JP3499683B2 - Resin composition for water-based paint - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for an aqueous paint. More specifically, for example, it is preferably used for coating the interior and exterior of buildings, automobiles, home appliances, plastic products, and the like, which are particularly required to have weather resistance, water resistance, and stain resistance. The present invention relates to a resin composition for water-based coatings capable of forming a coating film having excellent coating film performance.

[0002]

2. Description of the Related Art Recently, in the field of paints and adhesives,
From the viewpoints of pollution control and resource saving, it has been attempted to convert a resin containing an organic solvent into a water-soluble resin containing no organic solvent, a water-dispersible resin, or a powder resin.

Particularly in the field of paints, from the viewpoint of workability, conversion from powder paints using the above-mentioned powder resin to water-based paints using the above-mentioned water-soluble resin or water-dispersible resin is more vigorous. Has been carried out.

However, since the resins used in conventional water-based paints generally do not have a crosslinkable functional group in the molecule, they are affected by the strong influence of the surfactant used during polymerization. The coating film formed from the paint is
Its weather resistance, water resistance, stain resistance, etc. are extremely low, and it has the drawback of being inferior in coating film performance to organic solvent-based paints.

Therefore, various attempts have been made to improve the above-mentioned drawbacks. For example, an aqueous paint using an emulsion of a polymer having a hydrolyzable silyl group as a crosslinkable functional group (JP-A-3-227312), or a crosslinked structure between particles is formed by a reaction between a carboxyl group and a hydrazyl group. Water-based emulsion paint
-59305), water-based paints such as water-dispersed fluororesin paints (JP-A-5-25421) in which a fluororesin exhibiting high performance in an organic solvent system is made water-based are proposed.

However, although the weather resistance and water resistance of the coating film formed are improved to some extent by using these water-based paints, such water-based paints can be used as an object to be coated which is particularly required to have weather resistance and water resistance. To use,
The weather resistance and water resistance of such a coating film are still insufficient. Further, among these water-based paints, the water-dispersible fluororesin paint has a drawback that the weather resistance of the coating film is improved because the fluororesin is made water-based, but the appearance and stain resistance are markedly reduced. It is a thing.

Further, especially with respect to the stain resistance of the coating film,
Considering the increasing demands in various fields in recent years, there is a need for an aqueous paint capable of forming a coating film having excellent stain resistance. However, the water-based paint has a drawback that the stain resistance of the coating film is considerably inferior to the stain resistance of the coating film formed from the organic solvent-based paint.

[0008] As described above, development of a water-based coating having excellent weather resistance and water resistance and capable of forming a coating film excellent in stain resistance is desired.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and can form a coating film having excellent weather resistance and water resistance as well as stain resistance. It is an object to provide a resin composition for water-based paint.

[0010]

The present invention has the general formula (I):

[0011]

[Chemical 3]

(Wherein R ¹ is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, X ¹ is the same or different, and a halogen atom , Alkoxy group, hydroxy group,
(Acyloxy group, aminoxy group, phenoxy group, thioalkoxy group or amino group, a represents 0, 1 or 2)
A vinyl-based monomer containing a silyl group represented by (a-
1) and 100 parts by weight of an emulsion copolymer (A) obtained by emulsion-polymerizing a polymerization component comprising the vinyl-based monomer (a-1) and a vinyl-based monomer (a-2) copolymerizable with the vinyl-based monomer (a-1). for,
General formula (II):

[0013]

[Chemical 4]

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms and 6 to 1 carbon atoms.
An aryl group having 0 or an aralkyl group having 7 to 10 carbon atoms,
R ⁶ is a direct bond, an alkylene group having 1 to 20 carbon atoms or an alkyleneoxy group having 1 to 20 carbon atoms, X ² is an alkoxy group, a hydroxy group, an acyloxy group, a phenoxy group, a thioalkoxy group, an amino group, an epoxy group , vinyl-based,
(Meth) acryloyloxy group, styryl group, group containing a polyether structure, group containing a polyester structure or group containing a polycarbonate structure , l, m and n each have a molar ratio of formula: 1 / m / n = 1 to 50 / 1 to 50/0
1 to 50 parts by weight of a silicon-containing compound (B) represented by an integer satisfying 50) and a curing catalyst (C) 0
The present invention relates to a resin composition for water-based coating composition containing about 20 parts by weight.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the resin composition for aqueous paint of the present invention has the general formula (I):

[0016]

[Chemical 5]

(Wherein R ¹ is the same or different, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, X ¹ is the same or different, and a halogen atom , Alkoxy group, hydroxy group,
(Acyloxy group, aminoxy group, phenoxy group, thioalkoxy group or amino group, a represents 0, 1 or 2)
A vinyl-based monomer containing a silyl group represented by (a-
1) and 100 parts by weight of an emulsion copolymer (A) obtained by emulsion-polymerizing a polymerization component comprising the vinyl-based monomer (a-1) and a vinyl-based monomer (a-2) copolymerizable with the vinyl-based monomer (a-1). for,
General formula (II):

[0018]

[Chemical 6]

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms and 6 to 1 carbon atoms.
An aryl group having 0 or an aralkyl group having 7 to 10 carbon atoms,
R ⁶ is a direct bond, an alkylene group having 1 to 20 carbon atoms or an alkyleneoxy group having 1 to 20 carbon atoms, X ² is an alkoxy group, a hydroxy group, an acyloxy group, a phenoxy group, a thioalkoxy group, an amino group, an epoxy group , vinyl-based,
(Meth) acryloyloxy group, styryl group, group containing a polyether structure, group containing a polyester structure or group containing a polycarbonate structure , l, m and n each have a molar ratio of formula: 1 / m / n = 1 to 50 / 1 to 50/0
1 to 50 parts by weight of a silicon-containing compound (B) represented by an integer satisfying 50) and a curing catalyst (C) 0
It is obtained by blending up to 20 parts by weight.

The present invention is particularly characterized in that the emulsion copolymer (A) containing a specific silyl group and the specific silicon-containing compound (B) are used in a specific blending ratio. There is one. As a result, the resin composition for water-based paints of the present invention exhibits superior water resistance and weather resistance as compared with the case of using the resin composition for conventional water-based paints, and also has excellent stain resistance. A coated film can be formed.

The stain resistance is effectively exhibited by applying the resin composition for water-based paint to the article to be coated, particularly, immediately after the resin composition is prepared. Although the mechanism by which such stain resistance is expressed is not clear, it is probable that the silicon-containing compound (B) is present on the surface of the coating film during the crosslinking reaction to impart hydrophilicity to the surface of the coating film. Since the coating film is hydrophilic in this way, it is considered that the coating film is less likely to be contaminated by exhibiting a cleaning effect due to rain or the like.

