JP6688096B2 - Resin composition for base repair - Google Patents

Description

  The present invention relates to a resin composition for base repair. More specifically, the present invention can be suitably used, for example, in a repairing base paint that can be suitably used in repairing a base used for the outer wall of a building, and in the repairing base paint. The present invention relates to a resin composition for base repair, a method for producing the same, and a building material coated with the base paint for repair.

  Exterior materials such as siding boards are widely used for outer walls of houses and the like. In order to prevent the deterioration of the surface of the exterior material, a coating film is generally formed on the surface, but in recent years, not only a variety of coloring and design, but also a coating having weather resistance is used, It is desired to maintain the coating film for a long period of time. In particular, recently, in order to impart weather resistance, a coating film which has been subjected to a photocatalytic treatment, a hydrophilization treatment, a fluorine coating treatment and the like having a low contamination property is formed on the outermost surface layer of the siding board. However, the coating film deteriorates due to long-term irradiation of sunlight, changes in temperature, exposure to rainwater, and so on, there is an increasing need for repainting, that is, repairing of the coating film.

  Therefore, in recent years, a resin emulsion (A), a glycidyl group-containing silane coupling agent (B), and an amino group-containing silane coupling agent (C) are used as an undercoat paint for repairing exterior materials such as outer walls of buildings. A water-based undercoat paint composition for repairing, which contains the above three components, has been proposed (for example, refer to claim 1 of Patent Document 1). In addition, as the water-based undercoat coating composition for repair, from the viewpoint of improving workability in the field of repairing exterior materials, a first liquid containing a resin emulsion (A) and a glycidyl group-containing silane coupling agent (B). A two-pack type coating composition with a second liquid containing an amino group-containing silane coupling agent (C) has been proposed (see, for example, paragraphs [0062]-[0064] of Cited Document 1).

  However, the resin emulsion (A), the glycidyl group-containing silane coupling agent (B) and the amino group-containing silane coupling agent (C) used in the above-mentioned repairing aqueous undercoat coating composition react rapidly upon mixing. Therefore, it is necessary to weigh and mix these three components into predetermined amounts at the site where the exterior material is repaired, and to use them promptly. Therefore, it is necessary to quickly perform a complicated mixing operation for the operator. Even when the water-based undercoating coating composition for repair is a two-pack type coating composition, it is necessary to quickly perform a complicated operation of mixing the first liquid and the second liquid in a predetermined ratio. If the mixing ratio of the second liquid and the second liquid is incorrect, it may not be possible to form a coating film having desired properties.

  Therefore, in recent years, in order to improve workability in the field of repairing a base used for the outer wall of a building, it is necessary to perform a complicated operation of mixing a plurality of components like the above-mentioned repair aqueous undercoat paint composition. There is a demand for the development of a one-component undercoating resin composition that does not form a coating film having excellent water resistance, blister resistance, and adhesion to a substrate.

  Incidentally, in the present specification, the base repair resin composition, in order to repair the coating film already formed on the article to be coated, when applied on the coating film to form a new coating film, It means a resin composition used as an undercoat.

JP, 2012-251094, A

  The present invention has been made in view of the above-mentioned conventional techniques, and in order to improve workability in the field of repairing a base used for the outer wall of a building, as in the case of the water-based undercoat paint composition for repair, It is a one-pack type resin composition for base repair that does not require the complicated operation of mixing multiple components at the site of repainting, and has excellent water resistance, blister resistance, and adhesion to the substrate. It is an object of the present invention to provide a resin composition for repairing an underlayer, a method for producing the same, a base paint for repair containing the resin composition for base repair, and a building material coated with the base paint for repair.

The present invention is
(1) A resin composition used for repairing an underlayer, which contains emulsion particles and uses a monomer component containing an acetoacetoxy group-containing monomer and a styrene-based monomer as a raw material of the emulsion particles. A resin composition for undercoat repair, characterized in that
(2) A method for producing a resin composition used for repairing an underlayer, wherein an acetoacetoxy group-containing monomer and a styrene-based monomer are used as raw materials for the emulsion particles when preparing a resin composition containing the emulsion particles. Using a monomer component containing a monomer, a method for producing a resin composition for base repair, which comprises emulsion-polymerizing the monomer component,
(3) A base resin for repair, which contains the resin composition for base repair according to (1), and (4) a building material coated with the base paint for repair according to (3). Regarding

  ADVANTAGE OF THE INVENTION According to this invention, in order to improve workability in the field which repairs the groundwork used for the outer wall of a building, multiple components are used in the field which is repainted like the conventional water-based undercoat paint composition for repair. Without requiring a complicated operation of mixing, water resistance, a blister resistance and a resin composition for base repair forming a coating film excellent in adhesion to a substrate and a method for producing the same, the resin composition for base repair There is provided a repairing base coating material and a building material coated with the repairing base coating material.

  As described above, the resin composition for undercoat repair of the present invention is a resin composition used for undercoat repair, contains emulsion particles, and a acetoacetoxy group-containing monomer and a styrene-based monomer as raw materials for the emulsion particles. It is characterized in that a monomer component containing a monomer is used.

  The base repair resin composition of the present invention, for example, when preparing a resin composition containing emulsion particles, a monomer containing an acetoacetoxy group-containing monomer and a styrene-based monomer as a raw material of the emulsion particles. It can be produced by emulsion polymerization of the monomer component using a monomer component.

  As the acetoacetoxy group-containing monomer, for example, the formula (I):

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, X ¹ and X ³ are each independently an oxygen atom, a sulfur atom or a group represented by the formula: —N (R ² ) — (R ² is A hydrogen atom or an alkyl group having 1 to 6 carbon atoms), p is 0 or 1, X ² is an alkylene group having 1 to 12 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms, and Y is a substituent. Is a good vinyl group-containing group)
Examples include acetoacetoxy group-containing monomers represented by, but the present invention is not limited to these examples.

R ¹ is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate.

X ¹ and X ³ are each independently an oxygen atom, a sulfur atom or a formula: —N (R ² ) — from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. Is a group (R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and p is 0 or 1. When p is 0, X ² and Y are directly bonded.

X ² is an alkylene group having 1 to 12 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms, preferably a carbon number, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. It is an alkylene group having 1 to 8, more preferably an alkylene group having 1 to 4 carbon atoms.

  Y is a vinyl group-containing group which may have a substituent, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. Examples of the vinyl group-containing group which may have a substituent include, for example, formula (II):

(In the formula, R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylthio group having 1 to 6 carbon atoms, R ⁴ is a hydrogen atom or a halogen atom, and q is 0 or 1.)
Examples include groups represented by, but the present invention is not limited to these examples.

R ³ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkylthio group having 1 to 6 carbon atoms. R ⁴ is a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but the present invention is not limited to these examples. Incidentally, in the formula (II), when q is 0, -C (R ³⁾ group and (X ³⁾ _p - is a group directly bonded.

  Among the acetoacetoxy group-containing monomers represented by the formula (I), from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate, the formula (III):

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and r represents an integer of 1 to 4)
The acetoacetoxy group-containing monomer represented by is preferable.

  Specific examples of the acetoacetoxy group-containing monomer include, for example, acetoacetoxymethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, allylacetoacetate. , Acetoacetamidoethyl (meth) acrylate, vinyl acetate acetoacetate and the like, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more kinds.

  Among the acetoacetoxy group-containing monomers, acetoacetoxyethyl (meth) acrylate is preferable, and acetoacetoxyethyl methacrylate is more preferable, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. preferable.

  In addition, in this specification, "(meth) acrylate" means "acrylate" or "methacrylate", "(meth) acryl" means "acryl" or "methacryl", and "(meth) acryloyl" means Means "acryloyl" or "methacryloyl".

  The content of the acetoacetoxy group-containing monomer in the monomer component is preferably 0.1% by mass or more, more preferably from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. It is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. , More preferably 8% by mass or less, further preferably 5% by mass or less.

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

  The content of the styrene-based monomer in the monomer component is preferably 20% by mass or more, and more preferably 25% by mass from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. % Or more, more preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. , And more preferably 60% by mass or less.

  As the monomer component, a monomer other than the acetoacetoxy group-containing monomer and the styrene-based monomer (hereinafter, simply referred to as “other monomer”) can be used.

