JP2018059007A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition forming a coated film which is excellent in storage stability and in adhesion to a base material and elongation.SOLUTION: A resin composition using a hydroxyl group-containing compound as a raw material contains (meth)acrylic resin emulsion, where the hydroxyl group-containing compound is represented by formula (I): (HO)-Z-R. In formula (I), Z represents a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R represents a hydrocarbon group which may have at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group and has 1 to 18 carbon atoms, and m represents a number smaller than the number of unpaired electrons that Z has by 1.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. More specifically, the present invention is suitable for, for example, a water-based paint that can be suitably used for repairing a base used in a building material constituting an outer wall, an inner wall, a floor, or the like of a building, and the water-based paint. The present invention relates to a resin composition that can be used, a manufacturing method thereof, and a building material to which the water-based paint is applied.

  Exterior materials such as siding boards are widely used on outer walls of houses and the like. In order to prevent deterioration of the surface of the exterior material, a coating film is generally formed on the surface. On the surface of the exterior material, a coating film having not only various colors and design properties but also weather resistance is formed. Moreover, in order to give a weather resistance to a coating film, the coating film in which the low-contamination photocatalyst process, the hydrophilization process, the fluorine coating process, etc. were given as an outermost layer coating film is formed. However, since the coating film deteriorates due to long-term irradiation with sunlight, changes in temperature, exposure to rainwater, etc., there is an increasing need for repainting, that is, repairing of the coating film.

  As an undercoat paint for repairing exterior materials such as exterior walls of buildings, three components of resin emulsion (A), glycidyl group-containing silane coupling agent (B), and amino group-containing silane coupling agent (C) A water-based undercoat paint composition for repair containing it has been proposed (see, for example, claim 1 of Patent Document 1). Moreover, from the viewpoint of improving workability in the field of repairing exterior materials, the first liquid containing the resin emulsion (A) and the glycidyl group-containing silane coupling agent (B) are used as the water-based undercoat paint composition for repair. And a two-component 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 water-based undercoating composition for repair react quickly with mixing. Therefore, these three components need to be weighed and mixed in a predetermined amount at the site where the exterior material is repaired, and it is necessary to quickly use them, so it is necessary to quickly perform a complicated mixing operation for the operator. . In addition, even when the water-based undercoating composition for repair is a two-component coating composition, it is necessary to quickly perform a complicated operation of mixing the first liquid and the second liquid at a predetermined ratio. If the mixing ratio of the liquid and the second liquid is wrong, there is a possibility that a coating film having desired properties cannot be formed.

  Therefore, in recent years, in order to improve the workability at the site of repairing the foundation used for building materials constituting the outer wall, inner wall, floor, etc. of the building, a plurality of components are mixed at the site where the coating film is repainted. Development of a resin composition that forms a coating film that is excellent in storage stability and excellent in adhesion and extensibility to a substrate is desired.

  In this specification, in order to repair a coating film already formed on the object to be coated, the resin composition is applied to the coating film to form a new coating film. It means a resin composition used for a base treatment agent such as paint, building material, concrete, etc., coating agent, surface treatment agent, adhesive agent, sealing agent, etc. used as paint or top coat. Water-based paints are used as undercoats, intermediate coats, or topcoats when a new paint film is formed by applying on a paint film to repair a paint film already formed on an object. Means paint. The resin composition and water-based paint of the present invention are suitable as an undercoat when a new paint film is formed by applying on the paint film in order to repair the paint film already formed on the object. It is used.

JP 2012-251094 A

  The present invention has been made in view of the prior art, and does not require a complicated operation of mixing a plurality of components at the site where the coating film is repainted, and has excellent storage stability and adhesion to the substrate. An object of the present invention is to provide a water-based paint that forms a coating film having excellent properties and extensibility, a resin composition that can be suitably used for the water-based paint, a method for producing the same, and a building material to which the water-based paint is applied. To do.

The present invention
(1) A resin composition using a hydroxyl group-containing compound as a raw material, comprising a (meth) acrylic resin emulsion, wherein the hydroxyl group-containing compound is represented by the formula (I):
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
A resin composition characterized by being a hydroxyl group-containing compound represented by:
(2) A water-based paint comprising the resin composition according to (1),
(3) A building material to which the water-based paint according to (2) is applied,
(4) A method for producing a resin composition containing a (meth) acrylic resin emulsion, wherein the (meth) acrylic resin emulsion and the formula (I):
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
And (5) a method for producing a resin composition containing a (meth) acrylic resin emulsion, which comprises mixing a hydroxyl group-containing compound represented by formula (I): :
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
And a monomer component used as a raw material for the (meth) acrylic resin emulsion in the presence of a hydroxyl group-containing compound.

  According to the present invention, a complicated operation of mixing a plurality of components at the site where the coating film is repainted is not required, and the coating film has excellent storage stability and excellent adhesion to the substrate and extensibility. Provided are a water-based paint to be formed, a resin composition that can be suitably used for the water-based paint, a method for producing the same, and a building material to which the water-based paint is applied.

As described above, the resin composition of the present invention is a resin composition in which a hydroxyl group-containing compound is used as a raw material, contains a (meth) acrylic resin emulsion, and the hydroxyl group-containing compound has the formula (I):
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
It is a hydroxyl-containing compound represented by these.

  In the present specification, “(meth) acryl” means “acryl” or “methacryl”, “(meth) acrylate” means “acrylate” or “methacrylate”, and “(meth) acryloyl” means It means “acryloyl” or “methacryloyl”.

  The present invention has one major feature in that the hydroxyl group-containing compound represented by the formula (I) is used. The resin composition of the present invention uses a hydroxyl group-containing compound represented by the formula (I), so that it has excellent storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. Excellent effect.

  In the hydroxyl group-containing compound represented by the formula (I), Z is excellent in storage stability, and from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the base material and extensibility, boron atom, aluminum An atom, a titanium atom or a zirconium atom. Among these atoms, aluminum atoms are preferable from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. In Z, two or more kinds of atoms may be used as long as the object of the present invention is not impaired.

  In the hydroxyl group-containing compound represented by the formula (I), X is excellent in storage stability, and from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility, hydroxyl group, carboxyl group , An amino group, a mercapto group, a pyrrolidine group, a piperidine group, and a disulfide group, which may have at least one group selected from the group consisting of a disulfide group.

  Examples of X include alkyl group, hydroxyl group-containing alkyl group, carboxyl group-containing alkyl group, aminoalkyl group, diaminoalkyl group, mercaptoalkyl group, mercaptoaminoalkyl group, pyrrolidine group (pyrrolidine skeleton) -containing alkyl group, piperidine group ( Piperidine skeleton) containing alkyl group, aminoalkyl group-containing phenyl group, alkyl group having carboxyl group and hydroxyl group, vinyl group-containing alkyl group, propylene group-containing alkyl group, alkyl group having carboxyl group and disulfide group, C 1-18 Although the phenyl group etc. which have the aminoalkyl group of these are mentioned, this invention is not limited only to this illustration. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 2 to 2 from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. 12, more preferably 2-8.

  Among the above X, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility, a C 1-8 mercaptoalkyl group, C 1 A mercaptoaminoalkyl group of ˜8, an aminoalkyl group of 1 to 8 carbon atoms, a diaminoalkyl group of 1 to 8 carbon atoms, a piperidine group (piperidine skeleton) -containing alkyl group having an alkyl group of 1 to 8 carbon atoms, carbon An aminoalkyl group-containing phenyl group having an aminoalkyl group having 1 to 8 carbon atoms, a carboxyl group having 1 to 8 carbon atoms, a carboxyl group having a carboxyl group and a hydroxyl group, and an alkyl group containing a hydroxyl group, an alkyl having 1 to 8 carbon atoms A carboxyl group-containing alkyl group having a group, an alkyl group having 1 to 8 carbon atoms and a vinyl group-containing alkyl group having a vinyl group, 1 to 8 carbon atoms A propylene group-containing alkyl group having an alkyl group and a propylene group, a carboxyl group having 1 to 8 carbon atoms, a carboxyl group having a carboxyl group and a disulfide group, and a disulfide group-containing alkyl group are preferred, and an aminoalkyl group having 1 to 6 carbon atoms And a mercaptoalkyl group having 1 to 6 carbon atoms is preferred, and an aminoalkyl group having 1 to 4 carbon atoms is more preferred.