Emulsion copolymer (A) used in the present invention
Is a vinyl monomer (a-1) containing a silyl group represented by the general formula (I) (hereinafter referred to as monomer (a-1)) and vinyl copolymerizable with the monomer (a-1). It is obtained by emulsion-polymerizing a polymerization component composed of the system monomer (a-2) (hereinafter referred to as the monomer (a-2)). Examples of such an emulsion copolymer (A) include epoxy resins, polyester resins, polyether resins, acrylic resins, urethane resins, fluororesins, etc. containing a silyl group represented by the above general formula (I). These may be used alone or in admixture of two or more. Among these, acrylic resins and urethane resins are preferable because the coating film formed from the obtained resin composition for water-based coating has excellent weather resistance and chemical resistance, and the range of resin design can be widened. , Fluororesins and the like are preferable, and acrylic resins are preferable from the viewpoint of low cost.

In the general formula (I), R
¹ is an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, preferably 7 to 8 carbon atoms , in view of ease of Si-X ¹ reactive sites and synthetic, it is desirable according R ¹ is an alkyl group. From the viewpoint of reactivity and stability of the functional group, X ¹ in the general formula (I) is preferably an alkoxy group, a hydroxy group or an acyloxy group.

Examples of the monomer (a-1) used for obtaining the emulsion copolymer (A) include:

[0025]

[Chemical 7]

General formula (III) such as:

[0027]

[Chemical 8]

(In the formula, R ¹ and a are the same as above, R ⁷ is a hydrogen atom or a methyl group, and X ³ is a halogen atom.)
A compound represented by:

[0029]

[Chemical 9]

General formula (IV) such as:

[0031]

[Chemical 10]

A compound represented by the formula: wherein R ¹ , R ⁷ , X ³ and a are the same as defined above, and p is an integer of 1 to 12;

[0033]

[Chemical 11]

General formula (V) such as:

[0035]

[Chemical 12]

(Wherein R ¹ , R ⁷ and a are the same as above,
R ⁸ represents an alkyl group having 1 to 16 carbon atoms);

[0037]

[Chemical 13]

General formula (VI) such as:

[0039]

[Chemical 14]

A compound represented by the formula (wherein R ¹ , R ⁷ , R ⁸ , a and p are the same as defined above);

[0041]

[Chemical 15]

General formula (VII) such as:

[0043]

[Chemical 16]

A compound represented by the formula (wherein R ¹ , R ⁷ , R ⁸ , a and p are the same as defined above);

[0045]

[Chemical 17]

General formula (VIII) such as:

[0047]

[Chemical 18]

A compound represented by the formula (wherein R ¹ , R ⁷ , R ⁸ , a and p are the same as defined above);

[0049]

[Chemical 19]

General formula (IX) such as:

[0051]

[Chemical 20]

A compound represented by the formula (wherein R ¹ , R ⁷ , R ⁸ and a are the same as defined above);

[0053]

[Chemical 21]

General formula (X) such as:

[0055]

[Chemical formula 22]

A compound represented by the formula (wherein R ¹ , R ⁷ , R ⁸ , a and p are the same as defined above);

[0057]

[Chemical formula 23]

General formula (XI) such as:

[0059]

[Chemical formula 24]

A compound represented by the formula (wherein R ¹ , R ⁷ , R ⁸ , a and p are the same as defined above, and R ⁹ is --CH ₂ O-- or --CH ₂ OCO--);

[0061]

[Chemical 25]

General formula (XII) such as:

[0063]

[Chemical formula 26]

(Wherein R ¹ , R ⁷ , R ⁸ , a and p are the same as defined above, q is an integer of 1 to 12) and the like. These may be used alone or in combination. The above can be mixed and used. Among these, an alkoxysilyl group-containing vinyl monomer is particularly preferable because it has excellent stability, is easy to handle, is inexpensive, and produces no reaction by-products.

The monomer (a-2) used for obtaining the emulsion copolymer (A) is not particularly limited and includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth). Acrylates, alkyl (meth) acrylates such as i-butyl (meth) acrylate and t-butyl (meth) acrylate, cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, and (meth) acrylics such as benzyl (meth) acrylate. Acid ester; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 2- (perfluorooctyl)
Ethyl (meth) acrylate, trifluoroethylene,
Fluorine-containing vinyl monomers such as tetrafluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene and vinylidene fluoride; styrene, α-methylstyrene, chlorostyrene,
Aromatic hydrocarbon vinyl monomers such as 4-hydroxystyrene and vinyltoluene; (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride,
Α, β-ethylenically unsaturated carboxylic acids such as crotonic acid, fumaric acid and citraconic acid; acids having a polymerizable carbon-carbon double bond such as styrene sulfonic acid and vinyl sulfonic acid, or alkali metal salts thereof. Salts such as ammonium salts and amine salts; acid anhydrides such as maleic anhydride or half esters of these with linear or branched alcohols having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate, dimethylamino Amino group-containing (meth) acrylates such as propyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
(Meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, (meth) acryloylmorpholine, or their hydrochlorides or acetates; vinyl acetate, vinyl propionate, diallyl phthalate, triallyl cyanurate, etc. Esters and allyl compounds; vinyl monomers containing nitrile groups such as (meth) acrylonitrile; vinyl monomers containing epoxy groups such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Aronix 5700 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), PlaccelFA-1, Placcel
FA-4, PlaccelFM-1, PlaccelF
M-4 (above, manufactured by Daicel Chemical Industries, Ltd.), HE-1
0, HE-20, HP-10, HP-20 (above,
(Manufactured by Nippon Shokubai Co., Ltd.), Bremmer PP series, Bremmer PE series, Bremmer PEP series, Bremmer AP-400, Bremmer AE-350, Bremmer NKH-5050, Bremmer GLM (above, Nippon Oil & Fats Co., Ltd.), MA-. 30, MA-50, MA-10
0, MA-150, RA-1120, RA-2614,
RMA-564, RMA-568, RMA-1114,
MPG130-MA (above, manufactured by Nippon Emulsifier Co., Ltd.), hydroxyl-containing vinyl-based modified hydroxyalkyl vinyl-based monomers and other hydroxyl-containing vinyl-based monomers; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. An alkylene glycol di (meth) acrylate of, for example, having an ethyleneoxy group number of 5 or more, preferably 5 to 30, more preferably 5 to 2
A hydrophilic vinyl monomer having a polyoxyethylene chain such as polyoxyethylene (meth) acrylate of 0,
The number of propyleneoxy groups is 5 or more, preferably 5 to 20,
More preferably, a hydrophilic vinyl monomer having a polyoxyalkylene chain such as a hydrophilic vinyl monomer having a polyoxypropylene chain such as 5 to 10 polyoxypropylene (meth) acrylate (wherein the alkyleneoxy terminal is a hydroxyl group). Or an alkoxy group); a phosphoric acid ester such as a condensation product of a hydroxyalkyl ester of an α, β-ethylenically unsaturated carboxylic acid such as a hydroxyalkyl ester of (meth) acrylic acid and phosphoric acid or a phosphoric acid ester Group-containing vinyl compound, vinyl compound such as urethane bond or siloxane bond-containing (meth) acrylate; AS-6, AN-6, AA-6, AB-6, AK which are macromonomers manufactured by Toagosei Kagaku Kogyo Co., Ltd. −
Compounds such as 5, vinyl methyl ether, vinyl chloride,
Other vinyl monomers such as vinylidene chloride, chloroprene, propylene, butadiene, N-vinylimidazole, vinyl sulfonic acid; LA8 manufactured by Asahi Denka Co., Ltd.
7, LA82, LA22, and other polymerization light stabilizers, and polymerization UV absorbers, which may be used alone or
A mixture of two or more species can be used.