  Examples of the other monomer include a phosphoric acid group-containing monomer, an alkyl (meth) acrylate, a hydroxyl group-containing (meth) acrylate, a carboxyl group-containing monomer, a silane group-containing monomer, and a nitrogen atom-containing monomer. Body, aromatic monomer other than styrene monomer, oxo group-containing monomer, fluorine atom-containing monomer, epoxy group-containing monomer, UV absorbing monomer, UV stable monomer However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more kinds. Among these other monomers, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate, phosphoric acid group-containing monomer, alkyl (meth) acrylate, hydroxyl group-containing monomer (Meth) acrylate, carboxyl group-containing monomer, silane group-containing monomer and nitrogen atom-containing monomer are preferable, and phosphoric acid group-containing monomer is more preferable from the viewpoint of further improving the water resistance of the coating film. . These monomers may be used alone or in combination of two or more kinds.

  Examples of the phosphate group-containing monomer include, for example, formula (IV):

(In the formula, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is a carbonyl group, an alkylene group having 1 to 4 carbon atoms or a direct bond, R ⁹ is an ethylene group or a propylene group, and R ¹⁰ is A hydrogen atom, a methyl group or an alkyl group having 6 to 22 carbon atoms, M represents a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, a And b are each independently 0 or an integer of 1 to 50, and c is 1 or 2.)
Examples of the phosphoric acid group-containing monomer represented by are, but the present invention is not limited to these examples.

In the formula (IV), R ⁶ is a hydrogen atom or a methyl group, preferably a hydrogen atom, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. R ⁷ is a hydrogen atom or a methyl group from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. R ⁸ is a carbonyl group, an alkylene group having 1 to 4 carbon atoms or a direct bond, preferably a carbonyl group or 1 carbon atoms, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. Or, it is an alkylene group of 2, more preferably a carbonyl group or a methylene group. Note that when R ⁸ is a direct bond, (R ⁷⁾ and C- group and -O (R ⁹ _{O) a} group is directly bonded. R ⁹ is an ethylene group or a propylene group from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. R ¹⁰ is a hydrogen atom, a methyl group or an alkyl group having 6 to 22 carbon atoms, preferably a hydrogen atom or a methyl group, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. is there. M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms, or 1 carbon atom from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. 10 to 10 alkanolamine residues, preferably a hydrogen atom or an ammonium group. Examples of the alkali metal atom include lithium, sodium, potassium and the like. Examples of the alkylamine residue having 1 to 10 carbon atoms include monoethylamine, diethylamine, triethylamine and the like. Examples of the alkanolamine residue having 1 to 10 carbon atoms include monoethanolamine, diethanolamine and triethanolamine. a and b are each independently an integer of 0 or 1 to 50, preferably an integer of 0 or 1 to 30, from the viewpoint of forming a coating film having excellent water resistance, blister resistance and adhesion to a substrate. It is more preferably 0 or an integer of 1 to 20, still more preferably 0 or an integer of 1 to 10, still more preferably 0 or an integer of 1 to 5. Note that when a is 0, and R ⁸ O-group and -CH ₂ CH (R ¹⁰⁾ group directly bonded. When b is 0, CH (R ¹⁰⁾ and O- group and -P = O group is directly bonded. c is 1 or 2 from the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate.

  Specific examples of the phosphate group-containing monomer represented by formula (IV) include formula (V):

(In the formula, R ⁷ , R ⁹ , M, b and c are the same as above)
A phosphoric acid group-containing monomer represented by the formula (VI):

(In the formula, R ⁹ , M, b and c are the same as above)
In a phosphoric acid group-containing monomers are exemplified represented, but the present invention is not limited only to those exemplified. These monomers may be used alone or in combination of two or more kinds.

In formula (V), R ⁷ , R ⁹ , M, b and c are the same as R ⁷ , R ⁹ , M, b and c described in formula (IV). R ⁷ is a hydrogen atom or a methyl group, preferably a methyl group, from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. R ⁹ is an ethylene group or a propylene group, preferably an ethylene group, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or 1 carbon atom from the viewpoint of forming a coating film having excellent water resistance, blister resistance and adhesion to a substrate. 10 to 10 alkanolamine residues, preferably a hydrogen atom or an ammonium group, more preferably a hydrogen atom. When b is 0, the CO- group and the -P = O group are directly bonded. c is 1 or 2, preferably 1, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate.

Specific examples of the phosphoric acid group-containing monomer represented by the formula (V) include, for example, 2- (meth) acryloyloxyethyl acid phosphate [eg, Kyoeisha Chemical Co., Ltd., trade name: Light Ester P-1M. [In the formula (V), R ⁷ is a methyl group, R ⁹ is an ethylene group, M is a hydrogen atom, b is 1 and c is 1 and a phosphoric acid group-containing monomer], P-2M [Formula (V) In the formula, R ⁷ is a methyl group, R ⁹ is an ethylene group, M is a hydrogen atom, b is 1 and c is 2, and a phosphoric acid group-containing monomer], P-1A (N) [in the formula (V), R ⁷ is a hydrogen atom, R ⁹ is an ethylene group, M is a hydrogen atom, b is a phosphoric acid group-containing monomer having 1 and c], Unichemical Co., Ltd., trade name: Phosmer M [formula ( In V), R ⁷ is a methyl group, R ⁹ is an ethylene group, M is a hydrogen atom, b is 1 and c is 1 and a phosphoric acid group-containing monomer], phosmer P E [in the formula (V), R ⁷ is a methyl group, R ⁹ is an ethylene group, M is a hydrogen atom, b is 4 or 5, and c is 1 and is a phosphate group-containing monomer], 2- ( Examples thereof include phosphoric acid group-containing (meth) acrylates such as (meth) acryloyloxypropyl acid phosphate, but the present invention is not limited to these examples. These monomers may be used alone or in combination of two or more kinds.

Among the phosphoric acid group-containing monomers represented by the formula (V), 2-methacryloyloxyethyl acid phosphate [formula] from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. In (V), a phosphoric acid group-containing monomer in which R ⁷ is a methyl group, R ⁹ is an ethylene group, M is a hydrogen atom, b is 1 and c is 1] is preferred.

In Formula (VI), R ⁹ , M, b and c are the same as R ⁹ , M, b and c described in Formula (IV). Note that R ⁹ is an ethylene group or a propylene group, preferably a propylene group, from the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate. When b is 0, and the CH ₂ O- groups and -P = O group directly bonded.

Among the phosphoric acid group-containing monomers represented by the formula (VI), from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate, polyoxypropylene allyl ether phosphate ester [ In formula (VI), R ⁹ is a propylene group, M is a hydrogen atom or an ammonium group, b is an integer of 5 to 20, and phosphoric acid group-containing monomer in which c is 1 or 2] is preferable.

  Specific examples of the phosphoric acid group-containing monomer represented by the formula (VI) include, for example, polyoxyalkylene allyl ether phosphoric acid ester [for example, manufactured by ADEKA, trade name: Adecarya soap PP-70, etc.]. However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more kinds.

  Among the phosphoric acid group-containing monomers, the phosphoric acid group-containing monomer represented by the formula (VI) is preferable from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. .

  The content of the phosphoric acid group-containing monomer in the monomer component is preferably 0.03% by mass or more, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 20% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. , More preferably 15% by mass or less, further preferably 10% by mass or less.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth). Alkyl having 1 to 18 carbon atoms in the ester group such as acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, and n-lauryl (meth) acrylate. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. These alkyl (meth) acrylates may be used alone or in combination of two or more. Among these alkyl (meth) acrylates, from the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate, an alkyl (meth) acrylate having an alkyl group with 4 to 8 carbon atoms. Is preferred, an alkyl (meth) acrylate having 6 to 8 carbon atoms is more preferred, 2-ethylhexyl (meth) acrylate is further preferred, and 2-ethylhexyl acrylate is even more preferred.

  The content of the alkyl (meth) acrylate in the monomer component is preferably 10% by mass or more, more preferably 15% by mass, from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. % Or more, more preferably 20% by mass or more, preferably 50% by mass or less, and more preferably 45% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. , And more preferably 40 mass% or less.

  Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy. Examples thereof include hydroxyl group-containing (meth) acrylates having an ester group having 1 to 18 carbon atoms such as butyl (meth) acrylate, but the present invention is not limited to these examples. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more. Among these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) acrylate is preferable, and 2-hydroxyethyl is preferable, from the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate. Methacrylate is more preferred.

  The content of the hydroxyl group-containing (meth) acrylate in the monomer component is preferably 0.1% by mass or more, more preferably from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. Is 0.3% by mass or more, preferably 1% by mass or less, and more preferably 0.8% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. is there.

  Examples of the carboxyl group-containing monomer include, for example, (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, and other carboxyl group-containing aliphatic monomers. The invention is not limited to just such examples. These carboxyl group-containing monomers may be used alone or in combination of two or more kinds. Among these carboxyl group-containing monomers, (meth) acrylic acid is preferable, and acrylic acid is more preferable, from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate.

  The content of the carboxyl group-containing monomer in the monomer component is preferably 1% by mass or more, and more preferably 2 from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. It is preferably 8% by mass or less, more preferably 5% by mass or less from the viewpoint of forming a coating film having a mass% or more and excellent water resistance, blister resistance and adhesion to a substrate.

  Examples of the silane group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane and vinyltrimethoxysilane. Examples thereof include chlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to these examples. These silane group-containing monomers may be used alone or in combination of two or more. Among these silane group-containing monomers, γ- (meth) acryloyloxypropyltrimethoxysilane is preferable from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. -Methacryloyloxypropyltrimethoxysilane is more preferred.

  The content of the silane group-containing monomer in the monomer component is preferably 0.01% by mass or more, more preferably from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. Is 0.05% by mass or more, preferably 1% by mass or less, and more preferably 0.5% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. is there.

  Examples of the nitrogen atom-containing monomer include (meth) acrylamide, diacetone (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N. -N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, (Meth) acrylamide compounds such as N-dimethylaminopropyl (meth) acrylamide and diacetone (meth) acrylamide, nitrogen such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate Child-containing (meth) acrylate compounds, N- vinylpyrrolidone, but like (meth) acrylonitrile, the present invention is not limited only to those exemplified. These nitrogen atom-containing monomers may be used alone or in combination of two or more. Among these nitrogen atom-containing monomers, (meth) acrylonitrile is preferable, and acrylonitrile is more preferable, from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate.

  The content of the nitrogen atom-containing monomer in the monomer component is preferably 1% by mass or more, and more preferably 2 from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. The content is preferably 5% by mass or more, and more preferably 5% by mass or less, and more preferably 3% by mass or less, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate.

  Examples of the aromatic monomer other than the styrene monomer include aralkyl (meth) acrylate, but the present invention is not limited to these examples. Examples of the aralkyl (meth) acrylate include aralkyl 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 thereof include (meth) acrylate, but the present invention is not limited to such examples. These aromatic monomers other than the styrene-based monomer may be used alone or in combination of two or more kinds.

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

  Examples of the fluorine atom-containing monomer include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate and like ester group-containing fluorine atom-containing alkyl having 2 to 6 carbon atoms. Examples thereof include (meth) acrylate, but the present invention is not limited to such examples. These fluorine atom-containing monomers may be used alone or in combination of two or more kinds.

  Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, but the present invention is not limited to these examples. These epoxy group-containing monomers may be used alone or in combination of two or more kinds.

  Examples of the ultraviolet ray absorbing monomer include benzotriazole type ultraviolet ray absorbing monomer and benzophenone type ultraviolet ray absorbing monomer, 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 kinds.

  Examples of the benzotriazole-based UV absorbing monomer include 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -2H-benzotriazole and 2- [2'-hydroxy-5'-. (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2' -Hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzo Triazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhexoxy Luphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'. -Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(meth ) Acryloyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydr Xy-5 '-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-(β- (meth) acryloyloxyethoxy) -3'- Examples thereof include tert-butylphenyl] -4-tert-butyl-2H-benzotriazole, but the present invention is not limited to these examples. These benzotriazole-based UV absorbing monomers may be used alone or in combination of two or more kinds.

  Examples of the benzophenone-based UV absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone and 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone. Hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- Examples include [2- (meth) acryloyloxy] butoxybenzophenone, but the present invention is not limited to these examples. These benzophenone-based UV absorbing monomers may be used alone or in combination of two or more kinds.

  Examples of the UV stable monomer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine and 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. , 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano- 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-croto Noylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-sia -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano- 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like can be mentioned. However, the present invention is not limited to such an example. These UV stable monomers may be used alone or in combination of two or more kinds.

  The content of the other monomer in the monomer component is preferably 15% by mass or more, more preferably 20% by mass, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. % Or more, more preferably 25% by mass or more, preferably 60% by mass or less, and more preferably 55% by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. , And more preferably 50 mass% or less.

  As a method of emulsion-polymerizing a monomer component, 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, a single amount under heating and stirring. A method of dropping a body component and a polymerization initiator, a method of dropping a monomer component previously emulsified with an emulsifier and water into water or an aqueous medium, and the like, the present invention is only such a method. It is not limited. The amount of the medium may be set as appropriate in consideration of the amount of non-volatile components contained in the obtained resin emulsion.

  Examples of emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, and polymeric emulsifiers. These emulsifiers may be used alone or in combination of two or more kinds.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; The polyoxyethylene alkyl sulfate salt; the polyoxyethylene alkyl aryl sulfate salt; the dialkyl sulfosuccinate salt; the aryl sulfonic acid-formalin condensate; the fatty acid salt such as ammonium laurate and sodium stearate. It is not limited to the examples.

  Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, condensation product of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Examples thereof include condensates with amines, but the present invention is not limited to such examples.

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

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

  Examples of the polymeric emulsifier include poly (meth) acrylic acid salts such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; Examples thereof include polymers having one or more kinds of monomers as copolymerization components, but the present invention is not limited to these examples.

  The reactive emulsifier can be preferably used from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate, and among them, from the viewpoint of environmental protection, non-nonylphenyl type Is preferred.

  As the reactive emulsifier, for example, propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, polyoxyethylene alkylpropenyl phenyl ether ammonium sulfate [eg, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, Aqualon BC-10, etc.], sulfonate salt of allyloxymethylalkyloxypolyoxyethylene [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10], allyloxymethylnonylphenoxy Sulfonate salt of ethylhydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: ADEKA REASOAP SE-10 etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt [for example, (stock ADEKA, trade name: ADEKA rear soap SR-10, SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [for example, manufactured by Nippon Emulsifier Co., Ltd., trade name: Antox MS- 60, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, trade name: ADEKA REASOAP ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, Dai-ichi Kogyo Seiyaku Co., Ltd. ), Trade name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: Adecaria Soap NE-10, etc.] and the like. The invention is limited to such examples No. Each of these reactive emulsifiers may be used alone or in combination of two or more.

  The phosphoric acid group-containing monomer represented by the formula (IV) and the phosphoric acid group-containing monomer represented by the formula (VI) both have a function as an emulsifier, and therefore, should be used as a reactive emulsifier. You can also

  The amount of the emulsifier per 100 parts by mass of the monomer component is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, further preferably 2 parts by mass or more, from the viewpoint of improving the polymerization stability. From the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.

  When the phosphoric acid group-containing monomer represented by the formula (IV) or the phosphoric acid group-containing monomer represented by the formula (VI) is used as the monomer component, these monomers are Since all have a function as an emulsifier, the balance obtained by subtracting the amount of these monomers used from the amount of the emulsifiers used can be used as an emulsifier other than these monomers.

  When polymerizing the monomer components, a polymerization initiator can be used. Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid) and 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate and ammonium persulfate; Examples thereof include hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and peroxides such as 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 kinds.

  The amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.01 parts by mass or more, more preferably 0, from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component. The amount is 0.03 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less from the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate.

  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. From the viewpoint of accelerating the end time of the polymerization reaction, a part of the polymerization initiator may be added to the flask before or after the addition of the monomer component into the reaction system.

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

  In addition, if necessary, in the reaction system, for example, a chain transfer agent such as a compound having a thiol group such as tert-dodecyl mercaptan, a pH buffer, a chelating agent, an additive such as a film-forming assistant, and the like are added in an appropriate amount in the flask. May be added in. The amount of the additive cannot be unconditionally determined because it varies depending on its type, but is usually 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass per 100 parts by mass of the monomer component. Parts by mass.

  The atmosphere for emulsion-polymerizing the monomer component is not particularly limited, but an inert gas such as nitrogen gas is preferable from the viewpoint of increasing the efficiency of the polymerization initiator.

