JP5919131B2 - Resin composition for paint - Google Patents

Description

  The present invention relates to a coating resin composition. More specifically, for example, a coating resin composition and a topcoat resin emulsion useful for a topcoat called a topcoat to be coated on the surface of a building exterior or a ceramic building material, and the paint The present invention relates to a top coating composition containing a resin composition or a resin emulsion for top coat.

  In recent years, in order to avoid environmental problems caused by the release of volatile organic compounds into the atmosphere, water-based paints using water-dispersible resins such as water-soluble resins and emulsions have been used instead of solvent-based paints. . However, water-based paints generally have a technical problem that they are inferior in water resistance, weather resistance and the like as compared with organic solvent-based paints due to water as a solvent.

  Therefore, as an aqueous coating composition excellent in weather resistance and water resistance, 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 (for example, And Patent Document 1) have been proposed.

  However, the water-based paint composition has a certain degree of weather resistance and water resistance, but in recent years, it is not only excellent in weather resistance and water resistance, but also when a coating film is formed in the vertical direction. Resin composition for coating and resin emulsion for top coat, and coating resin composition or top for forming coating film excellent in properties (hereinafter referred to as “pattern retention”) for preventing the coating film from flowing down The development of a top coating containing a resin emulsion for coating is awaited.

JP 2002-138123 A

  The present invention has been made in view of the prior art, and includes a coating resin composition that forms a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance, and the coating resin composition. It is an object of the present invention to provide an overcoating material to be applied. Another object of the present invention is to provide a topcoat resin emulsion that forms a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance, and a topcoat paint that contains the topcoat resin emulsion. To do.

The present invention
(1) A top coat resin emulsions containing emulsion particles having an inner layer and an outer layer, the monomer components only n- butyl methacrylate and cyclohexyl methacrylate used as a raw material of the polymer constituting the outer layer contains The mass ratio of cyclohexyl methacrylate to butyl methacrylate (cyclohexyl methacrylate / butyl methacrylate) is 25/75 to 50/50, and the glass transition temperature of the polymer constituting the inner layer is −40 to 60 ° C. Topcoat resin emulsion,
(2) a inner and top manufacturing method of the coating resin emulsions containing emulsion particles having an outer layer, in preparing the resin emulsion, the monomer used as a raw material of the polymer constituting the outer layer N-butyl methacrylate and cyclohexyl methacrylate are contained only in the components, the mass ratio of cyclohexyl methacrylate to butyl methacrylate (cyclohexyl methacrylate / butyl methacrylate) is adjusted to 25/75 to 50/50, and the polymer constituting the inner layer the glass transition temperature was adjusted to -40～60 ° C., the top method of manufacturing coated resin emulsion, characterized in that to each emulsion polymerizing a monomer component for forming the monomer component and the outer layer forming the inner layer, And (3) For the top coat according to (1) The present invention relates to a top coating composition containing a resin emulsion.

  The resin composition for coatings of the present invention has an excellent effect of forming a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance. The resin emulsion for top coats of the present invention has an excellent effect of forming a coating film that is comprehensively excellent in pattern retention, water resistance and weather resistance. In addition, the top coating composition of the present invention has an excellent effect of forming a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance.

  As described above, the coating resin composition of the present invention is a coating resin composition containing emulsion particles having a plurality of layers. The topcoat resin emulsion of the present invention (hereinafter also simply referred to as a resin emulsion) is a resin emulsion containing emulsion particles having a plurality of layers as described above.

  In the following description, for the sake of convenience, the explanation will be based on a resin emulsion containing emulsion particles having an inner layer and an outermost layer. However, if the purpose of the present invention is within the range not hindered, an inner layer further exists inside the inner layer. And other layers may exist between the inner layer and the outermost layer. When the emulsion particles are composed of a plurality of layers, the number of the layers is preferably 2 to 5 layers, more preferably 2 to 4 layers, and further preferably 2 layers or 3 layers.

  The present invention is characterized in that at least one of a plurality of layers of the emulsion particles is formed of a polymer obtained by emulsion polymerization of a monomer component containing n-butyl methacrylate and cyclohexyl methacrylate. In the resin emulsion of the present invention, at least one of the plural layers of the emulsion particles is formed of a polymer obtained by emulsion polymerization of a monomer component containing n-butyl methacrylate and cyclohexyl methacrylate. Therefore, a coating film excellent in overall pattern retention, water resistance and weather resistance is formed.

  Among the resin emulsions of the present invention, a polymer comprising emulsion particles having a plurality of layers, wherein only the outermost layer of the plurality of layers is obtained by emulsion polymerization of a monomer component containing n-butyl methacrylate and cyclohexyl methacrylate. It is preferable from the viewpoint of forming a coating film that is more excellent in overall pattern retention, water resistance, and weather resistance.

  In the present invention, for example, after preparing the inner layer made of the polymer (I) by emulsion polymerization of the monomer component forming the inner layer, the monomer component forming the outermost layer is subjected to emulsion polymerization. By preparing the outermost layer composed of the combined (II), a resin emulsion containing emulsion particles having an inner layer and an outermost layer can be produced. The resin emulsion can be suitably used for a resin composition for coatings and a top coating. The top coating composition of the present invention contains the resin emulsion.