The type of the monomer (a-2) may be appropriately selected depending on the desired physical properties of the obtained resin composition for water-based paint.

For example, in order to improve the stability of the obtained emulsion copolymer (A), (meth) acrylic acid, maleic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide, a hydroxyl group-containing vinyl system is used. It is preferable to use a hydrophilic vinyl-based monomer such as a monomer, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate.

In order to improve the water resistance and durability of the coating film formed from the obtained resin composition for water-based paint, vinyl such as fluorine-containing vinyl-based monomer or siloxane bond-containing (meth) acrylate is used. Using compounds,
It is preferable to use a vinyl-based monomer having a functional group capable of forming a crosslinked structure between particles of the emulsion copolymer (A). When a crosslinked structure is to be formed in this way, for example, two or more polymerizable unsaturated double bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triallyl cyanurate and the like are used. It is also possible to use a monomer that has.

When the acidic vinyl monomer is used, there is an advantage that the mechanical stability of the emulsion copolymer (A) is improved.

Further, as the monomer (a-2),
For example, when a hydrophilic vinyl-based monomer having a polyoxyethylene chain is used, the stability of the silyl group represented by the general formula (I) in the monomer (a-1) does not decrease, There are advantages that the mechanical stability and chemical stability of the emulsion copolymer (A) and the water resistance and gloss of the coating film formed from the obtained resin composition for water-based paint are improved.

Alkyl having 4 or more carbon atoms, such as n-butyl (meth) acrylate, i-butyl (meth) acrylate and t-butyl (meth) acrylate, preferably 4 to 12 and more preferably 4 to 10 carbon atoms. When a cycloalkyl (meth) acrylate having a cycloalkyl group having 4 or more carbon atoms, preferably 6-10, more preferably 6-8, such as an alkyl (meth) acrylate having a group or cyclohexyl (meth) acrylate is used. In the meanwhile, the stability of the silyl group in the emulsion copolymer (A) is improved, which is preferable.

The polymerization component used to obtain the emulsion copolymer (A) is composed of the monomer (a-1) and the monomer (a-2).

The monomer (a-1) and the monomer (a-
The blending ratio with 2) is for improving the water resistance and weather resistance of the coating film formed from the resin composition for an aqueous coating obtained by using the emulsion copolymer (A), and the emulsion copolymer (A). In order to improve the reactivity between the polymer and the silicon-containing compound (B), the amount of the monomer (a-1) is 0.1% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more based on the total amount of the polymerization components. That is, it is desirable that the monomer (a-2) is adjusted to 99.9% by weight or less, preferably 99% by weight or less, and more preferably 98% by weight or less of the total amount of the polymerization components. Further, in order to improve the stability of the emulsion copolymer (A) and the storage stability of the obtained resin composition for water-based paint, the monomer (a-1) is 30% by weight or less based on the total amount of the polymerization components. , Preferably 25 wt% or less, more preferably 20 wt% or less, that is, the monomer (a-2) is 70 wt% or more, preferably 75 wt% or more, more preferably 80 wt% of the total amount of the polymerization component. It is desirable to make adjustments as described above.

When the hydrophilic vinyl-based monomer having a polyoxyethylene chain is used as the monomer (a-2), the mechanical stability of the emulsion copolymer (A) and the resulting polymer (A) can be obtained. In order to eliminate the risk that the water resistance and gloss of the coating film formed from the resin composition for water-based coating composition will be reduced, the amount of the hydrophilic vinyl-based monomer having a polyoxyethylene chain is 0 based on the total amount of the polymerization components. It is preferably at least 1% by weight, more preferably at least 1% by weight. Further, in order to eliminate the risk that the coating film is softened and stains are likely to adhere, the amount of the hydrophilic vinyl-based monomer having the polyoxyethylene chain is 10% by weight or less based on the total amount of the polymerization components,
It is preferably 5% by weight or less.

Emulsion copolymer (A) used in the present invention
Can be obtained by emulsion-polymerizing a polymerization component composed of the monomer (a-1) and the monomer (a-2).

The emulsion polymerization method is not particularly limited and can be appropriately selected from various emulsion polymerization methods such as batch polymerization method, monomer dropping polymerization method and emulsion monomer dropping polymerization method. In the present invention, the monomer dropping polymerization method and the emulsion monomer dropping polymerization method are particularly preferable for ensuring the stability of the emulsion during production.

In order to improve the stability of the emulsion, it is preferable to use an emulsifier.

The emulsifier is not particularly limited as long as it is used in ordinary emulsion polymerization, and examples thereof include an ionic surfactant and a nonionic surfactant.

Examples of the ionic surfactants include sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; Newcol-723.
SF, Newcol-707SN, Newcol-70
7SF, Newcol-740SF, Newcol-5
(Poly) such as 60SN (above, manufactured by Nippon Emulsifier Co., Ltd.)
Representative examples include anionic surfactants having an oxyethylene chain; imidazoline laurate, ammonium salts such as ammonium hydroxide, and the like.

Further, as the nonionic surfactant,
For example, polyethylene glycol nonyl phenyl ether; polyoxyethylenes such as polyoxyethylene nonyl phenyl ether and polyoxyethylene lauryl ether; L-77, L-720, L-5410, L-7.
Representative examples include silicon-containing nonionic surfactants such as 602 and L-7607 (all manufactured by Union Carbide Co.).

Further, as an emulsifier, for example, ADEKA REASOAP NE-10, NE-20, NE-30, NE-4
0, SE-10N (all manufactured by Asahi Denka Co., Ltd.), An
tox-MS-60, Antox-MS-2N, RMA
-653 (Nippon Emulsifier Co., Ltd.), Aqualon R
N20, RN30, RN50, HS05, HS10, H
S20, HS1025 (above, Daiichi Kogyo Seiyaku Co., Ltd.)
When a polymerization-reactive emulsifier such as the above is used, the water resistance of the coating film formed from the obtained resin composition for water-based paint is further improved.