  In the hydroxyl group-containing compound represented by the formula (I), m is an element possessed by Z from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. The number is one smaller than the number of counter electrons. When Z is composed of a plurality of atoms, m is a number that is 1 smaller than the number of unpaired electrons that Z has when a plurality of metals are bonded. For example, when Z is a metal in which trivalent aluminum and tetravalent zirconium are bonded, the number of unpaired electrons that Z has is five, and m is one smaller than five unpaired electrons. Since it is a number, it is 4.

  Specific examples of the hydroxyl group-containing compound represented by the formula (I) include, for example, a hydroxyl group containing, in the formula (I), Z is an aluminum atom, X is an aminoalkyl group having 1 to 3 carbon atoms, and m is an integer of 2. Compound (manufactured by Chartwell International, product number: B-515.71W), in formula (I), Z is an aluminum atom and a zirconium atom, X is an aminoamino group having 1 to 3 carbon atoms, and m is the valence of the entire Z In the formula (I), Z is an aluminum atom, X is a C 4-6 aminoalkyl group, m Is a hydroxyl group-containing compound (product number: B-516.71HRW, manufactured by Chartwell International, Inc.), wherein in formula (I), Z represents an aluminum atom and di And a hydroxy group-containing compound (product number: B-505.1, manufactured by Chartwell International, Inc.) in which X is a mercaptoalkyl group having 1 to 5 carbon atoms, m is 1 smaller than the valence of the entire Z, and the like. However, the present invention is not limited to such examples. These hydroxyl group-containing compounds may be used alone or in combination of two or more.

  Among the hydroxyl group-containing compounds represented by the formula (I), in terms of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility, in the formula (I) Z is an aluminum atom, X is an aminoalkyl group having 1 to 4 carbon atoms, and m is a hydroxyl group-containing compound wherein m is an integer of 2.

  The resin composition of the present invention uses a hydroxyl group-containing compound represented by the formula (I) as a raw material, and contains a (meth) acrylic resin emulsion. Since the resin composition of the present invention uses a (meth) acrylic resin emulsion, it is possible to form a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility.

  The hydroxyl group-containing compound represented by the formula (I) is used as a mixture with a (meth) acrylic resin emulsion or as a mixture with a monomer component used as a raw material of a (meth) acrylic resin emulsion. It is preferable that When the hydroxyl group-containing compound represented by the formula (I) is used as a mixture with the monomer component used as a raw material of the (meth) acrylic resin emulsion, in the presence of the hydroxyl group-containing compound represented by the formula (I) ( The monomer component used as a raw material for the (meth) acrylic resin emulsion is emulsion-polymerized, or the monomer component used as the raw material for the (meth) acrylic resin emulsion is added with a hydroxyl group-containing compound represented by the formula (I) The monomer component containing the hydroxyl group-containing compound can be emulsion polymerized.

  In the present invention, the hydroxyl group-containing compound represented by the formula (I) may be present in the resin composition in combination with the polymer constituting the emulsion particles, and is independent without being bonded to the polymer. And may be present in the resin composition.

As a method for producing the resin composition of the present invention, for example,
(1) A method of mixing a (meth) acrylic resin emulsion and a hydroxyl group-containing compound represented by the formula (I),
(2) A method in which the monomer component used as a raw material for the (meth) acrylic resin emulsion is emulsion-polymerized in the presence of the hydroxyl group-containing compound represented by the formula (I) can be mentioned. It is not limited to only.

  First, a method for producing a resin composition by mixing the (1) (meth) acrylic resin emulsion and a hydroxyl group-containing compound represented by the formula (I) will be described.

  In the method of mixing the (1) (meth) acrylic resin emulsion and the hydroxyl group-containing compound represented by the formula (I), the (meth) acrylic resin emulsion and the hydroxyl group-containing compound represented by the formula (I) are mixed. The order to do is arbitrary, for example, the (meth) acrylic resin emulsion may be added and mixed with the hydroxyl group-containing compound represented by the formula (I), and the (meth) acrylic resin emulsion and the formula (I) And a hydroxyl group-containing compound represented by:

  The (meth) acrylic resin emulsion can be obtained, for example, by emulsion polymerization of a monomer component containing a (meth) acrylic monomer.

  The content of the (meth) acrylic monomer in the monomer component is preferably from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. Is 30% by mass or more, more preferably 40% by mass or more, and preferably 70% by mass or less, more preferably from the viewpoint of obtaining a resin composition that forms a coating film having excellent adhesion to the substrate and extensibility. 60% by mass or less.

  Examples of the (meth) acrylic monomer include (meth) acrylic acid, alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate, acetoacetoxy group-containing (meth) acrylate, phosphate group-containing (meth) acrylate, Silane group-containing (meth) acrylate, nitrogen atom-containing (meth) acrylic monomer, aralkyl (meth) acrylate, oxo group-containing (meth) acrylate, fluorine atom-containing (meth) acrylate, epoxy group-containing (meth) acrylate, Examples include ultraviolet-absorbing (meth) acrylic monomers and ultraviolet-stable (meth) acrylic monomers, but the present invention is not limited to such examples. These (meth) acrylic monomers may be used alone or in combination of two or more. Among these (meth) acrylic monomers, (meth) acrylic acid is excellent in terms of storage stability and from the viewpoint of obtaining a resin composition that forms a coating film with excellent adhesion to the substrate and extensibility. , Alkyl (meth) acrylate, hydroxyl group-containing (meth) acrylate, acetoacetoxy group-containing (meth) acrylate, phosphate group-containing (meth) acrylate, silane group-containing (meth) acrylate and nitrogen atom-containing (meth) acrylic monomer The body is preferred.

  Among (meth) acrylic acids, methacrylic acid is preferable from the viewpoint of improving the low water absorption of the coating film. The content of (meth) acrylic acid in the monomer component is preferably from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. 5% by mass or more, more preferably 1% by mass or more, and further preferably 1.5% by mass or more, and a resin composition that forms a coating film having excellent storage stability and excellent adhesion to substrates and extensibility. From the viewpoint of obtaining a product, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 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, and sec-butyl (meth). Alkyl having 1 to 18 carbon atoms in an ester group such as acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These alkyl (meth) acrylates may be used alone or in combination of two or more. Among these alkyl (meth) acrylates, the alkyl group has 1 to 1 carbon atoms from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film having excellent adhesion to the substrate and extensibility. An alkyl (meth) acrylate that is 8 is preferable, an alkyl (meth) acrylate having 4 to 8 carbon atoms is more preferable, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are more preferable, and 2-ethylhexyl. Acrylates are even more preferred.

  The content of the alkyl (meth) acrylate in the monomer component is preferably 10% from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. % Or more, more preferably 15% by mass or more, and further preferably 20% by mass or more, and the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to substrates and extensibility. Therefore, it is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by 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 include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the ester group such as butyl (meth) acrylate, but the present invention is not limited to such examples. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more. Among these hydroxyl group-containing (meth) acrylates, 2-hydroxyethyl (meth) is used from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to substrates and extensibility. Acrylate is preferred, and 2-hydroxyethyl methacrylate is more preferred.

  The content of the hydroxyl group-containing (meth) acrylate in the monomer component is preferably 0 from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. .1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more, forming a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. From the viewpoint of obtaining a resin composition, the content is preferably 2% by mass or less, more preferably 1.5% by mass or less, and further preferably 1% by mass or less.

  As the acetoacetoxy group-containing (meth) acrylate, for example, the formula (II):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and r represents an integer of 1 to 4)
Although the acetoacetoxy group containing (meth) acrylate etc. which are represented by these are mentioned, this invention is not limited only to this illustration.

R ¹ is a hydrogen atom or a methyl group, preferably a methyl group, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility.

  r is an integer of 1 to 4, preferably an integer of 1 and 2, and more preferably an integer of 2, from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility.

  Specific examples of the acetoacetoxy group-containing (meth) acrylate represented by the formula (II) include, for example, acetoacetoxymethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl Although (meth) acrylate, acetoacetamidoethyl (meth) acrylate, etc. are mentioned, this invention is not limited only to this illustration. These monomers may be used alone or in combination of two or more.

  Among the acetoacetoxy group-containing (meth) acrylates represented by the formula (II), in addition to excellent storage stability, from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to substrates and extensibility, Acetoacetoxyethyl (meth) acrylate is preferred, and acetoacetoxyethyl methacrylate is more preferred.

  The content of the acetoacetoxy group-containing (meth) acrylate in the monomer component is preferably from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. Is 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more, and has excellent storage stability and excellent adhesion to the substrate and extensibility. From the viewpoint of obtaining a resin composition that forms, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.

