JP6259145B2 - 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 that is applied to the surface of a building exterior or building material, and the coating resin composition. The present invention relates to a top coating material containing a product 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 that form a coating with excellent properties for preventing the coating from flowing down (hereinafter referred to as pattern retention), and resin composition for top coating or for top coat The development of a top coating containing a resin emulsion is awaited.

JP 2002-138123 A

  This invention is made | formed in view of the said prior art, and contains the resin composition for coatings which forms the coating film which was excellent also in weather resistance, water resistance, and also pattern retention property, and the said resin composition for coatings It is an object to provide a top coat. Another object of the present invention is to provide a topcoat resin emulsion that forms a coating film excellent in weather resistance, water resistance, and pattern retention, and a topcoat paint containing the topcoat resin emulsion. .

The present invention
(1) A resin Emarusho down topcoat comprising the monomer component is emulsion polymerization, alkyl in all the monomer component used as a raw material of the resin constituting the emulsion particles contained in the resin emulsion (meth) An acrylate, a piperidine group-containing monomer and an acid group-containing monomer, the content of the acid group-containing monomer is 0.3% by mass or less, the emulsion particles are composed of a plurality of layers, resin topcoat that the absolute value of the difference between the glass transition temperature of the resin forming the inner layer of the plural layers and a glass transition temperature of the resin constituting the outermost layer of a plurality of layers and wherein 35 to 70 ° C. der Rukoto Emulsion,
(2) A top-coat paint containing the topcoat resin emulsion according to (1), and
(3) A method for producing a resin emulsion for a top coat containing emulsion particles composed of a plurality of layers by emulsion polymerization of a monomer component, and as a raw material for the resin constituting the outer layer and the inner layer in the plurality of layers Inclusion of an acid group-containing monomer in all monomer components used as a raw material for the resin constituting the emulsion particles by containing an alkyl (meth) acrylate and a nitrogen atom-containing monomer in each monomer component used The ratio is adjusted to 0.3% by mass or less, and the difference between the glass transition temperature of the resin constituting the outermost layer in the plurality of layers and the glass transition temperature of the resin constituting the inner layer is determined using each monomer component. The present invention relates to a method for producing a resin emulsion for topcoat, characterized in that an absolute value is adjusted to 35 to 70C .

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

  As described above, the coating resin composition of the present invention is a coating resin composition containing a resin emulsion obtained by emulsion polymerization of a monomer component, and emulsion particles contained in the coating resin composition. The content ratio of the acid group-containing monomer in the monomer component used as a raw material of the constituent resin is 0.3% by mass or less. Further, the resin emulsion for topcoat of the present invention (hereinafter also simply referred to as resin emulsion) is a resin emulsion obtained by emulsion polymerization of monomer components as described above, and emulsion particles contained in the resin emulsion The content ratio of the acid group-containing monomer in the monomer component used as a raw material of the constituent resin is 0.3% by mass or less.

  The resin composition for coatings of the present invention contains a resin emulsion obtained by emulsion polymerization of a monomer component, and the monomer component used as a raw material for the resin constituting the emulsion particles contained in the resin emulsion Since the content of the acid group-containing monomer is 0.3% by mass or less, an excellent effect of forming a coating film having not only excellent weather resistance and water resistance but also excellent pattern retention is achieved. Is done. In addition, the resin emulsion of the present invention is a resin emulsion obtained by emulsion polymerization of a monomer component, and an acid group-containing simple substance in the monomer component used as a raw material for the resin constituting the emulsion particles contained in the resin emulsion. Since the content of the monomer is 0.3% by mass or less, an excellent effect of forming a coating film not only excellent in weather resistance and water resistance but also excellent in pattern retention is exhibited.

  The content of the acid group-containing monomer in the monomer component is 0.3% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass from the viewpoint of improving pattern retention. It is as follows.

  Examples of the acid 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 acid group-containing monomers may be used alone or in combination of two or more. Among these acid 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.

  The emulsion particles contained in the resin emulsion of the present invention may be composed of only one layer or may be composed of a plurality of layers. 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.

  The resin emulsion of the present invention is obtained by emulsion polymerization of monomer components.

  The monomer component 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. These monomers may be used alone or in combination of two or more.

  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, piperidine 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 piperidine group-containing monomer 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- Ano-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. Is not limited to such examples. These piperidine group-containing monomers may be used alone or in combination of two or more.