The emulsifiers can be used alone or in admixture of two or more. The amount of the emulsifier is 10 with respect to 100 parts by weight of the total amount of the polymerization components (parts by weight, the same applies hereinafter) in order to eliminate the possibility that the water resistance of the coating film formed is reduced.
It is desirable that the content is not more than a part, preferably 0.5 to 8 parts.

In order to further improve the water resistance of the coating film, it is preferable to use a water-soluble resin having a silyl group represented by the general formula (I) introduced therein, instead of using such an emulsifier.

Further, in order to carry out the polymerization of the monomer (a-1) and the monomer (a-2) more stably, it is preferable to use a redox catalyst as a polymerization initiator.
Further, in order to maintain the stability of the mixed solution during the polymerization and to carry out the polymerization stably, it is desirable that the temperature of the mixed solution is 70 ° C. or lower, preferably 40 to 65 ° C. In order to achieve this, the pH of the mixed solution is 5 to 8, preferably 5
It is desirable that it is ~ 7.

The redox catalyst is not particularly limited and may be, for example, potassium persulfate or ammonium persulfate in combination with acidic sodium sulfite or rongalite, hydrogen peroxide in combination with ascorbic acid, t
Examples include combinations of organic peroxides such as -butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and p-methane hydroperoxide with acidic sodium sulfite, Rongalit and the like. In particular, a combination of an organic peroxide and a reducing agent is preferable from the viewpoint of more stable polymerization.

The amount of the polymerization initiator is preferably 0.01 parts or more, and more preferably 0.05 parts or more, based on 100 parts of the total amount of the polymerization components, in order to eliminate the possibility that the polymerization is difficult to proceed. . Further, in order to eliminate the possibility that the molecular weight of the obtained emulsion copolymer (A) is lowered and the durability of the coating film formed from the resin composition for water-based coating is lowered, the amount of the polymerization initiator is It is desirable that the amount is 10 parts or less, preferably 5 parts or less, based on 100 parts of the total amount of the polymerization component.

In order to stably impart the catalytic activity of the polymerization initiator, for example, a compound containing a divalent iron ion such as iron sulfate and a sodium salt of ethylenediaminetetraacetic acid such as disodium ethylenediaminetetraacetate. You may use the chelating agent of. The amount of the chelating agent is 0.0001 to 1 with respect to 100 parts of the total amount of the polymerization components.
Parts, especially 0.001 to 0.5 parts.

The solid content concentration of the emulsion copolymer (A) thus obtained does not cause any problem in terms of polymerization operation,
The amount of resin produced by one polymerization operation is small, which is economically disadvantageous, and the thickness of the coating film becomes thin during coating film formation, resulting in performance deterioration and disadvantageous in coating workability. In order to eliminate the risk of becoming
It is desirable to adjust the content to be preferably 30% by weight or more. Further, since the viscosity of the system increases remarkably, it is difficult to remove the heat generated by the polymerization reaction, and in order to eliminate the possibility that it takes a long time to remove from the polymerization vessel, such an emulsification Copolymer (A)
It is desirable to adjust the solid content concentration of 70% by weight or less, preferably 60% by weight or less.

Since the emulsion copolymer (A) is composed of ultrafine particles having an average particle diameter of about 0.02 to 1 μm, it has an excellent film forming ability.

In the present invention, the hydrolyzable silyl group is stable in water and the cost is low, and when a coating film is formed from the obtained resin composition for water-based coating, the by-product is applied. The emulsion copolymer (A) has an alkoxysilyl group-containing vinyl monomer as the monomer (a-1) and a polyoxyethylene chain as the monomer (a-2) from the viewpoint of not adversely affecting the film. An emulsion copolymer obtained by copolymerizing a polymerization component composed of a hydrophilic vinyl-based monomer and another vinyl-based monomer with an anionic surfactant having a polyoxyethylene chain is preferable. . In particular, the polymerization component is an alkoxysilyl group-containing vinyl monomer 0.1 to 30% by weight, preferably 1 to 25
% By weight, 0.1 to 10% by weight of a hydrophilic vinyl-based monomer having a polyoxyethylene chain, preferably 0.5 to 10% by weight, and the balance being another vinyl-based monomer, It is desirable in terms of stability of the alkoxysilyl group, mechanical stability of the emulsion copolymer (A), and excellent water resistance and gloss of the formed coating film. In addition,
As described above, when an emulsion copolymer is obtained by using a vinyl monomer having an alkoxysilyl group and a hydrophilic vinyl monomer having a polyoxyethylene chain as a polymerization component, the polyoxyethylene compound as an emulsifier is used. From the viewpoint of the stability of the alkoxysilyl group, it is preferable to use an anionic surfactant having an ethylene chain in an amount of 0.2 to 10 parts, preferably 0.5 to 8 parts, based on 100 parts of the total amount of the polymerization components.

Further, in the present invention, the emulsion copolymer (A) is used because the stability of the silyl group is excellent and the weather resistance of the coating film formed from the obtained resin composition for water-based coating is improved. , A vinyl-based monomer (a-2) having an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, preferably 4 to 10 and a cyclo having an cycloalkyl group having 4 or more carbon atoms, preferably 4 to 10 carbon atoms. At least one kind of alkyl (meth) acrylate, 60 to 9
It is preferably an emulsion copolymer obtained by copolymerizing a polymerization component contained in an amount of 0% by weight, preferably 60 to 80% by weight.

The silicon-containing compound (B) used in the present invention is represented by the general formula (II).

In the above general formula (II),
R ² , R ³ , R ⁴ and R ⁵ each independently have 1 carbon atom.
-10, preferably 1 to 6 alkyl groups, 6 to 1 carbon atoms
0, preferably 6-8 aryl group or C7-1
Although it is an aralkyl group of 0, preferably 7 to 8, such R ² , R ³ , R ⁴ and R ⁵ are preferably alkyl groups from the viewpoint of reactivity and ease of synthesis. Also, R ⁶
Is a direct bond or having 1 to 20 carbon atoms, preferably 2-1
5 alkylene group or 1 to 20 carbon atoms, preferably 2
To 15 alkyleneoxy groups. Further, l, m and n each have a molar ratio of the formula: 1 / m / n = 1 to 50 /
An integer satisfying 1 to 50/0 to 50 is shown, but the molar ratio (l / m / n) is 1 to 40/1 to 40/0 to 30.
Is preferred.

Typical examples of the silicon-containing compound (B) are, for example,

[0095]

[Chemical 27]

General formula (XIII) such as:

[0097]

[Chemical 28]

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are the same as above, and 1 and m have a molar ratio of the formula: 1 / m = 1 to
A compound represented by an integer satisfying 50/1 to 50);

[0099]

[Chemical 29]

[0100]

[Chemical 30]

[0101]

[Chemical 31]

[0102]

[Chemical 32]

General formula (XIV) such as:

[0104]

[Chemical 33]

(In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X ² are the same as described above, and l, m and r each have a molar ratio of the formula: 1 / m / r = 1-50. / 1-50 / indicates an integer satisfying 50/1) and the like.
These may be used alone or in combination of two or more.