  Examples of the phosphoric acid group-containing (meth) acrylate include the formula (III):

(Wherein R ² is independently a hydrogen atom or a methyl group, R ³ 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 a carbon atom) An alkanolamine residue of formula 1 to 10, a is independently an integer of 0 or 1 to 50, and b is 1 or 2)
Although the phosphate group containing (meth) acrylate etc. which are represented by these are mentioned, this invention is not limited only to this illustration.

R ² is a hydrogen atom or a methyl group, preferably a methyl group, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility.

R ³ is an ethylene group or a propylene group, preferably an ethylene group, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility.

  M is a hydrogen atom, an alkali metal atom, an ammonium group, having 1 to 10 carbon atoms from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion and extensibility to a substrate. An alkylamine residue or an alkanolamine residue having 1 to 10 carbon atoms, preferably a hydrogen atom or an ammonium group, more preferably a hydrogen atom. 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, and triethylamine. Examples of the alkanolamine residue having 1 to 10 carbon atoms include monoethanolamine, diethanolamine, and triethanolamine.

  a is independently an integer of 0 or 1 to 50, preferably 0 or from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. It is an integer of 1-30, more preferably an integer of 0 or 1-20, still more preferably an integer of 0 or 1-10, still more preferably an integer of 0 or 1-5. When a is 0, the C (O) O— group and the —P═O group are directly bonded.

  b is 1 or 2, preferably 1, from the viewpoint of obtaining a resin composition which is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility.

Specific examples of the phosphoric acid group-containing (meth) acrylate represented by the formula (III) include, for example, 2- (meth) acryloyloxyethyl acid phosphate [for example, Kyoeisha Chemical Co., Ltd., trade name: Light Ester P- 1M [Phosphorus group-containing (meth) acrylate in which R ² is a methyl group, R ³ is an ethylene group, M is a hydrogen atom, a is 1 and b is 1], P-2M [formula (III) In III), R ² is a methyl group, R ³ is an ethylene group, M is a hydrogen atom, a is 1, and b is 2, a phosphate group-containing (meth) acrylate], P-1A (N) [formula (III ), R ² is a hydrogen atom, R ³ is an ethylene group, M is a hydrogen atom, a is 1, and b is 1, a phosphate group-containing (meth) acrylate], manufactured by Unichemical Co., Ltd., trade name: Phosmer M [in formula (III), R ² is a methyl group, R ³ is an ethylene group, M Hydrogen atom, a is 1, b is phosphate group containing 1 (meth) acrylate], in Phosmer PE [Formula (III), R ² is a methyl group, R ³ is an ethylene group, M is a hydrogen atom, a is 4 or 5, phosphoric acid group-containing (meth) acrylate in which b is 1, etc.], and phosphoric acid group-containing (meth) acrylates such as 2- (meth) acryloyloxypropyl acid phosphate. However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

Among the phosphoric acid group-containing (meth) acrylates represented by the formula (III), in addition to excellent storage stability, from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to substrates and extensibility, 2-methacryloyloxyethyl acid phosphate [in formula (III), R ² is a methyl group, R ³ is an ethylene group, M is a hydrogen atom, a is 1 and b is 1 containing (meth) acrylate] preferable.

  The content of the phosphoric acid group-containing (meth) acrylate in the monomer component is preferably from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. Is 0.03% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, and it is excellent in storage stability and has excellent adhesion to the substrate and extensibility. From the viewpoint of obtaining a resin composition that forms, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.

  Examples of the silane group-containing (meth) acrylate include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylhydroxysilane, γ- (meth) acryloyloxypropylmethylhydroxysilane, and the like. However, the present invention is not limited to such examples. These silane group-containing (meth) acrylates may be used alone or in combination of two or more. Among these silane group-containing (meth) acrylates, γ- (meth) acryloyl is used from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to substrates and extensibility. Oxypropyltrimethoxysilane is preferred, and γ-methacryloyloxypropyltrimethoxysilane is more preferred.

  The content of the silane group-containing (meth) acrylate in the monomer component is preferably 0.01% by mass or more, more preferably 0.03% by mass from the viewpoint of improving the low water absorption and water absorption whitening resistance of the coating film. % Or more, more preferably 0.05% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less, from the viewpoint of improving the low water absorption and water absorption whitening resistance of the coating film. Preferably it is 0.3 mass% or less.

  Examples of the nitrogen atom-containing (meth) acrylic monomer include (meth) acrylamide, diacetone (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meta) ) Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acrylamide compounds such as diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Examples thereof include nitrogen atom-containing (meth) acrylate compounds such as a rate, (meth) acrylonitrile, and the like, but the present invention is not limited to such examples. These nitrogen atom-containing (meth) acrylic monomers may be used alone or in combination of two or more. Among these nitrogen atom-containing (meth) acrylic monomers, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. ) Acrylonitrile is preferred, and acrylonitrile is more preferred.

  The content of the nitrogen atom-containing (meth) acrylic monomer in the monomer component is excellent in storage stability, and a viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the base material and extensibility Therefore, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass or more, and it is excellent in storage stability and excellent in adhesion to the substrate and extensibility. From the viewpoint of obtaining a resin composition for forming a film, the content is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

  Examples of the aralkyl (meth) acrylate include aralkyl having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate and the like. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These aralkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the oxo group-containing (meth) acrylate include (di) ethylene glycol (methoxy) (ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate) ( Examples thereof include, but are not limited to such examples. These oxo group-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the fluorine atom-containing (meth) acrylate include fluorine atoms having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Although alkyl (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These fluorine atom-containing (meth) acrylates may be used alone or in combination of two or more.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, but the present invention is not limited to such examples.

  Examples of the UV-absorbing (meth) acrylic monomer include benzotriazole-based UV-absorbing monomers and benzophenone-based UV-absorbing monomers, but the present invention is limited only to such examples. It is not something. These ultraviolet absorbing monomers may be used alone or in combination of two or more.

  Examples of the benzotriazole-based UV-absorbing monomer include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5′- (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2 ′ -Hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzo Triazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyhex Ruphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′ -Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acrylyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydride Xyl-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′- tert-butylphenyl] -4-tert-butyl-2H-benzotriazole and the like, but the present invention is not limited to such examples. These benzotriazole-based UV-absorbing monomers may be used alone or in combination of two or more.

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

  Examples of the UV-stable (meth) acrylic monomer include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6, 6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine 4-cyano-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethyl Piperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6 Examples include 6-tetramethylpiperidine and 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, but the present invention is limited to such examples. It is not limited. These ultraviolet-stable (meth) acrylic monomers may be used alone or in combination of two or more.

  A monomer other than the (meth) acrylic monomer can be used as the monomer component. Examples of the monomer other than the (meth) acrylic monomer include, for example, a styrene monomer, a phosphate group-containing monomer, a carboxyl group-containing monomer, a silane group-containing monomer, and a nitrogen atom-containing monomer. Examples thereof include UV-stable monomers other than monomers and UV-stable (meth) acrylic monomers, but the present invention is not limited to such examples. Monomers other than these (meth) acrylic monomers may be used alone or in combination of two or more. Among the monomers other than these (meth) acrylic monomers, from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility, Styrenic monomers and phosphate group-containing monomers are preferred.

  Examples of the styrenic monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, and the like, but the present invention is limited only to such examples. is not. These monomers may be used alone or in combination of two or more. The styrene monomer may have an alkyl group such as a methyl group or 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 monomers, styrene is preferable from the viewpoint of improving the low water absorption of the coating film.

  The content of the styrene monomer in the monomer component is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more, from the viewpoint of improving the low water absorption of the coating film. From the viewpoint of improving the low water absorption of the coating film, it is preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.

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

(Wherein R ³ , M, a and b are the same as above)
Although the phosphate group containing single quantity etc. which are represented by these are mentioned, this invention is not limited only to this illustration.

In the formula (IV), R ³ , M, a and b are the same as R ³ , M, a and b described in the formula (III). R ³ is an ethylene group or a propylene group, preferably a propylene group, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film having excellent adhesion to the substrate and extensibility. When a is 0, the CH ₂ O— group and the —P═O group are directly bonded.

Among the phosphate group-containing monomers represented by the formula (IV), from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to substrates and extensibility. Oxypropylene allyl ether phosphate ester [wherein R ³ is a propylene group, M is a hydrogen atom or an ammonium group, a is an integer of 5 to 20, and b is 1 or 2] ] Is preferable.

  Specific examples of the phosphate group-containing monomer represented by the formula (IV) include, for example, polyoxyalkylene allyl ether phosphate ester (for example, trade name: Adeka Soap PP-70 manufactured by ADEKA Corporation) However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  The content of the phosphate group-containing monomer in the monomer component is preferably from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. 0.03% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, and a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. From the viewpoint of obtaining a resin composition to be formed, the content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less.