  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, piperidine group-containing monomers, oxo group-containing monomers, fluorine atom-containing monomers, nitrogen atom-containing monomers. A monomer, an epoxy group-containing monomer, a styrene-based monomer, and the like may be mentioned. These monomers may be used alone or in combination of two or more. Among monofunctional monomers, piperidine group-containing monomers are preferable from the viewpoint of improving weather resistance, and 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine is more preferable. .

  From the viewpoint of improving the weather resistance, the content of the piperidine monomer in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more. From the viewpoint of improving water resistance, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. In the case where the emulsion particles are formed in a plurality of layers, the piperidine group-containing monomer may be contained in the monomer component constituting any layer, but from the viewpoint of improving the weather resistance It is preferably contained in at least the monomer component constituting the outermost layer. Therefore, it is preferable that the monomer component contains a piperidine group-containing monomer. When the emulsion particles are formed in a plurality of layers, at least the monomer component constituting the outermost layer contains a piperidine group. It is preferable that the monomer is contained, and the content of the piperidine group-containing monomer in the monomer component is more preferably 0.5 to 30% by mass, and 0.5 to 20% by mass. It is still more preferable, and it is still more preferable that it is 0.5-10 mass%.

  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.

  Among polyfunctional monomers, from the viewpoint of achieving both coating film hardness and film formability, the alkyl di (meth) acrylate having 2 to 8 alkyl groups having 2 hydroxyl groups and the number of moles of ethylene oxide added are as follows. Polyethylene glycol di (meth) acrylate having 2 to 50, polypropylene glycol di (meth) acrylate having an addition mole number of propylene oxide of 2 to 50, tri (meth) acrylate of polyhydric alcohol, tetra (meth) acrylate of polyhydric alcohol Polyethylene alcohol penta (meth) acrylate and polyhydric alcohol hexa (meth) acrylate are preferable, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 50 addition moles of ethylene oxide, , 4-Butanediol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are more preferred.

  In the present invention, from the viewpoint of imparting ultraviolet absorption to the emulsion particles, an ultraviolet absorbing monomer may be contained in the monomer component within a range that does not impair the object of the present invention.

  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 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. 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. 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.

  Further, as the emulsifier, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable from the viewpoint of improving water 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 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: Adeka such REASOAP NE-10) but 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 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 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. From the viewpoint of improving 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. 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 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 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 is preferably about 0.01 to 5 parts by mass, more preferably about 0.1 to 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 or alkaline earth metal carbonates such as sodium hydrogen carbonate and calcium carbonate; ammonia, monomethylamine and the like. Although alkaline substances, such as organic amine, are mentioned, this invention is not limited only to this illustration. Among these neutralizing agents, volatile alkaline substances such as ammonia are preferable from the viewpoint of improving water resistance, and sodium hydrogen carbonate is preferable from the viewpoint of improving the storage stability of emulsion particles. The neutralizing agent can be used as an aqueous solution, for example.

  Moreover, when carrying out emulsion polymerization of a monomer component, you may use a silane coupling agent in a suitable quantity from a 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”.

  A resin emulsion is obtained by emulsion polymerization of the monomer component as described above.

  From the viewpoint of improving water resistance and weather resistance, the weight average molecular weight of the polymer constituting the emulsion particles contained in the resin emulsion is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 550,000 or more. Especially preferably, it is 600,000 or more. The upper limit of the weight average molecular weight of the polymer is preferably 5 million or less from the viewpoint of improving film formability and water resistance.

  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

  When the outer layer is formed on the emulsion particles obtained above, the monomer component constituting the outer layer after the polymerization reaction rate in producing the resin emulsion reaches 90% or more, preferably 95% or more Is preferably emulsion-polymerized from the viewpoint of forming a layer separation structure in the emulsion particles.

  In addition, after forming the inner layer of emulsion particle | grains, before forming an outer layer, the layer which consists of another polymer may be formed if needed in the range which does not inhibit the objective of this invention. Therefore, when producing the resin emulsion of the present invention, after forming the inner layer of the emulsion particles, before forming the outer layer, as long as the purpose of the present invention is not hindered, if necessary, from another polymer. A layer may be formed.

  The monomer component used for constituting the outer layer may be the same as the monomer component used as a raw material for the resin emulsion. Moreover, the emulsion polymerization method and polymerization conditions for forming the outer layer may be the same as the method and polymerization conditions for producing the resin emulsion.

  As described above, emulsion particles having an inner layer and an outer layer can be obtained. In addition, on the surface of the outer layer, a surface layer made of another polymer may be further formed as necessary within the range that does not impair the object of the present invention.

