JP7454993B2 - Water-based resin composition - Google Patents

Description

The present invention relates to an aqueous resin composition. More specifically, the present invention provides an aqueous resin composition that can be suitably used as an olefin resin base material used in, for example, automobile parts, household appliances, miscellaneous goods, etc., and a method for producing the same. The present invention relates to an aqueous primer containing an aqueous resin composition.

In the present invention, the aqueous primer means a water-based undercoat paint, and the aqueous primer of the present invention can be applied to various base materials, but is useful as a primer for olefin resin base materials.

Polyolefins, such as polyethylene and polypropylene, have excellent chemical stability and moldability, and are easily recycled, so they are widely used in applications such as automobile parts, household appliances, and miscellaneous goods. A primer is generally applied to the surface of the olefin resin base material used for these purposes in order to improve adhesion with the top coat applied to the surface.

An aqueous dispersion of composite resin particles having a core/shell structure is used as an aqueous resin composition that can be used in a primer because of its excellent adhesion to olefin resin base materials, stain resistance, and water resistance. The shell of the composite resin particle contains an olefin resin as a main component, the core contains a polymer obtained by polymerizing a radically polymerizable monomer other than olefin as a main component, and the weight ratio of the core to the shell is 95:5. A polyolefin composite resin aqueous dispersion with a ratio of 5:95 to 5:95 has been proposed (see, for example, Patent Document 1).

However, in recent years, primers that not only have high peel strength against olefin resin base materials but also form a coating film with excellent water resistance and adhesion, and water-based resin compositions that can be suitably used in the primers have been developed. development is desired.

Japanese Patent Application Publication No. 2011-46777

The present invention has been made in view of the above-mentioned prior art, and provides a primer that forms a coating film with high peel strength and excellent water resistance and adhesion, and an aqueous resin composition that can be suitably used in the primer. The task is to do so.

The present invention
(1) An aqueous resin composition containing (meth)acrylic resin particles and olefin resin particles, wherein the (meth)acrylic resin constituting the (meth)acrylic resin particles is a nitrogen atom-containing ethylenic monomer. An aqueous resin composition obtained by polymerizing a monomer component containing a functional monomer at a content of 0.1 to 10% by mass, and characterized in that the (meth)acrylic resin has a glass transition temperature of 0 to 60°C. thing,
(2) A method for producing an aqueous resin composition containing (meth)acrylic resin particles and carboxyl group-containing olefin resin particles, the method comprising 0.1 to 10% by mass of a nitrogen atom-containing ethylenic monofunctional monomer. An aqueous dispersion of (meth)acrylic resin particles having a glass transition temperature of 0 to 60°C and aqueous dispersion of (meth)acrylic resin particles obtained by polymerizing monomer components contained at and (3) a water-based primer containing the aqueous resin composition described in (1) above.

According to the present invention, there are provided a primer that forms a coating film with high peel strength and excellent water-resistant adhesion, and an aqueous resin composition that can be suitably used in the primer.

As described above, the aqueous resin composition of the present invention is an aqueous resin composition containing (meth)acrylic resin particles and olefin resin particles, and (meth)constitutes the (meth)acrylic resin particles. The acrylic resin is obtained by polymerizing a monomer component containing a nitrogen atom-containing ethylenic monofunctional monomer at a content of 0.1 to 10% by mass, and the (meth)acrylic resin has a glass transition temperature of 0 to 60°C. It is characterized by Since the aqueous resin composition of the present invention and the aqueous primer containing the aqueous resin composition have the above-mentioned constituent requirements, they form a coating film with high peel strength and excellent water-resistant adhesion.

In addition, in the present invention, "(meth)acrylic" means "acrylic" or "methacrylic". "(Meth)acrylate" means "acrylate" or "methacrylate". Moreover, "(meth)acryloyl" means "acryloyl" or "methacryloyl".

The aqueous resin composition of the present invention is, for example, the glass transition temperature of a (meth)acrylic resin obtained by polymerizing a monomer component containing a nitrogen atom-containing ethylenic monofunctional monomer at a content of 0.1 to 10% by mass. It can be prepared by mixing an aqueous dispersion of (meth)acrylic resin particles having a temperature of 0 to 60° C. and an aqueous dispersion of carboxyl group-containing olefin resin particles.

1. (Meth)acrylic resin particles The (meth)acrylic resin particles are prepared, for example, by emulsion polymerization of a monomer component containing a nitrogen atom-containing ethylenic monofunctional monomer at a content of 0.1 to 10% by mass. be able to.

Examples of nitrogen atom-containing ethylenic monofunctional monomers include acrylamide compounds, piperidyl (meth)acrylate compounds, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, ethylene oxide addition (meth)acrylate of morpholine, N- Vinylpyrrolidone, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylmethylcarbamate, N,N-methylvinylacetamide, (meth)acryloyloxyethyltrimethyl Examples include ammonium chloride, 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, but the present invention is not limited to these examples. These nitrogen atom-containing ethylenic monofunctional monomers may be used alone, or two or more types may be used in combination.

Examples of the acrylamide compound include (meth)acrylonitrile; (meth)acrylamide, N-monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, Nn-propyl ( meth)acrylamide, N-isopropyl(meth)acrylamide, methylenebis(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl Examples include acrylamide and diacetone acrylamide, but the present invention is not limited to these examples. These acrylamide compounds may be used alone or in combination of two or more.

Examples of the piperidyl (meth)acrylate compound include 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate, (meth)acryloyl-1-methoxy-2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate, cyano- 4-(meth)acryloyloxy-2,2,6,6-tetramethyl-4-piperidyl(meth)acrylate, (meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethyl -1-piperidyl (meth)acrylate, crotonoylamino-2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate, (meth)acryloylamino-1,2,2,6,6-pentamethyl- 4-piperidyl (meth)acrylate, cyano-4-(meth)acryloylamino-2,2,6,6-tetramethyl-4-piperidyl (meth)acrylate, crotonoyloxy-2,2,6,6-tetra Methyl-4-piperidyl (meth)acrylate, (meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethyl-1-piperidyl (meth)acrylate, Crotonoyl-4- Examples include crotonoyloxy-2,2,6,6-tetramethyl-1-piperidyl (meth)acrylate, but the present invention is not limited to such examples. These piperidyl (meth)acrylate compounds may be used alone, or two or more types may be used in combination.

Among the nitrogen atom-containing ethylenic monofunctional monomers, (meth)acrylonitrile and (meth)acrylamide are preferred, and (meth)acrylonitrile is more preferred, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. . Among the nitrogen atom-containing ethylenic monofunctional monomers, piperidyl (meth)acrylate compounds are preferred from the viewpoint of imparting weather resistance, and provide coating films with weather resistance, high peel strength, and excellent water-resistant adhesion. From the viewpoint of forming , 2,6,6-pentamethyl-4-piperidyl (meth)acrylate is more preferred.

The content of the nitrogen atom-containing ethylenic monofunctional monomer in the monomer component is 0.1 to 10% by mass, preferably 0.3 to 5% by mass, from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. % by mass, more preferably 0.5 to 3% by mass. In addition, the content of the piperidyl (meth)acrylate compound in the monomer component is preferably 0 to 5% by mass, more preferably 0 to 5% by mass, from the viewpoint of imparting weather resistance, having high peel strength, and forming a coating film with excellent water-resistant adhesion. Preferably it is 0 to 3% by mass.

Representative examples of monofunctional monomers other than nitrogen atom-containing ethylenic monofunctional monomers include ethylenically monofunctional radically polymerizable monomers other than nitrogen atom-containing ethylenic monofunctional monomers. Examples of ethylenic monofunctional radically polymerizable monomers other than nitrogen atom-containing ethylenic monofunctional monomers include alkyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, carboxyl group-containing ethylenic monofunctional monomers, and styrene monofunctional monomers. , silane group-containing ethylenic monofunctional monomer, aralkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, oxo group-containing ethylenic monofunctional monomer, fluorine atom-containing ethylenic monofunctional monomer, epoxy group-containing ethylenic monofunctional monomer, Examples include carbonyl group-containing ethylenic monofunctional monomers and aziridinyl group-containing ethylenic monofunctional monomers, but the present invention is not limited to these examples. These ethylenic monofunctional radically polymerizable monomers may be used alone, or two or more types may be used in combination.

Among monofunctional monomers other than nitrogen atom-containing ethylenic monofunctional monomers, alkyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, and carboxyl Group-containing ethylenic monofunctional monomers and styrenic monofunctional monomers are preferred. In addition, among monofunctional monomers other than nitrogen atom-containing ethylenic monofunctional monomers used as monomer components, (meth)acrylic monomers are preferred from the viewpoint of forming coating films with high peel strength and excellent water-resistant adhesion. preferable. A (meth)acrylic monomer is a monomer having a (meth)acryloyl group.

Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, tridecyl (meth)acrylate, n-lauryl (meth)acrylate, dodecyl (meth)acrylate Acrylate, stearyl (meth)acrylate, 2-(acetoacetoxy)ethyl (meth)acrylate, 2-ethylhexylcarbitol (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-methylcyclohexylmethyl ( Examples thereof include meth)acrylate, tert-butylcyclohexyl(meth)acrylate, and cyclododecyl(meth)acrylate, but the present invention is not limited to these examples. These alkyl (meth)acrylates may be used alone or in combination of two or more.

Among the alkyl (meth)acrylates, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion, alkyl (meth)acrylates in which the alkyl group has 1 to 18 carbon atoms are preferred; Alkyl (meth)acrylates having 1 to 12 carbon atoms are more preferred, alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms are even more preferred, and alkyl (meth)acrylates having an alkyl group having 2 to 8 carbon atoms. are more preferred, and alkyl (meth)acrylates in which the alkyl group has 4 to 8 carbon atoms are even more preferred. In addition, among alkyl (meth)acrylates in which the alkyl group has 1 to 8 carbon atoms, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion, Alkyl acrylates are preferred.

The content of alkyl (meth)acrylate in the monomer component is preferably 10 to 95% by mass, more preferably 70 to 90% by mass from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. .

The content of methyl (meth)acrylate in the monomer component is preferably 0 to 80% by mass, more preferably 20 to 80% by mass, and more preferably from 0 to 80% by mass, from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. Preferably it is 50 to 75% by mass.

The content of alkyl (meth)acrylate whose alkyl group has 2 to 8 carbon atoms in the monomer component is preferably 5 to 45% by mass, from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. More preferably, it is 10 to 40% by mass. Among the alkyl (meth)acrylates in which the alkyl group has 2 to 8 carbon atoms, alkyl (meth)acrylates in which the alkyl group has 4 to 8 carbon atoms ( Meth)acrylates are preferred.

Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxy Examples include butyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate, but the present invention is not limited to these examples. These hydroxyl group-containing (meth)acrylates may be used alone, or two or more types may be used in combination. Among these hydroxyl group-containing (meth)acrylates, hydroxyalkyl (meth)acrylates in which the hydroxyalkyl group has 1 to 18 carbon atoms are preferred from the viewpoint of forming a coating film with high peel strength and excellent water resistance. , hydroxyalkyl (meth)acrylates in which the hydroxyalkyl group has 1 to 12 carbon atoms are more preferred, hydroxyalkyl (meth)acrylates in which the hydroxyalkyl group has 2 to 8 carbon atoms are more preferred, and hydroxyalkyl (meth)acrylates in which the hydroxyalkyl group has 1 to 8 carbon atoms are more preferred; Even more preferred are 2-4 hydroxyalkyl (meth)acrylates.

The content of the hydroxyl group-containing (meth)acrylate in the monomer component is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. be.

Examples of carboxyl group-containing ethylenic monofunctional monomers 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 itacon. Examples include carboxyl group-containing aliphatic monomers such as acid monomethyl ester, itaconate monobutyl ester, vinylbenzoic acid, oxalic acid monohydroxyethyl (meth)acrylate, and carboxyl group-terminated caprolactone-modified (meth)acrylate. is not limited to these examples. These carboxyl group-containing ethylenic monofunctional monomers may be used alone, or two or more types may be used in combination. Among these carboxyl group-containing ethylenic monofunctional monomers, acrylic acid, methacrylic acid, and itaconic acid are preferred from the viewpoint of forming a coating film with high peel strength and excellent water resistance adhesion, and acrylic acid and methacrylic acid are preferred. More preferred.

The content of the carboxyl group-containing ethylenic monofunctional monomer in the monomer component is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. %.

Examples of styrenic monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, o-tert-butoxystyrene, m-tert-butoxystyrene, p -tert-butoxystyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, vinyltoluene, etc., but the present invention is not limited to these examples. These styrene monomers may be used alone or in combination of two or more. Styrenic monomers have functional groups such as alkyl groups such as methyl groups and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms in the benzene ring. good. Among the styrene monomers, styrene is preferred from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion.

The content of the styrene monomer in the monomer component is preferably 0 to 80% by mass, more preferably 0 to 60% by mass, and even more preferably It is 0 to 30% by mass.

Examples of silane group-containing ethylenic monofunctional monomers include vinyl silane monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(methoxyethoxy)silane, and vinyltrichlorosilane; styrylsilane monomers such as p-styryltrimethoxysilane; (meth)acryloyloxypropylmethyldimethoxysilane, (meth)acryloyloxypropyltrimethoxysilane, (meth)acryloyloxypropylmethyldiethoxysilane, (meth)acryloyloxypropylmethyltriethoxysilane, (meth)acryloyloxystyrylethyltri Examples include (meth)acryloyloxysilane monomers such as methoxysilane, (meth)acryloyloxypropylhydroxysilane, and (meth)acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to these examples. . These silane group-containing ethylenic monofunctional monomers may be used alone, or two or more types may be used in combination. Among these silane group-containing ethylenic monofunctional monomers, the number of carbon atoms in the oxyalkyl group is 1 to 3, and the number of carbon atoms in the alkoxy group is from 1 to 3, from the viewpoint of forming a coating film with high peel strength and excellent water resistance. (Meth)acryloyloxyalkyltrialkoxysilanes having a number of 1 to 3 are preferred.

The content of the silane group-containing ethylenic monofunctional monomer in the monomer component is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. %.

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

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

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

Examples of fluorine atom-containing ethylenic monofunctional monomers include trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, and perfluoroisononyl. Examples include fluorine atom-containing alkyl (meth)acrylates having a fluorine atom in the ester moiety, such as ethyl (meth)acrylate and perfluorooctylethyl (meth)acrylate, but the present invention is not limited to such examples. do not have. These fluorine atom-containing ethylenic monofunctional monomers may be used alone or in combination of two or more.

Examples of epoxy group-containing ethylenic monofunctional monomers include glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, glycidyl allyl ether, oxocyclohexylmethyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Examples include epoxy group-containing (meth)acrylates such as acrylates, but the present invention is not limited to such examples. These epoxy group-containing ethylenic monofunctional monomers may be used alone, or two or more types may be used in combination.

Examples of carbonyl group-containing ethylenic monofunctional monomers include acrolein, homylstyrene, vinyl ethyl ketone, (meth)acryloxyalkylpropenal, acetonyl (meth)acrylate, diacetone (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. ) acrylate acetylacetate, butanediol-1,4-acrylate acetylacetate, etc., but the present invention is not limited to these examples. These carbonyl group-containing ethylenic monofunctional monomers may be used alone or in combination of two or more.

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

In addition to the monofunctional monomers mentioned above, polyfunctional monomers can be used as monomer components. As the monomer component, usually only a monofunctional monomer is used, or a combination of a monofunctional monomer and a polyfunctional monomer is used.

Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, tripropylene Di(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms, such as glycol di(meth)acrylate; polyethylene glycol di(meth)acrylate with an added mole of ethylene oxide of 2 to 50, and a polyethylene glycol di(meth)acrylate with an added mole of propylene oxide of 2 ~50 polypropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and other alkyl di(meth)acrylates with 2 to 50 moles of alkylene oxide groups having 2 to 4 carbon atoms; ethoxylated glycerin triacrylate; (meth)acrylate, propylene oxide modified glycerol tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, trimethylolpropane triethoxy Tri(meth)acrylates of polyhydric alcohols having 1 to 10 carbon atoms such as tri(meth)acrylate; pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, etc. Tetra(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms; Penta(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol penta(meth)acrylate, dipentaerythritol (monohydroxy) penta(meth)acrylate meth)acrylate; Hexa(meth)acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa(meth)acrylate; Bisphenol A di(meth)acrylate, 2-(2'-vinyloxyethoxyethyl)(meth)acrylate; ) acrylates, epoxy group-containing (meth)acrylates such as epoxy (meth)acrylates; polyfunctional (meth)acrylates such as urethane (meth)acrylates, but are not limited to these examples. These polyfunctional monomers may be used alone, or two or more types may be used in combination.

In the present invention, from the viewpoint of imparting ultraviolet absorbency to the (meth)acrylic resin particles, it is preferable to include an ultraviolet absorbing monomer in the monomer component within a range that does not impede the object of the present invention.

Examples of the ultraviolet absorbing monomer include benzotriazole ultraviolet absorbing monomers and benzophenone 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 benzotriazole-based ultraviolet absorbing monomers include 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth) ) acryloyloxyethylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxymethylphenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy -5'-(meth)acryloylaminomethyl-5'-tert-octylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxypropylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(meth)acryloyloxyhexylphenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl ]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(meth)acryloyloxyethylphenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy -5'-tert-butyl-3'-(meth)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)acryloyloxyethyl phenyl]-5-tert-butyl-2H-benzotriazole, 2-[2'-hydroxy-5'-(β-(meth)acryloyloxyethoxy)-3'-tert-butylphenyl]-4-tert-butyl Examples include -2H-benzotriazole, but the present invention is not limited to such examples. These benzotriazole-based ultraviolet absorbing monomers may be used alone, or two or more types may be used in combination.

Examples of benzophenone-based ultraviolet absorbing monomers 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 -(meth)acryloyloxy]butoxybenzophenone and the like, but the present invention is not limited to such examples. These benzophenone ultraviolet absorbing monomers may be used alone or in combination of two or more.

As a method for emulsion polymerization of monomer components, for example, an aqueous medium containing a water-soluble organic solvent such as a lower alcohol such as methanol and water, an emulsifier is dissolved in a medium such as water, and the monomer components and polymerization are initiated under stirring. Examples include a method in which a monomer component is dropped into water or an aqueous medium that has been emulsified in advance using an emulsifier and water, but the present invention is not limited to such methods. . Note that the amount of the medium may be appropriately set in consideration of the amount of nonvolatile components contained in the resulting resin emulsion. The medium may be charged in advance to the reaction vessel or may be used as a pre-emulsion. Further, the medium may be used, if necessary, when monomer components are emulsion polymerized to produce a resin emulsion.

When emulsion polymerizing monomer components, emulsion polymerization may be performed after mixing the monomer components, emulsifier, and medium, or emulsion polymerization may be performed after stirring the monomer components, emulsifier, and medium to prepare a pre-emulsion. Alternatively, emulsion polymerization may be performed by mixing at least one of the monomer components, the emulsifier, and the medium with the remaining preemulsion. The monomer component, emulsifier, and medium may be added all at once, added in portions, or added dropwise continuously.

When forming an outer layer on (meth)acrylic resin particles contained in a resin emulsion obtained by emulsion polymerization of monomer components, emulsion polymerization of the monomer components in the resin emulsion in the same manner as described above is performed. By doing so, an outer layer can be formed on the (meth)acrylic resin particles. In addition, when further forming an outer layer on the (meth)acrylic resin particles on which the outer layer has been formed, the (meth)acrylic An outer layer can further be formed on the resin particles. As described above, a resin emulsion containing (meth)acrylic resin particles having a multilayer structure can be prepared by the multistage emulsion polymerization method.

Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, etc. These emulsifiers may be used alone, or two or more types may be used in combination.

Examples of anionic emulsifiers include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, and sodium alkyl diphenyl ether disulfonate; ammonium dodecylbenzene sulfonate, sodium dodecyl naphthalene sulfonate, etc. alkylaryl sulfonate salt; polyoxyethylene alkyl sulfonate salt; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkylaryl sulfate salt; dialkyl sulfosuccinate; aryl sulfonic acid-formalin condensate; ammonium laurylate, sodium stearate, etc. Fatty acid salt; bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate salt, (meth)acrylic acid polyoxyethylene sulfonate salt, (meth)acrylic acid polyoxyethylene phosphonate salt, allyl Allyl group-containing sulfate esters or their salts such as oxymethylalkyloxypolyoxyethylene sulfonate salts; polyoxyethylene alkylphenyl ether sulfate salts, allyloxymethylalkoxyethyl polyoxyethylene sulfate ester salts, polyoxyalkylene alkenyl ethers Examples include ammonium sulfate salts, but the present invention is not limited to such examples.

Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensates of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, ethylene oxide and aliphatic Examples include condensates with amines, allyloxymethylalkoxyethylhydroxypolyoxyethylene, and polyoxyalkylene alkenyl ethers, but the present invention is not limited to these examples.

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

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

Examples of polymer emulsifiers include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth)acrylates such as polyhydroxyethyl acrylate; Examples include copolymers containing one or more of these as a copolymerization component, but the present invention is not limited to such examples.

In addition, from the viewpoint of forming a coating film with high peel strength and excellent water adhesion resistance, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable, and from the viewpoint of environmental protection, a non-nonylphenyl type emulsifier is preferable. preferable.

Examples of the reactive emulsifier include propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, polyoxyethylene alkyl propenyl phenyl ether ammonium sulfate [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, Aqualon BC-10, etc.], allyloxymethylalkyloxypolyoxyethylene sulfonate salts (for example, Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), allyloxymethylnonylphenoxy Ethylhydroxypolyoxyethylene sulfonate salts (for example, manufactured by ADEKA Co., Ltd., trade name: ADEKA Reasorp SE-10, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate salts (for example, manufactured by ADEKA Co., Ltd., product name: ADEKA Reasoap SE-10), Product name: Adekaria Soap SR-10, SR-20, SR-30, etc.], Bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [For example, manufactured by Nippon Nyukazai Co., Ltd., product name: Antox MS -60, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA Co., Ltd., trade name: ADEKA Reasap ER-10, ER-20, ER-30, ER-40, etc.], polyoxyethylene Alkyl propenyl phenyl ether [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20], allyloxymethylnonyl phenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Co., Ltd., trade name: Adecaria] Soap NE-10, NE-20, NE-30, etc.], but the present invention is not limited to these examples. These reactive emulsifiers may be used alone or in combination of two or more.

The amount of emulsifier per 100 parts by mass of monomer components is preferably 0.01 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, from the viewpoint of improving polymerization stability. From the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 12 parts by mass or less. In the present invention, the reactive emulsifier has reactivity but is not included in the monomer components.

It is preferable to use a polymerization initiator when polymerizing the monomer components. Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), and 2,2-azobis( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; Examples 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 polymerization initiator per 100 parts by mass of monomer components is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass, from the viewpoint of increasing the polymerization rate and reducing the residual amount of unreacted monomer components. Above, more preferably 0.1 part by mass or more, and from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion, preferably 1 part by mass or less, more preferably 0.8 part by mass or less, More preferably, it is 0.5 part by mass or less.

The method of adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, continuous dropping, and the like. Moreover, from the viewpoint of bringing the timing of completion of the polymerization reaction earlier, a portion of the polymerization initiator may be added before or after the addition of monomer components into the reaction system is completed.

In addition, in order to accelerate the decomposition of the polymerization initiator, an appropriate amount of a decomposing agent for the polymerization initiator, such as a reducing agent such as sodium bisulfite or a transition metal salt such as ferrous sulfate, may be added to the reaction system. Good too.

Furthermore, in order to adjust the weight average molecular weight of the (meth)acrylic resin, a chain transfer agent can be used in the monomer component. When a chain transfer agent is used as a monomer component, it is generally possible to lower the molecular weight of a (meth)acrylic resin compared to when a chain transfer agent is not used as a monomer component. Examples of chain transfer agents include 2-ethylhexyl thioglycolate, tert-dodecylmercaptan, n-octylmercaptan, n-dodecylmercaptan, mercaptoacetic acid, β-mercaptopropionic acid, 2-mercaptoethanol, α-methylstyrene, α -methylstyrene dimer, etc., 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 chain transfer agent per 100 parts by mass of monomer components is preferably 0 to 10 parts by mass from the viewpoint of adjusting the weight average molecular weight of the (meth)acrylic resin.

If necessary, additives such as a pH buffer, a chelating agent, and a film-forming aid may be added to the reaction system when polymerizing the monomer components. The amount of additive cannot be determined unconditionally since it varies depending on the type of additive. Usually, the amount of additive per 100 parts by mass of monomer components is preferably about 0 to 5 parts by mass, more preferably about 0.1 to 3 parts by mass.

The atmosphere during emulsion polymerization of monomer components is not particularly limited, but from the viewpoint of increasing the efficiency of the polymerization reaction, an inert gas such as nitrogen gas is preferable.

The polymerization temperature during emulsion polymerization of monomer components is not particularly limited, but is usually preferably 50 to 100°C, more preferably 60 to 95°C, and still more preferably 70 to 90°C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

The polymerization time for emulsion polymerization of the monomer components is not particularly limited, and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 8 hours.

In addition, when carrying out emulsion polymerization of a monomer component, some or all of the acidic groups which the obtained (meth)acrylic resin has may be neutralized with a neutralizing agent. The neutralizing agent may be used after adding the monomer component in the final stage, for example, it may be used between the first stage polymerization reaction and the second stage polymerization reaction, or it may be used during the initial emulsion polymerization reaction. May be used at the end of the

Examples of neutralizing agents include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide; carbonates of alkali metals and alkaline earth metals such as calcium carbonate; organic amines such as ammonia and monomethylamine; Examples include alkaline substances, but the present invention is not limited to such examples. Among these neutralizing agents, volatile alkaline substances such as ammonia are preferred from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. The neutralizing agent may be used in the form of an aqueous solution.

By emulsion polymerizing the monomer components as described above, a resin emulsion containing (meth)acrylic resin particles is obtained. The (meth)acrylic resin may have a crosslinked structure.

The (meth)acrylic resin particles contained in the resin emulsion may have a single resin layer prepared by one-stage emulsion polymerization, or may have a plurality of resin layers prepared by multi-stage emulsion polymerization. It may be something that you have. (Meth)acrylic resin particles having a single resin layer can be prepared by emulsion polymerization of the monomer components. In addition, (meth)acrylic resin particles having multiple resin layers can be obtained by, for example, emulsion polymerizing the monomer components forming the inner layer using the same polymerization method and polymerization conditions as when emulsion polymerizing the monomer components. It can be prepared by multistage emulsion polymerization in which monomer components forming the outer layer are subjected to emulsion polymerization in the presence of (meth)acrylic resin particles. When forming the outer layer on the (meth)acrylic resin particles, the outer layer is formed after the polymerization reaction rate in producing the (meth)acrylic resin particles constituting the inner layer reaches 90% or more, preferably 95% or more. Emulsion polymerization of monomer components for formation is preferable from the viewpoint of forming a layer-separated structure of an inner layer and an outer layer within the (meth)acrylic resin particles.

The number of resin layers of the (meth)acrylic resin particles is preferably 1 to 5 layers, more preferably 1 to 3 layers, and even more preferably is one layer or two layers, and even more preferably one layer. Note that when the (meth)acrylic resin particles have a plurality of resin layers, the boundaries between each resin layer do not necessarily need to be clear, and adjacent resin layers may be mixed with each other.

The glass transition temperature of the (meth)acrylic resin constituting the (meth)acrylic resin particles is preferably 0 to 60°C from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. is 5 to 45°C, more preferably 10 to 40°C. The glass transition temperature of the (meth)acrylic resin constituting the (meth)acrylic resin particles can be easily adjusted by adjusting the type and amount of the monomer used in the monomer component.

In the present invention, the glass transition temperature (Tg) of the (meth)acrylic resin constituting the (meth)acrylic resin particles is determined by the glass transition temperature (Tg) of the monomer used in the monomer component constituting the (meth)acrylic resin. Using the glass transition temperature of the homopolymer, the formula:
1/Tg=Σ(Wm/Tgm)/100
[In the formula, Wm indicates the content (mass%) of monomer m in the monomer components constituting the (meth)acrylic resin, and Tgm indicates the glass transition temperature (absolute temperature: K) of the homopolymer of monomer m.]
It means the temperature determined based on the Fox equation expressed by

In the present invention, unless otherwise specified, the glass transition temperature of the (meth)acrylic resin constituting the (meth)acrylic resin particles is the glass transition temperature determined based on the Fox equation. means.

Regarding monomers whose glass transition temperature is unknown, such as special monomers and polyfunctional monomers, if the total amount of monomers whose glass transition temperature is unknown in the monomer components is 10% by mass or less, the glass The glass transition temperature can be determined using only monomers with known transition temperatures. If the total amount of monomers whose glass transition temperature is unknown in the monomer components exceeds 10% by mass, the glass transition temperature of the polymer can be determined by differential scanning calorimetry (DSC), differential calorimetry (DTA), or thermal analysis. It is determined by mechanical analysis (TMA), etc.

The glass transition temperature of the entire plurality of resin layers is determined by using the glass transition temperature of the homopolymer of the monomers used in all the monomer components constituting all the resin layers used in the multi-stage emulsion polymerization. It means the glass transition temperature determined based on the formula (FOX).

