JP7033568B2 - Resin composition for paint - Google Patents

Description

The present invention relates to a resin composition for paints. More specifically, for example, a resin composition for a paint and a resin emulsion for a top coat, which are useful for a top coat called a top coat to be applied to the exterior of a building or the surface of a building material, and a resin composition for the paint. The present invention relates to a top coat coating material containing a resin emulsion for a product or a 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-soluble resins, emulsions and other water-dispersible paints have been used instead of solvent-based paints. .. However, the water-based paint generally has a technical problem that it is inferior in water resistance, weather resistance, etc. as compared with the organic solvent-based paint due to the fact that water is used as a solvent.

Therefore, as an aqueous coating composition having excellent weather resistance and water resistance, an aqueous coating composition in which multilayer structure particles having a core portion and a shell portion made of an acrylic polymer having a specific glass transition temperature are dispersed in water (for example, , Patent Document 1) and the like have been proposed.

However, although the water-based paint composition has a certain degree of weather resistance and water resistance, in recent years, a paint that forms a coating film that is not only excellent in weather resistance and water resistance but also excellent in mechanical stability. There is a long-awaited development of a topcoat paint containing a resin composition for use and a resin emulsion for topcoat, and the resin composition for paint or a resin emulsion for topcoat.

Japanese Unexamined Patent Publication No. 2002-138123

The present invention has been made in view of the above-mentioned prior art, and includes a resin composition for a paint and a resin composition for the paint, which form a coating film having excellent weather resistance, water resistance, and mechanical stability. It is an object to provide a topcoat paint to be used. Another object of the present invention is to provide a topcoat resin emulsion that forms a coating film having excellent weather resistance, water resistance, and mechanical stability, and a topcoat coating material containing the topcoat resin emulsion. do.

The present invention is a resin composition for paints containing a resin emulsion obtained by emulsion-polymerizing a monomer component, and is characterized in that a plurality of emulsifiers are used when the monomer component is emulsion-polymerized. The present invention relates to a resin composition for a paint. The present invention is also a resin emulsion containing emulsion particles obtained by emulsion polymerization of a monomer component, and has an anionic emulsifier having reactivity with the monomer component and non-reactivity with the monomer component. The present invention relates to a resin emulsion for a top coat, wherein the monomer component is emulsion-polymerized in the presence of an anionic emulsifier. The present invention further relates to a topcoat coating material, which further contains the resin emulsion for a top coat. The present invention is a method for producing a resin emulsion containing emulsion particles obtained by further emulsion polymerization of a monomer component, with respect to an anionic emulsifier having reactivity with the monomer component and the monomer component. The present invention relates to a method for producing a resin emulsion for a top coat, which comprises emulsion-polymerizing the monomer component in the presence of a non-reactive anionic emulsifier.

The resin composition for a paint of the present invention has an excellent effect of forming a coating film having overall excellent weather resistance, water resistance and mechanical stability. The resin emulsion for a top coat of the present invention has an excellent effect of forming a coating film having overall excellent weather resistance, water resistance and mechanical stability. The topcoat coating material of the present invention has an excellent effect of forming a coating film having overall excellent weather resistance, water resistance and mechanical stability. According to the method for producing a resin emulsion for a top coat of the present invention, it is possible to form a coating film having overall excellent weather resistance, water resistance and mechanical stability.

As described above, the resin composition for paint of the present invention is a resin composition for paint containing a resin emulsion obtained by emulsion-polymerizing a monomer component, and a plurality of the resin composition for paint is emulsion-polymerized when the monomer component is emulsion-polymerized. It is characterized in that the emulsifier of is used. Further, the resin emulsion for a top coat of the present invention (hereinafter, also simply referred to as a resin emulsion) is a resin emulsion containing emulsion particles obtained by emulsion polymerization of a monomer component as described above, and the monomer. The monomer component is emulsion-polymerized in the presence of an anionic emulsifier having reactivity with the component and an anionic emulsifier having no reactivity with the monomer component. According to the present invention, when emulsion-polymerizing a monomer component, a plurality of emulsifiers, particularly an anionic emulsifier having reactivity with the monomer component and an anionic emulsifier having non-reactivity with the monomer component. Since the monomer component is emulsion-polymerized in the presence of, the excellent effect of forming a coating film having not only excellent weather resistance and water resistance but also excellent mechanical stability is exhibited.

The resin emulsion of the present invention is prepared by emulsion polymerization of a monomer component in the presence of an anionic emulsifier having a reactivity with a monomer component and an anionic emulsifier having a non-reactivity with a monomer component. be able to.

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, and more preferably 2 to 4 layers.

When the emulsion particles contained in the resin emulsion are formed of a plurality of layers, the outermost layer of the plurality of layers is an anionic emulsifier having a reactivity with a monomer component and an anion having a non-reactivity with a monomer component. It is preferable that the monomer component is formed by emulsion polymerization in the presence of a sex emulsifier from the viewpoint of forming a coating film having overall excellent weather resistance, water resistance and mechanical stability. Therefore, when the emulsion particles are formed of a plurality of layers, only the outermost layer of the plurality of layers is an anionic emulsifier having reactivity with the monomer component and an anionic emulsifier having non-reactivity with the monomer component. It is preferable that the monomer component is formed by emulsion polymerization in the presence of and from the viewpoint of forming a coating film having overall excellent weather resistance, water resistance and mechanical stability.

As the monomer component, there are a monofunctional monomer and a polyfunctional monomer, and both of them 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 an example. These monomers may be used alone or in combination of two or more.

In addition, in this specification, "(meth) acrylate" means "acrylate" or "methacrylate", and "(meth) acrylic" means "acrylic" or "methacrylic".

Examples of the ethylenically unsaturated double bond-containing monomer include a carboxyl group-containing monomer, an alkyl (meth) acrylate, a hydroxyl group-containing (meth) acrylate, a piperidine group-containing monomer, and an 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 Examples thereof include system monomers and aralkyl (meth) acrylates, but the present invention is not limited to these examples. These ethylenically unsaturated double bond-containing monomers 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 esters, and vinyl benzoic acid, but the present invention is not limited to these 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 alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and 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 thereof include alkyl (meth) acrylates having 1 to 18 carbon atoms in ester groups such as acrylates, dodecyl (meth) acrylates, stearyl (meth) acrylates, and isobornyl (meth) acrylates. Not limited. 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 thereof include hydroxyl group-containing (meth) acrylates in which ester groups such as butyl (meth) acrylate have 1 to 18 carbon atoms, but the present invention is not limited to these examples. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more.