  The weight average molecular weight of the polymer forming the outer layer is preferably 10,000 or more, more preferably 100,000 or more, still more preferably 300,000 or more, particularly preferably 500,000 or more, from the viewpoint of improving water resistance and weather resistance. From the viewpoint of improving film formability and water resistance, it is preferably 5 million or less.

  When the emulsion particles are composed of one layer, the polymer constituting the emulsion particles, and when the emulsion particles are composed of a plurality of layers, the glass transition temperature of the polymer constituting the outermost layer is From the viewpoint of improving film formability, it is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, further preferably 40 ° C. or lower, and from the viewpoint of improving blocking resistance, preferably −40 ° C. or higher, more preferably Is −25 ° C. or higher, more preferably −10 ° C. or higher. 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
[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, 130 ° C. for methacrylic acid homopolymer, 105 ° C. for methyl methacrylate homopolymer, 100 ° C. for styrene homopolymer, cyclohexyl 83 ° C. for homopolymer of methacrylate, 20 ° C. for homopolymer of n-butyl methacrylate, −70 ° C. for homopolymer of 2-ethylhexyl acrylate, −56 ° C. for homopolymer of n-butyl acrylate, hydroxyethyl methacrylate 55 ° C. for homopolymers of acrylamide, 165 ° C. for homopolymers of acrylamide, 130 ° C. for homopolymers of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, 2- [2′-hydroxy -5′-methacryloyloxyethylphenyl] -2H-benzotriazo It is a homopolymer of Le 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.

  Examples of the differential scanning calorimeter measuring device include Seiko Instruments Inc., product number: DSC220C. Further, when measuring the differential scanning calorific value, a method of drawing a differential scanning calorific value (DSC) curve, a method of obtaining a first derivative curve from the differential scanning calorific value (DSC) curve, a method of performing a smoothing process, and a method of obtaining a target peak temperature There is no limitation in particular. For example, when the measuring device is used, the drawing may be performed from data obtained by using the measuring device. At that time, analysis software capable of performing mathematical processing can be used. Examples of the analysis software include analysis software [manufactured by Seiko Instruments Inc., product number: EXSTAR6000], but the present invention is not limited to such examples. In addition, the peak temperature obtained in this way may include an error due to plotting of about 5 ° C. up and down.

  When the emulsion particles have a multilayer structure, the absolute value of the difference between the glass transition temperature of the resin constituting the outermost layer and the glass transition temperature of the resin constituting the inner layer is preferably from the viewpoint of improving water resistance. It is 35 ° C. or higher, more preferably 40 ° C. or higher. From the viewpoint of improving water resistance and stain resistance, it is preferably 70 ° C. or lower, more preferably 60 ° C. or lower.

  When the emulsion particles are composed of two layers, the mass ratio of the polymer constituting the inner layer and the polymer constituting the outer layer [polymer constituting the inner layer / polymer constituting the outer layer] is weather resistance, water resistance Coating film excellent in weather resistance, water resistance, and pattern holding property, from the viewpoint of forming a coating film having excellent overall properties and pattern holding properties, 25/75 or more, preferably 35/65 or more Is 75/25 or less, preferably 65/35 or less.

  The total content of the polymer constituting the inner layer and the polymer constituting the outer layer in the emulsion particles is 50% by mass or more, preferably 65% by mass or more from the viewpoint of improving pattern retention, and the inner layer in the emulsion particles The higher the total content of the polymer constituting the outer layer and the polymer constituting the outer layer, the better. The upper limit is 100% by mass.

  After preparing the inner layer of emulsion particles as described above, a resin emulsion containing emulsion particles having an inner layer and an outer layer is obtained by forming an outer layer on the inner layer. The resin emulsion of the present invention may contain the emulsion particles thus obtained.

  From the viewpoint of improving the weather resistance and water 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 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, more preferably 10 ° 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 weather resistance and water 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 including a crosslinking agent in the resin emulsion of the present invention, weather 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.

  An oxazoline group-containing compound is a compound having two or more oxazoline groups in the molecule. 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 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 can be suitably used for, for example, a top coat material (water-based paint) called a top coat that is coated on the surface of a building exterior or a ceramic building material.

  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. An overcoat material (water-based paint) may be applied to the surface of the building material in order to impart a desired design.

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. In the following examples, Examples 1 to 3 are all treated as reference examples.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 716 parts of deionized water was charged. In a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 350 parts of methyl methacrylate, 99 parts of styrene, 100 parts of n-butyl methacrylate, 2 -A pre-emulsion for dropping consisting of 220 parts of ethylhexyl acrylate, 200 parts of n-butyl acrylate, 30 parts of hydroxyethyl methacrylate and 1 part of acrylic acid was prepared, of which 77 parts corresponding to 5% of the total amount of all monomer components were contained in the flask. The temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of 5% aqueous ammonium persulfate solution were uniformly dropped 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 content of nonvolatile content in this resin emulsion is 45%, the content of acid group-containing monomer (acrylic acid) in the monomer component is 0.1%, and the emulsion particles contained in the resin emulsion The glass transition temperature of the resin constituting the resin was 2 ° C.

Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 716 parts of deionized water was charged. In a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekariasorb SR-10], 400 parts of cyclohexyl methacrylate, 200 parts of n-butyl methacrylate, 200 of 2-ethylhexyl acrylate Part, n-butyl acrylate 150 parts, acrylamide 20 parts and 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 30 parts, 77 parts corresponding to 5% of the total amount was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, 10 parts of 5% ammonium persulfate aqueous solution was added, and polymerization was started. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of 5% aqueous ammonium persulfate solution were uniformly dropped 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 the resin emulsion is 45%, the acid group-containing monomer content in the monomer component is 0%, and the glass transition temperature of the resin contained in the resin emulsion is 5 ° C. Met.

Example 3
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 716 parts of deionized water was charged. In a full funnel, 209 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 200 parts of cyclohexyl methacrylate, 230 parts of 2-ethylhexyl acrylate, n-butyl acrylate A pre-emulsion for first-stage dripping consisting of 59 parts, 10 parts of hydroxyethyl methacrylate and 1 part of methacrylic acid was prepared, of which 77 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 a 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. Subsequently, 209 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], methyl Pre-emulsion for the second stage addition consisting of 250 parts of methacrylate, 100 parts of cyclohexyl methacrylate, 130 parts of 2-ethylhexyl acrylate and 10 parts of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine and 5% ammonium persulfate 15 parts of the aqueous solution 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 content of the acid group-containing monomer (methacrylic acid) in the monomer component is 0.1%, and the emulsion particles contained in the resin emulsion The glass transition temperature of the resin of the inner layer constituting the resin is −23 ° C., the glass transition temperature of the resin of the outer layer is 32 ° C., and the glass transition temperature of the resin constituting the inner layer and the glass transition temperature of the resin constituting the inner layer. The absolute value of the difference from temperature was 55 ° C.

Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 716 parts of deionized water was charged. In a full funnel, 209 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 208 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 100 parts of n-butyl acrylate , 10 parts of acrylamide and 10 parts of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine were prepared, and the pre-emulsion for first-stage dropping was prepared, which corresponds to 5% of the total amount of all monomer components. 77 parts were added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 15 parts of a 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, followed by 209 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA, trade name: Adeka Resorb SR-10), cyclohexyl 200 parts of methacrylate, 200 parts of 2-ethylhexyl acrylate, 70 parts of n-butyl acrylate, 10 parts of acrylamide, 10 parts of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine and 2- [2′-hydroxy [-5'-methacryloyloxyethylphenyl] -2H-benzotriazole 10 parts second drop pre-emulsion and 5% ammonium persulfate aqueous solution 15 parts were uniformly added dropwise 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 content of the acid group-containing monomer (methacrylic acid) in the monomer component is 0.1%, and the emulsion particles contained in the resin emulsion The glass transition temperature of the resin of the inner layer constituting the outer layer is 54 ° C., the glass transition temperature of the resin of the outer layer is −16 ° C., and the glass transition temperature of the resin constituting the inner layer and the glass transition temperature of the resin constituting the inner layer. The absolute value of the difference from temperature was 70 ° C.

Comparative Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer, and a reflux condenser, 716 parts of deionized water was charged. In a dropping funnel, 417 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Resorb SR-10], 10 parts of acrylic acid, 350 parts of methyl methacrylate, 90 parts of styrene, n-butyl A pre-emulsion for dropping consisting of 100 parts of methacrylate, 220 parts of 2-ethylhexyl acrylate, 200 parts of n-butyl acrylate and 30 parts of hydroxyethyl methacrylate was prepared, of which 77 parts corresponding to 5% of the total amount of all monomer components were contained in the flask. The temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping and 30 parts of 5% aqueous ammonium persulfate solution were uniformly dropped 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 is 45%, the content of the acid group-containing monomer (acrylic acid) in the monomer component is 1%, and constitutes emulsion particles contained in the resin emulsion. The glass transition temperature of the resin used was 2 ° C.

Next, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number as a film forming aid to 100 parts of the resin emulsion obtained in each Example or Comparative Example 1 : CS-12] After adding 10 parts and stirring with a homodisper at a rotational speed of 1500 min ^{-1 for} 10 minutes, 30 parts of white paste and antifoaming agent (manufactured by San Nopco, trade name: Nopco 8034L). 5 parts was added, and a thickener [manufactured by Nippon Shokubai Co., Ltd.] was added so that the viscosity was 80 KU when measured at 25 ° C. using a Craves unit viscometer (Brookfield, product number: KU-1). (Trade name: Acreset WR-503A) was added, and the sample was prepared by stirring in that state for 30 minutes.

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.

  The following physical properties were examined using the samples obtained above. 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) 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) Water resistance A slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) is sealed with an air sprayer [SK Kaken Co., Ltd., trade name: EX sealer]. It was uniformly applied at a coating amount of 150 g / m ² and dried at 23 ° C. for 1 week.

  Next, the sample was applied to the slate plate coated with the sealer with a 10 mil applicator, dried at 23 ° C. for 1 day, and then immersed in water at room temperature for 1 day. Then, the slate plate was taken out of the water and applied. The appearance of the film was visually observed, and the water resistance was evaluated based on the following evaluation criteria.

〔Evaluation criteria〕
A: No abnormality B: A small swollen portion exists slightly.
Δ: Slightly swollen portions exist.
X: The part which swelled in the whole surface exists.

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

Next, the sample was applied with a 10 mil applicator and dried at 23 ° C. for 1 week, and then the side surface and the back surface of the slate plate on which the sample was applied were sealed with aluminum tape, and 60 ° of the surface on which the sample was applied. The specular gloss was measured with a gloss meter (Nippon Denshoku Industries Co., Ltd., product number: VG2000), and a weather resistance test was conducted for 1000 hours under the following conditions. The gloss on the coated surface of the slate plate was measured with the gloss meter. Measure and formula:
[Gloss retention (%)]
= [[Gloss after weathering test] ÷ [Gloss before weathering 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%

(4) Comprehensive evaluation In the evaluation of pattern retention, water resistance and weather resistance, the evaluation of x is 0 points, the evaluation of △ is 10 points, the evaluation of ○ is 20 points, the evaluation of ◎ is 30 points, The total score was used as an index for comprehensive evaluation (maximum score: 90 points).

  From the results shown in Table 1, it can be seen that all of the resin emulsions obtained in each Example are comprehensively excellent in pattern retention, water resistance and weather resistance.

  The resin composition for coatings and resin emulsion of the present invention are preferably used for, for example, a top coat material (water-based paint) called a top coat that is applied to the surface of a building exterior or a ceramic building material. Can do.

Claims (3)

A resin Emarusho down topcoat comprised by emulsion polymerization of a monomer component, an alkyl (meth) acrylate in the total monomer component used as a raw material of the resin constituting the emulsion particles contained in the resin emulsion, piperidine A group-containing monomer and an acid group-containing monomer, wherein the content of the acid group-containing monomer is 0.3% by mass or less, and the emulsion particles are composed of a plurality of layers. topcoat resin emulsion absolute value of the difference between the glass transition temperature of the resin forming the inner layer at the glass transition temperature and the plurality of layers of resin constituting the outermost layer is characterized by 35 to 70 ° C. der Rukoto. A top coat paint comprising the topcoat resin emulsion according to claim 1. A method for producing a resin emulsion for a top coat containing emulsion particles composed of a plurality of layers by emulsion polymerization of a monomer component, each used as a raw material for a resin constituting the outer layer and the inner layer in the plurality of layers The monomer component contains an alkyl (meth) acrylate and a nitrogen atom-containing monomer, and the content of acid group-containing monomers in all monomer components used as a raw material for the resin constituting the emulsion particles is 0. The absolute value of the difference between the glass transition temperature of the resin constituting the outermost layer in the plurality of layers and the glass transition temperature of the resin constituting the inner layer is adjusted to 3% by mass or less. The manufacturing method of the resin emulsion for topcoats characterized by adjusting to 35-70 degreeC.