The number average molecular weight of the silicon-containing compound (B) is 500 in view of imparting sufficient stain resistance to a coating film formed from the obtained resin composition for water-based paint.
Or more, preferably 800 or more. Further, the number average molecular weight of the silicon-containing compound (B) is preferably 50,000 or less, preferably 30,000 or less, from the viewpoint that the appearance of the coating film is not deteriorated.

The amount of the silicon-containing compound (B) is adjusted so that the coating film formed from the obtained resin composition for water-based coating has sufficient emulsion hydrophilicity to improve the stain resistance. 1 part or more based on 100 parts of the solid content of the coalescence (A),
It is preferably at least 2 parts. Further, in order to eliminate the possibility that the water resistance of the coating film is reduced, the amount of the silicon-containing compound (B) is 50 parts or less, preferably 30 parts, relative to 100 parts of the solid content of the emulsion copolymer (A). Below the section.

The silicon-containing compound (B) is
When preparing the resin composition for an aqueous coating composition, it may be blended with the emulsion copolymer (A) in advance, or it may be mixed with the emulsion copolymer (A) at the same time as other components.

In the present invention, the monomer (a-) is used as the emulsion copolymer (A) and the silicon-containing compound (B) from the viewpoint that the effect of imparting stain resistance by the silicon-containing compound (B) can be sufficiently brought out. The mixture of the polymerization component consisting of 1) and the monomer (a-2) and the silicon-containing compound (B) can be polymerized by, for example, an emulsion polymerization method adopted when obtaining the emulsion copolymer (A). Preference is given to using the products obtained. The product may be a mixture of the emulsion copolymer (A) and the silicon-containing compound (B), and the emulsion copolymer (A)
Constituting the monomer (a-1) and the monomer (a-
It may be a copolymer of the polymerization component consisting of 2) and the silicon-containing compound (B). The ratio of the polymerization component and the silicon-containing compound (B) in the mixture when obtaining the product is the ratio of the emulsion copolymer (A) and the silicon-containing compound (B) in the obtained product. May be appropriately adjusted so that is within the above range.

The curing catalyst (C) used in the present invention is a component used for promoting the curability and obtaining the required cured physical properties.

Specific examples of the curing catalyst (C) include organic tin compounds such as dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate;
Phosphoric acid or phosphoric acid ester such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; hexylamine, di -2-
Organic amines such as ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; Mixtures or reactants of these organic amines and acidic phosphates;
Reactive silane compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane; propylene Epoxy compounds such as oxide, butylene oxide, cyclohexene oxide, glycidyl (meth) acrylate, glycidol, (meth) acrylic glycidyl ether, cardura (E), Epicoat 828, Epicoat 1001 (all manufactured by Yuka Shell Epoxy Co., Ltd.) Addition reaction product with phosphoric acid and / or acidic monophosphoric acid ester; isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pie) Organic titanate compounds such as phosphate) oxyacetate titanate; organoaluminum compounds such as tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum; tetrabutylzirconate, tetrakis (acetylacetonato) zirconium, tetraisobutylzirconate, Organozirconium compounds such as butoxytris (acetylacetonato) zirconium; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, phthalic acid, trimellitic acid,
Organic carboxylic acids such as saturated or unsaturated polyvalent carboxylic acids such as pyromellitic acid and their acid anhydrides; Mixtures or reaction products of organic carboxylic acids and organic amines;
Examples thereof include acidic compounds such as paratoluenesulfonic acid; alkaline compounds such as sodium hydroxide and potassium hydroxide, and these can be used alone or in combination of two or more kinds.

In the present invention, an organometallic compound, particularly an organoaluminum compound or an organotin compound, such as polyoxyethylene nonylphenyl, is used because the resulting resin composition for water-based paints has excellent curability and storage stability. An emulsified product obtained by emulsifying with a surfactant containing an alkyl ether type surfactant such as ether or polyoxyethylene lauryl ether as a main component is preferably used as the curing catalyst (C).

The amount of the surfactant used to obtain the emulsion is such that the amount of the alkyl ether type surfactant as the main component is 10 to 200 with respect to 100 parts of the organometallic compound.
Parts, preferably 20 to 100 parts. Further, when obtaining the emulsion, usually,
Deionized water is 80-
1500 parts, preferably 200 to 1200 parts, and 10 to 200 antifreeze agents such as polyethylene glycol.
Parts, preferably 20 to 100 parts, and it is desirable to use these.

The thus obtained emulsion contains the organometallic compound in an amount of usually 5 to 50% by weight, preferably 7 to 30% by weight.

In the present invention, a mixture or reaction product of an acidic phosphoric acid ester or an organic carboxylic acid and an organic amine is preferable from the viewpoint of high curing activity.

The curing catalyst (C) is preferably used as necessary, but in order to prevent the curability of the obtained resin composition for water-based coatings from decreasing, the amount of the curing catalyst (C) is required. Is 0.1 part or more, preferably 0.5 part or more, relative to 100 parts of the solid content of the emulsion copolymer (A). Further, in order not to deteriorate the appearance of the coating film formed from the obtained resin composition for water-based paint, the amount of the curing catalyst (C) is 100 parts by weight of the solid content of the emulsion copolymer (A). On the other hand, it is 20 parts or less, preferably 10 parts or less.

The resin composition for an aqueous coating material of the present invention is a mixture of the emulsion-containing copolymer (A) with the silicon-containing compound (B) and the curing catalyst (C), and has a good film-forming ability. However, by using the cosolvent, the coating film forming ability can be further enhanced.

Specific examples of the co-solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, hexyl alcohol and octyl alcohol; methyl cellosolve, ethyl cellosolve. , Butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monoisobutyl ether,
Ethers such as dipropylene glycol monoethyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-butyl ether, tripropylene glycol monoisobutyl ether; Examples include glycol ether esters such as butyl cellosolve acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol mono-n-butyl ether acetate, and tripropylene glycol monoisobutyl ether acetate, which may be used alone or in combination. The above can be mixed and used.

These cosolvents may be added during the polymerization of the emulsion copolymer (A), or may be added together with other components after the polymerization.

Further, in order to further improve the weather resistance of the coating film formed from the resin composition for water-based paint of the present invention, an ultraviolet absorber or a light stabilizer should be added to the resin composition for water-based paint. Is preferred.

The ultraviolet absorber is not particularly limited, but a liquid one is preferable from the viewpoint of easy handling. Specific examples of such an ultraviolet absorber include, for example, i-octyl-3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl) propionate and methyl-3- (3. -(2H
-Benzotriazol-2-yl) -5-t-butyl-
Reaction product of 4-hydroxyphenyl) propionate and polyethylene glycol (registered trademark TINUVIN
Examples include benzotriazole-based UV absorbers such as 1130, manufactured by Nippon Ciba Geigy Co., Ltd., which are liquid at room temperature, and these may be used alone or in admixture of two or more.

The light stabilizer is not particularly limited, but a liquid one is preferable from the viewpoint of easy handling. Specific examples of such a light stabilizer include, for example, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,2).
Examples thereof include hindered amine-based light stabilizers such as 2,6,6-pentamethyl-4-piperidyl) sebacate which are liquid at room temperature, and these may be used alone or in combination of two or more.

The ultraviolet absorber and the light stabilizer can be used in combination.

From the viewpoint of the stability of the emulsion copolymer (A), among these ultraviolet absorbers and light stabilizers, those having no imino group in the structure are preferable.

Further, in the present invention, for example, white pigments such as titanium dioxide, calcium carbonate, barium carbonate and kaolin which are usually used for paints, pigments such as colored pigments such as carbon black, red iron oxide and cyanine blue, Plasticizer, solvent, dispersant, thickener, defoamer,
Additives such as preservatives, anti-settling agents, leveling agents, and wetting agents can be added to the resin composition for water-based paints, if necessary. When the titanium dioxide is blended, for example, when titanium dioxide having an isoelectric point of 7 or more such as JR901, JR603, JR602 (above, manufactured by Teika Co., Ltd.) is used, the gloss and weather resistance of the coating film formed are increased. There is an advantage that the property is further improved.

Further, a commercially available water-based paint can be added to the resin composition for water-based paint of the present invention. Such water-based paints include, for example, acrylic paints, thermosetting acrylic paints such as acrylic melamine paints, alkyd paints, epoxy paints, fluororesin paints, and the like, and when these paints are blended, Weather resistance of the coating film formed from the resin composition for water-based coating obtained,
The acid resistance and solvent resistance can be further improved.

The method for obtaining the resin composition for an aqueous coating material of the present invention is not particularly limited and, for example, the emulsion copolymer (A) is used.
And the silicon-containing compound (B) and, if necessary, other additives, etc., are adjusted in their respective blending amounts and stirred at, for example, about 300 to 1000 rpm for about 2 to 10 minutes, and then the curing catalyst (C) is further blended. A method etc. can be adopted.

To prepare an aqueous coating composition from the resin composition for an aqueous coating composition of the present invention, a method of blending a pigment paste for coating composition when preparing the resin composition can be employed.

The resin composition for an aqueous coating composition of the present invention is applied to an object to be coated by a conventional method such as dipping, spraying, coating using a brush, etc., and then usually cured at about 10 ° C. or higher. A cured product (coating film) having appropriate hardness and excellent physical properties such as stain resistance, weather resistance, water resistance, adhesiveness and durability can be formed on the surface of the article to be coated.

The resin composition for water-based paints of the present invention is used for interior and exterior of buildings, automobiles such as metallic bases or clears on metallic bases, home appliances, plastic products, metals such as aluminum, stainless steel and silver. For direct coating, slate, concrete, roof tile, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium silicate board, for direct coating of ceramic base materials such as tiles and bricks, for glass, natural It can be suitably used as a surface treatment agent, including paints for stone materials such as marble and granite. Also,
In addition to the direct coating, the resin composition of the present invention is a water-based or solvent-based penetrative agent for coating an inorganic base material such as a water-based or solvent-based primer, an acrylic rubber, a topcoat with a double finish, or concrete. It is also suitable for use as a topcoat paint to be coated on a water absorption inhibitor.

[0131]

EXAMPLES Next, the resin composition for an aqueous coating material of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Production Examples 1 to 4 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introducing pipe and a dropping funnel, 40 parts of deionized water and 1 part of polyoxyethylene nonylphenyl ether sulfate (Production Example 1) 3) or 1 part of sodium dodecylbenzenesulfonate (Production Example 4), 1 part of polyoxyethylene nonyl phenyl ether, 0.5 part of ammonium acetate, 0.3 part of Rongalit and 0.1 part of t-butyl hydroperoxide. After charging, the temperature was raised to 50 ° C. while introducing nitrogen gas. Then, 20 parts of 158 parts of the mixture having the composition shown in Table 1 was dropped over 30 minutes using a dropping funnel,
Initial polymerization was performed. One hour after the completion of the dropping, the remaining 138 parts in 158 parts of the mixture and 0.1 part of t-butyl hydroperoxide were added dropwise at a constant rate over 3 hours using a dropping funnel. After this, polymerization is carried out for 1 hour,
Deionized water was added, the solid concentration was 50% by weight,
Emulsions (emulsion copolymers) (A-1) to (A-4) composed of fine particles having the average particle diameter shown in Table 1 were obtained.

Production Example 5 A solid content concentration was 50% by weight in the same manner as in Production Example 1 except that the mixture having the composition shown in Table 2 was used instead of the mixture having the composition shown in Table 1. , An emulsion (product) containing the emulsion copolymer (A) composed of fine particles having an average particle diameter of 0.22 μm ((A + B) −
I got 1).

Production Example 6 A solid content concentration was 50% by weight in the same manner as in Production Example 4, except that the mixture having the composition shown in Table 1 was used instead of the mixture having the composition shown in Table 1. , An emulsion (product) containing the emulsion copolymer (A) composed of fine particles having an average particle diameter of 0.22 μm ((A + B) −
I got 2).

The abbreviations in Tables 1 and 2 indicate the following.

MPTMSi: γ-methacryloxypropyltrimethoxysilane MPTESi: γ-methacryloxypropyltriethoxysilane BMA: butyl methacrylate MMA: methyl methacrylate BA: butyl acrylate MA100: polyoxyethylene (10) methacrylate (trade name MA-100 POENPE: polyoxyethylene nonylphenyl ether POENPES: polyoxyethylene nonyl phenyl ether sulfate SDBS: sodium dodecylbenzene sulfonate DIW: deionized water b-14: compound (b-14) (silicon) Containing compound (B), number average molecular weight 2000) b-15: Compound (b-15) (silicon-containing compound (B), number average molecular weight 2500)

[0137]

[Table 1]

[0138]

[Table 2]

Example 1 SMA1440 (manufactured by ATOCHEM, dispersant) per 100 parts of titanium oxide CR97 (manufactured by Ishihara Sangyo Co., Ltd.)
3 parts, Emulgen A-60 (manufactured by Kao Corporation, wetting agent) 1
Part, Tyrose H-4000P (manufactured by Hoechst Synthesis Co., Ltd.,
Thickener) 2% aqueous solution 10 parts, SN deformer 24
7 (manufactured by San Nopco Ltd., antifoaming agent) 0.5 part, 15% ammonia water 0.5 part and deionized water 25 parts were blended,
A required amount of glass beads having a particle diameter of 2 mm was added thereto, and the mixture was stirred at 1000 rpm for 1 hour using a sand mill to prepare a pigment paste.

With respect to 60 parts of emulsion (A-1),
After adding 3 parts of CS-12 (manufactured by Chisso Corp.) and thoroughly stirring, 30 parts of pigment paste and chillose H-4000.
2 parts of 2% aqueous solution of P, 2 parts of 20% aqueous solution of Adecanol UH-420 (manufactured by Asahi Denka Co., Ltd.), 2.9 parts of propylene glycol and SN deformer 247 0.1.
Parts and stir at 500 rpm for 10 minutes, and then add 3 parts of compound (b-1) (number average molecular weight 1000) and add 5 parts.
Stir at 00 rpm for another 10 minutes and then mix with white enamel (A-
I).

To 100 parts of this white enamel (AI) was added 3 parts of an emulsion of dibutyltin dilaurate (emulsified with polyoxyethylene nonylphenyl ether, content of dibutyltin dilaurate was 10% by weight), and deionized. A paint was obtained by diluting with water to a viscosity suitable for painting.

After the obtained paint is applied to the slate plate by air spray, the applied slate plate is applied to the slate plate for 20 minutes.
It was aged at 0 ° C. for 10 days to form a coating film having a thickness of 50 μm.

Examples 2 to 6 In Example 1, the emulsion (A-2) was used in place of the emulsion (A-1), and the compound (b-4) (number average molecular weight) was used in place of the compound (b-1). 3000, Example 2), compound (b-6) (number average molecular weight 2500, Example 3), compound (b-9) (number average molecular weight 3000,
Example 4), compound (b-10) (number average molecular weight 500
0, Example 5) or compound (b-12) (number average molecular weight 4000, Example 6) was used, and white enamel (A-II) to (A-VI) were prepared in the same manner as in Example 1. I got it.

Then, instead of the white enamel (AI), white enamel (A-II) (Example 2) and white enamel (A-) were used.
III) (Example 3), white enamel (A-IV) (Example 4), white enamel (A-V) (Example 5) or white enamel (A-VI) (Example 6) Example 1
A coating film having a thickness of 50 μm was formed in the same manner as in.

Example 7 In Example 1, the emulsion (A-3) was used instead of the emulsion (A-1), and the compound (b-8) (number average molecular weight) was used instead of 3 parts of the compound (b-1). 3500)
White enamel (A-VII) was obtained in the same manner as in Example 1 except that 5 parts were used.

Then, white enamel (A-VII) was used instead of white enamel (A-I), and the amount of the emulsion of dibutyltin dilaurate was changed from 3 parts to 5 parts. To form a coating film having a thickness of 50 μm.

Examples 8 to 11 A pigment paste was prepared in the same manner as in Example 1.

With respect to 60 parts of emulsion (A-2),
After adding 3 parts of CS-12 and stirring sufficiently, 30 parts of pigment paste and 2% aqueous solution of chillose H-4000P 2
Parts, 2 parts of a 20% aqueous solution of ADECANOL UH-420, 2.9 parts of propylene glycol and 0.1 part of SN deformer 247 were mixed and stirred at 500 rpm for 10 minutes to obtain white enamel (A-VIII).

Immediately before coating, 100 parts of this white enamel (A-VIII) was mixed with 3 parts of compound (b-4) (Example 8) or compound (b-9) (Example 9) and dibutyltin dilaurate. 3 parts of an emulsion (emulsified with polyoxyethylene nonyl phenyl ether, dibutyltin dilaurate content of 10% by weight) is mixed and diluted with deionized water to a viscosity suitable for coating to form a paint. I got it.

After the obtained paint is applied to the slate board by air spray, the applied slate board is applied to the slate board for 20 minutes.
It was aged at 0 ° C. for 10 days to form a coating film having a thickness of 50 μm.

Further, with respect to 100 parts of white enamel (A-VIII), an emulsion of compound (b-10) (Example 10) or an emulsion of compound (b-12) (Example 11) (both) Emulsified liquid containing 30% by weight of the silicon-containing compound (B), which was previously emulsified with a nonionic surfactant (polyoxyethylene nonylphenyl ether).
10 parts and 3 parts of the same emulsion of dibutyltin dilaurate as described above were blended and diluted with deionized water to a viscosity suitable for coating to obtain a coating.

After the obtained paint is applied to the slate plate by air spray, the coated slate plate is applied to the slate plate for 20 minutes.
It was aged at 0 ° C. for 10 days to form a coating film having a thickness of 50 μm.

Examples 12 and 13 A pigment paste was prepared in the same manner as in Example 1.

To 60 parts of the emulsion ((A + B) -1) (Example 12) or the emulsion ((A + B) -2) (Example 13), 3 parts of CS-12 was added and stirred sufficiently, 30 parts of pigment paste and chillose H-4
2 parts of 2% aqueous solution of 000P, Adecanol UH-420
20% aqueous solution of 2 parts, propylene glycol 2.9 parts and SN deformer 247 0.1 parts are mixed, and 5
Stir at 00 rpm for 10 minutes and then white enamel (A-IX) ~
(AX) was obtained.

This white enamel (A-IX) (Example 12)
Alternatively, to 100 parts of white enamel (AX) (Example 13), 3 parts of an emulsified product of dibutyltin dilaurate (emulsified using polyoxyethylene nonylphenyl ether, content of dibutyltin dilaurate of 10% by weight) was added. The paint was diluted with deionized water to a viscosity suitable for painting.

After the obtained paint is applied to the slate plate by air spray, the coated slate plate is applied to the slate plate for 20 minutes.
It was aged at 0 ° C. for 10 days to form a coating film having a thickness of 50 μm.

Examples 14 to 16 The white enamel obtained in Example 7, 12 or 13 (A-
VII) (Example 14), white enamel (A-IX) (Example 15) or white enamel (AX) (Example 16),
A paint was obtained by diluting with deionized water to a viscosity suitable for coating.

After applying the obtained coating material to the slate plate by air spray, 20
It was aged at 0 ° C. for 10 days to form a coating film having a thickness of 50 μm.

Comparative Examples 1 to 4 A pigment paste was prepared in the same manner as in Example 1.

Emulsion (A-1) (Comparative Example 1), Emulsion (A-2) (Comparative Example 2), Emulsion (A
-3) (Comparative Example 3) or emulsion (A-4) (Comparative Example 4) 60 parts, CS-12 3 parts were added, and after sufficiently stirring, 30 parts of pigment paste and Tyrose H-.
2 parts of 2% aqueous solution of 4000P, ADEKA NOL UH-42
2 parts of a 20% aqueous solution of 0, 2.9 parts of propylene glycol and 0.1 part of SN deformer 247 were added,
Stir at 500 rpm for 10 minutes and then white enamel (A-XI)
~ (A-XIV) was obtained.

Then, instead of the white enamel (AI), white enamel (A-XI) (Comparative Example 1) and white enamel (A-
XII) (Comparative Example 2), white enamel (A-XIII) (Comparative Example 3) or white enamel (A-XIV) (Comparative Example 4) was used in the same manner as in Example 1 except that the thickness was 50 μm. A coating film was formed.

Next, Examples 1 to 16 and Comparative Examples 1 to 1
The physical properties of the coating film formed in No. 4 are stain resistance, hydrophilicity,
The hardness, weather resistance and water resistance were examined according to the following methods. The results are shown in Tables 3 and 4.

(A) Using a stain resistance color difference meter (CR300, manufactured by Minolta Co., Ltd.),
With respect to the formed coating film, the lightness represented by the L ^* a ^* b ^* color system was measured. The measurement of the lightness was performed before and after the outdoor exposure of 30 ° on the south surface in Osaka Prefecture at 30 ° for three months between June and August, and the lightness of the coating film after the exposure and the exposure. The absolute value (ΔL value) of the difference from the brightness of the previous coating film was determined.

The smaller the ΔL value, the better the stain resistance.

(B) Hydrophilicity [0165] The contact angle measuring device (Kyowa Interface Science Co., Ltd.)
Manufactured by CA-S150 type) was used to measure the contact angle (°) with water.

The smaller the value of the contact angle, the higher the hydrophilicity.

(C) Hardness The coating film after outdoor exposure was carried out in the same manner as in the above (A) stain resistance, and a pendulum hardness tester (Erichsen Co., Ltd.) was used.
Manufactured by PERSOZ Hardness Tester) was used to measure the Perozos hardness.

[0168] The higher the value of the Perosus hardness, the higher the hardness.

(D) Weather resistance An accelerated weather resistance test was performed on the coating film using a sunshine carbon arc lamp, and the gloss retention rate of the coating film after 3000 hours was calculated based on the following formula. The 60 ° specular gloss was measured as the gloss of the coating film.

Gloss retention (%) = (Gloss after 3000 hours / Gloss before execution) × 100 Note that the larger the value of the gloss retention, the better the weather resistance.

(E) Water resistance The gloss retention of the coating film after being immersed in water at 23 ° C. for 7 days was calculated based on the following formula. The gloss of the coating film is 6
The 0 ° specular gloss was measured.

Gloss retention (%) = (Gloss after immersion for 7 days / Gloss before immersion) × 100 Incidentally, the larger the value of the gloss retention, the better the water resistance.

[0173]

[Table 3]

[0174]

[Table 4]

From the results shown in Tables 3 and 4, the coating films formed in Examples 1 to 16 are the coating films of Comparative Examples 1 to 4 in which the resin composition for water-based paint of the present invention is not used. Compared with, the ΔL value is small, so it has excellent stain resistance and
It has excellent hydrophilicity due to its small contact angle, and shows excellent stain resistance based on such excellent hydrophilicity. It also has an appropriate hardness and excellent weather resistance and water resistance. I understand.

Further, Examples 7 and 14 and Examples 12 and 15
Also, comparing Examples 13 and 16 with each other, it can be seen that the hardness of the coating film is further improved when the curing catalyst (C) is used.

[0177]

The coating film formed from the resin composition for an aqueous coating material of the present invention has appropriate hardness, excellent weather resistance and water resistance, and excellent stain resistance.

Therefore, the resin composition for water-based coating composition of the present invention can be applied to articles to be coated, such as building interior and exterior, automobiles, home appliances, plastic products, etc., which are particularly required to have weather resistance, water resistance and stain resistance. It can be suitably used for coating and can form a coating film having excellent coating film performance on the article to be coated.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-299037 (JP, A) JP-A-7-18149 (JP, A) JP-A 61-9463 (JP, A) JP-A 55- 750 (JP, A) JP-A-5-271607 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 143/04 C09D 183/00-183/16 C08L 43/04

Claims (7)

(57) [Claims] 1. A compound represented by the general formula (I): (In the formula, R ¹ is the same or different and is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or 7 carbon atoms.
10 aralkyl groups, X ¹ are the same or different, and are represented by halogen atom, alkoxy group, hydroxy group, acyloxy group, aminoxy group, phenoxy group, thioalkoxy group or amino group, and a is 0, 1 or 2. Emulsion polymerization of a polymerization component comprising a vinyl monomer (a-1) containing a silyl group and a vinyl monomer (a-2) copolymerizable with the vinyl monomer (a-1) Based on 100 parts by weight of the resulting emulsion copolymer (A), the compound represented by the general formula (II): (In the formula, R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ⁶ is Direct bond, alkylene group having 1 to 20 carbon atoms or 1 to 2 carbon atoms
0 alkyleneoxy group, X ² include an alkoxy group, hydroxy group, an acyloxy group, a phenoxy group, a thioalkoxy group, an amino group, an epoxy group, a bicycloalkyl group, (meth) acryloyloxy group, a styryl group, a polyether structure <br/> Group, group containing polyester structure or polycarbonate
The groups containing the structure , l, m and n each have a molar ratio of the formula:
1 / m / n = 1 to 50/1 to 50/0 to 50) representing a silicon-containing compound (B) 1
˜50 parts by weight, and 0 to 20 parts by weight of the curing catalyst (C) are mixed, and a resin composition for an aqueous coating composition. 2. The emulsion copolymer (A) comprises an alkoxysilyl group-containing vinyl monomer as a vinyl monomer (a-1) in an amount of 0.1 to 30% by weight, and a vinyl monomer (a). −
As 2), a polymerization component composed of 0.1 to 10% by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain and the balance of other vinyl monomer is used, and an anionic surfactant having a polyoxyethylene chain is used. The resin composition for an aqueous coating composition according to claim 1, which is an emulsion copolymer obtained by copolymerization. 3. The emulsion copolymer (A) has an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms and a cycloalkyl group having 4 or more carbon atoms as the vinyl-based monomer (a-2). At least one selected from the group consisting of cycloalkyl (meth) acrylates 60 to 90
The resin composition for an aqueous coating composition according to claim 1, which is an emulsion copolymer obtained by copolymerizing a polymerization component containing 10% by weight. 4. A polymerization component comprising a vinyl-based monomer (a-1) and a vinyl-based monomer (a-2) as the emulsion copolymer (A) and the silicon-containing compound (B), and a silicon-containing compound. The resin composition for an aqueous coating composition according to claim 1, which comprises a product obtained by polymerizing a mixture with the compound (B). 5. The resin composition for an aqueous coating composition according to claim 1, wherein the silicon-containing compound (B) has a number average molecular weight of 500 to 50,000. 6. The curing catalyst (C) is an emulsion obtained by emulsifying an organoaluminum compound or an organotin compound with a surfactant containing an alkyl ether type surfactant as a main component. The resin composition for water-based paints of. 7. The resin composition for an aqueous coating composition according to claim 1, wherein the curing catalyst (C) is a mixture or reaction product of an acidic phosphoric acid ester or an organic carboxylic acid and an organic amine.