylate, 1,2,2,6,6-pentamethylpiperlidyl (meth) acrylate; sodium (meth) acrylate, potassium (meth) acrylate, (Meth) acrylates such as ammonium (meth) acrylate; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide Unsaturated amides such as; 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; and halogen-containing α, such as vinyl chloride, vinylidene chloride, and vinyl fluoride β-unsaturated fat Family 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, Nippon Polyurethane Industry Co., Ltd., trade names: Aquanate 100, Aquanate 110, Aquanate 200, Aquanate 210, etc .; Sumika Bayer Urethane Co., Ltd., trade name: Bihijoule 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 .; 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.

  The water-dispersed block polyisocyanate is, for example, manufactured by Mitsui Takeda Chemical Co., Ltd., trade names: Takenate WB-720, Takenate WB-730, Takenate WB-920, etc .; manufactured by Sumika Bayer Urethane Co., Ltd. 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, manufactured 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 above-mentioned crosslinking agents, for example, hydrazine compounds; carbodiimide compounds; crosslinking agents such as polyvalent metal compounds represented by zirconium compounds, zinc compounds, titanium compounds, aluminum compounds, etc. Can be used as long as the purpose of the above is not inhibited.

  If necessary, the water-based paint may 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.

  The water-based paint may contain a resin emulsion other than the resin emulsion as long as the object of the present invention is not impaired.

  In addition, the water-based 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, a plasticizer, and the like within a range that does not impair the object of the present invention. Additives such as additives, stabilizers, antifoaming agents, preservatives, dyes and antioxidants may be contained in appropriate amounts.

  The paint used for the lower layer coating film can be used as a matte paint by adding a matting agent to the paint.

  A matte paint can be prepared, for example, by mixing the water-based paint and a matting agent.

  Examples of matting agents include inorganic matting agents such as wet silica, dry silica, magnesium carbonate, and talc, polyethylene fine particles, polypropylene fine particles, polyurethane fine particles, polymethyl methacrylate fine particles, polycarbonate fine particles, urea formaldehyde resin fine particles, and benzoguanamine. Examples include organic matting agents such as formaldehyde resin fine particles, benzoguanamine / melamine / formaldehyde resin fine particles, melamine / formaldehyde resin fine particles, and polytetrafluoroethylene fine particles, but the present invention is not limited to such examples. . The matting agent can be easily obtained commercially as, for example, product name: Epostor L15, MS, M30, MA1010, S, S6, S12 manufactured by Nippon Shokubai Co., Ltd.

  The particle size of the matting agent is usually preferably in the range of 2 to 50 μm from the viewpoint of uniformly dispersing in the paint and forming a smooth coating film.

  Since the amount of the matting agent per 100 parts by mass of the non-volatile content of the matting paint varies depending on the use of the laminated coating film of the present invention and cannot be unconditionally determined, Although it is preferable to adjust suitably according to this, it is about 5-40 mass parts normally.

  In the present invention, a coating film formed from the water-based paint and / or a coating film formed from the matte paint is formed, and then a hydrophilic coating film is formed as the outermost coating film. A coating film can be produced. In that case, the coating film formed under the outermost hydrophilic coating film may be only the coating film formed from the water-based paint, or only the coating film formed from the matte coating. Alternatively, it may be a laminated coating of a coating formed from the water-based coating and a coating formed from the matte coating.

  In addition, before forming a matte coating film, it is possible to form the coating film by applying the water-based paint to the base material, which is combined with warm water resistance, water permeability resistance, weather resistance and hot water freezing stability. From the viewpoint of forming a particularly excellent laminated coating film.

  Examples of the method for applying the water-based paint or the matte paint on the surface of the substrate include an application 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. Although mentioned, this invention is not limited only to this illustration.

Each coating amount of the water-based paint and the matte paint applied to the substrate is warm water resistance, water permeability resistance, weather resistance and hot water freezing stability even when the outermost coating film is formed of a hydrophilic coating film. From the viewpoint of forming a generally excellent laminated coating film, 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.