  Among the phosphoric acid group-containing (meth) acrylates represented by the formula (III) and the phosphoric acid group-containing monomers represented by the formula (IV), the storage stability is excellent, and the adhesion to the substrate and elongation are also excellent. From the viewpoint of obtaining a resin composition that forms a coating film having excellent properties, a phosphate group-containing monomer represented by the formula (IV) is preferable.

  Examples of the carboxyl group-containing monomer include carboxyl group-containing aliphatic monomers such as maleic acid, fumaric acid, crotonic acid, itaconic acid, and maleic anhydride, but the present invention is only such examples. It is not limited to. These carboxyl group-containing monomers may be used alone or in combination of two or more.

  Examples of the silane group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, 2-styrylethyltrimethoxysilane, vinyltrichlorosilane, and the like. It is not limited to illustration only. These silane group-containing monomers may be used alone or in combination of two or more.

  Examples of the nitrogen atom-containing monomer include N-vinylpyrrolidone, but the present invention is not limited to such examples.

  Examples of UV-stable monomers other than UV-stable (meth) acrylic monomers include 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2, Examples include 2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, and the present invention is not limited to such examples. Absent. These ultraviolet-stable monomers other than these ultraviolet-stable (meth) acrylic monomers may be used alone or in combination of two or more.

  As a method for emulsion polymerization of the monomer component, for example, an aqueous medium containing a water-soluble organic solvent such as methanol and a lower alcohol, and water, an emulsifier is dissolved in a medium such as water, and a single amount is obtained 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. It is not limited. In addition, what is necessary is just to set the quantity of a medium suitably in consideration of the non volatile matter amount contained in the (meth) acrylic-type resin emulsion obtained.

  Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, and a polymer emulsifier. These emulsifiers may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate. It is not limited to illustration only.

  Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Although the condensate with an amine etc. are mentioned, this invention is not limited only to this illustration.

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

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

  Examples of the polymer emulsifier include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinyl pyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; single polymers constituting these polymers. Although the polymer etc. which use a 1 or more types of monomer of a monomer as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  The reactive emulsifier can be preferably used from the viewpoint of improving the low water absorption and water absorption whitening resistance of the coating film, and among these, a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.

  Examples of the reactive emulsifier include propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, polyoxyethylene alkylpropenyl phenyl ether ammonium sulfate [for example, trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Aqualon HS-10, Aqualon BC-10, etc.], sulfonate salts of allyloxymethylalkyloxypolyoxyethylene (for example, Dairon Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), allyloxymethylnonylphenoxy Sulphonate salt of ethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA, trade name: Adekaria soap SE-10, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate salt [for example, (strain Made by ADEKA, trade names: ADEKA rear soap SR-10, SR-20, SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt [for example, made by Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA, trade names: Adeka Soap ER-10, ER-20, ER-30, ER-40, etc.], Polyoxyethylene alkylpropenyl phenyl ether [for example, product name: Aqualon RN-20, etc., manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene [for example, product name, manufactured by ADEKA Corporation, product name : Adekaria soap NE-10, NE-20, NE 30, etc.] Although the like, the present invention is not limited only to those exemplified. Any of these reactive emulsifiers may be used alone or in combination of two or more.

  The phosphate group-containing monomer represented by the formula (IV) can also be used as a reactive emulsifier because it has a function as an emulsifier.

  The amount of the emulsifier per 100 parts by mass of the monomer component is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass from the viewpoint of improving the polymerization stability. From the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. More preferably, it is 10 mass parts or less.

  When the phosphate group-containing monomer represented by the formula (IV) is used, the phosphate group-containing monomer represented by the formula (IV) has a function as an emulsifier. The remainder obtained by subtracting the amount used of these monomers from the amount used can be used as an emulsifier other than these monomers.

  A polymerization initiator can be used when the monomer component is polymerized. Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate and ammonium persulfate; Examples of the peroxide include peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. However, the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator per 100 parts by mass of the monomer component is preferably 0.01 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. 0.03 parts by mass or more, and from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent extensibility, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less. is there.

  The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. From the viewpoint of advancing the completion time of the polymerization reaction, a part of the polymerization initiator may be added to the flask before or after the monomer component is added to the reaction system.

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

  In addition, in the reaction system, for example, an appropriate amount of additives such as a chain transfer agent such as a compound having a thiol group such as tert-dodecyl mercaptan, a pH buffering agent, a chelating agent, and a film forming aid may be appropriately added to the flask. May be added. Since the amount of the additive varies depending on the type, it cannot be determined unconditionally, but is usually preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts per 100 parts by mass of the monomer component. Part by mass.

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

  Although the polymerization temperature at the time of carrying out emulsion polymerization of a monomer component does not have limitation, Usually, Preferably it is 50-100 degreeC, More preferably, it is 60-95 degreeC. The polymerization temperature may be constant or may be changed during the polymerization reaction.

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

  Emulsion particles are obtained by emulsion polymerization of the monomer component 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, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. Above, more preferably 550,000 or more, 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 cross-linked structure, but when it does not have a cross-linked structure, the film-forming property is improved. From the viewpoint, it is preferably 5 million or less.

  In addition, in this specification, the weight average molecular weight of a polymer uses gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L in series. ] Is used to mean the weight average molecular weight (in terms of polystyrene) measured.

  The emulsion particles may have a single resin layer prepared by one-stage emulsion polymerization or may have a plurality of resin layers prepared by multi-stage emulsion polymerization. Among these emulsion particles, having a plurality of resin layers is preferable from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. When the emulsion particles have a plurality of resin layers, the boundary between the resin layers is not necessarily clear, and adjacent resin layers may be mixed with each other.

  The number of the resin layers constituting the emulsion particles is preferably 1 to 5 layers from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. Preferably 1 to 3 layers, more preferably 2 and 3 layers.

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

  When the emulsion particles have a plurality of resin layers, the outermost layer of the emulsion particles is excellent in storage stability, and from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility, It is preferably formed of a polymer obtained by emulsion polymerization of the monomer component. In this case, layers other than the outermost layer, for example, when the emulsion particles are formed of two resin layers, the inner layer, and when the emulsion particles are formed of three resin layers, the intermediate layer and the inner layer are The same kind of monomer as that used for the monomer component can be used. Emulsion particles having a plurality of resin layers can be prepared, for example, by subjecting the monomer component to multistage emulsion polymerization under the same polymerization method and polymerization conditions as in the case of emulsion polymerization of the monomer component.

  When the emulsion particles have two resin layers, an inner layer and an outer layer, the emulsion particles having the inner layer and the outer layer are obtained by emulsion polymerization of monomer components forming the inner layer, and the outer layer in the presence of the obtained emulsion particles. The monomer component to be formed can be prepared by emulsion polymerization. In this case, the monomer component forming the inner layer is preferably composed of a styrene monomer, and preferably composed of styrene, from the viewpoint of improving the low water absorption of the coating film. In addition, the monomer component forming the outer layer is the monomer component from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. It is preferable.

  When the emulsion particles have two resin layers, an inner layer and an outer layer, the mass ratio between the resin layer constituting the inner layer and the resin layer constituting the outer layer (resin layer / outer layer constituting the inner layer) The constituent resin layer) is preferably 10/90 or more, more preferably 20/80 or more, and still more preferably, from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility. Is 30/70 or more, and preferably 70/30 or less, more preferably 60/40 or less, and still more preferably 50/50 or less, from the viewpoint of improving film-forming properties and adhesion to a substrate.

  When the emulsion particles have three resin layers, an inner layer, an intermediate layer, and an outer layer, the emulsion particles having the three resin layers of the inner layer, the intermediate layer, and the outer layer are emulsion-polymerized monomer components that form the inner layer. The monomer component forming the intermediate layer is emulsion-polymerized in the presence of the obtained emulsion particles, and the monomer component forming the outer layer is emulsion-polymerized in the presence of the obtained emulsion particles. be able to. In this case, the monomer component forming the inner layer is preferably composed of a styrene monomer, and preferably composed of styrene, from the viewpoint of improving the low water absorption of the coating film. The monomer component that forms the intermediate layer is (meth) acrylic acid as a (meth) acrylic monomer from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to substrates and extensibility. 1 to 5% by mass, alkyl (meth) acrylate 40 to 70% by mass, hydroxyl group-containing (meth) acrylate 0.1 to 5% by mass, acetoacetoxy group-containing (meth) acrylate 0 to 10% by mass, phosphoric acid group-containing ( It preferably contains 0 to 5% by weight of (meth) acrylate, 0.05 to 1% by weight of silane group-containing (meth) acrylate and 1 to 5% by weight of nitrogen atom-containing (meth) acrylic monomer, (meth) As a monomer other than the acrylic monomer, it is preferable to contain 20 to 50% by mass of a styrene monomer and 0 to 5% by mass of a phosphate group-containing monomer. In addition, the monomer component forming the outer layer is the monomer component from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. It is preferable.