By the way, the glass transition temperature of a polymer is, for example, 105°C for a homopolymer of methyl methacrylate, -70°C for a homopolymer of 2-ethylhexyl acrylate, 100°C for a homopolymer of styrene, and 95°C for a homopolymer of acrylic acid. 55°C for a homopolymer of hydroxyethyl methacrylate, 96°C for a homopolymer of acrylonitrile, 130°C for a homopolymer of 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine, and a homopolymer of n-butyl acrylate. -56°C for n-butyl methacrylate homopolymer, 20°C for methacrylic acid homopolymer, and 83°C for cyclohexyl methacrylate homopolymer.

The weight average molecular weight of the (meth)acrylic resin is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 400,000 or more, from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. , even more preferably 500,000 or more. The upper limit of the weight average molecular weight of the (meth)acrylic resin is not particularly limited because it is difficult to measure the weight average molecular weight if it has a crosslinked structure, but if it does not have a crosslinked structure, it may cause peeling. From the viewpoint of forming a coating film with high strength and excellent water resistance and adhesion, it is preferably 4 million or less.

In the present invention, the weight average molecular weight of the (meth)acrylic resin is determined by gel permeation chromatography equipped with an RI detector [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL. -L in series, developing solvent: tetrahydrofuran (THF)] and standard polystyrene F-450, A-5000, A- manufactured by Tosoh Corporation. It means the weight average molecular weight (in terms of polystyrene) determined from a calibration curve created using 1000 and A-300.

The resin emulsion obtained as described above can be used as an aqueous dispersion of (meth)acrylic resin particles.

The average particle diameter of the (meth)acrylic resin particles is 100 nm or more, preferably 120 nm or more, more preferably 150 nm or more, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. From the viewpoint of forming a coating film with high water resistance and excellent adhesion, the thickness is 400 nm or less, preferably 360 nm or less.

In the present invention, the average particle diameter of the (meth)acrylic resin particles and the average particle diameter of the carboxyl group-containing olefin resin particles are measured using a multi-analyte nanoparticle diameter measurement system, which is a particle diameter measurement device using a dynamic light scattering method. This is the average particle diameter (hydrodynamic diameter) obtained by using a photon correlation method to obtain the autocorrelation function using [manufactured by Otsuka Electronics Co., Ltd., trade name: nanoSAQLA], and by cumulant analysis.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. The content is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion.

In the present invention, the amount of nonvolatile content in an aqueous dispersion is determined by weighing 1 g of the aqueous dispersion, drying it in a hot air dryer at a temperature of 150°C for 20 minutes, and using the obtained dry residue as the nonvolatile content, and formula:
[Nonvolatile content (mass%) in water dispersion]
= ([mass of dry residue] ÷ [1 g of water dispersion]) x 100
This is the value calculated based on.

The minimum film-forming temperature of the aqueous dispersion of (meth)acrylic resin particles is preferably 60°C or lower, more preferably 50°C or lower, and even more preferably 40°C or lower, from the viewpoint of improving adhesion to the substrate. From the viewpoint of improving water resistance and blocking resistance, the temperature is preferably -5°C or higher, more preferably 5°C or higher, and still more preferably 10°C or higher. The minimum film-forming temperature of the aqueous dispersion of (meth)acrylic resin particles is determined by applying the emulsion to a thickness of 0.2 mm using an applicator on a glass plate placed on a thermal gradient tester. The temperature at which cracks appear after drying.

2. Aqueous dispersion of carboxyl group-containing olefin resin particles In the present invention, carboxyl group-containing olefin resin particles are used as the olefin resin particles. The carboxyl group-containing olefin resin particles are olefin resin particles having a carboxyl group. Note that olefin resins include chlorinated olefin resins and non-chlorinated olefin resins, and both can be used, but non-chlorinated olefin resins are preferred from the viewpoint of environmental conservation. Non-chlorinated olefin resin means an olefin resin that is not chlorinated.

Examples of the olefin resin include polyethylene, polypropylene, and a copolymer of propylene and α-olefin, but the present invention is not limited to these examples. Examples of the α-olefin include ethylene, 1-butene, 1-heptene, 1-octene, and 4-methyl-1-pentene, but the present invention is not limited to these examples. These α-olefins may be used alone or in combination of two or more. Further, the olefin used in the olefin resin may contain, for example, a diene monomer in an appropriate amount within a range that does not impede the object of the present invention.

The carboxyl group-containing olefin resin can be prepared, for example, by acid-modifying the olefin resin. Examples of methods for acid-modifying olefin resins include methods of graft copolymerizing unsaturated carboxylic acids or their acid anhydrides to olefin resins, but the present invention is limited only to such methods. isn't it.

Examples of unsaturated carboxylic acids or acid anhydrides include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, crotonic acid, maleic anhydride, and itaconic anhydride. However, the present invention is not limited to these examples. Among the unsaturated carboxylic acids or their acid anhydrides, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred.

As a method for graft copolymerizing an unsaturated carboxylic acid or its acid anhydride to an olefin resin, for example, the olefin resin is dissolved in an aromatic organic solvent such as toluene at a temperature of 100 to 180°C, and then the obtained A solution polymerization method in which an unsaturated carboxylic acid or its acid anhydride is added to the solution, and a radical generator such as benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide is added and reacted. Examples include a melt polymerization method in which an unsaturated carboxylic acid or its acid anhydride and the radical generator are added to the resulting molten olefin resin to react with the radical generator. However, the present invention is not limited to such examples.

The amount of carboxyl groups in the carboxyl group-containing olefin resin (the content of carboxylic acid bonded to the olefin resin) is preferably 0.1 from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion. ~10% by weight, more preferably 1~5% by weight.

The weight average molecular weight of the carboxyl group-containing olefin resin is preferably 5,000 to 200,000, more preferably 30,000 to 120,000 from the viewpoint of forming a coating film with high peel strength and excellent water resistance and adhesion. The weight average molecular weight of the carboxyl group-containing olefin resin is a polystyrene equivalent molecular weight measured using gel permeation chromatography (GPC).

Carboxyl group-containing olefin resin particles are usually used as an aqueous dispersion. The content of carboxyl group-containing olefin resin particles in an aqueous dispersion cannot be determined unconditionally because it varies depending on the use of the aqueous dispersion. Therefore, the content of the carboxyl group-containing olefin resin particles in the aqueous dispersion is preferably adjusted appropriately depending on the use of the aqueous dispersion, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. % by mass, more preferably 15 to 45% by mass.

The average particle diameter of the carboxyl group-containing olefin resin particles is 50 nm or more, preferably 60 nm or more, more preferably 90 nm or more, from the viewpoint of forming a coating film with high peel strength and excellent water resistance adhesion. From the viewpoint of forming a coating film with high water resistance and excellent adhesion, the thickness is 200 nm or less, preferably 180 nm or less.

An aqueous dispersion of carboxyl group-containing olefin resin particles is easily commercially available, and an example thereof is manufactured by Toyobo Co., Ltd. under the trade name Hardren (registered trademark) NZ-1004 (resin). Solids content: 30% by mass), Hardren (registered trademark) NZ-1015 (resin solids content: 30% by mass), Hardren (registered trademark) NA-6600 (resin solids content: 30% by mass), Nippon Paper Industries ( Co., Ltd., product name: Auroren (registered trademark) AE-202 (resin solids content: 30% by mass), Auroren (registered trademark) AE-301 (resin solids content: 30% by mass), etc. However, the present invention is not limited to such examples. These water dispersions may be used alone or in combination of two or more.