  As a base material used when forming a laminated coating film, for example, a base material typified by a building material such as a ceramic building material can be cited, but the present invention is not limited to such illustration.

  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).

  In addition, the surface of the base material may be previously subjected to, for example, primer treatment or sealer treatment, if necessary.

  Next, a hydrophilic coating film is formed 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 coating is such that even when the outermost coating is formed of a hydrophilic coating, a laminated coating with excellent heat resistance, water permeability, weather resistance and hot water freeze stability is formed. In view of the above, it is usually preferable that the nonvolatile content is 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.

  A laminated coating film can be produced as described above. The obtained laminated coating film is comprehensively excellent in hot water resistance, water permeability resistance, weather resistance, and hot water freezing stability even though 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 (Preparation of white paste)
210 parts of deionized water, 60 parts of dispersant [manufactured by Kao Corporation, trade name: Demol EP], 50 parts of dispersant [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: DISCOAT N-14], wetting agent [Kao Co., Ltd., product name: Emulgen LS-106] 10 parts, propylene glycol 60 parts, titanium oxide [Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads (diameter: 1 mm) 200 A white paste was prepared by dispersing the part 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. In a dropping funnel, 417 parts of deionized water, 60 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], emulsifier [trade name: ADEKA rear soap, manufactured by ADEKA Corporation] SR-10] 60 parts, 2-ethylhexyl acrylate 170 parts, n-butyl acrylate 100 parts, n-butyl methacrylate 100 parts, methyl methacrylate 500 parts, hydroxyethyl methacrylate 10 parts, γ-methacryloyloxypropyltrimethoxysilane 10 parts, A pre-emulsion for dripping consisting of 100 parts of trifluoroethyl methacrylate and 10 parts of acrylic acid was prepared, of which 77 parts corresponding to 5% of the total amount of all the monomer components were added into the flask, and while slowly blowing nitrogen gas, 70 parts were added. Raised to 5 ° C and 5% ammonium persulfate aqueous solution 10 parts were added to initiate the 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 27 ° C.

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. In a dropping funnel, 417 parts of deionized water, 60 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], emulsifier [trade name: ADEKA rear soap, manufactured by ADEKA Corporation] SR-10] 60 parts, 2-ethylhexyl acrylate 220 parts, n-butyl acrylate 100 parts, n-butyl methacrylate 100 parts, cyclohexyl methacrylate 500 parts, hydroxyethyl methacrylate 10 parts, γ-methacryloyloxypropyltrimethoxysilane 10 parts, A pre-emulsion for dripping consisting of 50 parts of trifluoroethyl methacrylate and 10 parts of acrylic acid is prepared, of which 77 parts, which is 5% of the total amount of all monomer components, are added into the flask, and 70 parts are added while gently blowing nitrogen gas. Raised to 5 ° C and 5% ammonium persulfate 10 parts of an 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 11 ° C.

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, 60 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], emulsifier [trade name: ADEKA rear soap, manufactured by ADEKA Corporation] SR-10] 60 parts, 2-ethylhexyl acrylate 160 parts, n-butyl acrylate 100 parts, cyclohexyl methacrylate 200 parts, tert-butyl methacrylate 200 parts, isobornyl methacrylate 100 parts, hydroxyethyl methacrylate 30 parts, trifluoroethyl methacrylate A dropping pre-emulsion consisting of 200 parts and 10 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate was prepared, of which 77 parts corresponding to 5% of the total amount of all monomer components were added to the flask, 70 ° C while gently blowing nitrogen gas In heated, it was added a 5% aqueous solution of ammonium persulfate 10 parts, 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 37 ° C.