  In the following description, the monomer component used as a raw material for polymer (I) is referred to as monomer component A, and the monomer component used as a raw material for polymer (II) is referred to as monomer component B.

  The monomer component A includes a monofunctional monomer and a polyfunctional monomer, and any of these can be used in the present invention. The monofunctional monomer and the polyfunctional monomer may be used alone or in combination.

  Examples of the monofunctional monomer include an ethylenically unsaturated double bond-containing monomer, but 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”.

  Examples of the ethylenically unsaturated double bond-containing monomer include alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate, carboxyl group-containing monomer, oxo group-containing monomer, fluorine atom-containing monomer, Nitrogen atom-containing monomer, epoxy group-containing monomer, alkoxyalkyl (meth) acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer, styrene monomer, aralkyl ( Examples thereof include, but are not limited to such examples. These ethylenically unsaturated double bond-containing 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, cyclohexyl (meth) acrylate, n-lauryl (meth) Examples include acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, and other alkyl (meth) acrylates having 1 to 18 carbon atoms. It is not limited only to those exemplified. 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.

  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 styrenic 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.

  Suitable monofunctional monomers include, for example, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, oxo group-containing monomers, fluorine atom-containing monomers, nitrogen atom-containing monomers, and epoxy group-containing monomers. A monomer, a styrene monomer, etc. are mentioned, These monomers may be used independently, respectively, and may use 2 or more types together.

  Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, Di (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as tripropylene glycol di (meth) acrylate; polyethylene glycol di (meth) acrylate having 2 to 50 addition moles of ethylene oxide, addition moles of propylene oxide 2 An alkyl di (meth) acrylate having an addition mole number of an alkylene oxide group having 2 to 4 carbon atoms such as 50 polypropylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate; ethoxylated glycerin tri ( (Meth) acrylate, propylene oxide modified glycerol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylolpropane triethoxytri Tri (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as (meth) acrylate; pentaerythritol tetra (meth) acrylate, dipentaeri Tetra (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as lithol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate; pentaerythritol penta (meth) acrylate, dipentaerythritol (monohydroxy) penta (meth) ) Penta (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as acrylate; Hexa (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate; Bisphenol A di (meth) ) Acrylate, 2- (2′-vinyloxyethoxyethyl) (meth) acrylate, epoxy group-containing (meth) acrylates such as epoxy (meth) acrylate; polyfunctional (meth) acrylates such as urethane (meth) acrylate Examples include chlorate, but the present invention is not limited to such examples. These polyfunctional monomers may be used alone or in combination of two or more.

  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. It may be contained in the monomer component A.

  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-croto Noylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-sia -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, the present invention is not limited to such examples. These ultraviolet stable 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 ultraviolet absorbing 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 monomer component A 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 a single amount under stirring. The method of dropping the body component A and the polymerization initiator, the method of dropping the monomer component A previously emulsified using an emulsifier and water, into water or an aqueous medium, and the like are mentioned. It is not limited only to the method. In addition, what is necessary is just to set the quantity of a medium suitably in consideration of the non volatile matter amount contained in the resin emulsion obtained. The medium may be charged in the reaction vessel in advance or used as a pre-emulsion. Moreover, you may use a medium when the monomer component A is emulsion-polymerized and the resin emulsion is manufactured as needed.

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

  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.

  Among the emulsifiers, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable, 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 Daiichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salt [eg, Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], Sulphonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [eg, ADEKA Corporation, trade name: ADEKA Rear soap SE-10 Allyloxymethylalkoxyethylhydroxy polyoxyethylene 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, manufactured by Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by 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.], allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, Co., Ltd. Made by ADEKA, quotient Name: Adekariasoap NE-10, etc.] Although the like, the present invention is not limited only to those exemplified.

  The amount of the emulsifier per 100 parts by mass of the monomer component A 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. Is 3 parts by mass or more, and from the viewpoint of improving water resistance, it 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, and particularly preferably 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 ammonium persulfate and potassium persulfate; Examples of the peroxide include peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. However, 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 per 100 parts by mass of the monomer component A is preferably 0.05 parts by mass or more, more preferably from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component A. From the viewpoint of improving the water resistance, it is preferably 1 part by mass or less, and 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. Further, from the viewpoint of accelerating the completion time of the polymerization reaction, a part of the polymerization initiator may be added before or after the monomer component A 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 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 per 100 parts by mass of the monomer component A is preferably 0.01 to 10 parts by mass from the viewpoint of appropriately 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. Usually, the amount of the additive per 100 parts by mass of the monomer component A is preferably about 0.01 to 5 parts by mass, more preferably about 0.1 to 3 parts by mass.

  Although the atmosphere at the time of carrying out emulsion polymerization of the monomer component A is not specifically limited, It is preferable that it is inert gas, such as nitrogen gas, from a viewpoint of improving the efficiency of a polymerization initiator.

  Although the polymerization temperature at the time of carrying out emulsion polymerization of the monomer component A 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 A 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 the monomer component A is emulsion-polymerized, part or all of the acidic groups of the obtained polymer may be neutralized with a neutralizing agent. The neutralizing agent may be used after the monomer component A 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 emulsion 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, alkaline substances having volatility such as ammonia are preferable. The neutralizing agent can be used as an aqueous solution, for example.