3. Aqueous Resin Composition The aqueous resin composition of the present invention is a (meth)acrylic resin glass obtained by polymerizing a monomer component containing a nitrogen atom-containing ethylenic monofunctional monomer at a content of 0.1 to 10% by mass. Contains (meth)acrylic resin particles and carboxyl group-containing olefin resin particles having a transition temperature of 0 to 60°C. The aqueous resin composition of the present invention is, for example, the glass transition temperature of a (meth)acrylic resin obtained by polymerizing a monomer component containing a nitrogen atom-containing ethylenic monofunctional monomer at a content of 0.1 to 10% by mass. It can be easily prepared by mixing an aqueous dispersion of (meth)acrylic resin particles having a temperature of 0 to 60° C. and an aqueous dispersion of carboxyl group-containing olefin resin particles.

When mixing an aqueous dispersion of (meth)acrylic resin particles and an aqueous dispersion of carboxyl group-containing olefin resin particles, the average particle diameter of the (meth)acrylic resin particles and the average of the carboxyl group-containing olefin resin particles are The ratio to the particle diameter [average particle diameter of (meth)acrylic resin particles/average particle diameter of carboxyl group-containing olefin resin particles] is adjusted to be 2 to 4.

Mixing ratio of the aqueous dispersion of (meth)acrylic resin particles and the aqueous dispersion of carboxyl group-containing olefin resin particles [resin solid content of (meth)acrylic resin particles/resin solids of carboxyl group-containing olefin resin particles (mass ratio)] is not particularly limited, but from the viewpoint of forming a coating film with high peel strength and excellent water-resistant adhesion, it is preferably 10/90 to 90/10, more preferably 20/80 to 80. /20, more preferably 25/75 to 75/25.

By mixing the aqueous dispersion of (meth)acrylic resin particles and the aqueous dispersion of carboxyl group-containing olefin resin particles as described above, the (meth)acrylic resin particles and the carboxyl group-containing olefin resin particles are mixed. An aqueous resin composition containing the following is obtained.

The nonvolatile content in the aqueous resin composition of the present invention is preferably 20% by mass or more, more preferably 25% by mass or more from the viewpoint of improving productivity, and preferably 70% by mass or more from the viewpoint of improving handleability. It is not more than 60% by mass, more preferably not more than 60% by mass. The amount of non-volatile content in the aqueous resin composition is determined by weighing 1 g of the aqueous resin composition, drying it in a hot air dryer at a temperature of 150°C for 20 minutes, and using the resulting residue as the non-volatile content, using the formula:
[Nonvolatile content (mass%) in aqueous resin composition]
= ([mass of residue] ÷ [1 g of aqueous resin composition]) x 100
means the value determined based on

4. Water-Based Primer The water-based primer of the present invention contains the above-mentioned water-based resin composition. In the aqueous primer of the present invention, only the aqueous resin composition may be used, or additives may be used in addition to the aqueous resin composition within a range that does not impede the object of the present invention.

Examples of additives include colorants such as pigments, leveling agents, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust preventives, antibacterial agents, and metal deactivators. agents, wetting agents, antifoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosion agents, pigment dispersants, flow regulators, peroxide decomposers, mold decolorizers, fluorescence enhancers. Whitening agents, organic flame retardants, inorganic flame retardants, drip prevention agents, melt flow modifiers, antistatic agents, algaecides, fungicides, flame retardants, slip agents, metal chelating agents, anti-blocking agents, Heat-resistant stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, anti-aging agents, preservatives, antistatic agents, silane coupling agents, antioxidants, film-forming aids, etc. However, the present invention is not limited to such examples. These additives may be used alone or in combination of two or more. The amount of these additives varies depending on the type of the additive and cannot be determined unconditionally, so it is preferable to appropriately determine the amount depending on the type of the additive.

The aqueous primer of the present invention may be applied alone to a substrate in one layer, or may be applied to a substrate in two or more layers. When coating a base material by overcoating two or more layers, only some of the layers may be formed with the water-based primer, or all the layers may be formed with the water-based primer. Examples of methods for applying the water-based primer to the substrate include methods using a brush, bar coater, applicator, air spray, airless spray, roll coater, flow coater, etc.; however, the present invention is limited to such examples only. It is not limited to.

Since the aqueous primer of the present invention has high peel strength and forms a coating film with excellent water resistance and adhesion, it can be applied to various substrates. Examples of substrates to which the aqueous primer of the present invention can be applied include olefin resin substrates made of polyolefins such as polyethylene and polypropylene, (meth)acrylic resin substrates, polystyrene resin substrates, and polycarbonate substrates. , resin base materials such as vinyl chloride resin base materials, ABS resin base materials, AS resin base materials, polyester base materials, amide resin base materials, cellulose resin base materials, silicone resin base materials; glass base materials, ceramic base materials , inorganic base materials such as calcium silicate boards and cement slate boards; metal base materials such as iron plates, copper plates, aluminum plates, and stainless steel plates; and wood base materials such as particle boards and wooden plywood. is not limited to these examples. The aqueous primer of the present invention has high peel strength even on olefin resin substrates and forms a coating film with excellent water resistance and adhesion, so it is useful as a primer for olefin resin substrates.

The water-based primer of the present invention can therefore be suitably used on olefin-based resin substrates used in, for example, automobile parts, household electrical appliances, and miscellaneous goods.

Next, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1
426.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. In a dropping funnel were placed 448.1 g of deionized water, 234.3 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA Reasap SR-10], 539.0 g of methyl methacrylate, and 394.0 g of 2-ethylhexyl acrylate. 9g, styrene 137.5g, 2-hydroxyethyl methacrylate 16.5g, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [manufactured by ADEKA Co., Ltd., product name: ADEKA STAB LA-82] 11.0g and 1.1 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503]. A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 63.9 g of the pre-emulsion for dropping obtained above and 66 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping was uniformly dropped into the flask over 180 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 60 minutes, and the pH was adjusted to 9 by adding a 10% aqueous sodium bicarbonate solution to complete the polymerization. The obtained reaction solution was cooled to room temperature and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

In each Example and each Comparative Example, the pH is a value measured at 25° C. using a pH meter [manufactured by Horiba, Ltd., product number: F-71].

The content of nonvolatile matter in the aqueous dispersion of (meth)acrylic resin particles obtained above was 49.8% by mass, and the (meth)acrylic content contained in the aqueous dispersion of (meth)acrylic resin particles obtained above was 49.8% by mass. The average particle diameter of the resin particles was 155 nm. The (meth)acrylic resin had a glass transition temperature of 15° C. and a weight average molecular weight of 500,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Example 2
426.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. In a dropping funnel were placed 448.1 g of deionized water, 234.3 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA Reasap SR-10], 623.7 g of methyl methacrylate, and 310 g of 2-ethylhexyl acrylate. 2g, styrene 137.5g, 2-hydroxyethyl methacrylate 16.5g, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [manufactured by ADEKA Co., Ltd., product name: ADEKA STAB LA-82] 11.0g and 1.1 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503]. A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 63.9 g of the pre-emulsion for dropping obtained above and 66 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping was uniformly dropped into the flask over 180 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 60 minutes, and the pH was adjusted to 9 by adding a 10% aqueous sodium bicarbonate solution to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The content of nonvolatile matter in the aqueous dispersion of (meth)acrylic resin particles obtained above was 49.8% by mass, and the (meth)acrylic content contained in the aqueous dispersion of (meth)acrylic resin particles obtained above was 49.8% by mass. The average particle diameter of the resin particles was 150 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 500,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 30% by mass.