  The polymerization temperature when emulsion-polymerizing the monomer component is not particularly limited, but is usually preferably 50 to 100 ° C, more preferably 60 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for emulsion-polymerizing the monomer component is not particularly limited and may be appropriately set depending on the progress of the polymerization reaction, but is usually about 2 to 9 hours.

  Emulsion particles are obtained by emulsion-polymerizing the monomer components as described above.

  The polymer constituting the emulsion particles may have a crosslinked structure. The weight average molecular weight of the polymer is preferably 100,000 or more, more preferably 300,000 or more, further preferably 550,000 or more from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. , Particularly preferably 600,000 or more. The upper limit of the weight average molecular weight of the polymer is not particularly limited because it is difficult to measure the weight average molecular weight when it has a crosslinked structure, but when it does not have a crosslinked structure, it improves the film-forming property. From the viewpoint, it is preferably 5 million or less.

  In addition, in the present specification, the weight average molecular weight of the polymer is gel permeation chromatography [manufactured by Tosoh Corp., product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series. ] It means the weight average molecular weight (polystyrene conversion) measured using.

  The emulsion particles contained in the resin emulsion may have a single-layer resin layer prepared by one-stage emulsion polymerization, or may have a plurality of resin layers prepared by multi-stage emulsion polymerization. Good. Among these, it is preferable that the emulsion particles have a plurality of resin layers from the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate. When the emulsion particles have a plurality of resin layers, the boundaries between the resin layers do not necessarily have to be clear, and adjacent resin layers may be mixed with each other.

  The number of resin layers constituting the emulsion particles is preferably 1 to 5 layers, more preferably 1 to 3 layers, and more preferably 1 to 5 layers from the viewpoint of forming a coating film having excellent water resistance, blister resistance and adhesion to a substrate. It is preferably 2 or 3 layers.

  When the emulsion particles have a plurality of resin layers, the outermost layer of the emulsion particles, from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to the substrate, emulsion polymerization of the monomer component. It is preferably formed of a polymer. In this case, layers other than the outermost layer, for example, the inner layer when the emulsion particles are formed of two resin layers, the intermediate layer and the inner layer when the emulsion particles are formed of three resin layers A monomer of the same type as the monomer used for the monomer component can be used. Emulsion particles having a plurality of resin layers can be prepared, for example, by carrying out multistage emulsion polymerization of the monomer components under the same polymerization method and polymerization conditions as in the case of emulsion polymerizing the monomer components.

  When the emulsion particles have a single resin layer, the emulsion particles composed of the resin layer can be prepared by emulsion polymerization of the monomer component.

  When the emulsion particles have two resin layers, an inner layer and an outer layer, the glass transition point of the inner layer is preferably 40 from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. ℃ or more, more preferably 45 ℃ or more, more preferably 50 ℃ or more, from the viewpoint of improving the film-forming property, preferably 120 ℃ or less, more preferably 115 ℃ or less, more preferably 110 ℃ or less. It is preferable to adjust the type and amount of the monomer used in the monomer component. Further, the resin layer forming the outer layer is preferably the same as the above-mentioned monomer component.

  When the emulsion particles have three resin layers, an inner layer, an intermediate layer and an outermost layer, the glass transition point of the inner layer is from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. The temperature is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, further preferably 50 ° C. or higher, and from the viewpoint of improving the film-forming property, preferably 120 ° C. or lower, more preferably 115 ° C. or lower, further preferably 110 ° C. or lower It is preferable to adjust the type and amount of the monomer used in the monomer component so that Further, it is preferable that the resin layers constituting the intermediate layer and the outermost layer have the same kind and amount of the monomer as the monomer component.

  When the emulsion particles have a plurality of resin layers, the glass transition temperature of the outermost layer is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, and further preferably −5 ° C., from the viewpoint of improving the film-forming property. From the viewpoint of forming a coating film excellent in water resistance, blister resistance, and adhesion to a substrate, the temperature is preferably 40 ° C or lower, more preferably 30 ° C or lower, and further preferably 20 ° C or lower.

  The glass transition temperature of the emulsion particles as a whole is preferably 0 ° C. or higher, more preferably 1 ° C. or higher, and further preferably from the viewpoint of forming a coating film having excellent water resistance, blister resistance, and adhesion to a substrate. From the viewpoint of forming a coating film having a temperature of 3 ° C or higher and having excellent water resistance, blister resistance and adhesion to a substrate, the temperature is preferably 30 ° C or lower, more preferably 25 ° C or lower, and further preferably 20 ° C or lower.

Incidentally, in the present specification, the glass transition temperature of the resin layer constituting the emulsion particles, using the glass transition temperature of the homopolymer of the monomer used in the monomer component constituting the polymer, formula:
1 / Tg = Σ (Wm / Tgm) / 100
[In the formula, Wm represents the content rate (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
It means the temperature determined based on the Fox equation.

  In the present specification, the glass transition temperature of the resin layer constituting the emulsion particles means the glass transition temperature obtained on the basis of the Fox, unless otherwise specified. For example, the glass transition temperature of the entire resin layer constituting the emulsion particles having a plurality of resin layers, the mass fraction of each monomer in all the monomer components used in the multi-stage emulsion polymerization and the corresponding Means the glass transition temperature obtained from the glass transition temperature of the homopolymer of the monomer. Incidentally, for monomers whose glass transition temperature is unknown, such as special monomers and polyfunctional monomers, the total amount of monomers whose glass transition temperature is unknown in the monomer component is the mass fraction. When it is 10% by mass or less, the glass transition temperature can be determined using only the monomer whose glass transition temperature is known. When the total amount of monomers whose glass transition temperature is unknown in the monomer component exceeds 10% by mass, the glass transition temperature of the polymer is measured by differential scanning calorimetry (DSC), differential calorimetric analysis. (DTA), thermomechanical analysis (TMA), etc.

  The glass transition temperature of the resin layer can be easily adjusted by adjusting the composition of the monomer components. The composition of the monomer component used as the raw material of the resin layer forming the emulsion particles can be determined in consideration of the glass transition temperature of the resin layer forming the emulsion particles.

  The glass transition temperature of the polymer is, for example, 100 ° C. for a styrene homopolymer, −70 ° C. for a 2-ethylhexyl acrylate homopolymer, 95 ° C. for an acrylic acid homopolymer, and 130 for a methacrylic acid homopolymer. 55 ° C. for homopolymers of 2-hydroxyethyl methacrylate, 96 ° C. for homopolymers of acrylonitrile, 18 ° C. for homopolymers of acetoacetoxyethyl methacrylate, and 70 for homopolymers of γ-methacryloyloxypropyltrimethoxysilane. C., 165.degree. C. for a homopolymer of 2-methacryloyloxyethyl acid phosphate, and 105.degree. C. for a homopolymer of methyl methacrylate.

  When the emulsion particles are composed of a plurality of resin layers, the solubility parameter (hereinafter, also referred to as SP value) of the resin layer forming the outer layer is higher than the SP value of the resin layer forming the inner layer. A high value is preferable from the viewpoint of improving the flexibility and film-forming property of the coating film. Further, the difference (absolute value) between the SP value of the resin layer forming the inner layer and the SP value of the resin layer forming the outer layer may be large from the viewpoint of forming a layer separation structure in the emulsion particles. preferable.

  The SP value is a value defined by the regular solution theory introduced by Hildebrand and is also a measure of the solubility of a binary solution. Generally, substances having similar SP values tend to be easily mixed with each other. Therefore, the SP value is also a standard for determining the ease of mixing the solute and the solvent.

  When the emulsion particles have two resin layers, the mass ratio of the resin layer forming the inner layer and the resin layer forming the outer layer (the resin layer forming the inner layer / the resin forming the outer layer) The layer is preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. From the viewpoint of improving the film forming property and the adhesion to the substrate, it is preferably 70/30 or less, more preferably 60/40 or less, and further preferably 50/50 or less.

  Further, when the emulsion particles have three resin layers, the resin layer forming the inner layer (first layer) from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. Content is 20 to 50% by mass, the content of the resin layer constituting the Chinese layer (second layer) between the inner layer and the outer layer is 30 to 60% by mass, and the outer layer (third layer) The content of the resin layer constituting (layer) is preferably 10 to 40% by mass.

  The average particle diameter of the emulsion particles is preferably 50 nm or more, more preferably 100 nm or more, from the viewpoint of improving the mechanical stability of the emulsion particles themselves, and is excellent in water resistance, blister resistance, and adhesion to a substrate. From the viewpoint of forming a coating film, the thickness is preferably 300 nm or less, more preferably 200 nm or less.

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

  The nonvolatile content in the resin emulsion is preferably 20% by mass or more, more preferably 30% by mass or more from the viewpoint of improving productivity, and preferably 60% by mass or less, more preferably from the viewpoint of improving handleability. It is 50 mass% or less.

The nonvolatile content in the resin emulsion was calculated by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour, and the resulting residue was used as the nonvolatile content.
[Nonvolatile content (mass%) in resin emulsion]
= ([Mass of residue] / [resin emulsion 1 g]) x 100
Means the value obtained based on.

  The minimum film forming temperature of the resin emulsion is preferably −20 to 50 ° C. from the viewpoint of improving film forming properties. The minimum film forming temperature of the resin emulsion can be adjusted, for example, by adjusting the glass transition temperature of the entire emulsion particles or the glass transition temperature of the outermost resin layer.

  In the present specification, the minimum film-forming temperature of the resin emulsion is determined by applying the resin emulsion onto a glass plate placed on a thermal gradient tester with an applicator so that the thickness becomes 0.2 mm, and cracking It means the temperature at which it occurs.

  The base repairing resin composition of the present invention contains the emulsion particles, and the resin emulsion containing the emulsion particles obtained above can be used. The base repairing resin composition of the present invention may be composed of the resin emulsion obtained above, and may contain a crosslinking agent or the like if necessary.

  As the crosslinking agent, for example, melamine-based crosslinking agent, oxazoline-based crosslinking agent, acrylamide-based crosslinking agent, polyamide-based crosslinking agent, epoxy-based crosslinking agent, isocyanate-based crosslinking agent, aziridine-based crosslinking agent, titanate-based crosslinking agent, urea-based crosslinking agent Agents, alkyl alcohol urea cross-linking agents, hydrazine compounds, carbodiimide compounds, zirconium compounds, zinc compounds, titanium compounds, polyvalent metal compounds such as aluminum compounds, and the like, but the present invention is limited only to such examples. Not a thing. These crosslinking agents may be used alone or in combination of two or more kinds. The amount of the cross-linking agent is preferably set appropriately according to the type of the cross-linking agent and the like.

  Among these cross-linking agents, oxazoline-based cross-linking agents and hydrazine compounds are preferable from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate.

  Examples of the oxazoline-based cross-linking agent include 2,2′-bis (2-oxazoline), 1,2-bis (2-oxazolin-2-yl) ethane, and 1,4-bis (2-oxazolin-2-yl). ) Butane, 1,8-bis (2-oxazolin-2-yl) butane, 1,4-bis (2-oxazolin-2-yl) cyclohexane, 1,2-bis (2-oxazolin-2-yl) benzene , 1,3-bis (2-oxazolin-2-yl) benzene, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2 -Isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline and the like, but the present invention, It is not limited only to hunt illustration. These oxazoline-based crosslinking agents may be used alone or in combination of two or more kinds. The oxazoline-based cross-linking agent can be easily obtained commercially, and for example, manufactured by Nippon Shokubai Co., Ltd., trade names: Epocros WS-500, Epocros WS-700, Epocros K-2010, Epocros K-. 2020, Epocros K-2030 and the like, but the present invention is not limited to these examples.

  Examples of the hydrazine compound include adipic acid dihydrazide and a polymer having a zirazide group, but the present invention is not limited to such examples. These compounds may be used alone or in combination of two or more kinds.

  The repairing base paint of the present invention contains the above-mentioned base repairing resin composition, and may contain only the above-mentioned base repairing resin composition, or may further contain an additive. Good.

  Examples of additives include coloring agents such as pigments, leveling agents, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust preventives, antibacterial agents, metal deactivating agents. Agents, wetting agents, defoaming agents, surfactants, reinforcing agents, plasticizers, lubricants, antifogging agents, anticorrosive agents, pigment dispersants, flow control agents, peroxide decomposing agents, template decolorizing agents, increasing fluorescence Whitening agent, organic flameproofing agent, inorganic flameproofing agent, anti-dripping agent, melt flow modifier, antistatic agent, antialgal agent, antifungal agent, flame retardant, slip agent, metal chelating agent, antiblocking agent, Heat resistance stabilizer, processing stabilizer, dispersant, thickener, rheology control agent, foaming agent, anti-aging agent, antiseptic agent, antistatic agent, silane coupling agent, antioxidant, film forming aid, etc. However, the present invention is not limited to such examples. These additives may be used alone or in combination of two or more kinds.

  Since the amount of the additive varies depending on the type of the additive and cannot be determined unconditionally, it is preferable to appropriately determine the amount of the additive according to the type of the additive.

  The content of non-volatile components in the repairing base coating material of the present invention is preferably 10% by mass or more, more preferably from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. It is 20% by mass or more, and preferably 60% by mass or less, and more preferably 50% by mass or less, from the viewpoint of improving handleability.

  The undercoating resin composition of the present invention and the undercoating paint for repair containing the undercoating resin composition each form a coating film excellent in water resistance, blister resistance and adhesion to a substrate. Therefore, for example, it can be suitably used when repairing exterior building materials that constitute the outer wall of a building.

  Examples of the exterior building material include metal base materials, resin base materials, and inorganic base materials. Examples of the metal base material include an aluminum plate, an iron plate, an aluminum zinc plated steel plate, a stainless steel plate, and a tin plate. Examples of the resin base material include an acrylic resin plate, a vinyl chloride resin plate, a polycarbonate plate, an ABS resin plate, a polyester plate, a polyethylene plate, and a polypropylene plate. Examples of the inorganic base material include ceramic building materials and glass base materials described in JIS A5422, JIS A5430, etc., but the present invention is not limited to such examples.

  The outermost surface of the building material for exterior is usually, for example, an inorganic paint containing silica, titanium oxide, etc., a low-polluting paint, an organic-inorganic composite paint, a fluororesin paint, an acrylic silicone-based paint, an acrylic urethane-based paint, etc. A coating film made of paint is formed. The exterior building material on which the coating film is formed can be easily obtained commercially, and as an example, Keimu Co., Ltd., trade name: EXCELISE / Hydrophilic Cera 15, EXCELAGE / OPTERA 15, Nichiha Co., Ltd., trade name: Moen Excellad 18, Moen Excellade 16, Asahi Tostem Exterior Co., Ltd., trade name: AT-WALL 15, Toray ACE Co., Ltd., trade name: Trestage (registered Trademark), Purestage (registered trademark), etc., but the present invention is not limited to these examples.

  The base repair resin composition of the present invention and the repair base paint containing the base repair resin composition are not only excellent in adhesion to a coating film made of an inorganic paint, but also from an organic paint. It also has excellent adhesiveness to the coating film and can be suitably used for various bases requiring repair.

  The repairing base coating material of the present invention may be applied by only one layer, or may be applied by applying multiple layers so as to form a coating film of two or more layers. When multiple coatings are formed so that a coating of two or more layers is formed, only a part of the coating may be formed by the repairing base paint of the present invention, and all coatings may be formed by the repairing base paint of the present invention. It may be formed.

  Examples of the method for forming a coating film using the repairing base coating material of the present invention include dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, and static coating. The drawings include coating methods such as electrocoating and die coating, and the present invention is not limited to such examples.

  The coating film formed using the repairing base coating material of the present invention may be dried at room temperature, or may be dried by heating.

  The thickness of the coating film formed using the repairing base coating material of the present invention is usually 10 to 100 μm from the viewpoint of forming a coating film excellent in water resistance, blister resistance and adhesion to a substrate. It is preferably about the same.

The coating amount of the base paint for repair on the substrate cannot be unconditionally determined because it varies depending on the type of the substrate, etc., but it forms a coating film with excellent water resistance, blister resistance and adhesion to the substrate. From this viewpoint, it is usually preferable that the nonvolatile content is about ²⁰ to 200 g / m ² .

  By applying the repairing base paint to the substrate as described above, a building material coated with the repairing base paint can be obtained.

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

Example 1
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , 1.2 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70], 39.7 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 1. 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 51.7 parts, acrylic acid 5.0 parts, acrylonitrile 2.0 parts And 0.5 part of 2-hydroxyethylmethacrylate were charged, The Luchon was prepared.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh (JIS mesh, the same applies hereinafter) wire mesh to obtain a resin emulsion having a nonvolatile content of 40 mass%.

  The glass transition temperature of all emulsion particles contained in the resin emulsion obtained above was 5.9 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 2
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70] 4.0% in 25% aqueous solution, 2-ethylhexyl acrylate 39.7 parts, acetoacetoxyethyl methacrylate 1. 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 51.7 parts, acrylic acid 5.0 parts, acrylonitrile 2.0 parts And 0.5 part of 2-hydroxyethylmethacrylate were charged, The Luchon was prepared.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all emulsion particles contained in the resin emulsion obtained above was 5.9 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 3
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70], 8.0 parts of 25% aqueous solution, 39.7 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 1. 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 51.7 parts, acrylic acid 5.0 parts, acrylonitrile 2.0 parts And 0.5 part of 2-hydroxyethylmethacrylate were charged, The Luchon was prepared.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all emulsion particles contained in the resin emulsion obtained above was 5.9 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 4
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA Corporation, trade name: ADEKA REASOAP PP-70] 4.0% in 25% aqueous solution, 39.5 parts 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 2. 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 50.9 parts, acrylic acid 5.0 parts, acrylonitrile 2.0 parts And 0.5 part of 2-hydroxyethylmethacrylate were charged, The Luchon was prepared.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 5.7 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 5
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA rear soap SR-10] as an emulsifier , 2-ethylhexyl acrylate 39.5 parts, acetoacetoxyethyl methacrylate 2.0 parts, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 49. .9 parts, 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd., trade name: Light Ester P-1M] 1.0 part, acrylic acid 5.0 parts, acrylonitrile 2.0 parts and 2-hydroxyethyl. Prepare 0.5 parts of methacrylate and prepare a pre-emulsion for dripping It was.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 5.7 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 6
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA rear soap SR-10] as an emulsifier , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70] 2.0% 25% aqueous solution, 2-ethylhexyl acrylate 39.5 parts, acetoacetoxyethyl methacrylate 2. 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 50.4 parts, 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd. ), Trade name: Light Ester P-1M] 0.5 part, 5.0 parts of acrylic acid were charged 2.0 parts and 0.5 parts of 2-hydroxyethyl methacrylate acrylonitrile was prepared dropping pre-emulsion.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 5.7 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 7
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , 2-ethylhexyl acrylate 39.5 parts, acetoacetoxyethyl methacrylate 2.0 parts, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 50 .9 parts, 5.0 parts of acrylic acid, 2.0 parts of acrylonitrile and 0.5 parts of 2-hydroxyethyl methacrylate were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 5.7 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 8
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA rear soap SR-10] as an emulsifier , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70] 2.0% 25% aqueous solution, 2-ethylhexyl acrylate 39.5 parts, acetoacetoxyethyl methacrylate 2. 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 50.9 parts, methacrylic acid 5.0 parts, acrylonitrile 2.0 parts And 0.5 part of 2-hydroxyethylmethacrylate were charged, The Marushon was prepared.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 6.7 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 9
90.4 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 40.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dripping, 2.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: ADEKA REASORP SR-10) as an emulsifier, 2.0 parts of a 25% aqueous solution of polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70], 38.9 parts of 2-ethylhexyl acrylate, 1.0 of acetoacetoxyethyl methacrylate. Parts, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 parts, styrene 14.5 parts, acrylic acid 3.0 parts, acrylonitrile 2.0 parts and Second stage pre-emulsion consisting of 0.5 part of 2-hydroxyethyl methacrylate Down, 3.5% 2.9 part of ammonium persulfate aqueous solution and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution was added dropwise into the flask over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 7.4 ° C. The average particle size of the emulsion particles was 150 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 10
90.4 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 40.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dripping, 2.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: ADEKA REASORP SR-10) as an emulsifier, 4.0 parts of a 25% aqueous solution of polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70], 38.9 parts of 2-ethylhexyl acrylate, 1.0 of acetoacetoxyethyl methacrylate. Parts, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 parts, styrene 14.5 parts, acrylic acid 3.0 parts, acrylonitrile 2.0 parts and Second stage pre-emulsion consisting of 0.5 part of 2-hydroxyethyl methacrylate Down, 3.5% 2.9 part of ammonium persulfate aqueous solution and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution was added dropwise into the flask over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 7.4 ° C. The average particle size of the emulsion particles was 150 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 11
90.4 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 40.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dripping, 2.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: ADEKA REASORP SR-10) as an emulsifier, 12.0 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70], 38.9 parts of 2-ethylhexyl acrylate, 1.0 of acetoacetoxyethyl methacrylate. Parts, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 parts, styrene 14.5 parts, acrylic acid 3.0 parts, acrylonitrile 2.0 parts and Second stage pre-emul consisting of 0.5 parts of 2-hydroxyethyl methacrylate ® down, 3.5% 2.9 part of ammonium persulfate aqueous solution and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution was added dropwise into the flask over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 7.4 ° C. The average particle size of the emulsion particles was 150 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 12
90.4 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 40.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dripping, 2.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, 2-ethylhexyl acrylate 37.9 parts, acetoacetoxyethyl methacrylate 1.0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 14. 5 parts, 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd., trade name: light ester P-1M] 1.0 part, acrylic acid 3.0 parts, acrylonitrile 2.0 parts and 2-hydroxyethyl methacrylate. Second stage pre-emulsion consisting of 0.5 parts, 3.5% It was added dropwise to the flask 2.9 parts of aqueous solution of ammonium sulfate and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 9.2 ° C. The average particle size of the emulsion particles was 150 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 13
90.4 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 40.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dripping, 2.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, 33.9 parts of 2-ethylhexyl acrylate, 1.0 part of acetoacetoxyethyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 14. 5 parts, 2-methacryloyloxyethyl acid phosphate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester P-1M] 5.0 parts, acrylic acid 3.0 parts, acrylonitrile 2.0 parts and 2-hydroxyethyl methacrylate. Second stage pre-emulsion consisting of 0.5 parts, 3.5% It was added dropwise to the flask 2.9 parts of aqueous solution of ammonium sulfate and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 16.4 ° C. The average particle size of the emulsion particles was 150 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 14
90.4 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 40.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dripping, 2.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: ADEKA REASORP SR-10) as an emulsifier, 2.0 parts of a 25% aqueous solution of polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA REASOAP PP-70], 38.9 parts of 2-ethylhexyl acrylate, 1.0 of acetoacetoxyethyl methacrylate. Parts, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 parts, styrene 14.5 parts, methacrylic acid 3.0 parts, acrylonitrile 2.0 parts and Second stage pre-emul consisting of 0.5 parts of 2-hydroxyethyl methacrylate ® down, 3.5% 2.9 part of ammonium persulfate aqueous solution and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution was added dropwise into the flask over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 8.0 ° C. The average particle size of the emulsion particles was 150 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 15
85 parts of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  10.3 parts of deionized water in a dropping funnel, 4.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1.5 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Then, 11.8 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, 28.2 parts of 2-ethylhexyl acrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 18.4 parts, acrylic acid 1.0 part A second stage pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 parts of 2-hydroxyethyl methacrylate, 2.9 parts of 3.5% ammonium persulfate aqueous solution and 2.0 parts of 2.5% sodium bisulfite aqueous solution. It dripped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water and 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA Corporation, trade name: ADEKA REASOAP PP-70] 4.0 parts of 25% aqueous solution, 6.0 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 2. A third stage pre-emulsion consisting of 0 part, 7.8 parts of styrene, 3.0 parts of acrylic acid, 1.0 part of acrylonitrile and 0.2 part of 2-hydroxyethyl methacrylate, 3.5% ammonium persulfate aqueous solution 2.9. And 2.0 parts of 2.5% sodium bisulfite aqueous solution over 90 minutes. It was dropped in the child. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 15.3 ° C. The average particle size of the emulsion particles was 130 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 16
85 parts of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  10.3 parts of deionized water in a dropping funnel, 4.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1.5 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Then, 11.8 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, 28.2 parts of 2-ethylhexyl acrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 18.4 parts, acrylic acid 1.0 part A second stage pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 parts of 2-hydroxyethyl methacrylate, 2.9 parts of 3.5% ammonium persulfate aqueous solution and 2.0 parts of 2.5% sodium bisulfite aqueous solution. It dripped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water and 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , 2-ethylhexyl acrylate 6.0 parts, acetoacetoxyethyl methacrylate 2.0 parts, styrene 6.8 parts, 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd., trade name: light ester P-1M] 1 0.0 parts, 3.0 parts of acrylic acid, 1.0 part of acrylonitrile and 0.2 part of 2-hydroxyethyl methacrylate, a third stage pre-emulsion, 2.9 parts and 2.5 parts of 3.5% ammonium persulfate aqueous solution. % Aqueous sodium hydrogen sulfite solution (2.0 parts) was added dropwise to the flask over 90 minutes.After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 15.3 ° C. The average particle size of the emulsion particles was 130 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 17
85 parts of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  10.3 parts of deionized water in a dropping funnel, 4.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1.5 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Then, 11.8 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, 28.2 parts of 2-ethylhexyl acrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 18.4 parts, acrylic acid 1.0 part A second stage pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 parts of 2-hydroxyethyl methacrylate, 2.9 parts of 3.5% ammonium persulfate aqueous solution and 2.0 parts of 2.5% sodium bisulfite aqueous solution. It dripped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water and 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA Corporation, trade name: ADEKA REASOAP PP-70] 4.0 parts of 25% aqueous solution, 6.0 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 2. 0 part, styrene 6.8 parts, 2-methacryloyloxyethyl acid phosphate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester P-1M] 1.0 part, acrylic acid 3.0 parts, acrylonitrile 1.0 part And a third stage pre-emulsion consisting of 0.2 part of 2-hydroxyethyl methacrylate Down, 3.5% 2.9 part of ammonium persulfate aqueous solution and 2.5% 2.0 parts of sodium hydrogen sulfite aqueous solution was added dropwise into the flask over a period of 90 minutes. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 15.3 ° C. The average particle size of the emulsion particles was 130 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Example 18
85 parts of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  10.3 parts of deionized water in a dropping funnel, 4.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

  Of the obtained pre-emulsion for dropping, 1.5 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate (1.4 parts) was added to the flask to initiate polymerization.

  Next, the rest of the dropping pre-emulsion, 2.9 parts of a 3.5% aqueous solution of ammonium persulfate and 2.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Then, 11.8 parts of deionized water, 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier, 28.2 parts of 2-ethylhexyl acrylate, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, styrene 18.4 parts, acrylic acid 1.0 part A second stage pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 parts of 2-hydroxyethyl methacrylate, 2.9 parts of 3.5% ammonium persulfate aqueous solution and 2.0 parts of 2.5% sodium bisulfite aqueous solution. It dripped into the flask over 90 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water and 6.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate ester salt [manufactured by ADEKA, trade name: ADEKA REASOAP SR-10] as an emulsifier. , Polyoxypropylene allyl ether phosphate [manufactured by ADEKA Corporation, trade name: ADEKA REASOAP PP-70] 4.0 parts of 25% aqueous solution, 6.0 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 2. A third stage pre-emulsion consisting of 0 part, 7.8 parts of styrene, 3.0 parts of methacrylic acid, 1.0 part of acrylonitrile and 0.2 part of 2-hydroxyethyl methacrylate, 3.5% ammonium persulfate aqueous solution 2.9. Parts and 2.0 parts of 2.5% aqueous sodium hydrogen sulfite solution over 90 minutes. It was dropped into the score. After the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, 25% aqueous ammonia was added to adjust the pH to 9.0, and the emulsion polymerization reaction was terminated. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 15.9 ° C. The average particle size of the emulsion particles was 130 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Comparative Example 1
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , 2-ethylhexyl acrylate 39.5 parts, styrene 53.0 parts, acrylic acid 5.0 parts, acrylonitrile 2.0 parts and 2-hydroxyethyl methacrylate 0.5 parts were prepared to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the resin emulsion obtained above was 7.0 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Comparative example 2
96.7 parts of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser.

  32.6 parts of deionized water in a dropping funnel, 12.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [manufactured by ADEKA, trade name: Adecaria Soap SR-10] as an emulsifier , 3-ethylhexyl acrylate (39.5 parts), methyl methacrylate (53.0 parts), acrylic acid (5.0 parts), acrylonitrile (2.0 parts) and 2-hydroxyethyl methacrylate (0.5 parts) were prepared to prepare a pre-emulsion for dropping.

  In the obtained pre-emulsion for dropping, 5.0 parts corresponding to 5% by mass of the total amount of monomer components was added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas to 3.5. % Aqueous solution of ammonium persulfate was added to the flask to start emulsion polymerization.

  Next, the rest of the dropping pre-emulsion, 8.6 parts of a 3.5% aqueous solution of ammonium persulfate and 6.0 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were dropped into the flask over 240 minutes. After the dropping was completed, the temperature was maintained at 80 ° C. for 120 minutes.

  Thereafter, 25% ammonia water was added, and the pH [measured by Horiba, Ltd., product number: F-23 at 23 ° C., the same applies hereinafter] was adjusted to 9.0 to terminate the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire net to obtain a resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of all the emulsion particles contained in the resin emulsion obtained above was 8.4 ° C. The average particle size of the emulsion particles was 120 nm. The resin emulsion obtained above was used as a resin composition for base repair.

Experimental Example While dispersing the resin composition for undercoat repair obtained in each Example or each Comparative Example at a rotation speed of 1000 min ^{−1 with a} homodisper, 2,2,4-trimethyl-1,3 as a film forming aid. -Pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12] is added to the resin composition for base repair so that the film-forming temperature is 0 ° C, and dilution water and silicone defoaming are added. Agent (manufactured by San Nopco Ltd., trade name: SN deformer 777) is added to the resin composition for undercoat repair in an appropriate amount, and dilution water is added to the resin composition for undercoat repair so that the nonvolatile content is 32% by mass. A coating material for evaluation was obtained by adding it to.

  Next, using the above-obtained coating composition for evaluation, water resistance, blister resistance, and adhesion to a substrate were examined as physical properties of the resin composition for undercoat repair of the present invention based on the following methods. The results are shown in Table 1.

〔water resistant〕
A black acrylic resin plate (manufactured by Nippon Test Panel Co., Ltd., length: 150 mm, width: 75 mm, thickness: 3 mm) so that the thickness of the coating film after drying the evaluation coating material obtained above is about 80 μm. ] Was applied using a 10 mil applicator and dried in the atmosphere at 25 ° C. for 1 week to obtain a test plate for evaluation.

The L value (L value before the test) of the evaluation test plate obtained above was measured by a color difference meter [spectroscopic color difference meter SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.]. Next, the test plate for evaluation was immersed in warm water kept at a water temperature of 50 ° C. for 1 day, then taken out from the warm water, wiped off water sufficiently, and within 1 minute the L value of the test plate (after the test) L value) was measured with the color difference meter and the formula:
[ΔL] = [L value after test] − [L value before test]
The color difference ΔL was determined based on the above, and the water resistance was evaluated based on the following evaluation criteria. Water resistance is judged to be acceptable when the evaluation is 10 points or more.

(Evaluation criteria)
50 points: ΔL is 0 or more and less than 3 30 points: ΔL is 3 or more and less than 10 10 points: ΔL is 10 or more and less than 20 0 point: ΔL is 20 or more (fail)

[Blister resistance]
The evaluation coating material obtained above was applied to a hydrophilic coating outer wall material [manufactured by Keimu Co., Ltd., trade name: EXCELLAGE / Hydrophilic Cera 15, length: 150 mm, width: 75 mm, thickness: 15 mm] with a brush of 50 g / m ² . A test piece for evaluation was obtained by uniformly applying the coating amount and drying it in the atmosphere at 25 ° C. for 1 week. The test piece for evaluation obtained above was immersed in warm water kept at a water temperature of 50 ° C. for 1 day, then taken out from the warm water, and the appearance of the coating film was visually observed, based on the following evaluation criteria. The blister resistance was evaluated. The blister resistance is considered to be acceptable when the evaluation is 30 points or more.

(Evaluation criteria)
50 points: No change is observed in the coating film.
30 points: Slight blisters are observed in the coating film.
0 points: The coating film has blisters and peeling is recognized (failure).