  In the case where the emulsion particles have three resin layers of an inner layer, an intermediate layer, and an outer layer, from the viewpoint of obtaining a resin composition that forms a coating film having excellent storage stability and excellent adhesion to the substrate and extensibility. The content of the resin layer constituting the inner layer (first layer) is 20 to 40% by mass, and the content of the resin layer constituting the intermediate layer (second layer) between the inner layer and the outer layer The rate is 40 to 60% by mass, and the content of the resin layer constituting the outer layer (third layer) is preferably 10 to 30% by mass.

  When the emulsion particles have two resin layers, an inner layer and an outer layer, the glass transition temperature of the inner resin layer is from the viewpoint of obtaining a resin composition that forms a coating film having excellent adhesion to the substrate and extensibility. The temperature is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, further preferably 90 ° C. or higher. From the viewpoint of improving the film forming property, it is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, and further preferably 110 ° C. It is as follows. In addition, the glass transition temperature of the outer resin layer is preferably −50 ° C. or higher, more preferably −45 ° C. or higher, and further preferably −40 ° C. or higher, from the viewpoint of improving the film forming property. From the viewpoint of obtaining a resin composition that forms a coating film having excellent properties and extensibility, it is preferably −10 ° C. or lower, more preferably −15 ° C. or lower, and further preferably −20 ° C. or lower.

  When the emulsion particles have three resin layers of an inner layer, an intermediate layer, and an outer layer, the glass transition temperature of the inner resin layer is a resin composition that forms a coating film having excellent adhesion to the substrate and extensibility. From the viewpoint of obtaining, it is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and further preferably 90 ° C. or higher. From the viewpoint of improving the film forming property, it is preferably 120 ° C. or lower, more preferably 115 ° C. or lower. Is 110 ° C. or lower. From the viewpoint of obtaining a resin composition in which the glass transition temperature of the resin layer of the intermediate layer forms a coating film excellent in adhesion to the substrate and extensibility, preferably −40 ° C. or higher, more preferably −35 ° C. or higher, More preferably, it is −30 ° C. or higher, and from the viewpoint of improving the film forming property, it is preferably 0 ° C. or lower, more preferably −5 ° C. or lower, and further preferably −10 ° C. or lower. The glass transition temperature of the outer resin layer is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and further preferably 10 ° C. or higher from the viewpoint of improving the film-forming property. From the viewpoint of obtaining a resin composition that forms a coating film having excellent properties, it is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, and further preferably 30 ° C. or lower.

  Further, the glass transition temperature of the entire emulsion particles is preferably −10 ° C. or higher, more preferably −5 ° C. or higher, from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility. More preferably, it is 0 ° C. or higher, and preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and still more preferably 20 from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility. It is below ℃.

In the present specification, the glass transition temperature of the resin layer constituting the emulsion particles is determined by using the glass transition temperature of the monomer homopolymer used in the monomer component constituting the polymer, formula:
1 / Tg = Σ (Wm / Tgm) / 100
[Wherein Wm represents the content (% 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. ]
The temperature calculated | required based on the Formula of Fox (Fox) represented by these.

  In this specification, unless otherwise indicated, the glass transition temperature of the resin layer which comprises emulsion particles means the glass transition temperature calculated | required based on the said Fox (Fox). For example, the glass transition temperature of the entire resin layer constituting the emulsion particles having a plurality of resin layers corresponds to the mass fraction of each monomer in all monomer components used in the multistage emulsion polymerization. It means the glass transition temperature determined from the glass transition temperature of the homopolymer of the monomer. For monomers with unknown glass transition temperature, such as special monomers and polyfunctional monomers, the total amount of monomers with unknown glass transition temperature in the monomer component is the mass fraction. If 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 with unknown glass transition temperature in the monomer component exceeds 10% by mass, the glass transition temperature of the polymer is determined by differential scanning calorimetry (DSC) or differential calorimetry. (DTA), thermomechanical analysis (TMA), etc.

  The glass transition temperature of the resin layer can be easily adjusted by adjusting the composition of the monomer component. In consideration of the glass transition temperature of the resin layer constituting the emulsion particles, the composition of the monomer component used as a raw material for the resin layer constituting the emulsion particles can be determined.

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

  In addition, 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 constituting the outer layer is larger than the SP value of the resin layer constituting the inner layer. High is preferable from the viewpoint of improving the flexibility and film-forming property of the coating film. Also, the difference (absolute value) between the SP value of the resin layer constituting the inner layer and the resin layer constituting the outer layer is 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 the binary solution. In general, substances having similar SP values tend to be mixed with each other. Therefore, the SP value is also a measure for judging the ease of mixing of the solute and the solvent.

  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 preferably from the viewpoint of improving storage stability and film-forming properties. It is 300 nm or less, more preferably 200 nm or less.

  In the present specification, the average particle size of the emulsion particles is measured using a particle size distribution measuring instrument (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 (meth) acrylic 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 from the viewpoint of improving handleability. Hereinafter, it is more preferably 50% by mass or less.

The non-volatile content in the (meth) acrylic resin emulsion is obtained by weighing 1 g of the (meth) acrylic resin emulsion and drying it at a temperature of 110 ° C. for 1 hour with a hot air dryer.
[Nonvolatile content in (meth) acrylic resin emulsion (% by mass)]
= ([Mass of residue] ÷ [(Meth) acrylic resin emulsion 1 g]) × 100
Means the value obtained based on

  Moreover, the minimum film-forming temperature of the (meth) acrylic resin emulsion is preferably −20 to 50 ° C. from the viewpoint of improving the film-forming property. The minimum film-forming temperature of the (meth) acrylic resin emulsion can be adjusted, for example, by adjusting the glass transition temperature of the entire emulsion particle or the glass transition temperature of the outermost resin layer.

  In this specification, the minimum film-forming temperature of the (meth) acrylic resin emulsion is such that the thickness of the (meth) acrylic resin emulsion is 0.2 mm on a glass plate placed on a thermal gradient tester. It means the temperature when it is coated with an applicator and cracks occur.

  As described above, a (meth) acrylic resin emulsion containing emulsion particles can be obtained.

  Next, the resin composition can be obtained by mixing the (meth) acrylic resin emulsion obtained above and the hydroxyl group-containing compound represented by the formula (I).

  The amount of the hydroxyl group-containing compound represented by the formula (I) per 100 parts by mass of the nonvolatile content of the (meth) acrylic resin emulsion is excellent in storage stability, and has a coating film excellent in adhesion to the substrate and extensibility. From the viewpoint of obtaining a resin composition to be formed, it is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, further preferably 0.3 parts by mass or more, and still more preferably 0.35 parts by mass or more. Yes, from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably Is 2 parts by mass or less, more preferably 1.5 parts by mass or less.

  Next, (2) A method for producing a resin composition by emulsion polymerization of a monomer component used as a raw material of a (meth) acrylic resin emulsion in the presence of a hydroxyl group-containing compound represented by the formula (I) Will be described.

  Examples of the method for emulsion polymerization of the monomer component used as the raw material for the (2) (meth) acrylic resin emulsion in the presence of the hydroxyl group-containing compound represented by the formula (I) include, for example, (meth) acrylic resins Examples include a method in which the monomer component used as a raw material for the emulsion contains a hydroxyl group-containing compound represented by the formula (I) and emulsion polymerization of the monomer component is performed, but the present invention is limited only to such a method. Is not to be done.

  Examples of the method for adding the hydroxyl group-containing compound represented by the formula (I) to the monomer component used as a raw material for the (meth) acrylic resin emulsion include, for example, a single amount used as a raw material for the (meth) acrylic resin emulsion Examples thereof include a method of mixing a body component and a hydroxyl group-containing compound represented by the formula (I), but the present invention is not limited to such a method. The order of mixing the monomer component used as a raw material for the (meth) acrylic resin emulsion and the hydroxyl group-containing compound represented by the formula (I) is arbitrary, for example, the monomer component is represented by the formula (I) And the monomer component and the hydroxyl group-containing compound represented by the formula (I) may be mixed together.