  Moreover, when the monomer component A is emulsion-polymerized, a silane coupling agent may be used in an appropriate amount from the viewpoint of improving water 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. “(Meth) acryloyl” means “acryloyl” or “methacryloyl”.

  By emulsion polymerization of the monomer component A as described above, a resin emulsion containing emulsion particles made of the polymer (I) forming the inner layer is obtained.

  In 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 weight average molecular weight of the polymer (I) is preferably 100,000 or more, more preferably 300,000 or more, and still more preferably from the viewpoint of forming a coating film excellent in overall pattern retention, water resistance and weather resistance. 550,000 or more, particularly preferably 600,000 or more. The upper limit of the weight average molecular weight of the polymer (I) is not particularly limited when the polymer (I) has a crosslinked structure, since it is difficult to measure the weight average molecular weight. From the viewpoint of forming a coating film that is comprehensively excellent in water resistance and weather resistance, 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

  In addition, after forming the inner layer which consists of polymer (I), before forming an outermost layer, you may form the outer layer of 1 layer or 2 layers or more on the surface of the said inner layer as needed. Therefore, when the resin emulsion of the present invention is produced, the object of the present invention is not hindered after the inner layer made of the polymer (I) is formed and before the outermost layer made of the polymer (II) is formed. Within the range, if necessary, a layer made of another polymer may be formed.

  When forming the outer layer, the outer layer is formed on the emulsion particles constituting the inner layer by emulsion polymerization in the same manner as in the method and polymerization conditions of the monomer component A in the resin emulsion. Can be made. Examples of the monomer used to form the outer layer include a monofunctional monomer and a polyfunctional monomer used for the monomer component A, but the present invention is limited to such examples. It is not limited.

  Suitable monofunctional monomers include, for example, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, carboxyl group-containing monomers, oxo group-containing monomers, fluorine atom-containing monomers, nitrogen atom-containing monomers. Monomer, epoxy group-containing monomer, alkoxyalkyl (meth) acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer, styrene monomer, aralkyl (meth) acrylate, etc. These monomers may be used alone or in combination of two or more. Further, when the outer layer is further formed on the emulsion particles on which the outer layer has been formed, the same monomer component as the monomer component A is emulsion-polymerized in the same manner as described above in the resin emulsion. Thus, an outer layer can be further formed on the emulsion particles. Thus, a resin emulsion containing emulsion particles having a multilayer structure can be prepared by a multistage emulsion polymerization method.

  Next, the outermost layer made of the polymer (II) is formed on the surface of the emulsion particles having the inner layer by emulsion polymerization of the monomer component B forming the outermost layer.

  For example, when the outermost layer made of the polymer (II) is formed on the inner layer made of the polymer (I), when the monomer component B is emulsion-polymerized, the polymerization reaction rate of the polymer (I) is 90. From the viewpoint of forming a layer separation structure in the emulsion particles, it is preferable to emulsion polymerize the monomer component B after reaching% or more, preferably 95% or more.

  Examples of the monomer used for the monomer component B include monofunctional monomers and polyfunctional monomers used for the monomer component A, but the present invention is limited only to such examples. It is not a thing.

  Suitable monofunctional monomers include, for example, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, carboxyl group-containing monomers, oxo group-containing monomers, fluorine atom-containing monomers, nitrogen atom-containing monomers. Monomer, epoxy group-containing monomer, alkoxyalkyl (meth) acrylate, silane group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer, styrene monomer, aralkyl (meth) acrylate, etc. These monomers may be used alone or in combination of two or more.

  In the present invention, pattern retention, water resistance and weather resistance are such that only the monomer component B used as a raw material for the polymer (II) constituting the outermost layer contains cyclohexyl methacrylate and butyl methacrylate. From the viewpoint of forming a coating film that is comprehensively excellent in properties. In other words, it is preferable that cyclohexyl methacrylate and butyl methacrylate are contained only in the monomer component used in the outermost layer. Thus, in the monomer component B, by using cyclohexyl methacrylate and butyl methacrylate in combination, as a synergistic effect of the combined use of both, pattern retention, water resistance and weather resistance are comprehensively remarkably excellent. Is done. The total content of cyclohexyl methacrylate and butyl methacrylate in the monomer component B is preferably 10% by mass or more, more preferably from the viewpoint of forming a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance. 30 mass% or more, More preferably, it is 50 mass% or more, More preferably, it is 70 mass% or more. The upper limit of the total content of cyclohexyl methacrylate and butyl methacrylate in the monomer component B is 100% by mass.

  Further, the mass ratio of cyclohexyl methacrylate to butyl methacrylate (cyclohexyl methacrylate / butyl methacrylate) is preferably 10/90 to 90 from the viewpoint of forming a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance. / 10, more preferably 25/75 to 75/25, still more preferably 25/75 to 50/50.

  The method for emulsion polymerization of the monomer component B and the polymerization conditions may be the same as the method for polymerization of the monomer component A and the polymerization conditions.