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. In a dropping funnel, 417 parts of deionized water, 60 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], emulsifier [trade name: ADEKA rear soap, manufactured by ADEKA Corporation] SR-10] 60 parts, 270 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, 100 parts of n-butyl methacrylate, 500 parts of methyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and A pre-emulsion for dripping consisting of 10 parts of acrylic acid was prepared. Among them, 77 parts corresponding to 5% of the total amount of all monomer components were added to the flask, and the temperature was raised to 70 ° C. while gently blowing nitrogen gas. Polymerization was started by adding 10 parts of an aqueous ammonium persulfate solution. 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 9 ° C.

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. In a dropping funnel, 417 parts of deionized water, 60 parts of a 25% aqueous solution of emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10], emulsifier [trade name: ADEKA rear soap, manufactured by ADEKA Corporation] SR-10] 60 parts, 270 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, 100 parts of n-butyl methacrylate, 500 parts of cyclohexyl methacrylate, 10 parts of hydroxyethyl methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and A pre-emulsion for dripping consisting of 10 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate was prepared, 77 parts corresponding to 5% of the total amount of all monomer components were added to the flask, and nitrogen was gently added. While blowing gas, raise the temperature to 70 ° C and 5% ammonium persulfate 10 parts of an aqueous nium 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 3 ° C.

[Production example of first layer coating material A]
In 100 parts of the resin emulsion obtained in each production example, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as a film forming aid [manufactured by Chisso Corporation, product number: CS- 12] Add 5 parts, further add 21.5 parts of water and 0.5 part of 25% aqueous ammonia, stir with homodisper at a rotational speed of 1500 min ^{-1 for} 30 minutes, and then obtain the white color obtained in the preparation example. 30 parts of paste and 0.5 part of an antifoaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L) were added, and at 25 ° C. using a Craves unit viscometer [manufactured by Brookfield, product number: KU-1]. A thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRISE WR-503A] was added so that the viscosity when measured was 61 KU, and the mixture was stirred for 30 minutes in that state. It was prepared A.

  In addition, the coating material A obtained by using the resin emulsion obtained by manufacture examples 1-5 is called coating material A1-A5 in order, respectively.

[Production example of second layer paint B]
In 100 parts of the resin emulsion obtained in each production example, 5 parts of butyl cellosolve and 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as a film forming aid [manufactured by Chisso Corporation, product number: CS- 12] 5 parts were added, and further 21.5 parts of water and 0.5 parts of 25% aqueous ammonia and 5 parts of resin fine particles (trade name: Eposta MA1010, manufactured by Nippon Shokubai Co., Ltd.) were added. Use a thickener [manufactured by Nippon Shokubai Co., Ltd., trade name: ACRRESET WR-503A] so that the viscosity is 61 KU when measured at 25 ° C. using [manufactured by Brookfield, product number: KU-1]. In this state, paint B was prepared by stirring for 30 minutes using a homodisper at a rotational speed of 1500 min ⁻¹ .

  In addition, the coating material B obtained by using the resin emulsion obtained by manufacture examples 1-5 is called coating material B1-B5 in order, respectively.

[Production example of second layer paint C]
In 100 parts of the resin emulsion obtained in each production example, 21.5 parts of an aqueous fluororesin [manufactured by Asahi Glass Co., Ltd., trade name: Lumiflon FE-4300], 5 parts of butyl cellosolve as a film forming aid, and 2,2,4- 5 parts of trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12] was added, and 25 parts of water, 0.5 part of 25% ammonia water and resin fine particles [(stock ) Made by Nippon Shokubai Co., Ltd., trade name: Eposta MA1010] 5 parts are added, and the viscosity is 61 KU when measured at 25 ° C. using a Crave's unit viscometer [manufactured by Brookfield, product number: KU-1]. A thickener [made by Nippon Shokubai Co., Ltd., trade name: Acryset WR-503A] is added, and the mixture is stirred for 30 minutes at a rotational speed of 1500 min ^-1 using a homodisper in that state. Thus, paint C was prepared.

  In addition, the coating material C obtained by using the resin emulsion obtained by manufacture examples 1-5 is called the coating materials C1-C5 in order, respectively.