Example 3
426.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. In a dropping funnel were placed 448.1 g of deionized water, 234.3 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA Reasap SR-10], 698.5 g of methyl methacrylate, and 235 g of 2-ethylhexyl acrylate. 4g, styrene 137.5g, 2-hydroxyethyl methacrylate 16.5g, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate [manufactured by ADEKA Co., Ltd., product name: ADEKA STAB LA-82] 11.0g and 1.1 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503]. A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 63.9 g of the pre-emulsion for dropping obtained above and 66 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the pre-emulsion for dropping was uniformly dropped into the flask over 180 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The content of nonvolatile matter in the aqueous dispersion of (meth)acrylic resin particles obtained above was 49.8% by mass, and the (meth)acrylic content contained in the aqueous dispersion of (meth)acrylic resin particles obtained above was 49.8% by mass. The average particle diameter of the resin particles was 150 nm. The glass transition temperature of the (meth)acrylic resin was 45°C, and the weight average molecular weight was 500,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Example 4
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA Reasap SR-10], 6.0 g of methyl methacrylate, 84.0 g of 2-ethylhexyl acrylate, From 467.4 g of styrene, 18.0 g of acrylic acid, 12.0 g of 2-hydroxyethyl methacrylate, 12.0 g of acrylonitrile, and 0.6 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 105 nm. The glass transition temperature of the (meth)acrylic resin was 55°C, and the weight average molecular weight was 320,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Example 5
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 359.0 g of methyl methacrylate, 168.4 g of 2-ethylhexyl acrylate, From 30.0 g of styrene, 18.0 g of acrylic acid, 12.0 g of 2-hydroxyethyl methacrylate, 12.0 g of acrylonitrile, and 0.6 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 120 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 300,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Example 6
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 359.0 g of methyl methacrylate, 168.4 g of 2-ethylhexyl acrylate, Dropped with 30.0 g of styrene, 18.0 g of acrylic acid, 12 g of 2-hydroxyethyl methacrylate, 12.0 g of acrylonitrile, and 0.6 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] A pre-emulsion was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80°C for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to terminate the polymerization. The resulting reaction liquid was cooled to room temperature and then filtered through a 300-mesh wire screen to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 120 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 300,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., trade name: Hardren (registered trademark) NA-6600, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of 30% by mass, average particle diameter of particles: 95 nm, and weight average molecular weight of resin: 90,000.

Example 7
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into a dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a non-reactive emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hitenol NF-08], 359.0 g of methyl methacrylate, and 168 g of 2-ethylhexyl acrylate. .4g, styrene 30.0g, acrylic acid 18.0g, 2-hydroxyethyl methacrylate 12.0g, acrylonitrile 12.0g and methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] 0 A pre-emulsion for dropping consisting of .6 g was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 120 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 300,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Example 8
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 359.0 g of methyl methacrylate, 168.4 g of 2-ethylhexyl acrylate, From 30.0 g of styrene, 18.0 g of acrylic acid, 12.0 g of 2-hydroxyethyl methacrylate, 12.0 g of acrylonitrile, and 0.6 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 120 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 300,000.

40 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., trade name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 60 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000.

Example 9
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 359.0 g of methyl methacrylate, 168.4 g of 2-ethylhexyl acrylate, From 30.0 g of styrene, 18.0 g of acrylic acid, 12.0 g of 2-hydroxyethyl methacrylate, 12.0 g of acrylonitrile, and 0.6 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 120 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 300,000.

60 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., trade name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 40 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Comparative example 1
1053.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into a dropping funnel were placed 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA REA SOAP SR-10], 410.8 g of methyl methacrylate, 171.2 g of 2-ethylhexyl acrylate, and A pre-emulsion for dropping consisting of 18.0 g of acrylic acid was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 130 nm. The (meth)acrylic resin had a glass transition temperature of 30° C. and a weight average molecular weight of 220,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Comparative example 2
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 400.8 g of methyl methacrylate, 169.2 g of 2-ethylhexyl acrylate, A pre-emulsion for dropping was prepared consisting of 18.0 g of acrylic acid and 12.0 g of 2-hydroxyethyl methacrylate, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 130 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 280,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Comparative example 3
1027.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA REA SOAP SR-10], 216.0 g of methyl methacrylate, 336.0 g of 2-ethylhexyl acrylate, A pre-emulsion for dropping was prepared consisting of 9.0 g of acrylic acid and 39.0 g of 2-hydroxyethyl methacrylate, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 130 nm. The (meth)acrylic resin had a glass transition temperature of -20°C and a weight average molecular weight of 350,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Comparative example 4
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 469.9 g of methyl methacrylate, 52.1 g of 2-ethylhexyl acrylate, A pre-emulsion for dropping was prepared consisting of 30.0 g of styrene, 9.0 g of acrylic acid, and 39.0 g of 2-hydroxyethyl methacrylate, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The obtained reaction solution was cooled to room temperature and then filtered through a 300 mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 130 nm. The glass transition temperature of the (meth)acrylic resin was 75°C, and the weight average molecular weight was 300,000.

50 parts by mass of the aqueous dispersion of (meth)acrylic resin particles obtained above and the aqueous dispersion of non-chlorine polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid] An aqueous resin composition was obtained by mixing 50 parts by mass of the following ingredients: content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin: 75,000].

Comparative example 5
1027.3 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser tube. Into the dropping funnel were 249.2 g of deionized water, 120 g of a 25% aqueous solution of a reactive emulsifier [manufactured by ADEKA Co., Ltd., trade name: ADEKA RIA SOAP SR-10], 359.0 g of methyl methacrylate, 168.4 g of 2-ethylhexyl acrylate, From 30.0 g of styrene, 18.0 g of acrylic acid, 12.0 g of 2-hydroxyethyl methacrylate, 12.0 g of acrylonitrile, and 0.6 g of methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., product number: KBM-503] A pre-emulsion for dropping was prepared, and the temperature was raised to 80° C. while slowly blowing nitrogen gas. 95.4 g of the pre-emulsion for dropping obtained above and 36 g of a 5% aqueous potassium persulfate solution were added into the flask to initiate polymerization. Thereafter, the remainder of the dropping pre-emulsion was uniformly dropped into the flask over 120 minutes.

After the dropwise addition was completed, the contents of the flask were maintained at 80° C. for 120 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. The resulting reaction solution was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain an aqueous dispersion of (meth)acrylic resin particles.

The nonvolatile content in the aqueous dispersion of (meth)acrylic resin particles obtained above is 30% by mass, and the (meth)acrylic resin contained in the aqueous dispersion of (meth)acrylic resin particles obtained above. The average particle diameter of the particles was 120 nm. The glass transition temperature of the (meth)acrylic resin was 30°C, and the weight average molecular weight was 300,000.

The aqueous dispersion of (meth)acrylic resin particles obtained above was used as an aqueous resin composition.

Comparative example 6
Aqueous dispersion of non-chlorinated polypropylene particles [manufactured by Toyobo Co., Ltd., product name: Hardren (registered trademark) NZ-1004, resin solid content: 30% by mass, average particle diameter of particles: 95 nm, weight average molecular weight of resin :75,000] was used as the aqueous resin composition.

Next, as physical properties of the aqueous resin composition obtained above, peel strength and water-resistant adhesion were evaluated based on the following methods. The results are shown in Table 1.

[Peel strength]
(1) Preparation of primer To 100 g of the aqueous resin composition, 4 g of dipropylene glycol n-butyl ether [manufactured by Dow Chemical Company, trade name: Dowanol (registered trademark) DPnB] as a film-forming agent and a wetting agent [ Nissin Chemical Industry Co., Ltd., trade name: Olfine (registered trademark) EXP. was prepared.