  By emulsion polymerization of the monomer component B as described above, emulsion particles in which the polymer (II) forming the outermost layer is formed on the surface of the inner layer can be obtained.

  The polymer (II) may have a crosslinked structure. The weight average molecular weight of the polymer (II) is comprehensive in pattern retention, water resistance and weather resistance, regardless of whether the polymer (II) has a crosslinked structure or not. Is preferably 10,000 or more, more preferably 100,000 or more, still more preferably 300,000 or more, and particularly preferably 500,000 or more. The upper limit of the weight average molecular weight of the polymer (II) is not particularly limited when it has a crosslinked structure, since it is difficult to measure the weight average molecular weight. From the viewpoint of forming a coating film that is comprehensively excellent in properties, water resistance and weather resistance, it is preferably 5 million or less.

  The glass transition temperature of the polymer (I) is preferably −40 ° C. or higher, more preferably −25 ° C. or higher, from the viewpoint of forming a coating film having excellent pattern retention, water resistance and weather resistance. The temperature is preferably −10 ° C. or higher, and preferably 60 ° C. or lower from the viewpoint of forming a coating film that is comprehensively excellent in pattern retention, water resistance and weather resistance. The glass transition temperature of the polymer (I) can be easily adjusted by adjusting the composition of the monomer used for the monomer component A.

  The glass transition temperature of the polymer (II) is preferably −40 ° C. or higher, more preferably −25 ° C. or higher, from the viewpoint of forming a coating film excellent in pattern retention, water resistance and weather resistance. Preferably, it is −10 ° C. or higher, and preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 40 ° C. from the viewpoint of forming a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance. It is as follows. In addition, the glass transition temperature of polymer (II) can be easily adjusted by adjusting the composition of the monomer used for the monomer component B.

  The glass transition temperature of the entire emulsion particles is preferably −10 ° C. or higher, more preferably 0 ° C. or higher, and even more preferably, from the viewpoint of forming a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance. From the viewpoint of forming a coating film that is 10 ° C. or higher and is comprehensively excellent in pattern retention, water resistance, and weather resistance, it is preferably 60 ° C. or lower, more preferably 55 ° C. or lower, and further preferably 50 ° C. or lower. .

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
[Wm represents the content (% by mass) of monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of 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, 95 ° C. for acrylic acid homopolymer, 105 ° C. for methyl methacrylate homopolymer, 83 ° C. for cyclohexyl methacrylate homopolymer, and 20 for n-butyl methacrylate homopolymer. ℃, 2-ethylhexyl acrylate homopolymer -70 ℃, n-butyl acrylate homopolymer -56 ℃, acrylamide homopolymer 165 ℃, methacrylic acid homopolymer 130 ℃, hydroxyethyl methacrylate 55 ° C. for the homopolymer of 1, and 130 ° C. for the homopolymer of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] 2H-benzotriazole homopolymer is 100 ° C

  The glass transition temperature of the polymer is a value obtained based on the Fox equation, but the measured value of the glass transition temperature of the polymer was obtained based on the Fox equation. The value is preferably the same. The actual measured value of the glass transition temperature of the polymer can be obtained, for example, by measuring the differential scanning calorific value.

  In the present specification, the glass transition temperature of the (meth) acrylic adhesive resin means a glass transition temperature obtained based on the above formula unless otherwise specified. 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 with unknown glass transition temperature in the monomer component exceeds 10% by mass, the glass transition temperature of the (meth) acrylic adhesive resin is determined by differential scanning calorimetry (DSC), differential. It is determined by calorimetric analysis (DTA), thermomechanical analysis (TMA) or the like.

  The mass ratio of the polymer (I) to the polymer (II) [polymer (I) / polymer (II)] forms a coating film that is comprehensively excellent in pattern retention, water resistance and weather resistance. From the viewpoint, it is 25/75 or more, preferably 35/65 or more, and from the viewpoint of forming a coating film excellent in pattern retention, water resistance and weather resistance, 75/25 or less, preferably 65 / 35 or less.

  The total content of the polymer (I) and the polymer (II) in the emulsion particles is 50% by mass or more, preferably from the viewpoint of forming a coating film excellent in pattern retention, water resistance and weather resistance. Is 65% by mass or more, and the higher the total content of the polymer (I) and the polymer (II) in the emulsion particles, the better, and the upper limit is 100% by mass.

  After preparing the inner layer composed of the polymer (I) as described above, the outermost layer composed of the polymer (II) is formed on the inner layer, whereby a resin emulsion containing emulsion particles having the inner layer and the outermost layer is obtained. can get. The resin emulsion of the present invention contains a resin emulsion containing the emulsion particles thus obtained.

  From the viewpoint of improving water resistance and weather resistance, the minimum film-forming temperature of the resin emulsion of the present invention is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 40 ° C. or lower. Further, the lower limit value of the minimum film-forming temperature of the resin emulsion of the present invention is preferably −5 ° C. or higher, more preferably 5 ° C. or higher, further preferably 20 ° C. or higher, from the viewpoint of improving water resistance and stain resistance. is there.

  In this specification, the minimum film-forming temperature of the resin emulsion is such that the resin emulsion is coated on a glass plate placed on a thermal gradient tester with an applicator so that the thickness is 0.2 mm and dried. It means the temperature when a crack occurs.