  The content of the hydroxyl group-containing compound represented by the formula (I) in the monomer component is excellent in storage stability and from the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion to the substrate and extensibility. And preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and still more preferably 0.35% by mass or more, and excellent storage stability. From the viewpoint of obtaining a resin composition that forms a coating film excellent in adhesion and extensibility to a substrate, it is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and still more preferably. Is 1.5 mass% or less.

  The kind and amount of the monomer used for the monomer component, the method of emulsion polymerization of the monomer component, etc. include (1) the (meth) acrylic resin emulsion and the hydroxyl group represented by the formula (I) It is preferable that it is the same as the method of manufacturing a resin composition by mixing a compound.

  In addition, when emulsion particles have a single-layer resin layer, emulsion particles having a single layer are contained by emulsion polymerization of a monomer component containing a hydroxyl group-containing compound represented by formula (I) (meta) An acrylic resin emulsion can be obtained. Further, when the emulsion particles have a plurality of resin layers, as monomer components used as raw materials for any of the resin layers, monomer components containing a hydroxyl group-containing compound represented by the formula (I) are used, By sequentially subjecting the monomer components constituting the resin layer to emulsion polymerization, a (meth) acrylic resin emulsion containing a multi-layered Marshon particle can be obtained.

  When the emulsion particles have a plurality of resin layers, from the viewpoint of obtaining a resin composition that forms a coating film that is excellent in storage stability and has excellent adhesion to the substrate and extensibility, as a raw material for the outermost resin layer It is preferable that the monomer component used contains a hydroxyl group-containing compound represented by the formula (I).

  The resin composition of the present invention obtained as described above may contain a crosslinking agent or the like as necessary.

  Examples of the crosslinking agent include melamine crosslinking agent, oxazoline crosslinking agent, acrylamide crosslinking agent, polyamide crosslinking agent, epoxy crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, titanate crosslinking agent, urea crosslinking. Agents, alkyl alcoholated urea-based crosslinking agents, hydrazine compounds, carbodiimide compounds, zirconium compounds, zinc compounds, titanium compounds, aluminum compounds, and the like, but the present invention is limited to such examples only. It is not a thing. These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent is preferably set as appropriate according to the type of the crosslinking agent.

  Among these crosslinking agents, an oxazoline-based crosslinking agent and a hydrazine compound are preferable from the viewpoint of obtaining a resin composition that is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility.

  Examples of the oxazoline-based crosslinking 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. It is not limited only to hunt illustration. These oxazoline-based crosslinking agents may be used alone or in combination of two or more. The oxazoline-based crosslinking agent can be easily obtained commercially, for example, manufactured by Nippon Shokubai Co., Ltd., trade names: Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K- 2020, Epochros K-2030, and the like, but the present invention is not limited to such examples.

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

  Since the amount of the cross-linking agent varies depending on the type of the cross-linking agent and cannot be determined unconditionally, it is preferably determined appropriately according to the type of the cross-linking agent.

  The nonvolatile content in the resin composition of the present invention 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 from the viewpoint of improving handleability. More preferably, it is 50 mass% or less.

  The water-based paint of the present invention contains the resin composition, may contain only the resin composition, and may further contain additives as necessary.

  Examples of additives include colorants such as pigments, leveling agents, UV absorbers, UV stabilizers, antioxidants, polymerization inhibitors, fillers, coupling agents, rust inhibitors, antibacterial agents, and metal deactivators. Agent, wetting agent, antifoaming agent, surfactant, reinforcing agent, plasticizer, lubricant, anti-fogging agent, anticorrosive agent, pigment dispersant, flow control agent, peroxide decomposing agent, mold decoloring agent, fluorescent enhancement White agent, organic flame retardant, inorganic flame retardant, anti-dripping agent, melt flow modifier, antistatic agent, anti-algae agent, anti-mold agent, flame retardant, slip agent, metal chelating agent, anti-blocking agent, Examples include heat stabilizers, processing stabilizers, dispersants, thickeners, rheology control agents, foaming agents, anti-aging agents, preservatives, antistatic agents, silane coupling agents, antioxidants, and film forming aids. However, the present invention is not limited to such examples. These additives may be used alone or in combination of two or more.

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

  The nonvolatile content in the water-based paint of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving productivity, and preferably 50% by mass or less from the viewpoint of improving handleability. More preferably, it is 40 mass% or less.

  Both the resin composition and the water-based paint of the present invention are excellent in storage stability and form a coating film excellent in adhesion to the substrate and extensibility. For example, the outer wall, inner wall, floor of a building Can be suitably used when repairing building materials and the like that constitute the building, and among these, it can be more suitably used when repairing exterior building materials and the like that constitute the outer wall of the building.

  Examples of the exterior building material include a metal substrate, a resin substrate, and an inorganic substrate. Examples of the metal substrate include an aluminum plate, an iron plate, an aluminum galvanized steel plate, a stainless steel plate, and a tin plate. Examples of the resin substrate 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, and the like, but the present invention is not limited to such examples.

  On the outermost surface of the exterior building material, usually, for example, inorganic paints containing silica, titanium oxide, etc., low-contamination paints, organic-inorganic composite paints, fluororesin paints, acrylic silicone paints, acrylic urethane paints, etc. A coating film made of a paint is formed. The exterior building material on which the coating film is formed can be easily obtained commercially. For example, trade names made by Keimu Co., Ltd., trade names: Exagege Hydrophilic Sera 15, Exagege HikariCera 15, manufactured by Nichiha Co., Ltd., trade name: Moen Xcellade 18, Moen Xcellade 16, manufactured by Asahi Tostem Co., Ltd., trade name: AT-WALL15, manufactured by Toray ACE Co., Ltd., trade name: Trestage (registered) Trademark), pure stage (registered trademark), and the like, but the present invention is not limited to such examples.

  Both the resin composition and the water-based paint of the present invention are excellent not only in adhesion to a film made of an inorganic paint but also in adhesion to a film made of an organic paint, and therefore require repair. It can be suitably used for various substrates.

  In addition, you may apply the water-based coating material of this invention only by 1 layer, and may apply | coat by recoating so that a film of two or more layers may be formed. When overcoating so that two or more layers are formed, only a part of the layer may be formed by the water-based paint of the present invention, or all the layers may be formed by the water-based paint of the present invention. Good.

  Examples of the method for forming a coating film using the aqueous paint 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 electrostatic coating. The figure which shows the coating method etc. by die-coat etc., this invention is not limited only to this illustration.

  The coating film formed using a water-based paint may be dried at room temperature, for example, or may be dried by heating.

The coating amount when applying the water-based paint to the base material varies depending on the type of the base material and the like, and thus cannot be determined unconditionally. However, the viewpoint of forming a coating film excellent in adhesion to the base material and extensibility Therefore, it is usually preferable that the nonvolatile content is about ²⁰ to 500 g / m ² .

  In addition, the thickness of the coating film after drying formed using a water-based paint is usually preferably about 10 to 1000 μm from the viewpoint of forming a coating film having excellent adhesion to the substrate and extensibility. .

  By applying the water-based paint of the present invention to a substrate as described above, a building material to which the water-based paint is applied can be obtained.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. In the following Examples, “part” means “part by mass” unless otherwise specified.

  Further, in the following examples, unless otherwise specified, a 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: ADEKA rear soap PP-70) contains 25% aqueous ammonia. The pH was adjusted to 7.0 (measured at 23 ° C. using Horiba, Ltd., product number: F-23, the same applies hereinafter).

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

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

  Of the obtained pre-emulsion for dripping, 5.0 parts corresponding to 5% by mass of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5 A 1.4% aqueous ammonium persulfate solution was added to the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 9.0 to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature, and then filtered through a 300 mesh (JIS mesh, hereinafter the same) wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 5.9 ° C. The average particle size of the emulsion particles was 120 nm.

  Next, a hydroxyl group-containing compound per 100 parts by mass of the solid content of the (meth) acrylic resin emulsion obtained above [Chartwell International, product number: B-515.71W, in formula (I), Z is aluminum. An atom, R is an alkyl group having 2 or 3 carbon atoms having an amino group, and m is an integer of 2. Hereinafter, a resin composition was obtained by mixing the (meth) acrylic resin emulsion and the hydroxyl group-containing compound X so that the amount of “hydroxy group-containing compound X” was 0.5 parts.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 2.0 parts of a 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 39.5 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 0 part, γ-methacryloyloxypropyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503] 0.1 part, 50.4 parts of styrene, 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd. Product name: Light Ester P-1M] 0.5 parts, 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.

  Of the obtained pre-emulsion for dripping, 5.0 parts corresponding to 5% by mass of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5 A 1.4% aqueous ammonium persulfate solution was added to the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 9.0 to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 5.7 ° C. The average particle size of the emulsion particles was 120 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 1.0 part. Were mixed to obtain a resin composition.