Examples of the piperidin group-containing monomer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. , 4- (Meta) 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-cyano-4- (meth) acryloylamino-2 , 2,6,6-Tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2, Examples thereof include 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, but the present invention is not limited to these examples. do not have. 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) (meth) 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 a fluorine atom-containing alkyl having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. 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, Examples thereof include acrylamide compounds such as diacetoneacrylamide, nitrogen atom-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, and (meth) acrylonitrile. Is not limited to such examples. 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. , The example is not limited to this. 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, and vinyltri. Examples thereof include chlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to these 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 achlorine, humylstyrene, vinyl ethyl ketone, (meth) acrylic oxyalkylpropenal, acetonyl (meth) acrylate, diacetone (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Acetyl acetate, butanediol-1,4-acrylate acetyl acetate, 2- (acetoacetoxy) ethyl (meth) acrylate and the like can be mentioned, but the present invention is not limited to these examples. These carbonyl group-containing monomers may be used alone or in combination of two or more.

Examples of the aziridinyl group-containing monomer include (meth) acryloyl aziridine, 2-aziridinyl ethyl (meth) acrylate, and the like, but the present invention is not limited to these examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

Examples of the styrene-based monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene and the like, but the present invention is limited to these examples only. is not it. These styrene-based monomers may be used alone or in combination of two or more. The styrene-based monomer has an alkyl group such as a methyl group and a tert-butyl group, a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group and a functional group such as a halogen atom in the benzene ring. You may. Among the styrene-based monomers, styrene is preferable from the viewpoint of increasing the water resistance of the coating film.

Examples of the aralkyl (meth) acrylate include benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, and naphthylmethyl (meth) acrylate, which have an aralkyl group having 7 to 18 carbon atoms. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. These aralkyl (meth) acrylates may be used alone or in combination of two or more.

Suitable monofunctional monomers include, for example, carboxyl group-containing monomers, alkyl (meth) acrylates, hydroxyl group-containing (meth) acrylates, piperidine group-containing monomers, oxo group-containing monomers, and fluorine atom-containing singles. Examples thereof include a weight, a nitrogen atom-containing monomer, an epoxy group-containing monomer, a styrene-based monomer, and the like, and these monomers may be used alone or in combination of two or more. good.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 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 trimethylolpropane di (meth) acrylate; polyethylene glycol di (meth) acrylate having 2 to 50 moles of ethylene oxide added, number of moles of propylene oxide added Alkyldi (meth) acrylates having 2 to 50 moles of alkylene oxide groups having 2 to 4 carbon atoms, such as 2 to 50 polypropylene glycol di (meth) acrylates and trimethylolpropane di (meth) acrylates; Glycerintri (meth) acrylate, propylene oxide-modified glyceroltri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylolpropane Tri (meth) acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as triethoxytri (meth) acrylates; pentaerythritol tetra (meth) acrylates, dipentaerythritol tetra (meth) acrylates, trimethylolpropane tetra (meth) acrylates. Tetra (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as; pentaerythritol Penta (meth) acrylate, dipentaerythritol (monohydroxy) Penta (meth) acrylate and other polyhydric alcohols having 1 to 10 carbon atoms. Penta (meth) acrylate; Hexa (meth) acrylate of polyvalent alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate; Bisphenol A di (meth) acrylate, 2- (2'-vinyloxyethoxyethyl) Epoxy group-containing (meth) acrylates such as (meth) acrylates and epoxy (meth) acrylates; polyfunctional (meth) acrylates such as urethane (meth) acrylates. Examples thereof include, but the present invention is not limited to such an example. These polyfunctional monomers may be used alone or in combination of two or more.

Among the polyfunctional monomers, the number of added moles of the alkyldi (meth) acrylate having 4 to 8 carbon atoms and the number of added moles of ethylene oxide of the alkyl group having two hydroxyl groups is from the viewpoint of achieving both the hardness of the coating film and the film forming property. 2 to 50 polyethylene glycol di (meth) acrylates, 2 to 50 polypropylene glycol di (meth) acrylates with 2 to 50 moles of propylene oxide, tri (meth) acrylates of polyhydric alcohols, tetra (meth) acrylates of polyhydric alcohols. , Penta (meth) acrylate of polyhydric alcohol and hexa (meth) acrylate of polyhydric alcohol are preferable, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having an addition molar number of 2 to 50 of ethylene oxide, 1 , 4-Butanediol di (meth) acrylate, trimethyl propanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate and ditrimethylol propanetetra (meth) acrylate are more preferred.

Further, 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 hinder the object of the present invention.

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

Examples of the benzotriazole-based ultraviolet absorbing monomer include 2- [2'-hydroxy-5'-(meth) acryloyloxymethylphenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'-. (Meta) 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) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxy Ethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2' -Hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxyethylphenyl] -5-chloro -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyl Oxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-(β- (meth) acryloyloxyethoxy) -3'-tert-butylphenyl] -4-tert -Butyl-2H-benzotriazole and the like can be mentioned, but the present invention is not limited to such examples. These benzotriazole-based ultraviolet absorbing monomers may be used alone or in combination of two or more.

Examples of the benzophenone-based ultraviolet absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, and 2-. Hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- [2- (Meta) acryloyloxy] butoxybenzophenone and the like can be mentioned, 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.

As a method of emulsion polymerization of the monomer component, for example, an emulsifier is dissolved in an aqueous medium containing water and a water-soluble organic solvent such as a lower alcohol such as methanol, or a medium such as water, and the emulsifier is dissolved under stirring. Examples thereof include a method of dropping a component and a polymerization initiator, a method of dropping a monomer component pre-emulsified with an emulsifier and water into water or an aqueous medium, and the like, but the present invention is limited to such a method. Not limited. The amount of the medium may be appropriately set in consideration of the non-volatile content contained in the obtained resin emulsion. The medium may be charged in a reaction vessel in advance, or may be used as a pre-emulsion. Further, if necessary, the medium may be used when the monomer component is emulsion-polymerized to produce a resin emulsion.

When the monomer component is emulsion-polymerized, the monomer component, the emulsifier and the medium may be mixed and then the emulsion polymerization may be carried out. Emulsion polymerization may be carried out after preparing the above, or at least one of a monomer component, an emulsifier and a medium and a preemulsion of the rest thereof may be mixed and emulsion polymerization may be carried out. The monomer component, emulsifier and medium may be added all at once, may be added separately, or may be continuously added dropwise.

When an 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, thereby forming the outer layer on the emulsion particles. An outer layer can be formed. Further, when the outer layer is further formed on the emulsion particles on which the outer layer is formed, the outer layer is further formed on the emulsion particles by emulsion polymerization of the monomer component in the resin emulsion in the same manner as described above. Can be made to. As described above, a resin emulsion containing emulsion particles having a multi-layer structure can be prepared by the multi-stage emulsification polymerization method.

When preparing the emulsion particles having a multi-layer structure, one stage or a plurality of stages of emulsion polymerization may be carried out before the emulsion polymerization for forming the inner layer is carried out, and the emulsion polymerization for forming the inner layer and the intermediate layer may be carried out. One-stage or multiple-stage emulsion polymerization may be performed between the emulsion polymerization to be formed. Further, one-stage or a plurality of stages of emulsion polymerization may be performed between the emulsion polymerization forming the intermediate layer and the emulsion polymerization forming the outer layer. Further, one-stage or multiple-stage emulsion polymerization may be performed after the emulsion polymerization forming the outer layer.

In the present invention, as described above, when the monomer component is emulsion-polymerized, a plurality of emulsifiers, particularly an anionic emulsifier having reactivity with the monomer component and an anion having non-reactivity with the monomer component, are present. One of the features of the present invention is that the monomer component is emulsion-polymerized in the presence of a sex emulsifier. In the present invention, the operation of emulsion-polymerizing the monomer component in the presence of the anionic emulsifier having reactivity with the monomer component and the anionic emulsifier having non-reactivity with the monomer component is adopted. Therefore, it is possible to obtain a resin emulsion that forms a coating film that is comprehensively excellent in weather resistance, water resistance, and mechanical stability, and a resin composition for a paint that contains the resin emulsion.

When the emulsion particles contained in the resin emulsion are formed of a plurality of layers, the outermost layer of the plurality of layers is an anionic emulsifier having a reactivity with a monomer component and a non-reactivity with the monomer component. It is preferable to form the monomer component by emulsion polymerization in the presence of an anionic emulsifier, from the viewpoint of forming a coating film having overall excellent weather resistance, water resistance and mechanical stability.

The anionic emulsifier having reactivity with the monomer component means an anionic emulsifier having a group reactive with the monomer component.

Examples of the anionic emulsifier having reactivity with the monomer component include propenyl-alkyl sulfosuccinate salt, (meth) acrylic acid polyoxyethylene sulfonate salt, and (meth) acrylic acid polyoxyethylene phosphonate salt [ For example, Sanyo Kasei Kogyo Co., Ltd., trade name: Eleminor RS-30, etc.], polyoxyethylene alkyl propenylphenyl ether sulfonate salt [for example, Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, etc.] , Allyloxymethylalkyloxypolyoxyethylene sulfonate salt [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], Allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene sulfonate salt [for example, Made by ADEKA Co., Ltd., trade name: Adecaria Soap SE-10, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [for example, manufactured by ADEKA Co., Ltd., trade name: Adecaria Soap SR-10, SR -30 etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [for example, manufactured by Nippon Embroidery Co., Ltd., trade name: Antox MS-60, etc.], etc. It is not limited to illustrations only. The anionic emulsifiers having reactivity with these monomer components may be used alone or in combination of two or more.

The anionic emulsifier having non-reactivity to the monomer component means an anionic emulsifier having no group reactive to the monomer component.

Examples of the anionic emulsifier having non-reactivity to the monomer component 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; Alkylaryl sulfonate salts such as ammonium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfonate; polyoxyethylene alkyl sulfonate salt; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkylaryl sulfate salt; dialkyl sulfosuccinate; aryl sulfonic acid-formalin condensate Fatty acid salts such as ammonium laurylate, sodium stearilate; bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic Sulfate ester having an allyl group such as acid polyoxyethylene phosphonate salt, allyloxymethylalkyloxypolyoxyethylene sulfonate salt or a salt thereof; allyloxymethylalkoxyethyl polyoxyethylene sulfate ester salt, polyoxyalkylene alkenyl ether Examples thereof include ammonium sulfate salts, but the present invention is not limited to these examples. The anionic emulsifiers having non-reactivity to these monomer components may be used alone or in combination of two or more.

Mass ratio of anionic emulsifier having reactivity to monomer component and anionic emulsifier having non-reactivity to monomer component (anionic emulsifier having reactivity to monomer component / non-reactive to monomer component) The reactive anionic emulsifier) is preferably 0.5 / 1 or more, more preferably 1/1 or more, still more preferably 2/1 or more, and is weather resistant and mechanical, from the viewpoint of improving water resistance. From the viewpoint of improving stability, it is preferably 9/1 or less, more preferably 8/1 or less, and further preferably 7/1 or less. Therefore, the mass ratio is preferably 0.5 / 1 to 9/1, more preferably 0.5 / 1 to 9/1, from the viewpoint of obtaining a resin emulsion that forms a coating film having overall excellent weather resistance, water resistance, and mechanical stability. It is 1/1 to 8/1, more preferably 2/1 to 7/1.

The total amount of the anionic emulsifier having reactivity with the monomer component and the anionic emulsifier having non-reactivity with the monomer component per 100 parts by mass of the monomer component improves weather resistance and mechanical stability. From the viewpoint of making it, it is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and from the viewpoint of improving water resistance, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, still more preferably 5. It is not more than parts by mass, particularly preferably 3 parts by mass or less.

In the present invention, an emulsifier other than the anionic emulsifier having reactivity with the monomer component and the anionic emulsifier having non-reactivity with the monomer component is used within the range not hindering the object of the present invention. You may use it. Examples of other emulsifiers include nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, and the like, and these emulsifiers may be used alone or in combination of two or more.

When emulsifying and polymerizing the monomer component, a polymerization initiator can be used. Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (2,2-azobis). 2-Diaminopropane) Hydrochloride, azo compounds such as 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; Examples thereof include peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide, but the present invention is not limited to these 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. It is 1 part by mass or more, preferably 1 part by mass or less, and more preferably 0.5 part by mass or less from the viewpoint of improving water resistance.

The method of adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, split charging, continuous dropping and the like. Further, from the viewpoint of accelerating the end time of the polymerization reaction, a part of the polymerization initiator may be added before or after the end of adding the monomer component to the reaction system.

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

In addition, 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, and α-methyl. Examples thereof include styrene dimers, but the present invention is not limited to such examples. 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.

Further, if necessary, additives such as a pH buffer, a chelating agent, and a film-forming auxiliary may be added to the reaction system. Since the amount of the additive varies depending on the type, it cannot be unconditionally determined. 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 when the monomer component is emulsion-polymerized 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.

The polymerization temperature at the time of emulsion polymerization of the monomer component is not particularly limited, but is usually preferably 50 to 100 ° C, more preferably 60 to 95 ° C. 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.

When the monomer component is emulsion-polymerized, a 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 is added in the final stage, for example, it may be used between the polymerization reaction of the first stage and the polymerization reaction of the second stage, and the initial emulsification may be performed. It may be used at the end of the polymerization reaction.

Examples of the neutralizing agent include hydroxides of alkali metals such as sodium hydroxide and alkaline earth metals; alkali metals such as sodium hydrogencarbonate and calcium carbonate or carbon oxides of alkaline earth metals; ammonia, monomethylamine and the like. Alkaline substances such as organic amines may be mentioned, but the present invention is not limited to such examples. Among these neutralizing agents, a volatile alkaline substance such as ammonia is 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 neutralizer can be used, for example, as an aqueous solution.

Further, when the monomer component 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. Not limited. In addition, "(meth) acryloyl" means "acryloyl" or "methacryloyl".

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

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, still more preferably 550,000 or more, from the viewpoint of improving water resistance and weather resistance. , Particularly preferably 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 the film forming property and the water resistance.

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]. It means the weight average molecular weight (in terms of polystyrene) measured in the above.

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

After forming the inner layer of the emulsion particles and before forming the outer layer, a layer made of another polymer may be formed, if necessary, within a range that does not hinder the object of the present invention. Therefore, when producing the resin emulsion of the present invention, after the inner layer of the emulsion particles is formed and before the outer layer is formed, the object of the present invention is not impaired, and if necessary, from another polymer. Layers may be formed.

The monomer component used to form the outer layer may be the same as the monomer component used as the raw material of the resin emulsion. Further, the method and polymerization conditions for emulsion polymerization when forming the outer layer may be the same as the method and polymerization conditions for producing the resin emulsion.

When the emulsion particles contained in the resin emulsion are formed of a plurality of layers, when the outermost layer of the plurality of layers is formed, as described above, the outermost layer is subjected to reactivity with the monomer component. Forming by emulsion polymerization of the monomer component in the presence of the anionic emulsifier having and the anionic emulsifier having non-reactivity to the monomer component is comprehensive in weather resistance, water resistance and mechanical stability. It is preferable from the viewpoint of forming an excellent coating film. In this case, the type of anionic emulsifier having reactivity with the monomer component and the anionic emulsifier having non-reactivity with the monomer component, the mass ratio of both, the total amount of both per part by mass of the monomer component, etc. May be the same as described above.

As described above, emulsion particles having an inner layer and an outer layer can be obtained. If necessary, a surface layer made of another polymer may be further formed on the surface of the outer layer as long as the object of the present invention is not impaired.

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, and particularly preferably 500,000 or more, from the viewpoint of improving water resistance and weather resistance. It is preferably 5 million or less from the viewpoint of improving film forming property and water resistance.

When the emulsion particles are composed of one layer, the glass transition temperature of 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 the film-forming property, it is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, still more preferably 40 ° C. or lower, and from the viewpoint of improving the 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 the glass transition temperature of the homopolymer of the monomer used as the monomer component constituting the polymer, and the formula:
1 / Tg = Σ (Wm / Tgm) / 100
[In the formula, Wm indicates the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm indicates the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It means the temperature obtained based on the Fox equation represented by.

The glass transition temperature of the polymer is, for example, 95 ° C. for the homopolymer of acrylic acid, 130 ° C. for the homopolymer of methacrylic acid, 105 ° C. for the homopolymer of methylmethacrylate, 83 ° C. for the homopolymer of cyclohexylmethacrylate. -70 ° C for 2-ethylhexyl acrylate homopolymer, 100 ° C for styrene homopolymer, 165 ° C for acrylamide homopolymer, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidin The temperature is 130 ° C. for the homopolymer and 100 ° C. for the homopolymer of 2- [2'-hydroxy-5'-methacryloyloxyethylphenyl] -2H-benzotriazole.

The glass transition temperature of the polymer is a value obtained based on the Fox equation, while the measured value of the polymer glass transition temperature is determined based on the Fox equation. It is preferably the same as the value. The measured value of the glass transition temperature of the polymer can be obtained, for example, by measuring the differential scanning calorimetry.

In the present specification, the glass transition temperature of the (meth) acrylic adhesive resin means the glass transition temperature obtained based on the above formula unless otherwise specified. For monomers such as special monomers and polyfunctional monomers whose glass transition temperature is unknown, the total amount of the monomers whose glass transition temperature is unknown in the monomer component is 10% by mass. In the following cases, the glass transition temperature can be determined using only the monomers whose glass transition temperature is known. When the total amount of monomers whose glass transition temperature is unknown in the monomer component exceeds 10% by mass, the glass transition temperature of the (meth) acrylic adhesive resin is determined by differential scanning calorimetry (DSC). It is obtained by calorimetric analysis (DTA), thermomechanical analysis (TMA), and the like.

Examples of the device for measuring the differential scanning calorimetry include Seiko Instruments Co., Ltd., product number: DSC220C and the like. Further, when measuring the differential scanning calorimetry, a method of drawing a differential scanning calorimetry (DSC) curve, a method of obtaining a first-order differential curve from the differential scanning calorimetry (DSC) curve, a method of performing smoothing processing, and a method of obtaining a target peak temperature. There are no particular restrictions on such things. For example, when the measuring device is used, drawing may be performed from the 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. The peak temperature thus obtained may include an error due to drawing of about 5 ° C. above and below.

When the emulsion particles are composed of two layers, the mass ratio of the polymer constituting the inner layer to the polymer constituting the outer layer [polymer constituting the inner layer / polymer constituting the outer layer] is weather resistance and water resistance. From the viewpoint of forming a coating film having excellent properties and mechanical stability, it is 25/75 or more, preferably 35/65 or more, and is excellent in weather resistance, water resistance and mechanical stability. From the viewpoint of forming a coating film, it 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 mechanical stability, and is in the emulsion particles. The larger the total content of the polymer constituting the inner layer and the polymer constituting the outer layer, the more preferable, and the upper limit thereof is 100% by mass.

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

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, still more preferably 40 ° C. or lower, from the viewpoint of improving weather resistance and water resistance. 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, still more preferably 10 ° C. or higher from the viewpoint of improving water resistance and stain resistance. be.

In the present 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 heat gradient tester with an applicator so as to have a thickness of 0.2 mm and dried. , Means the temperature at which cracks occur.

The non-volatile 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% by mass or less.

In the present specification, the non-volatile content in the resin emulsion is determined by weighing 1 g of the resin emulsion and drying it in a hot air dryer at a temperature of 110 ° C. for 1 hour, and the obtained residue is used as the non-volatile content.
[Non-volatile content in resin emulsion (% by mass)]
= ([Mass of residue] ÷ [Resin emulsion 1 g]) × 100
Means the value obtained based on.

The average particle size of the emulsion particles is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more from the viewpoint of improving the storage stability of the emulsion particles, and from the viewpoint of improving weather resistance and water resistance. It is preferably 250 nm or less, more preferably 200 nm or less.

In the present specification, the average particle size of the emulsion particles is measured using a particle size distribution measuring device [Particle Sizing Systems, trade name: NICOMP Model 380] by a dynamic light scattering method. It means the volume average particle size obtained.

By further incorporating a cross-linking agent in the resin emulsion of the present invention, cross-linking property can be imparted. The cross-linking agent may be one that starts the cross-linking reaction at room temperature, or may be one that starts the cross-linking reaction by heat. By including a cross-linking 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 cross-linking agents may be used alone or in combination of two or more. Among these cross-linking 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 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), and 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) sulfide, bis (2-oxa Zolinyl norbornan) sulfides, oxazoline ring-containing polymers and the like can be mentioned, but the present invention is not limited to these examples. These oxazoline group-containing compounds may be used alone or in combination of two or more. Among the oxazoline group-containing compounds, a water-soluble oxazoline group-containing compound is preferable, and a water-soluble oxazoline ring-containing polymer is more preferable, from the viewpoint of improving reactivity.

The oxazoline ring-containing polymer is easily prepared by containing addition-polymerizable oxazoline as an essential component and, if necessary, polymerizing a monomer component containing a monomer copolymerizable with addition-polymerizable oxazoline. Can be done.

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, and the like. Examples thereof include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline and 2-isopropenyl-5-ethyl-2-oxazoline. Not limited to just. 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 the monomer copolymerizable with the addition-polymerizable oxazoline include 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, monoesteride of (meth) acrylic acid and polyethylene glycol, 2-aminoethyl (meth) acrylate and its salts, caprolactone modified (meth) acrylic acid, (meth) acrylic acid-2 , 2,6,6-tetramethylpiperidin, (meth) acrylic acid-1,2,2,6,6-pentamethylpiperidin (meth) acrylic acid esters; sodium (meth) acrylic acid, (meth) acrylic (Meta) acrylates such as potassium acetate, ammonium (meth) acrylate; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) ( Meta) Unsaturated amides such as 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; Halogen such as vinyl chloride, vinylidene chloride and vinyl fluoride Included α, β-unsaturated aliphatic hydrocarbon compounds; α, β-unsaturated aromatic hydrocarbon compounds such as styrene, α-methylstyrene, sodium styrene sulfonate, etc., but the present invention is only such an example. Not limited to. The monomers copolymerizable with these addition-polymerizable oxazolines may be used alone or in combination of two or more.

The oxazoline group-containing compound can be easily obtained commercially as, for example, manufactured by Nippon Shokubai Co., Ltd., trade names: Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K-2020, Epocross K-2030, and the like. can do. Among these, from the viewpoint of improving the reactivity, a water-soluble oxazoline group-containing compound such as Nippon Shokubai Co., Ltd., trade name: Epocross WS-500, Epocross WS-700 is preferable.

The isocyanate group-containing compound is a compound containing an isocyanate group capable of reacting with a hydroxyl group of the hydroxyl group-containing monomer used as a monomer component as a functional group.

Examples of the isocyanate group-containing compound include water-dispersed (block) polyisocyanates. The (blocked) polyisocyanate means a polyisocyanate and / or a blocked 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; derivatives (modified products) of polyisocyanates such as trimethylolpropane adduct, burette, and isocyanurate of these diisocyanates. The present invention is not limited to such examples. These polyisocyanates may be used alone or in combination of two or more.

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

The water-dispersed blocked 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, but the present invention is not limited to such examples. These blocking agents may be used alone or in combination of two or more. Among these blocking agents, those that cleave at a temperature of 160 ° C. or lower, preferably 150 ° C. or lower, are desirable. Suitable blocking agents include, for example, butanone oxime, cyclohexanone oxime, 3,5-dimethylpyrazole and the like. Of these, butanone oxime is more preferred.

The water-dispersed block polyisocyanate is, for example, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Takenate WB-720, Takenate WB-730, Takenate WB-920, etc .; manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Bayhijour. It is readily commercially available as BL116, Bayer Jules BL5140, Bayer Jules BL5235, Bayer Jules TPLS2186, Death Module VPLS2310 and the like.

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

Examples of the aminoplast resin include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkylated methylated melamine, fully alkylated butylated melamine, fully alkylated isobutylated melamine, and completely. Alkylated mixed etherified melamine, methylol-based methylated melamine, imino-based mixed etherified melamine, methylol-based mixed etherified melamine, imino-based mixed etherified melamine and other melamine resins; butylated benzoguanamine, methyl / ethyl mixed alkyl Examples thereof include benzoguanamines, methyl / butyl mixed alkylated benzoguanamines, guanamine resins such as butylated glycol uryl, and the like, but the present invention is not limited to these examples. These aminoplast resins may be used alone or in combination of two or more.

The aminoplast resin is, for example, manufactured by Mitsui Cytec Co., Ltd., trade names: Mycoat 506, Mycoat 1128, Cymel 232, Cymel 235, Cymel 254, Cymel 303, Cymel 325, Cymel 370, Cymel 771, Cymel 1170 and the like. It is readily available commercially.

The amount of aminoplast resin is usually 60/40 of the mass ratio of the solid content of the polymer contained in the emulsion particles to the solid content of the aminoplast resin [solid content of the polymer / solid content of the aminoplast resin]. It is preferable to adjust it to be about 99/1.

In addition to the above-mentioned cross-linking agent, the object of the present invention is to provide a cross-linking agent such as a carbodiimide compound; a polyvalent metal compound represented by a zirconium compound, a zinc compound, a titanium compound, an aluminum compound and the like. It can be used within a range that is not hindered.

The resin emulsion of the present invention may contain a pigment, if necessary. Examples of the pigment include organic pigments and inorganic pigments, which 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 iminoisoindrin. Pigments, iminoisoindolinone pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavantron pigments, indantron pigments, anthrapyrimidine pigments, carbazole pigments, monoallylide yellow, diaryride yellow, benzoimidazolone yellow, trill orange , Naftor 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 flower, lithopon, lead white, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, and ferric ferrocyanide (ferrousite). Pigments with flat shapes such as mica, clay, aluminum powder, talc, aluminum silicate, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, etc. , Constituent pigments such as magnesium carbonate, etc., 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 non-volatile 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 weather resistance, the amount is preferably 190 parts by mass or less.

The resin emulsion of the present invention may contain a resin emulsion other than the resin emulsion as long as the object of the present invention is not impaired. In that case, the emulsion contained in the resin emulsion may be contained. The average particle size of the entire particle may be adjusted to be within the above range.

Further, 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, and a plasticizer, as long as the object of the present invention is not impaired. Additives such as stabilizers, dyes and antioxidants may be contained in appropriate amounts.

The resin emulsion of the present invention may be applied by itself in one layer, or may be applied by applying two or more layers. When coating 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. The recoating is performed, for example, by applying the paint for the first layer (for example, the undercoat layer) to the object to be coated which has been subjected to the primer treatment or the sealer treatment and drying it, and then for the second layer (for example, the topcoat layer). Examples thereof include a method of overcoating and drying a paint, but the present invention is not limited to such a method. Examples of the method for 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. Not limited to.

The resin emulsion of the present invention can be suitably used, for example, as a topcoat material (water-based paint) called a top coat, which is applied to the surface of the exterior of a building or a ceramic building material.

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

The topcoat paint of the present invention is, for example, appropriately provided with one or more of the resin composition for paint or the resin emulsion and one or more of a film forming aid, a defoaming agent, a pigment, a thickener, a matting agent and the like. It can be easily prepared by mixing. Examples of the top coat paint include enamel paint and clear paint. The topcoat paint can be suitably used for the top coat of the base material.

The resin composition for paints, resin emulsions and topcoats of the present invention can all be suitably used for on-site painting on, for example, the outer wall of a building, and also for inorganic building materials such as ceramic building materials. It can be suitably used. Examples of ceramic building materials include roof tiles and outer wall materials. Ceramic building materials are made by adding an inorganic filler, fibrous material, etc. to a hydraulic adhesive that is a raw material for an inorganic cured product, molding the obtained mixture, and curing and curing the obtained molded product. can get. Examples of the inorganic building material constituting the exterior of the building include flexible board, calcium silicate board, gypsum slag parlite board, wood piece cement board, precast concrete board, ALC board, gypsum board and the like.

When the resin composition for paint, resin emulsion or topcoat of the present invention is applied to the front surface and the back surface of a building material, the building material may be used as necessary from the viewpoint of efficiently producing a building material having a coating film on both sides. It may be heated. When the resin composition for paint, the resin emulsion or the top coat of the present invention is applied to a building material, for example, a spray, a roller, a brush, a trowel or the like can be used. A topcoat material (water-based paint) may be applied to the surface of the building material in order to impart a desired design.

Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples. In the following examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

Example 1
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 455 parts of deionized water, 40 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with the monomer component, monomer. 20 parts of 25% aqueous solution of anionic emulsifier [manufactured by Nippon Emulsifier Co., Ltd., trade name: Neucol 707SF] having non-reactivity to components, 586 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 200 parts of 2-ethylhexyl acrylate, styrene. A pre-emulsifier for dropping consisting of 100 parts, 10 parts of acrylamide and 4 parts of methacrylic acid is prepared, of which 76 parts, which is 5% of the total amount of all monomer components, is added to the flask, and 70 parts are gently blown with nitrogen gas. The temperature was raised to ° C., 10 parts of a 5% aqueous ammonium persulfate solution was added, and polymerization was started. Then, the rest of the pre-emulsion for dropping and 30 parts of a 5% ammonium persulfate aqueous solution were uniformly dropped into the flask for 240 minutes.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a wire mesh of 300 mesh (JIS mesh, the same applies hereinafter) to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Example 2
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 228 parts of deionized water, 30 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, methyl methacrylate 293. A pre-emulsifier for dropping was prepared consisting of 50 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 50 parts of styrene, 5 parts of acrylamide and 2 parts of methacrylic acid, of which 76 parts accounted for 5% of the total amount of all monomer components. Was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Then, 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 dropping, the contents of the flask were maintained at 70 ° C. for 50 minutes, 6 parts of 25% aqueous ammonia was added into the flask, the contents of the flask were maintained at 70 ° C. for 10 minutes, and subsequently deionized into the dropping funnel. 228 parts of water, 10 parts of 25% aqueous solution of anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, non-reactivity with monomer components 20 parts of 25% aqueous solution of anionic emulsifier [manufactured by Nippon Emulsifier Co., Ltd., trade name: Neucol 707SF], 295 parts of methyl methacrylate, 50 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 45 parts of styrene, 5 parts of acrylamide. And 4-methacryloxy-1,2,2,6,6-pentamethylpiperidin 5 parts of a pre-emulsifier for second-stage dropping and 15 parts of a 5% ammonium persulfate aqueous solution were uniformly added dropwise to the flask over 120 minutes.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a 300 mesh wire mesh to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Example 3
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 228 parts of deionized water, 30 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, methyl methacrylate 293. A pre-emulsifier for dropping was prepared consisting of 50 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 50 parts of styrene, 5 parts of acrylamide and 2 parts of methacrylic acid, of which 76 parts accounted for 5% of the total amount of all monomer components. Was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Then, 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 dropping, the contents of the flask were maintained at 70 ° C. for 50 minutes, 6 parts of 25% aqueous ammonia was added into the flask, the contents of the flask were maintained at 70 ° C. for 10 minutes, and subsequently deionized into the dropping funnel. 228 parts of water, 10 parts of 25% aqueous solution of anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, non-reactivity with monomer components 20 parts of 25% aqueous solution of anionic emulsifier [manufactured by Nippon Emulsifier Co., Ltd., trade name: Neucol 707SF], 230 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 5 parts of acrylamide and 4-methacryloyl. A pre-emulsifier for second-stage dropping consisting of 15 parts of oxy-1,2,2,6,6-pentamethylpiperidin and 15 parts of a 5% aqueous ammonium persulfate solution were uniformly added dropwise to the flask over 120 minutes.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a 300 mesh wire mesh to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Example 4
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 228 parts of deionized water, 30 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, methyl methacrylate 293. A pre-emulsifier for dropping was prepared consisting of 50 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 50 parts of styrene, 5 parts of acrylamide and 2 parts of methacrylic acid, of which 76 parts accounted for 5% of the total amount of all monomer components. Was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Then, 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 dropping, the contents of the flask were maintained at 70 ° C. for 50 minutes, 6 parts of 25% aqueous ammonia was added into the flask, the contents of the flask were maintained at 70 ° C. for 10 minutes, and subsequently deionized into the dropping funnel. 228 parts of water, 10 parts of 25% aqueous solution of anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, non-reactivity with monomer components 10 parts of 25% aqueous solution of anionic emulsifier [manufactured by Nippon Emulsifier Co., Ltd., trade name: Neucol 707SF], 328 parts of methyl methacrylate, 50 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl acrylate, 5 parts of acrylamide, 2 parts of methacrylic acid. 1 part and 15 parts of 2- [2'-hydroxy-5'-methacryloyloxyethylphenyl] -2H-benzotriazole for second stage dropping and 15 parts of 5% ammonium persulfate aqueous solution uniformly in the flask for 120 minutes. Dropped in.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a 300 mesh wire mesh to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Comparative Example 1
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 455 parts of deionized water, 60 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with monomer components, methyl methacrylate 586. A pre-emulsifier for dropping was prepared consisting of 100 parts of cyclohexyl methacrylate, 200 parts of 2-ethylhexyl acrylate, 100 parts of styrene, 10 parts of acrylamide and 4 parts of methacrylic acid, of which 76 parts accounted for 5% of the total amount of all monomer components. Was added into the flask, the temperature was raised to 70 ° C. while gently blowing nitrogen gas, and 10 parts of a 5% ammonium persulfate aqueous solution was added to initiate polymerization. Then, the rest of the pre-emulsion for dropping and 30 parts of a 5% ammonium persulfate aqueous solution were uniformly dropped into the flask for 240 minutes.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a wire mesh of 300 mesh (JIS mesh, the same applies hereinafter) to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Comparative Example 2
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 455 parts of deionized water, 40 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with the monomer component, monomer. 20 parts of 25% aqueous solution of nonionic emulsifier [manufactured by ADEKA Co., Ltd., trade name: Adeca Asolute ER-20] having reactivity with components, 586 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 200 parts of 2-ethylhexyl acrylate, 100 parts of styrene. Prepare a pre-emulsifier for dropping consisting of 10 parts of acrylamide, 4 parts of acrylamide and 4 parts of methacrylic acid, add 76 parts, which is 5% of the total amount of all monomer components, into the flask, and gently blow nitrogen gas at 70 ° C. The temperature was raised to 10 parts, and 10 parts of a 5% aqueous ammonium persulfate solution was added to initiate polymerization. Then, the rest of the pre-emulsion for dropping and 30 parts of a 5% ammonium persulfate aqueous solution were uniformly dropped into the flask for 240 minutes.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a wire mesh of 300 mesh (JIS mesh, the same applies hereinafter) to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Comparative Example 3
479 parts of deionized water was placed in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser. In the dropping funnel, 455 parts of deionized water, 40 parts of a 25% aqueous solution of an anionic emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10] having reactivity with the monomer component, monomer. 20 parts of 25% aqueous solution of nonionic emulsifier [manufactured by Sanyo Kasei Kogyo Co., Ltd., trade name: Nonipol 200], 586 parts of methyl methacrylate, 100 parts of cyclohexyl methacrylate, 200 parts of 2-ethylhexyl acrylate, styrene A pre-emulsifier for dropping consisting of 100 parts, 10 parts of acrylamide and 4 parts of methacrylic acid is prepared, of which 76 parts, which is 5% of the total amount of all monomer components, is added to the flask, and 70 parts are gently blown with nitrogen gas. The temperature was raised to ° C., 10 parts of a 5% aqueous ammonium persulfate solution was added, and polymerization was started. Then, the rest of the pre-emulsion for dropping and 30 parts of a 5% ammonium persulfate aqueous solution were uniformly dropped into the flask for 240 minutes.

After completion of the dropping, the contents of the flask were maintained at 70 ° C. for 60 minutes, the pH was adjusted to 8 by adding 25% aqueous ammonia, and the polymerization was completed. The obtained reaction solution was cooled to room temperature and then filtered through a wire mesh of 300 mesh (JIS mesh, the same applies hereinafter) to prepare a resin emulsion. The non-volatile content in this resin emulsion was 50%.

Next, the following physical properties were investigated using the resin emulsions obtained in each Example or each Comparative Example. The results are shown in Table 1. It should be noted that a product having at least one evaluation of x in terms of physical properties is determined to be unacceptable.

(1) Weather resistance 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Co., Ltd.] as a film-forming aid in 100 parts of the resin emulsion obtained in each Example or Comparative Example. , Product number: CS-12] 15 parts was added, and after stirring with a homodisper at a rotation speed of 1500 min ^-1 for 10 minutes, 30 parts of white paste and an antifoaming agent [manufactured by San Nopco Ltd., trade name: Nopco 8034L] Add 0.5 part and thicken agent so that the viscosity when measured at 25 ° C using a Claves unit viscosity meter (manufactured by Brookfield, product number: KU-1) is 80 KU [Nippon Catalyst Co., Ltd.] , Trade name: Acryset WR-503A] was added, and the mixture was stirred in that state for 30 minutes to prepare a sample.

The white paste contains 210 parts of deionized water, 60 parts of dispersant [Kao Corporation, trade name: Demol EP], and dispersant [Daiichi Kogyo Seiyaku Co., Ltd., trade name: Discoat N-14. ] 50 parts, wetting agent [Kao Corporation, trade name: Emargen LS-106] 10 parts, propylene glycol 60 parts, titanium oxide [Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts and glass beads (Diameter: 1 mm) Prepared by dispersing 200 parts with a homodisper at a rotation speed of 3000 min ^-1 for 60 minutes.

Slate plate [manufactured by Japan Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm] and sealer [manufactured by SK KAKEN Co., Ltd., product name: EX sealer] at 150 g / m ² by air spray. It was applied uniformly in an application amount and dried at 23 ° C. for 1 week.

Next, the sample obtained above was applied to a slate plate with a 10 mil applicator, dried at 23 ° C. for 1 week, and then the side surfaces and the back surface of the slate plate to which the sample was applied were sealed with aluminum tape, and the sample was sampled. The 60 ° mirror surface gloss of the coated surface was measured with a gloss meter [Nippon Denshoku Kogyo Co., Ltd., product number: VG2000], and a weather resistance test was conducted for 1000 hours under the following conditions. Measure the gloss of the painted surface of the slate plate, and formula:
[Gloss retention rate (%)]
= [[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]
・ Testing machine: Metal weather [manufactured by Daipla 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 )
・ Wetness: 4 hours in an atmosphere with a temperature of 35 ° C and a relative humidity of 98% ・ Shower: 30 seconds each before and after wetting

〔Evaluation criteria〕
⊚: Gloss retention rate is 85% or more ○: Gloss retention rate is 70% or more and less than 85% Δ: Gloss retention rate is 60% or more and less than 70% ×: Gloss retention rate is less than 60%

(2) Water resistance 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Ltd.] as a film-forming aid in 100 parts of the resin emulsion obtained in each Example or Comparative Example. , Product number: CS-12] After adding 15 parts, add 0.5 part of defoaming agent [manufactured by San Nopco Ltd., trade name: Nopco 8034L], and use a homodisper at a rotation speed of 1500 min ^-1 for 30 minutes. Samples were prepared by stirring.

Next, a black acrylic plate obtained by molding methyl methacrylate by extrusion molding according to JIS K6717 (2006) [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 to a 5 mil applicator and drying it in a hot air dryer at 100 ° C. for 10 minutes.

After curing the test plate obtained above at 23 ° C. for 24 hours, the L value (L ₀ ) of the test plate is measured by a colorimeter [Nippon Denshoku Kogyo Co., Ltd., trade name: spectroscopic colorimeter SE-. 2000], and after immersing this test plate in water heated to 23 ° C for 24 hours, pull it out of the water, wipe off the water with a Kim towel [Nippon Paper Crecia Co., Ltd.], and within 1 minute. The L value (L ₁ ) was measured with the colorimeter.