  The nonvolatile content in the resin emulsion of the present invention 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 from the viewpoint of improving handleability. More preferably, it is 60 mass% or less.

In the present specification, the nonvolatile content in the resin emulsion is determined by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content in resin emulsion (mass%)]
= ([Residue mass] / [resin emulsion 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 water resistance and weather resistance. Preferably it is 250 nm or less, More preferably, it is 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.

  Crosslinking property can be imparted to the resin emulsion of the present invention by further containing a crosslinking agent. 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 resin emulsion of the present invention, water resistance and stain resistance can be improved.

  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 the storage stability of the resin emulsion of the present invention.

  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 Co., Ltd., trade name: Rezamin 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 functional group of polymer (II) contained in the emulsion particles (functional group for oxazoline group-containing compound: carboxyl group, functional group for isocyanate group-containing compound: hydroxyl group), oxazoline group-containing compound, isocyanate group-containing compound, etc. Equivalent ratio (functional group of polymer (II) / functional group of crosslinking agent) with the functional group of the crosslinking agent (functional group of oxazoline group-containing compound: oxazoline group, functional group of isocyanate group-containing compound: isocyanate group) is: Usually, it is preferably 0.1 to 2.5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.8.

  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 the aminoplast resin is usually such that the mass ratio of the solid content of the polymer and the solid content of the aminoplast resin contained in the emulsion particles [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 resin emulsion of the present invention 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, chromium oxide green, carbon black, chrome lead, molybdenum red, ferric ferrocyanide ( Prussian blue), ultramarine, lead chromate, etc., mica (mica), clay, aluminum powder, talc, aluminum silicate and other flat pigments, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate And extender pigments such as 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 the concealing property of the coating film formed from the resin emulsion of the present invention. From the viewpoint of improving the weather resistance, it is preferably 190 parts by mass or less.

  The resin emulsion of the present invention may contain other resin emulsions other than the resin emulsion as long as the object of the present invention is not hindered. In that case, the emulsion contained in the resin emulsion What is necessary is just to adjust so that the average particle diameter of the whole particle | grains may become in the said range.

  In addition, the resin emulsion of the present invention includes, for example, an ultraviolet absorber, an ultraviolet stabilizer, a filler, a leveling agent, a dispersant, a thickener, a wetting agent, a plasticizer, within a range where the object of the present invention is not hindered. Additives such as stabilizers, dyes and antioxidants may be contained in appropriate amounts.

  The resin emulsion of the present invention may be applied alone in one layer, or may be applied by recoating two or more layers. When applying by overcoating two or more layers, only a part of the layers may be formed by the resin emulsion of the present invention, or all the layers may be formed by the resin emulsion of the present invention. For overcoating, for example, a first layer (for example, undercoat layer) coating is applied to an object that has been subjected to primer treatment or sealer treatment, and then dried, and then for the second layer (for example, topcoat layer). Although the method of overcoating and drying a paint is mentioned, this invention is not limited by this method. Examples of the method of applying the resin emulsion of the present invention include a coating method using a brush, a bar coater, an applicator, an air spray, an airless spray, a roll coater, a flow coater, etc., but the present invention is only such examples. It is not limited to.

  The resin emulsion of the present invention is a resin emulsion containing emulsion particles having a plurality of layers, and at least one of the plurality of layers emulsion-polymerizes a monomer component containing n-butyl methacrylate and cyclohexyl methacrylate. Therefore, an excellent effect of forming a coating film that is comprehensively excellent in pattern retention, water resistance and weather resistance is exhibited. In particular, in the invention, when cyclohexyl methacrylate and butyl methacrylate are used in combination only in the monomer component B used as the raw material of the polymer (II) constituting the outermost layer, as a synergistic effect of the combined use of both, The effect that the pattern retention, water resistance and weather resistance are remarkably excellent overall is exhibited. Thus, since the resin emulsion of the present invention is comprehensively excellent in pattern retention, water resistance and weather resistance, for example, it is called a top coat that is painted on the surface of a building exterior or a ceramic building material. It can be suitably used for a top coating material (water-based paint).

  The resin composition for paints of this invention contains the said resin emulsion. The resin composition for paints of the present invention may be the resin emulsion itself or may contain additives.

  The top coating composition of the present invention suitably includes, for example, the resin composition for paint or the resin emulsion and one or more kinds of film forming aids, foam suppressors, pigments, thickeners, matting agents, and the like. It can be easily prepared by mixing. Examples of the top coat include enamel paint and clear paint. The top coat can be suitably used for a top coat.

  The coating resin composition, resin emulsion, and top coating composition of the present invention can be suitably used for on-site painting, for example, on the outer wall of a building, and also for inorganic building materials such as ceramic building materials. It can be preferably used. 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.

  In addition, when applying the resin composition for paints of the present invention, the resin emulsion or the top coat to the front and back surfaces of building materials, from the viewpoint of efficiently producing a building material having a coating film on both sides, the building materials are optionally added. It may be heated. When applying the resin composition for paints of the present invention, the resin emulsion, or the top coat to building materials, for example, sprays, rollers, brushes, or irons can be used.