(2) Preparation of coating film for evaluation The primer obtained above was applied onto the surface of a rectangular automotive polypropylene plate (manufactured by Standard Test Piece Co., Ltd.) with a smooth surface and a length of 10 cm and a width of 5 cm. A frame was made of duct tape (manufactured by Nichiban Co., Ltd., trade name: Cloth Adhesive Tape 102N) with a width of 5 mm, and coated with a glass rod so that the dry film thickness was 100 μm. Thereafter, the painted paint was dried in a jet oven at a room temperature of 80° C. at a wind speed of 3 m/sec for 40 minutes to prepare a test plate on which a dried paint film with a film thickness of 100±20 μm was formed.

(3) Measurement of peel strength A gummed tape (manufactured by Nichiban Co., Ltd., trade name: cloth adhesive tape 102N) was pasted on the dry coating surface of the test plate obtained above, and the room temperature was 23°C and the relative humidity was After standing in an atmosphere of 65% air for one day, a 10 mm wide cut was made in the dried coating film from above the gummed tape.

Next, when the gummed tape was pulled from the test plate in a direction of 180 degrees at a pulling speed of 50 mm/min using a tabletop precision universal testing machine [manufactured by Shimadzu Corporation, product name: Autograph AGS-100D]. After measuring the peel strength three times over a 20 mm interval, the average value was determined, and then the average value was used to determine the peel strength per 1 m width, and the peel strength was evaluated based on the following evaluation criteria.

(Evaluation criteria)
◎: Peel strength is 300 N/m or more.
○: Peel strength is 200 N/m or more and less than 300 N/m.
Δ: Peel strength is 100 N/m or more and less than 200 N/m.
×: Peel strength is less than 100 N/m.

[Water resistant adhesion]
The primer obtained above was applied to a rectangular polypropylene plate for automobiles (manufactured by Standard Test Piece Co., Ltd.), ABS resin plate, polycarbonate plate, acrylic resin plate, or automobile with a smooth surface and a rectangular shape of 5 cm in width. After coating the surface of a steel plate for use with a bar coater (No. 14), the formed coating film was dried in a jet oven at a room temperature of 80°C for 40 minutes at a wind speed of 3 m/sec to a film thickness of 10 A test plate on which a dry coating film of ±2 μm was formed was prepared.

The test plate obtained above was immersed in warm water at 50°C for 7 days, and after being pulled out of the warm water and dried, a grid test was conducted in accordance with JIS K5600-5-6. More specifically, 25 squares of 2 mm square grid cuts (vertical: 5 squares, horizontal: 5 squares) were made on the dry coating surface of the test plate using a sharp knife, and then a cellophane adhesive tape with a width of 25 mm was made. [manufactured by Nichiban Co., Ltd., product number: CT-24] was placed in close contact with a grid.

Within 1 minute after the cellophane adhesive tape was adhered to the grid grid, the cellophane adhesive tape was slowly peeled off from the test plate, the squares that were peeled off at that time were counted, and the water-resistant adhesion was evaluated based on the following evaluation criteria. .

(Evaluation criteria)
◎: The number of peeled squares is 0 to 4.
○: The number of peeled squares is 5 to 9.
Δ: The number of peeled squares is 10 to 14.
×: The number of peeled squares is 15 or more.

In addition, in the evaluation of peel strength and water-resistant adhesion, those with an evaluation of △ or × are rejected.

From the results shown in Table 1, the aqueous resin compositions obtained in each example had high peel strength and excellent water-resistant adhesion, especially excellent water-resistant adhesion to polypropylene plates. For example, it can be suitably used for olefin resin base materials used in automobile parts, household electrical appliances, miscellaneous goods, and the like.

In addition, the aqueous resin compositions obtained in each example have high peel strength and water-resistant adhesion not only to olefin resin substrates but also to ABS resin plates, polycarbonate plates, acrylic resin plates, and automobile steel plates. It can be seen that it can be used for various purposes because of its excellent properties.

Claims (5)

An aqueous resin composition containing (meth)acrylic resin particles and carboxyl group-containing olefin resin particles, wherein the (meth)acrylic resin constituting the (meth)acrylic resin particles is a nitrogen atom-containing ethylenic monomer. A monomer component containing a functional monomer at a content of 0.1 to 10% by mass is polymerized, and the nitrogen atom-containing ethylenic monofunctional monomer is (meth)acrylonitrile, (meth)acrylamide, N-monomethyl (meth) At least one nitrogen atom-containing ethylenic monofunctional monomer selected from the group consisting of acrylamide, N-monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, diacetone acrylamide and piperidyl (meth)acrylate compounds; used, the content of the hydroxyl group-containing (meth)acrylate in the monomer component is 0 to 5% by mass, the content of the carboxyl group-containing ethylenic monofunctional monomer in the monomer component is 0 to 5% by mass, and the The olefin resin of the carboxyl group-containing olefin resin is polyethylene, polypropylene, or a copolymer of propylene and α-olefin, and the α-olefin is ethylene, 1-butene, 1-heptene, 1-octene, or 4-methyl. -1-pentene, the resin solid content of the (meth)acrylic resin particles/resin solid content (mass ratio) of the carboxyl group-containing olefin resin particles is 10/90 to 90/10, and the aqueous resin composition An aqueous resin composition characterized in that the nonvolatile content of the (meth)acrylic resin is 20 to 70% by mass, and the glass transition temperature of the (meth)acrylic resin is 0 to 60°C. The aqueous resin composition according to claim 1, wherein the (meth)acrylic resin constituting the (meth)acrylic resin particles has a weight average molecular weight of 100,000 to 4,000,000. An aqueous primer comprising the aqueous resin composition according to claim 1 or 2 . A method for producing an aqueous resin composition containing (meth)acrylic resin particles and carboxyl group-containing olefin resin particles, the method comprising a nitrogen atom-containing ethylenic monofunctional monomer at a content of 0.1 to 10% by mass. When mixing an aqueous dispersion of (meth)acrylic resin particles obtained by polymerizing monomer components with a glass transition temperature of 0 to 60°C and an aqueous dispersion of carboxyl group-containing olefin resin particles, , as the nitrogen atom-containing ethylenic monofunctional monomer, (meth)acrylonitrile, (meth)acrylamide, N-monomethyl (meth)acrylamide, N-monoethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, diacetone acrylamide and piperidyl (meth)acrylate compounds, and adjust the content of hydroxyl group-containing (meth)acrylate in the monomer component to 0 to 5% by mass using at least one nitrogen atom-containing ethylenic monofunctional monomer selected from the group consisting of piperidyl (meth)acrylate compounds. Then, the content of the carboxyl group-containing ethylenic monofunctional monomer in the monomer component is adjusted to 0 to 5% by mass, and the olefin resin of the carboxyl group-containing olefin resin is polyethylene, polypropylene, or propylene and α-olefin. , using ethylene, 1-butene, 1-heptene, 1-octene, or 4-methyl-1-pentene as the α-olefin, and adjusting the resin solid content/carboxyl of the (meth)acrylic resin particles. An aqueous resin composition characterized in that the resin solid content (mass ratio) of the group-containing olefin resin particles is adjusted to 10/90 to 90/10, and the nonvolatile content in the aqueous resin composition is adjusted to 20 to 70% by mass. How things are manufactured. 5. The method for producing an aqueous resin composition according to claim 4, wherein the (meth)acrylic resin constituting the (meth)acrylic resin particles has a weight average molecular weight of 100,000 to 4,000,000.