Next, the change value (ΔL) of the L value is expressed by the equation:
ΔL = (L ₁ )-(L ₀ )
And evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
⊚: ΔL is less than 2.0 ○: ΔL is 2.0 or more and less than 4.0 Δ: ΔL is 4.0 or more and less than 6.0 ×: ΔL is 6.0 or more

(3) Mechanical stability Marlon stability tester [Kumaya Riki Kogyo Co., Ltd., No. 2312-I] was used to measure the coagulation rate of the resin emulsion obtained in each Example or each Comparative Example according to "5.8 Mechanical Stability" described in JIS K6828 (1996), and the following Mechanical stability was evaluated based on the evaluation criteria.

The amount of the resin emulsion used was 50 g, the scale of the table was 10 kg, the disk rotation speed was 1000 times / minute, the rotation time was 5 minutes, and the measurement temperature was 25 ° C.
〔Evaluation criteria〕
⊚: Coagulation rate after the test in the resin solid content is less than 0.05% ○: Coagulation rate after the test in the resin solid content is 0.05% or more and less than 0.1% Δ: Coagulation rate after the test in the resin solid content Is 0.1% or more and less than 0.2% ×: The solidification rate after the test in the resin solid content is 0.2% or more.

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

From the results shown in Table 1, it can be seen that the resin emulsions obtained in each example are all excellent in weather resistance, water resistance and mechanical stability.

The resin composition and resin emulsion for paints of the present invention are suitably used, for example, as a topcoat material (water-based paint) called a top coat to be applied to the surface of the exterior of a building or a ceramic building material. Can be done.

Claims (12)

A resin emulsion for a top coat to be applied to the surface of the exterior of a building or the surface of a building material, which contains emulsion particles composed of a plurality of layers, and the raw materials of the plurality of layers contain a monomer component and an emulsifier. The raw material of the outermost layer of the plurality of layers contains an anionic emulsifier having a reactivity with the monomer component and an anionic emulsifier having a non-reactivity with the monomer component as the emulsifier, and the single amount thereof. Mass ratio of anionic emulsifier having reactivity with body component and anionic emulsifier having non-reactivity with the monomer component (anionic emulsifier having reactivity with monomer component / non-reaction with monomer component) Anionic emulsifier having a property) is 1/1 to 8/1, and as an anionic emulsifier having reactivity with the monomer component, a sulfonate salt of allyloxymethylalkyloxypolyoxyethylene and the monomer component A polyoxyalkylene polycyclic phenyl ether sulfate ammonium salt is used as a non-reactive anionic emulsifier, and the monomer component used as a raw material for the inner layer of the plurality of layers contains a styrene-based monomer. A characteristic resin emulsion for top coats. The outermost layer of the plurality of layers emulsifies and polymerizes the monomer component in the presence of an anionic emulsifier having reactivity with the monomer component and an anionic emulsifier having non-reactivity with the monomer component. The resin emulsion for a top coat according to claim 1, which is formed of a polymer made of a mixture. A resin emulsion for a top coat to be applied to the surface of the exterior of a building or the surface of a building material, which contains emulsion particles, and the raw material of the emulsion particles has a monomer component and reactivity with the monomer component. An anionic emulsifier containing an anionic emulsifier and an anionic emulsifier having no reactivity with the monomer component, and an anionic emulsifier having reactivity with the monomer component and an anionic emulsifier having non-reactivity with the monomer component. The mass ratio with (anionic emulsifier having reactivity with the monomer component / anionic emulsifier having non-reactivity with the monomer component) is 2/1 to 8/1, and the reaction with the monomer component. A sulfonate salt of allyloxymethylalkyloxypolyoxyethylene is used as an anionic emulsifier having a property, and a polyoxyalkylene polycyclic phenyl ether sulfate ammonium salt is used as an anionic emulsifier having no reactivity with the monomer component. A resin emulsion for a top coat, characterized in that the weight component contains an acrylamide compound. The resin emulsion for a top coat according to claim 3, wherein the polymer constituting the emulsion particles has a glass transition temperature of −40 to 50 ° C. The topcoat resin emulsion according to claim 3 or 4, wherein the topcoat resin emulsion contains a pigment, and the amount of the pigment per 100 parts by mass of the non-volatile content of the topcoat resin emulsion is 50 to 190 parts by mass. .. The total amount of the anionic emulsifier having reactivity with the monomer component and the anionic emulsifier having no reactivity with the monomer component per 100 parts by mass of the monomer component is 0.5 to 10 parts by mass. The resin emulsion for a top coat according to any one of claims 1 to 5 . The emulsion particles have an inner layer and an outer layer, and the mass ratio of the polymer constituting the inner layer to the polymer constituting the outer layer (polymer constituting the inner layer / polymer constituting the outer layer) is 75/25 or less. The resin emulsion for a top coat according to any one of claims 1 to 6 . A resin composition for a top coat to be applied to the surface of the exterior of a building or the surface of a building material, which contains a resin emulsion containing emulsion particles composed of a plurality of layers, and the raw material of the plurality of layers is a monomer. An anionic emulsifier containing a component and an emulsifier, and the raw material of the outermost layer of the plurality of layers having reactivity with the monomer component as the emulsifier and an anionic emulsifier having non-reactivity with the monomer component. The mass ratio of the anionic emulsifier contained and reactive to the monomer component to the anionic emulsifier having no reactivity to the monomer component (anionic emulsifier having reactivity to the monomer component / simple). The anionic emulsifier having non-reactivity to the weight component) is 1/1 to 8/1, and the sulfonate salt of allyloxymethylalkyloxypolyoxyethylene and the sulfonate salt of allyloxymethylalkyloxypolyoxyethylene as the anionic emulsifier having reactivity to the monomer component. A polyoxyalkylene polycyclic phenyl ether sulfate ammonium salt is used as an anionic emulsifier having no reactivity with the monomer component, and the monomer component used as a raw material for the inner layer of the plurality of layers contains an acrylamide compound. A resin composition for a top coat, which is characterized by an emulsifier. The resin composition for a top coat according to claim 8 , wherein the monomer component used as a raw material for the inner layer of the plurality of layers further contains a styrene-based monomer. The total amount of the anionic emulsifier having reactivity with the monomer component and the anionic emulsifier having non-reactivity with the monomer component per 100 parts by mass of the monomer component is 0.5 to 10 parts by mass. The resin composition for a top coat according to claim 8 or 9 . The outermost layer of the plurality of layers is emulsion polymerization of the monomer component in the presence of an anionic emulsifier having reactivity with the monomer component and an anionic emulsifier having non-reactivity with the monomer component. The resin composition for a top coat according to any one of claims 8 to 10 , which is formed of a polymer made of a mixture. The emulsion particles have an inner layer and an outer layer, and the mass ratio of the polymer constituting the inner layer to the polymer constituting the outer layer (polymer constituting the inner layer / polymer constituting the outer layer) is 75/25 or less. The resin composition for a top coat according to any one of claims 8 to 11 .