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

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 2.0 parts of a 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 39.5 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 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-hydroxyethyl methacrylate are added, The Marushon was prepared.

  Of the obtained pre-emulsion for dripping, 5.0 parts corresponding to 5% by mass of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5 A 1.4% aqueous ammonium persulfate solution was added to the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 9.0 to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 6.7 ° C. The average particle size of the emulsion particles was 120 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 90.4 parts of deionized water was charged.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: ADEKA rear soap SR-10] as an emulsifier Then, 40.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 4.0 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: ADEKA rear soap PP-70), 38.9 parts of 2-ethylhexyl acrylate, 1.0 acetoacetoxyethyl methacrylate 1.0 Parts, γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 0.1 part, 14.5 parts of styrene, 3.0 parts of acrylic acid, 2.0 parts of acrylonitrile and 2nd stage pre-emulsy consisting of 0.5 parts 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 completion of the dropping, 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 mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 7.4 ° C. The average particle diameter of the emulsion particles was 150 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

Example 5
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 90.4 parts of deionized water was charged.

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: ADEKA rear soap SR-10] as an emulsifier Then, 40.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, Polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA rear soap PP-70] 25% aqueous solution 2.0 parts, 2-ethylhexyl acrylate 38.9 parts, acetoacetoxyethyl methacrylate 1.0 Parts, γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 0.1 part, 14.5 parts of styrene, 3.0 parts of methacrylic acid, 2.0 parts of acrylonitrile and 2nd stage pre-mal consisting of 0.5 parts 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 completion of the dropping, 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 mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 8.0 ° C. The average particle diameter of the emulsion particles was 150 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

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

  In a dropping funnel, 10.3 parts of deionized water, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 11.8 parts of deionized water, 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2-ethylhexyl acrylate 28.2 parts, 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 pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 part of 2-hydroxyethyl methacrylate, 2.9 parts of a 3.5% aqueous ammonium persulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution. The solution was dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water, and 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 4.0 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 6.0 parts of 2-ethylhexyl acrylate, 2. acetoacetoxyethyl methacrylate 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, pre-emulsion of 3.5% ammonium persulfate aqueous solution 2.9 And 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution over 90 minutes. It was dropped in the child. After completion of the dropping, 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 mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 15.3 ° C. The average particle diameter of the emulsion particles was 130 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

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

  In a dropping funnel, 10.3 parts of deionized water, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 11.8 parts of deionized water, 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2-ethylhexyl acrylate 28.2 parts, 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 pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 part of 2-hydroxyethyl methacrylate, 2.9 parts of a 3.5% aqueous ammonium persulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution. The solution was dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water, and 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 6.0 parts of 2-ethylhexyl acrylate, 2.0 parts of acetoacetoxyethyl methacrylate, 6.8 parts of styrene, 2-methacryloyloxyethyl acid phosphate [trade name: Light Ester P-1M] manufactured by Kyoeisha Chemical Co., Ltd. 0.0 part, 3.0 parts of acrylic acid, 1.0 part of acrylonitrile and 0.2 part of 2-hydroxyethyl methacrylate, the third pre-emulsion, 2.9 parts of 3.5% aqueous ammonium persulfate and 2.5 parts % Sodium hydrogensulfite aqueous solution 2.0 parts was dropped into the flask over 90 minutes.After completion of the dropping, 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 mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 15.3 ° C. The average particle diameter of the emulsion particles was 130 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

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

  In a dropping funnel, 10.3 parts of deionized water, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 11.8 parts of deionized water, 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2-ethylhexyl acrylate 28.2 parts, 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 pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 part of 2-hydroxyethyl methacrylate, 2.9 parts of a 3.5% aqueous ammonium persulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution. The solution was dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water, and 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 4.0 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 6.0 parts of 2-ethylhexyl acrylate, 2. acetoacetoxyethyl methacrylate 0 part, 6.8 parts of styrene, 2-methacryloyloxyethyl acid phosphate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester P-1M], 1.0 part, 3.0 parts of acrylic acid, 1.0 part of acrylonitrile And 3-stage pre-emulci comprising 0.2 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 completion of the dropping, 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 mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 15.3 ° C. The average particle diameter of the emulsion particles was 130 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

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

  In a dropping funnel, 10.3 parts of deionized water, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 11.8 parts of deionized water, 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2-ethylhexyl acrylate 28.2 parts, 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 pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 part of 2-hydroxyethyl methacrylate, 2.9 parts of a 3.5% aqueous ammonium persulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution. The solution was dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water, and 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 4.0 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 6.0 parts of 2-ethylhexyl acrylate, 2. acetoacetoxyethyl methacrylate 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, a 3.5% ammonium persulfate aqueous solution 2.9 And 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution over 90 minutes. It was dropped into the score. After completion of the dropping, 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 mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 15.9 ° C. The average particle diameter of the emulsion particles was 130 nm.

  Next, the (meth) acrylic resin emulsion and the hydroxyl group-containing compound so that the amount of the hydroxyl group-containing compound X per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is 0.5 parts. By mixing with X, a resin composition was obtained.

Example 10
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction tube, a thermometer, and a reflux condenser, 96.7 parts of deionized water was charged.

  32.6 parts of deionized water in a dropping funnel, 16.0 parts of a 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier , 2.0 parts of a 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 39.5 parts of 2-ethylhexyl acrylate, acetoacetoxyethyl methacrylate 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-hydroxyethyl methacrylate are added, The Marushon was prepared.

  Of the obtained pre-emulsion for dripping, 5.0 parts corresponding to 5% by mass of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5 A 1.4% aqueous ammonium persulfate solution was added to the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 8.0, and the temperature was maintained at 80 ° C. for 60 minutes. Thereafter, 0.5 part of the hydroxyl group-containing compound X was added to the flask and stirred at a temperature of 80 ° C. for 30 minutes to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 6.7 ° C. The average particle size of the emulsion particles was 120 nm. The (meth) acrylic resin emulsion obtained above was used as a resin composition.

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

  12.0 parts of deionized water in a dropping funnel, 8.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester [manufactured by ADEKA, trade name: ADEKA rear soap SR-10] as an emulsifier Then, 40.0 parts of styrene was charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 30.9 parts of deionized water, 8.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, Polyoxypropylene allyl ether phosphate [manufactured by ADEKA, trade name: ADEKA rear soap PP-70] 25% aqueous solution 2.0 parts, 2-ethylhexyl acrylate 38.9 parts, acetoacetoxyethyl methacrylate 1.0 Parts, γ-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503) 0.1 part, 14.5 parts of styrene, 3.0 parts of methacrylic acid, 2.0 parts of acrylonitrile and 2nd stage pre-mal consisting of 0.5 parts 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 8.0, and the temperature was maintained at 80 ° C. for 60 minutes. Thereafter, 0.5 part of the hydroxyl group-containing compound X was added to the flask and stirred at a temperature of 80 ° C. for 30 minutes to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 8.0 ° C. The average particle diameter of the emulsion particles was 150 nm. The (meth) acrylic resin emulsion obtained above was used as a resin composition.

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

  In a dropping funnel, 10.3 parts of deionized water, 4.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier And 30.0 parts of styrene were charged to prepare a pre-emulsion for dropping.

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

  Next, the remainder 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 completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 11.8 parts of deionized water, 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier, 2-ethylhexyl acrylate 28.2 parts, 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 pre-emulsion consisting of 2.0 parts of acrylonitrile and 0.3 part of 2-hydroxyethyl methacrylate, 2.9 parts of a 3.5% aqueous ammonium persulfate solution and 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution. The solution was dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Next, 17.8 parts of deionized water, and 6.0 parts of 25% aqueous solution of allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (manufactured by ADEKA, trade name: Adeka Soap SR-10) as an emulsifier 4.0 parts of 25% aqueous solution of polyoxypropylene allyl ether phosphate ester (manufactured by ADEKA, trade name: Adeka Soap PP-70), 6.0 parts of 2-ethylhexyl acrylate, 2. acetoacetoxyethyl methacrylate 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, a 3.5% ammonium persulfate aqueous solution 2.9 And 2.0 parts of a 2.5% aqueous sodium hydrogen sulfite solution over 90 minutes. It was dropped into the score. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 8.0, and the temperature was maintained at 80 ° C. for 60 minutes. Thereafter, 0.5 part of the hydroxyl group-containing compound X was added to the flask and stirred at a temperature of 80 ° C. for 30 minutes to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the whole emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 15.9 ° C. The average particle diameter of the emulsion particles was 130 nm. The (meth) acrylic resin emulsion obtained above was used as a resin composition.