[Production example of paint D for third layer]
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 dropping consisting of 30 parts of methacrylate, 10 parts of γ-methacryloyloxypropyltrimethoxysilane and 30 parts of acrylic acid was prepared, and 154 parts corresponding to 5% of the total amount of all the 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, 3.5 parts of butyl cellosolve is added as a film-forming aid to 8 parts of the resin emulsion obtained above, 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 a colloidal solution [manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex C], and stirred with a homodisper at a rotational speed of 1000 min ^{-1 for} 30 minutes, paint D is obtained. Prepared.

Example 1
A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and a sealer (manufactured by SK Kaken Co., Ltd., trade name: EX sealer) by air spray are 150 / m ^2. The coating amount was uniformly applied and dried at 100 ° C. for 10 minutes.

Next, in order to form a first-layer coating film on the formed coating film, paint A1 is uniformly applied by air spray at a coating amount of 150 g / m ² and dried at 100 ° C. for 10 minutes. As a result, a first-layer coating film was formed. Thereafter, the coating B1 is uniformly applied by air spray at a coating amount of 100 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes, whereby the second-layer coating is applied. A film was formed. Further, paint D is uniformly applied at a coating amount of 5 g / m ² by air spray on the second-layer coating film formed as described above, and dried at 100 ° C. for 1 minute to form the outermost coating film. By doing so, a test plate on which a 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], from the L value measured before and after the test, the formula:
[ΔL] = [ΔL value after test] − [ΔL value before test]
ΔL was calculated based on the above 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. 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 at an air temperature of 65 ° C. and a relative humidity of 70% (irradiation intensity: 80 mW / cm ² )
-Wet: Wet for 4 hours in an atmosphere of 35 ° C and relative humidity of 98%-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

[Hot water freezing stability]
The side surface and back surface of the test piece were sealed with a two-component curable solvent-based resin, and a freeze cycle test was performed. One cycle of the freezing cycle test was immersed in warm water at 50 ° C. for 3 hours, then frozen in an atmosphere at −20 ° C. for 2 hours, then immersed in warm water at 50 ° C. for 3 hours, and then in an atmosphere at 20 ° C. The operation was a series of 25 hours of drying for 16 hours.

After the freezing cycle test, the appearance of the coating film was visually observed with a magnifying glass having a magnification of 30 times, the cycle required until cracks occurred was measured, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
○: No cracks occurred even after 30 cycles. Δ: 15 cycles or more. Cracks occur in less than 30 cycles x: Cracks occur in less than 15 cycles

Example 2
A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and a sealer (manufactured by SK Kaken Co., Ltd., trade name: EX sealer) by air spray are 150 / m ^2. The coating amount was uniformly applied and dried at 100 ° C. for 10 minutes.

Next, in order to form a first-layer coating film on the formed coating film, paint A4 is uniformly applied by air spray at an application amount of 150 g / m ² and dried at 100 ° C. for 10 minutes. As a result, a first-layer coating film was formed. After that, paint B2 is uniformly applied by air spray at a coating amount of 100 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed. Further, paint D is uniformly applied at a coating amount of 5 g / m ² by air spray on the second-layer coating film formed as described above, and dried at 100 ° C. for 1 minute to form the outermost coating film. By doing so, a test plate on which a 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
A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and a sealer (manufactured by SK Kaken Co., Ltd., trade name: EX sealer) by air spray are 150 / m ^2. The coating amount was uniformly applied and dried at 100 ° C. for 10 minutes.

Next, in order to form a first-layer coating film on the formed coating film, paint A2 is uniformly applied by air spray at a coating amount of 150 g / m ² and dried at 100 ° C. for 10 minutes. As a result, a first-layer coating film was formed. After that, paint B2 is uniformly applied by air spray at a coating amount of 100 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed. Further, paint D is uniformly applied at a coating amount of 5 g / m ² by air spray on the second-layer coating film formed as described above, and dried at 100 ° C. for 1 minute to form the outermost coating film. By doing so, a test plate on which a 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
A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and a sealer (manufactured by SK Kaken Co., Ltd., trade name: EX sealer) by air spray are 150 / m ^2. The coating amount was uniformly applied and dried at 100 ° C. for 10 minutes.