  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.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 731 parts of deionized water was charged. In a dropping funnel, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 200 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, 200 of 2-ethylhexyl acrylate Part, 40 parts of n-butyl acrylate and 10 parts of acrylic acid are prepared as a first drop pre-emulsion, of which 78 parts, which is 5% of the total amount of all the monomer components, are added into the flask and gently nitrogen is added. The temperature was raised to 70 ° C. while blowing gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 15 parts of 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 120 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes. Subsequently, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], methyl 120 parts of methacrylate, 150 parts of cyclohexyl methacrylate, 150 parts of n-butyl methacrylate, 40 parts of n-butyl acrylate, 30 parts of hydroxyethyl methacrylate and 10 parts of acrylic acid and 15 parts of 5% aqueous ammonium persulfate solution Was dripped uniformly into the flask over 120 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 the resin emulsion is 45%, the glass transition temperature of the inner layer resin constituting the emulsion particles contained in the resin emulsion is −9 ° C., and the glass transition temperature of the outer layer resin. Was 49 ° C. The total content of n-butyl methacrylate and cyclohexyl methacrylate in the outer layer was 60% by mass.

Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 731 parts of deionized water was charged. In a dropping funnel, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 10 parts of acrylic acid, 240 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, 2- A pre-emulsion for first-stage dripping consisting of 90 parts of ethylhexyl acrylate and 10 parts of acrylamide was prepared, of which 78 parts corresponding to 5% of the total amount of all monomer components were added into the flask, and while gently blowing nitrogen gas, 70 parts was added. The temperature was raised to 0 ° C., 10 parts of a 5% aqueous ammonium persulfate solution was added, and polymerization was started. Thereafter, the remainder of the pre-emulsion for dropping and 15 parts of 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 120 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, followed by 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA, trade name: Adeka Resorb SR-10), acrylic 2-stage consisting of 10 parts of acid, 50 parts of cyclohexyl methacrylate, 110 parts of 2-ethylhexyl acrylate, 320 parts of n-butyl methacrylate and 10 parts of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole The pre-emulsion for eye drop and 15 parts of 5% ammonium persulfate aqueous solution were uniformly dropped into the flask over 120 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 the resin emulsion is 45%, the glass transition temperature of the inner layer resin constituting the emulsion particles contained in the resin emulsion is 50 ° C., and the glass transition temperature of the outer layer resin is It was 0 ° C. The total content of n-butyl methacrylate and cyclohexyl methacrylate in the outer layer was 74% by mass.

Example 3
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 731 parts of deionized water was charged. In a dropping funnel, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 10 parts of acrylic acid, 200 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, A pre-emulsion for first-stage dripping consisting of 200 parts of 2-ethylhexyl acrylate and 40 parts of n-butyl acrylate was prepared, of which 78 parts corresponding to 5% of the total amount of all monomer components were added into the flask, and gently nitrogen was added. The temperature was raised to 70 ° C. while blowing gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 15 parts of 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 120 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes. Subsequently, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], methyl A pre-emulsion for second-stage dropping comprising 10 parts of metallate, 240 parts of cyclohexyl methacrylate, 250 parts of n-butyl methacrylate and 10 parts of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole; 15 parts of a 5% aqueous solution of ammonium persulfate was uniformly dropped into the flask over 120 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 the resin emulsion is 45%, the glass transition temperature of the inner layer resin constituting the emulsion particles contained in the resin emulsion is −9 ° C., and the glass transition temperature of the outer layer resin. Was 49 ° C. The total content of n-butyl methacrylate and cyclohexyl methacrylate in the outer layer was 98% by mass.

Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 731 parts of deionized water was charged. In a dropping funnel, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 240 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, 90 parts of 2-ethylhexyl acrylate, A pre-emulsion for first-stage dripping consisting of 10 parts of acrylamide and 10 parts of acrylic acid is prepared, of which 78 parts, which is 5% of the total amount of all monomer components, are added into the flask and 70% while gently blowing nitrogen gas. The temperature was raised to 0 ° C., 10 parts of a 5% aqueous ammonium persulfate solution was added, and polymerization was started. Thereafter, the remainder of the pre-emulsion for dropping and 15 parts of 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 120 minutes.

  At the end of the addition, the contents of the flask are maintained at 70 ° C. for 50 minutes, 6 parts of 25% aqueous ammonia are added, the contents of the flask are maintained at 70 ° C. for 10 minutes, followed by 184 parts of deionized water, emulsifier. 100 parts of 25% aqueous solution [trade name: Adekariasorb SR-10, manufactured by ADEKA Corporation], 75 parts of cyclohexyl methacrylate, 75 parts of n-butyl methacrylate, 320 parts of 2-ethylhexyl acrylate and 4-methacryloyloxy-1,2, A pre-emulsion for second-stage dropping consisting of 30 parts of 2,6,6-pentamethylpiperidine and 15 parts of a 5% aqueous solution of ammonium persulfate were uniformly dropped into the flask over 120 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 the resin emulsion is 45%, the glass transition temperature of the inner layer resin constituting the emulsion particles contained in the resin emulsion is 50 ° C., and the glass transition temperature of the outer layer resin is -37 ° C. The total content of n-butyl methacrylate and cyclohexyl methacrylate in the outer layer was 30% by mass.

Comparative Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 731 parts of deionized water was charged. In a dropping funnel, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 10 parts of acrylic acid, 100 parts of methyl methacrylate, 150 parts of n-butyl methacrylate, A pre-emulsion for first-stage dripping consisting of 200 parts of 2-ethylhexyl acrylate and 40 parts of n-butyl acrylate was prepared, of which 78 parts corresponding to 5% of the total amount of all monomer components were added into the flask, and gently nitrogen was added. The temperature was raised to 70 ° C. while blowing gas, and 10 parts of 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 15 parts of 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 120 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, followed by 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA, trade name: Adeka Resorb SR-10), acrylic A flask containing 10 parts of acid, 210 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, 100 parts of n-butyl acrylate and 30 parts of hydroxyethyl methacrylate and 15 parts of 5% ammonium persulfate aqueous solution uniformly over 120 minutes It was dripped in.

  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 is 45%, the glass transition temperature of the inner layer resin constituting the emulsion particles contained in the resin emulsion is −20 ° C., and the glass transition temperature of the outer layer resin. Was 48 ° C. The content of cyclohexyl methacrylate in the outer layer was 30% by mass.

Comparative Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 731 parts of deionized water was charged. In a dropping funnel, 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 10 parts of acrylic acid, 50 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, n- A pre-emulsion for first-stage dropping consisting of 50 parts of butyl methacrylate, 200 parts of 2-ethylhexyl acrylate and 40 parts of n-butyl acrylate was prepared, and 78 parts corresponding to 5% of the total amount of all monomer components were added to the flask. Then, 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 pre-emulsion for dropping and 15 parts of 5% aqueous ammonium persulfate solution were uniformly dropped into the flask over 120 minutes.

  After completion of the dropwise addition, the contents of the flask were maintained at 70 ° C. for 60 minutes, followed by 184 parts of deionized water, 100 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA, trade name: Adeka Resorb SR-10), acrylic 10 parts of acid, 260 parts of methyl methacrylate, 150 parts of n-butyl methacrylate, 50 parts of n-butyl acrylate, and 30 parts of hydroxyethyl methacrylate and 15 parts of 5% aqueous ammonium persulfate solution over 120 minutes The solution was dropped into the flask.

  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 the resin emulsion is 45%, the glass transition temperature of the inner layer resin constituting the emulsion particles contained in the resin emulsion is −13 ° C., and the glass transition temperature of the outer layer resin. Was 50 ° C. The content of n-butyl methacrylate in the outer layer was 30% by mass.

  The following physical properties were examined using the resin emulsion obtained in each Example or each Comparative Example. The results are shown in Table 1. In addition, what has at least one evaluation of x in a physical property is determined to be unacceptable.

1. Evaluation of Pattern Retention and Weather Resistance 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate [Nisso (as a film forming aid) was added to 100 parts of the resin emulsion obtained in each Example or each Comparative Example. Co., Ltd., product number: CS-12] 10 parts was added and stirred with a homodisper at a rotational speed of 1500 min ^{-1 for} 10 minutes, followed by 30 parts of white paste and an antifoaming agent (San Nopco Co., Ltd., trade name: Nopco 8034L] 0.5 part was added, and a thickener [(Co., Ltd.) was used so that the viscosity was 80 KU when measured at 25 ° C. using a Craves unit viscometer (manufactured by Brookfield, product number: KU-1). ), Manufactured by Nippon Shokubai Co., Ltd., trade name: Acreset WR-503A], and stirred in that state for 30 minutes to prepare a sample.

The white paste is 210 parts of deionized water, 60 parts of a dispersant (trade name: Demol EP, manufactured by Kao Corporation), and a dispersant (made by Daiichi Kogyo Seiyaku Co., Ltd., trade name: DISCOAT N-14). ] 50 parts, 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] 1000 parts and glass beads It was prepared by dispersing 200 parts (diameter: 1 mm) with a homodisper at a rotational speed of 3000 min ^{−1 for} 60 minutes.

  Using the samples obtained above, pattern retention and weather resistance were examined according to the following method. The results are shown in Table 1. In addition, it is determined that it is a failure if there is even one evaluation of x.

(1) Pattern retention property A slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm] is air sprayed with a sealer [SK Kaken Co., Ltd., trade name: EX sealer]. Was uniformly applied at a coating amount of 150 g / m ² and dried at 23 ° C. for 1 week.

  Next, an aqueous solution of the sample is prepared by mixing the sample and water at a ratio of 10 parts of water per 100 parts of the sample, and this aqueous solution is subjected to a sag tester (4 mils, 8 mils, 10 mils, 15 mils, 20 mils). Can be applied at a time, with an interval of 5 mm between each coating film. Immediately after being applied vertically at an angle of 90 °, it is dried as it is at 23 ° C. for 1 day, and then the appearance of the coating film Was visually observed, and pattern retention was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
(Double-circle): Each coating film is divided clearly and the change from immediately after coating is not recognized.
○: Each coating film is close but separated.
(Triangle | delta): Since only the coating film with a film thickness of 10 mil or more approaches and is familiar with each coating film, the boundary between coating films is unclear.
X: Since all the coating films whose film thickness is less than 10 mil are familiar, the film thickness of each coating film is not hold | maintained.

(2) Weather resistance Sealer [ESK Kaken Co., Ltd., trade name: EX Sealer] is sprayed onto a slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm]. It was uniformly applied at a coating amount of 150 g / m ² and dried at 23 ° C. for 1 week.

Next, after applying the sample with a 10 mil applicator and drying at 23 ° C. for 1 week, the side surface and back surface of the slate plate on which the sample was applied were sealed with aluminum tape, and the 60 ° mirror surface of the surface on which the sample was applied Gloss is measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number: VG2000), a weather resistance test is performed for 1000 hours under the following conditions, and the gloss of the coated surface of the slate plate is measured with the gloss meter. And the formula:
[Gloss retention (%)] = [[Gloss after weather resistance test] / [Gloss before weather resistance test]] × 100
The weather resistance was evaluated based on the following evaluation criteria.

[Test conditions for weather resistance test]
Test machine: Metal weather [Daipura Wintes Co., Ltd., product number: KU-R4]
・ Irradiation: Irradiation for 4 hours in an atmosphere with a temperature of 65 ° C. and a relative humidity of 50% (irradiation intensity: 80 mW / cm ² )
-Wet: 4 hours in an atmosphere of 35% relative humidity and 98% relative humidity-Shower: 30 seconds each before and after wetting

〔Evaluation criteria〕
A: Gloss retention is 85% or more B: Gloss retention is 70% or more and less than 85% Δ: Gloss retention is 60% or more and less than 70% X: Gloss retention is less than 60%

2. Evaluation of water resistance 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation] as a film-forming auxiliary agent in 100 parts of the resin emulsion obtained in each Example or each Comparative Example Product No .: CS-12] 10 parts are added, and then 0.5 part of antifoaming agent (trade name: Nopco 8034L, manufactured by San Nopco Co., Ltd.) is added, followed by homodisper at a rotational speed of 1500 min ^{-1 for} 10 minutes. Samples were prepared by stirring.

  Next, in accordance with JIS K6717 (2006), a black acrylic plate obtained by molding methyl methacrylate by extrusion molding (manufactured by Nippon Test Panel Co., Ltd., length: 75 mm, width: 150 mm, thickness: 3 mm) A test plate was prepared by applying the sample obtained above with a 5 mil applicator and drying it with a hot air dryer at 100 ° C. for 10 minutes.

After the test plate obtained above was cured at 23 ° C. for 24 hours, the L value (L ₀ ) of the test plate was measured using a color difference meter [manufactured by Nippon Denshoku Industries Co., Ltd., trade name: spectroscopic color difference meter SE- 2000], and after immersing this test plate in warm water adjusted to 23 ° C. for 240 hours, pulling it up from the warm water and wiping off the moisture with Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.) within 1 minute. The L value (L ₁ ) was measured with the color difference meter.

Next, the change value of the L value is expressed by the formula:
ΔL = (L ₁ ) − (L ₀ )
And evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
◎: ΔL is less than 4 ○: ΔL is 4 or more and less than 6 Δ: ΔL is 6 or more and less than 10 ×: ΔL is 10 or more

3. Comprehensive evaluation In each of the above physical properties, the evaluation of ◎ is 30 points, the evaluation of ○ is 20 points, the evaluation of △ is 10 points, the evaluation of × is 0 points, the total score of each physical property is totaled, and based on the total score Overall evaluation was made (maximum score: 90 points).

  From the results shown in Table 2, it can be seen that each of the resin emulsions obtained in each example forms a coating film that is comprehensively excellent in pattern retention, water resistance, and weather resistance.

  Both the resin composition for paints and the resin emulsion of the present invention are used for, for example, a top coat material (water-based paint) called a top coat that is painted on the surface of a building exterior or a ceramic building material. Is expected.

Claims (3)

A top coat resin emulsions containing emulsion particles having an inner layer and an outer layer, the monomer components only n- butyl methacrylate and cyclohexyl methacrylate used as a raw material of the polymer constituting the outer layer is contained, cyclohexyl The weight ratio of methacrylate to butyl methacrylate (cyclohexyl methacrylate / butyl methacrylate) is 25/75 to 50/50, and the glass transition temperature of the polymer constituting the inner layer is −40 to 60 ° C. Resin emulsion for top coat. A top manufacturing method of the coating resin emulsions containing emulsion particles having an inner layer and an outer layer, in preparing the resin emulsion, only the monomer component used as a raw material for the polymer constituting the outer layer n-Butyl methacrylate and cyclohexyl methacrylate are contained , the mass ratio of cyclohexyl methacrylate to butyl methacrylate (cyclohexyl methacrylate / butyl methacrylate) is adjusted to 25/75 to 50/50, and the glass transition temperature of the polymer constituting the inner layer It was adjusted to -40~60 ℃, top manufacturing method of coating a resin emulsion, characterized in that to each emulsion polymerizing a monomer component for forming the monomer component and the outer layer forms the inner layer.   A top coat paint comprising the topcoat resin emulsion according to claim 1.