[Adhesion to substrate]
A cross-cut test was conducted in accordance with JIS K5600-5-6. The evaluation coating material obtained above was applied to a hydrophilic coating outer wall material [manufactured by Keimu Co., Ltd., trade name: EXCELLAGE / Hydrophilic Cera 15, length: 150 mm, width: 75 mm, thickness: 15 mm] with a brush of 50 g / m ² . After uniformly applying the coating amount and drying in the atmosphere at 25 ° C for 1 day, a super durable, low-contamination one-component water-based ceramic silicone resin coating [manufactured by SK Kaken Co., Ltd., trade name: Aqueous ceramisilicon (registered trademark)] was uniformly applied to the outer wall material with a brush at a coating amount of 50 g / m ² , and dried in the atmosphere at 25 ° C. for 7 weeks. Then, the outer wall material was immersed in warm water kept at a water temperature of 50 ° C. for 1 day, taken out from the warm water, and dried in the atmosphere at 25 ° C. for 6 hours to obtain a test piece for evaluation.

  After making 25 squares (length: 5 squares, width: 5 squares) in a 2 mm square grid with a sharp blade in the coating film of the test piece for evaluation obtained above, in accordance with JIS Z1522 The cellophane adhesive tape having a width of 25 mm was rubbed with a finger so that the cellophane adhesive tape was closely adhered in a grid pattern, allowed to stand in the atmosphere at 25 ° C. for 5 minutes, and then peeled off. The number of peeled squares was counted from the 25 squares produced, and the adhesion to the substrate was evaluated based on the following evaluation criteria. The adhesion to the substrate is judged to be acceptable when the evaluation is 20 points or more.

(Evaluation criteria)
50 points: The number of peeled grids is 0 40 points: The number of peeled grids is 1 to 4 30 points: The number of peeled grids is 5 to 9 20: The number of peeled grids is 10 to 19 0 points: 20 or more peeled cells (fail)

〔Comprehensive evaluation〕
An overall evaluation (maximum of 150 points) was performed by summing the evaluation scores in each test item. In addition, the resin composition for base repair which has even one evaluation of 0 in the physical property evaluation is unacceptable.

  From the results shown in Table 1, it can be seen that each of the resin compositions for undercoat repair obtained in each Example forms a coating film excellent in water resistance, blister resistance and adhesion to a substrate. .

  The base repair resin composition of the present invention is a coating film which is substantially free of volatile organic compounds and is a one-pack type, but which is excellent in water resistance, blister resistance and adhesion to a substrate. Therefore, it is expected to be suitably used, for example, as a base paint for repair which is used when repairing exterior building materials that constitute the outer wall of a building.

Claims (12)

A resin composition used for repairing a base, containing emulsion particles having a plurality of resin layers, the outermost layer of the emulsion particles is a unit amount containing an acetoacetoxy group-containing monomer and a styrene-based monomer A resin composition for undercoat repair, which is formed of a polymer obtained by emulsion polymerization of body components. The monomer component is further of formula (IV):

(In the formula, R ⁶ And R ⁷ Are each independently a hydrogen atom or a methyl group, R ⁸ Is a carbonyl group, an alkylene group having 1 to 4 carbon atoms or a direct bond, R ⁹ Is an ethylene group or a propylene group, R ^Ten Is a hydrogen atom, a methyl group or an alkyl group having 6 to 22 carbon atoms, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, a and b are each independently 0 or an integer of 1 to 50, and c is 1 or 2.)
The resin composition for undercoat repair according to claim 1, containing a phosphoric acid group-containing monomer represented by: The phosphoric acid group-containing monomer has the formula (V):

(In the formula, R ⁷ Is a hydrogen atom or a methyl group, R ⁹ Is an ethylene group or a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and b is 0 or an integer of 1 to 50. , C represents 1 or 2)
A phosphoric acid group-containing monomer represented by or formula (VI):

(In the formula, R ⁹ Is an ethylene group or a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and b is 0 or an integer of 1 to 50. , C represents 1 or 2)
The base repairing resin composition according to claim 2, which is a phosphoric acid group-containing monomer represented by: A method for producing a resin composition used for repairing an underlayer, wherein a monomer component forming an outermost layer of the emulsion particles when preparing a resin composition containing emulsion particles having a plurality of resin layers A method for producing a base repair resin composition, wherein a monomer component containing an acetoacetoxy group-containing monomer and a styrene-based monomer is used as the monomer, and the monomer component is emulsion-polymerized. The monomer component is further of formula (IV):

(In the formula, R ⁶ And R ⁷ Are each independently a hydrogen atom or a methyl group, R ⁸ Is a carbonyl group, an alkylene group having 1 to 4 carbon atoms or a direct bond, R ⁹ Is an ethylene group or a propylene group, R ^Ten Is a hydrogen atom, a methyl group or an alkyl group having 6 to 22 carbon atoms, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, a and b are each independently 0 or an integer of 1 to 50, and c is 1 or 2.)
The method for producing a resin composition for undercoat repair according to claim 4, which contains a phosphoric acid group-containing monomer represented by: The phosphoric acid group-containing monomer has the formula (V):

(In the formula, R ⁷ Is a hydrogen atom or a methyl group, R ⁹ Is an ethylene group or a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and b is 0 or an integer of 1 to 50. , C represents 1 or 2)
A phosphoric acid group-containing monomer represented by or formula (VI):

(In the formula, R ⁹ Is an ethylene group or a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and b is 0 or an integer of 1 to 50. , C represents 1 or 2)
The method for producing a resin composition for undercoat repair according to claim 5, which is a phosphoric acid group-containing monomer represented by: A resin composition used for repairing a base, containing emulsion particles, acetoacetoxy group-containing monomer as a raw material of the emulsion particles , a styrene-based monomer and formula (IV):

(In the formula, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is a carbonyl group, an alkylene group having 1 to 4 carbon atoms or a direct bond, R ⁹ is an ethylene group or a propylene group, and R ¹⁰ is A methyl group or an alkyl group having 6 to 22 carbon atoms, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and a and b are Each independently 0 or an integer of 1 to 50, and c represents 1 or 2)
A resin composition for base repair, comprising a monomer component containing a phosphoric acid group-containing monomer represented by: The phosphoric acid group-containing monomer has the formula (V):

(In the formula, R ⁷ is a hydrogen atom or a methyl group, R ⁹ is a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine having 1 to 10 carbon atoms. A residue, b is 0 or an integer of 1 to 50, and c is 1 or 2)
A phosphoric acid group-containing monomer represented by or formula (VI):

(In the formula, R ⁹ is a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and b is 0 or 1 to 1. 50 is an integer, c is 1 or 2)
The resin composition for undercoat repair according to claim 7, which is a phosphoric acid group-containing monomer represented by: A method for producing a resin composition used for repairing an underlayer, wherein an acetoacetoxy group-containing monomer and a styrene-based monomer are used as raw materials for the emulsion particles when preparing a resin composition containing the emulsion particles. And formula (IV):

(In the formula, R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, R ⁸ is a carbonyl group, an alkylene group having 1 to 4 carbon atoms or a direct bond, R ⁹ is an ethylene group or a propylene group, and R ¹⁰ is A methyl group or an alkyl group having 6 to 22 carbon atoms, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and a and b are Each independently 0 or an integer of 1 to 50, and c represents 1 or 2)
A method for producing a resin composition for undercoat repair, comprising using a monomer component containing a phosphoric acid group-containing monomer represented by and emulsion-polymerizing the monomer component. The phosphoric acid group-containing monomer has the formula (V):

(In the formula, R ⁷ is a hydrogen atom or a methyl group, R ⁹ is a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine having 1 to 10 carbon atoms. A residue, b is 0 or an integer of 1 to 50, and c is 1 or 2)
A phosphoric acid group-containing monomer represented by or formula (VI):

(In the formula, R ⁹ is a propylene group, M is a hydrogen atom, an alkali metal atom, an ammonium group, an alkylamine residue having 1 to 10 carbon atoms or an alkanolamine residue having 1 to 10 carbon atoms, and b is 0 or 1 to 1. 50 is an integer, c is 1 or 2)
The method for producing a resin composition for undercoat repair according to claim 9, which is a phosphoric acid group-containing monomer represented by : A base paint for repair, comprising the resin composition for base repair according to any one of claims 1 to 3 and claim 8 . A building material to which the repair base paint according to claim 11 is applied.