Next, in order to form a first-layer coating film on the formed coating film, paint A2 is uniformly applied by air spray at a coating amount of 150 g / m ² and dried at 100 ° C. for 10 minutes. As a result, a first-layer coating film was formed. Thereafter, the coating B3 is uniformly applied by air spray at a coating amount of 100 g / m ² on the coating film of the first layer formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed. Further, paint D is uniformly applied at a coating amount of 5 g / m ² by air spray on the second-layer coating film formed as described above, and dried at 100 ° C. for 1 minute to form the outermost coating film. By doing so, a test plate on which a 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 5
A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and a sealer (manufactured by SK Kaken Co., Ltd., trade name: EX sealer) by air spray are 150 / m ^2. The coating amount was uniformly applied and dried at 100 ° C. for 10 minutes.

Next, in order to form the first-layer coating film on the formed coating film, paint A5 is uniformly applied by air spray at a coating amount of 150 g / m ² and dried at 100 ° C. for 10 minutes. As a result, a first-layer coating film was formed. Thereafter, the coating C5 is uniformly applied by air spray at a coating amount of 100 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed. Further, paint D is uniformly applied at a coating amount of 5 g / m ² by air spray on the second-layer coating film formed as described above, and dried at 100 ° C. for 1 minute to form the outermost coating film. By doing so, a test plate on which a 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
A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) and a sealer (manufactured by SK Kaken Co., Ltd., trade name: EX sealer) by air spray are 150 / m ^2. The coating amount was uniformly applied and dried at 100 ° C. for 10 minutes.

Next, in order to form a first-layer coating film on the formed coating film, paint A4 is uniformly applied by air spray at an application amount of 150 g / m ² and dried at 100 ° C. for 10 minutes. As a result, a first-layer coating film was formed. Thereafter, the coating B4 is uniformly applied by air spray at a coating amount of 100 g / m ² on the first-layer coating film formed as described above, and dried at 100 ° C. for 20 minutes. A film was formed. Further, paint D is uniformly applied at a coating amount of 5 g / m ² by air spray on the second-layer coating film formed as described above, and dried at 100 ° C. for 1 minute to form the outermost coating film. By doing so, a test plate on which a 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 a coating film containing a resin component obtained by polymerizing a monomer component containing a fluorine-containing monomer is formed in the lower layer of the hydrophilic coating film, the hydrophilic coating film is used as the outermost coating film. It can be seen that despite the formation of, the water resistance, water permeability, weather resistance and hot water freezing stability are excellent overall. Further, from the results of Examples 2 and 3, when a fluorine-containing monomer and a monomer having an alicyclic structure are used in combination, warm water resistance, water permeability resistance, weather resistance, and hot water freeze stability It can be seen that a laminated coating film excellent in all of the above is formed.

Claims (4)

  A laminated coating film in which a hydrophilic coating film is formed as the outermost coating film, wherein the monomer component used as a raw material for the resin component of the coating film forming the lower layer of the hydrophilic coating film is a fluorine-containing single coating. A laminated coating film comprising a monomer component containing a monomer.   The laminated coating film according to claim 1, wherein the monomer component further contains a monomer having an alicyclic structure.   A method for producing a laminated coating film in which a hydrophilic coating film is formed as an outermost coating film, the coating film containing a resin component obtained by polymerizing a monomer component containing a fluorine-containing monomer After forming, the manufacturing method of the laminated coating film characterized by forming a hydrophilic coating film as a coating film of the outermost layer on the said coating film.   The method for producing a laminated coating film according to claim 3, wherein the monomer component further contains a monomer having an alicyclic structure.