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

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

  Of the obtained pre-emulsion for dripping, 5.0 parts corresponding to 5% by mass of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5 A 1.4% aqueous ammonium persulfate solution was added to the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 9.0 to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 5.9 ° C. The average particle size of the emulsion particles was 120 nm. The (meth) acrylic resin emulsion obtained above was used as a resin composition.

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

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

  Of the obtained pre-emulsion for dripping, 5.0 parts corresponding to 5% by mass of the total amount of the monomer components were added to the flask, and the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 3.5 A 1.4% aqueous ammonium persulfate solution was added to the flask to initiate emulsion polymerization.

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

  Thereafter, 25% aqueous ammonia was added to adjust the pH to 9.0 to complete the emulsion polymerization reaction. The obtained reaction mixture was cooled to room temperature and then filtered through a 300-mesh wire mesh to obtain a (meth) acrylic resin emulsion having a nonvolatile content of 40% by mass.

  The glass transition temperature of the entire emulsion particles contained in the (meth) acrylic resin emulsion obtained above was 5.9 ° C. The average particle size of the emulsion particles was 120 nm.

  Next, the amount of γ-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403) per 100 parts of the solid content of the (meth) acrylic resin emulsion obtained above is Γ-glycidoxy so that the amount of 45 parts and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602) is 5 parts. Propyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-403] and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM -602] was mixed well and the resulting mixture was mixed with the (meth) acrylic resin emulsion to obtain a resin composition.

Experimental Example 2,2,4-Trimethyl-1,3-pentanediol as a film forming aid while dispersing the resin composition obtained in each Example and each Comparative Example with a homodisper at a rotation speed of 1000 min ⁻¹ Monoisobutyrate [manufactured by Chisso Co., Ltd., product number: CS-12] was added to the resin composition so that the film forming temperature was 0 ° C., diluted water and a silicone-based antifoaming agent [San Nopco Co., Ltd. Manufactured, trade name: SN deformer 777] was added to the resin composition in an appropriate amount, and dilution water was added to the resin composition so that the nonvolatile content was 32% by mass, thereby obtaining an evaluation paint. .

  Next, using the coating material for evaluation obtained above, as a physical property of the resin composition, adhesion to the substrate and extensibility were examined based on the following methods. The results are shown in Table 1.

  Moreover, the storage stability was investigated based on the following method using the resin composition obtained in each Example and each Comparative Example. The results are shown in Table 1.

[Adhesion to substrate]
A cross cut test was conducted in accordance with JIS K5600-5-6. The coating material for evaluation obtained above was applied to a hydrophilic coating outer wall material (manufactured by Keimu Co., Ltd., trade name: Excelsi / Hydro Sera 15, length: 150 mm, width: 75 mm, thickness: 15 mm) and a film thickness of 50 g / m. ^It was uniformly applied with a brush so as to be ^2, and dried in the air at 25 ° C. for 1 week. Then, after immersing the said outer wall material in the warm water maintained at 50 degreeC water temperature for 3 days, it took out from warm water, and obtained the test piece for evaluation by making it dry in 25 degreeC air | atmosphere for 1 day.

  After cutting 25 squares (vertical: 5 squares, horizontal: 5 squares) into a 2 mm square grid pattern with a sharp blade on the coating film of the evaluation test piece obtained above, in accordance with JIS Z1522. The cellophane adhesive tape was adhered in a grid pattern by rubbing the cellophane adhesive tape having a width of 25 mm with a finger, allowed to stand in the atmosphere at 25 ° C. for 5 minutes, and then peeled off. Of the produced 25 squares, the number of peeled squares was counted, and the adhesion to the substrate was evaluated based on the following evaluation criteria. In addition, the adhesiveness with respect to a base material is set as the pass when the evaluation is 30 points or more.

(Evaluation criteria)
50 points: number of cells peeled off 0 40 points: number of cells peeled 1 to 4 30 points: number of cells peeled 5 to 9 10 points: number of cells peeled 10 to 19 (failure)
0 point: The number of peeling of the squares is 20 or more (failed)

[Extension]
The evaluation paint obtained above was applied to a polypropylene plate (length: 70 mm, width: 150 mm, thickness: 2 mm) with a 20 mil applicator so that the film thickness after drying was 100 μm, and in accordance with JIS A6909. After drying by standing for 7 days in an atmosphere having a temperature of 23 ° C. and a relative humidity of 65%, the formed coating film (vertical: about 1 cm, lateral: about 7 cm, thickness: 150 μm) is a polypropylene plate It was made to peel from.

Next, the peeled test piece was punched into a dumbbell-shaped No. 2 shape defined in 4.1 of JIS K6251 to obtain a test piece. The obtained test piece was attached so that the distance between chucks of a tensile tester [manufactured by Shimadzu Corporation, trade name: Autograph AGS-100D] was 20 mm, the temperature was 20 ° C., and the peeling speed was 200 mm / min. Pull the test piece under the conditions, the elongation rate of the test piece, the formula:
[Elongation rate of specimen (%)]
= [Length of test piece at break (mm) −Original length of test piece (20 mm)] ÷ [Original length of test piece (20 mm)] × 100
The extensibility was evaluated based on the following evaluation criteria. In addition, the extensibility makes the pass when the evaluation is 30 points or more.

(Evaluation criteria)
50 points: elongation rate of 200% or more and 30 points: elongation rate of 100% or more and less than 200% 0 point: elongation rate of less than 100% (failed)

[Storage stability]
The viscosity of the resin composition obtained in each example and each comparative example was measured with a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.) under conditions of a temperature of 25 ° C. and a rotation speed of 30 min ⁻¹ (initial viscosity). Next, after the said resin composition was stood and stored for one week in the atmosphere of the temperature of 40 degreeC, the viscosity of the said resin composition after storage was measured like the above (viscosity after storage). From these measurement results, the viscosity change rate of the resin composition is expressed by the formula:
[Viscosity change rate of resin composition (%)]
= [Viscosity after storage (mPa · s) −initial viscosity (mPa · s)] ÷ [initial viscosity (mPa · s)] × 100
The storage stability was evaluated based on the following evaluation criteria. In addition, storage stability makes pass when the evaluation is 30 points or more.

(Evaluation criteria)
50 points: Viscosity change rate is less than 10% 30 points: Viscosity change rate is 10% or more and less than 30% 0 point: Viscosity change rate is 30% or more (failed)

〔Comprehensive evaluation〕
A total evaluation (full score of 150) was performed by summing up the evaluation scores for each test item.

  From the results shown in Table 1, it can be seen that each of the resin compositions obtained in each Example is excellent in storage stability and forms a coating film excellent in adhesion to the substrate and extensibility. .

  The resin composition of the present invention is excellent in storage stability and forms a coating film excellent in adhesion and extensibility to a base material. For example, a building material constituting an outer wall, an inner wall, a floor, etc. of a building, etc. It is expected to be suitably used for undercoat, intermediate, or topcoat used in repairing paints, surface treatment agents such as building materials and concrete, coating agents, surface treatment agents, adhesives, and sealing agents. Is. Among these, the resin composition of the present invention is excellent in storage stability and forms a coating film excellent in adhesion to the base material and extensibility. That is expected.

Claims (5)

A resin composition comprising a hydroxyl group-containing compound as a raw material, comprising a (meth) acrylic resin emulsion, wherein the hydroxyl group-containing compound is represented by the formula (I):
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
A resin composition characterized by being a hydroxyl group-containing compound represented by the formula:   An aqueous paint comprising the resin composition according to claim 1.   A building material to which the water-based paint according to claim 2 is applied. A method for producing a resin composition containing a (meth) acrylic resin emulsion, comprising a (meth) acrylic resin emulsion and a formula (I):
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
A method for producing a resin composition comprising mixing a hydroxyl group-containing compound represented by the formula: A method for producing a resin composition containing a (meth) acrylic resin emulsion, wherein the formula (I):
(HO) _m -ZR (I)
[Wherein Z is a boron atom, an aluminum atom, a titanium atom or a zirconium atom, R is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a mercapto group, a pyrrolidine group, a piperidine group and a disulfide group. A hydrocarbon group having 1 to 18 carbon atoms which may have a group, m represents a number 1 smaller than the number of unpaired electrons of Z]
A method for producing a resin composition, comprising subjecting a monomer component used as a raw material of the (meth) acrylic resin emulsion to emulsion polymerization in the presence of a hydroxyl group-containing compound represented by the formula: