JPH08295826A - Resin composition for aqueous coating and formation of coating film excellent in stain resistance - Google Patents

Abstract

PURPOSE: To obtain a resin composition for aqueous coating, capable of providing a coating film excellent in weather resistance and durability as well as stain resistance on the surface of a material to be treated when applied to the material to be treated. CONSTITUTION: This resin composition for aqueous coating is composed of 100 pts.wt. (A) synthetic resin emulsion, 1-70 pts.wt. (B) silicon compound expressed by the formula (R<1> O)4-a SiR<2> a [R<1> is the same or different 1-10C alkyl group, a 6-10C aryl group or a 7-10C aralkyl group; R<2> is the same or different 1-10C alkyl group, 6-10C aryl group, 7-10C aralkyl group or 1-10C alkoxy; (a) is an integer of 0-2] and/or its partially hydrolyzed condensation product and/or (C) silicon compound having one hydrolyzable silyl group and 0-20 pts.wt. (D) curing catalyst.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various coatings for interior and exterior of buildings, automobiles, home appliances, plastics, etc., particularly in applications where weather resistance and durability are required,
The present invention relates to a resin composition for water-based paint having good coating film performance.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, from the viewpoint of pollution control and resource saving, from organic solvent to water-soluble or water-dispersive without organic solvent. Attempts have been made to switch to resin and powder resin. In the paint field, the transition to water-based paints is being carried out more vigorously than powder paints. However, the conventional water-based resin does not have a crosslinkable functional group in the molecule, and as a result, is strongly affected by the surfactant used for the polymerization, the weather resistance of the formed coating film,
It has a drawback that the water resistance and stain resistance are remarkably deteriorated, and the physical properties of the coating film are inferior to those of the solvent-based paint.

Various attempts have been proposed to improve this drawback. For example, a proposal is made to apply a polymer emulsion having a hydrolyzable silyl group as a crosslinkable functional group to an aqueous paint (JP-A-3-227312). No.), or
A proposal has been made regarding an aqueous emulsion paint in which crosslinking between particles is introduced by the reaction of a carboxyl group and a hydrazyl group (see JP-A-5-59305). Also,
A proposal has been made regarding a water-dispersed fluororesin coating in which a fluororesin that exhibits high performance in a solvent system is made water-based (see JP-A-5-25421).

As a result, although some improvements have been made in terms of weather resistance and water resistance, there is a problem due to the use of water, which is not sufficient.

There is also a problem that the stain resistance is considerably inferior to that of the solvent type. In particular, regarding the stain resistance, demands have recently been increased in various fields, and a level close to that of a solvent-based low-staining paint is required.

[0006]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that various water-based paints or water-based resin compositions contain tetra (tri) alkoxysilane and / or a portion thereof. Hydrolyzed condensate and /
Alternatively, by mixing an aminosilane compound and / or a derivative thereof in a specific ratio and a curing catalyst in a specific ratio, particularly by mixing immediately before coating, a stain resistance which cannot be achieved by a conventional water-based paint can be obtained. It was finally found that a coating film having the above properties and having excellent weather resistance and water resistance can be formed, and the present invention has been completed.

That is, according to the present invention, 100 parts by weight of a synthetic resin emulsion (A), a silicon compound represented by the general formula (I) and / or a partial hydrolyzed condensate thereof (B) and / or one molecule are contained. Silicon compounds (C) 1-70 having at least one amino group and / or derivative thereof and at least one hydrolyzable silyl group
The present invention relates to a resin composition for water-based paints, which comprises 1 part by weight and 0 to 20 parts by weight of a curing catalyst (D).

(R ¹ O) _4-a —Si—R ² _a (I) (wherein 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 An aralkyl group having 7 to 10 carbon atoms, R ^{2 s} are the same or different,
C1-C10 alkyl group, C6-C10 aryl group, C7-C10 aralkyl group or C1-C1
10 alkoxy groups, a is an integer of 0-2. )

Further, synthetic resin emulsion (A) 100
Based on parts by weight, the silicon compound represented by the general formula (I) and / or its partial hydrolysis-condensation product (B) and / or
Alternatively, 1 to 70 parts by weight of a silicon compound (C) having at least one amino group and / or its derivative and at least one hydrolyzable silyl group in one molecule, and 0 to 20 parts by weight of a curing catalyst (D). The present invention relates to a method for forming a coating film having excellent stain resistance, which comprises blending and coating the material with an object to be treated.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The synthetic resin emulsion (A) used in the present invention is a commercially available emulsion-type resin for water-based paints, and if it is made into a paint,
There is no particular limitation, and examples thereof include acrylic resins, urethane resins, fluororesins, melamine resins, silicone resins, epoxy resins, polyester resins, polyether resins, and the like. Acrylic resin, urethane resin, fluororesin, etc. are preferable because the coating film formed from the material has excellent weather resistance and chemical resistance, and the range of resin design can be widened. Acrylic resins are preferred because of their low price.

The vinyl monomer used in the synthesis of the polymer of the component (A) is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and isobutyl ( Meta)
Vinyl-based monomers such as acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate;
Styrene, α-methylstyrene, chlorostyrene, 4-
Aromatic hydrocarbon vinyl monomers such as hydroxystyrene and vinyltoluene; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid, etc. α, β
-Ethylenically unsaturated carboxylic acid, styrene sulfonic acid,
Acids having a polymerizable carbon-carbon double bond such as vinyl sulfonic acid; or salts thereof (alkali metal salts,
Ammonium salts, amine salts, etc.); acid anhydrides such as maleic anhydride or half esters of them with linear or branched alcohols having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth). Acrylate, diethylaminoethyl (meth)
(Meth) acrylate having an amino group such as acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine, or Their hydrochloric acid, acetate; vinyl acetate, vinyl propionate,
Vinyl ester or allyl compound such as diallyl phthalate; Vinyl monomer containing nitrile group such as (meth) acrylonitrile; Vinyl monomer containing epoxy group such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Aronix 5700 (Toagosei Kagaku Co., Ltd.)
Manufactured), PlaccelFA-1, PlaccelFA-
4, PlaccelFM-1, PlaccelFM-4
(Above, manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-
20, HP-10, HP-20 (all manufactured by Nippon Shokubai Chemical Co., Ltd.), Bremmer PP series, Bremmer PE
Series, Bremmer PEP Series, Bremmer AP
-400, Bremmer AE-350, Bremmer NKH
-5050, Bremmer GLM (above, NOF Corporation)
Manufactured), MA-30, MA-50, MA-100, MA-
150, RA-1120, RA-2614, RMA-5
64, RMA-568, RMA-1114, MPG13
0-MA (manufactured by Nippon Emulsifier Co., Ltd.), hydroxyl-containing vinyl-based modified hydroxyalkyl vinyl-based monomers such as hydroxyl-containing vinyl-based monomers; (meth) acrylic acid hydroxyalkyl esters such as α, β-ethylene Hydroxyalkyl esters of unsaturated carboxylic acids and phosphoric acid ester group-containing vinyl compounds or vinyl compounds such as (meth) acrylates containing urethane bonds or siloxane bonds; AS-6, a macromonomer manufactured by Toagosei Co., Ltd. , AN-6, AA-6, AB-6, AK-5 and the like compounds; vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene,
Other vinyl-based monomers such as N-vinylimidazole may be mentioned.

A silyl group-containing monomer represented by the general formula (II) can also be used.

[0013]

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As a concrete example, for example,

[0015]

Embedded image

[0016]

[Chemical 4]

And the like. Among these, the alkoxysilyl group-containing monomer is particularly preferable in terms of stability.

These silyl group-containing vinyl monomers are
One kind or two or more kinds may be used in combination, preferably 1 to 50% by weight is copolymerized, and more preferably 2 to 30% by weight. The amount of copolymerization is 1% by weight
If it is less, the water resistance and weather resistance are poor, and if it exceeds 50% by weight, the emulsion stability is lowered and the storage stability is also lowered.

The fluorine-containing vinyl monomer is not particularly limited, and specifically, for example, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate. 2,2,3,3-tetrafluoropropyl methacrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, tetrafluoropropylene And fluorine-containing vinyl monomers such as trifluoropropylene, chlorotrifluoroethylene, bromotrifluoroethylene, chlorodifluoroethylene, and dichlorodifluoroethylene.

These fluorine-containing vinyl monomers have 1
One kind or two or more kinds may be used in combination, preferably 1 to 50% by weight is copolymerized, and more preferably 2 to 30% by weight. If the amount of copolymerization is less than 1% by weight, water resistance and weather resistance are poor, and if it exceeds 50% by weight, the stability of the emulsion is lowered and the effect of introducing the fluorine-containing monomer is impaired.

In order to obtain a resin having a urethane bond, an isocyanate compound and a hydroxyl group-containing monomer may be reacted and introduced into a copolymer. Further, in order to obtain a resin that undergoes urethane crosslinking, urethane crosslinking is carried out by mixing and reacting a vinyl polymer containing a free isocyanate group and / or a blocked isocyanate group with a vinyl polymer containing a hydroxyl group. Just go.
The isocyanate compound has two isocyanate groups in one molecule and includes, for example, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,
Aliphatic, aromatic and alicyclic diisocyanate compounds such as 4′-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4 (2,6) -diisocyanate, isophorone diisocyanate and trimethylhexanediisocyanate, and these isocyanate compounds; Reaction products such as polyether resins, polyester resins, and polycarbonates containing two or more hydroxyl groups in one molecule are mentioned. The isocyanate-containing monomer may be prepared by reacting the diisocyanate compound and the hydroxyl group-containing monomer, and examples thereof include 2-isocyanate ethyl methacrylate and m.
-Isopropenyl-α, α'-dimethylbenzyl isocyanate, an adduct of 2-molar 2-hydroxyethyl methacrylate and isophorone diisocyanate, and the like are preferable.

Specific examples of the vinyl monomer containing a carbonyl group include, for example, acrolein, diacetone acrylamide and formyl styrene, preferably 4
Vinyl alkyl ketone having 7 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, etc.), diacetone acrylate, acetonyl acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate-acetyl acetate, Examples include butanediol-1,4-acrylate-acetylacetate. One kind of these carbonyl group-containing vinyl monomers may be used,
You may use 2 or more types together. The amount of the vinyl-based monomer containing the carbonyl group used is 0.1 with respect to the total amount of the monomers.
-30 parts by weight, preferably 3-10 parts by weight.

The compound having a hydrazine and a hydrazyl group to be reacted with the carbonyl group-containing polymer is 1
A hydrazine derivative containing at least two hydrazine residues in the molecule is preferable, and a dicarboxylic acid dihydrazide (which is a dehydration condensation product of a dicarboxylic acid having 2 to 10, more preferably 4 to 6 carbon atoms and hydrazine ( For example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide,
Itaconic acid dihydrazide and the like); Aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms (for example, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine Etc.)

The type of the vinyl-based monomer may be selected according to the desired physical properties of the obtained curable resin composition. For example, in order to improve the stability of the emulsion (A), ( It is preferable to use hydrophilic monomers such as (meth) acrylic acid, maleic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide, hydroxyl group-containing vinyl monomers, polyethylene glycol methacrylate and polypropylene glycol methacrylate. In addition, in order to improve the water resistance and durability of the coating film formed using the obtained resin composition, a functional group for crosslinking the particles in the emulsion or between particles is introduced, or a fluorine-containing vinyl is used. It is preferable to use a vinyl monomer or a siloxane-containing vinyl monomer. Further, when the acidic vinyl-based monomer is used, the mechanical stability of the emulsion (A) is improved.

When a hydrophilic monomer having a polyoxyethylene chain is used among the above-mentioned monomers, the stability of the silyl group in the above-mentioned monomer is not lowered and the emulsion (A The mechanical stability and the chemical stability of the above) and the water resistance and gloss of the coating film formed by using the curable resin composition that can be obtained are preferable. The amount of the hydrophilic monomer having a polyoxyethylene chain used is preferably adjusted to 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the polymerization components. When the blending amount is less than 0.1 parts by weight, the mechanical stability of the emulsion (A) and the gloss of the coating film formed using the curable resin composition which is obtained tend to be lowered. On the other hand, when the amount exceeds 10 parts by weight, the coating film tends to be softened and stains tend to be easily attached.

In addition to that, for example, a polymer produced by using a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate and the like is used. It is also possible to have a crosslinked structure.

Explaining the production method of the present invention, the emulsion polymerization method of the present invention includes batch polymerization, monomer dropping polymerization,
Means for emulsion polymerization such as emulsion monomer dropping polymerization can be appropriately selected. Particularly, monomer dropping polymerization and emulsion monomer dropping polymerization are suitable for ensuring stability during production.

The emulsifier used in emulsion polymerization is not particularly limited as long as it is a commonly used one, and examples thereof include ionic and nonionic surfactants. As the ionic surfactant, sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; New
col-723SF, Newcol-707SN, Ne
wcol-707SF, Newcol-740SF, N
ewcol-560SN (Nippon Emulsifier Co., Ltd.)
(Poly) oxyethylene group-containing anionic emulsifiers such as; imidazoline laurate, ammonium salts such as ammonium hydroxide; nonionic surfactants such as polyoxyethylene nonyl phenyl ether,
Polyoxyethylenes such as polyoxyethylene lauryl ether; L-77, L-720, L-5410, L
Typical examples include nonionic emulsifiers containing silicon such as -7602 and L-7607 (all manufactured by Union Carbide Co.). Further, as an emulsifier, ADEKA REASOAP NE-10, NE-20, NE having polymerization reactivity is used.
-30, NE-40, SE-10N (above, Asahi Denka Kogyo KK), Antox-MS-60, Antox-M
S-2N, RMA-653 (Nippon Emulsifier Co., Ltd.)
Made), AQUARON RN20, RN30, RN50, HS
Use of 05, HS10, HS20, and HS1025 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) can improve water resistance.

As the polymerization initiator, those usually used may be used, but from the viewpoint of the stability of the polymerization, it is preferable to use a redox catalyst, specifically, for example, potassium persulfate or ammonium persulfate. And acidic sodium sulfite or rongalite, hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, p-menthane hydroperoxide and other organic peroxides and acidic sulfite. A combination with sodium or Rongalit or the like is used. In particular, a combination of an organic peroxide and a reducing agent is preferable. Further, a compound containing a divalent iron ion such as iron sulfate may be used in combination with a chelating agent such as disodium ethylenediaminetetraacetate in order to stabilize the catalytic activity.

The amount of such an initiator used depends on the amount of monomer 10
It is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, relative to 0 parts by weight.

In the case of the method of the present invention, the solid content concentration of the synthetic resin emulsion (A) is preferably 20 to 70% by weight.

When the solid content concentration exceeds 70% by weight, the viscosity of the system remarkably increases, so that it is difficult to remove heat generated by the polymerization reaction, and it takes a long time to take it out from the polymerization machine. Occurs. Also, the solid content concentration is 2
When it is 0% by weight or less, no problem occurs in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is extremely disadvantageous from an economical point of view.
Also, from the requirements of the application, if the concentration is 20% by weight or less, the film thickness of the coating film becomes thin, resulting in performance deterioration,
It is disadvantageous in terms of coating workability.

The thus-obtained synthetic resin emulsion is composed of ultrafine particles having an average particle diameter of about 0.02 to 1.0 micron, and as a result, has excellent film forming ability.

The silicon compound represented by the general formula (I) and / or its partial hydrolysis-condensation product in the component (B) is, for example, tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate,
Tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, tetra-
t-butyl silicate, MSi51, ESi28, ES
i40 (above, manufactured by Colcoat Co., Ltd.) and the like and / or a partial hydrolyzed condensate thereof; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, Phenyltriethoxysilane, octadecyltriethoxysilane, 3-
Glycidoxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3-
(Meth) acryloxypropyltriethoxysilane, methyltri-sec-octyloxysilane, methyltributoxysilane, trialkoxysilane such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.) and / or its partial hydrolysis-condensation product; Can be given.

The component (B) may be used alone,
Two or more kinds may be used in combination. The mixing ratio of the component (B) is
1 to 70 relative to 100 parts by weight of the resin solid content of the component (A)
Parts by weight, preferably 2 to 50 parts by weight. If it is less than 1 part by weight, the hardness and hydrophilicity of the obtained coating film are not sufficient, and if it exceeds 70 parts by weight, problems such as appearance of the coating film and cracks occur.

The component (B) may be blended with the emulsion (A) in advance and then made into a paint, or may be blended with the emulsion (A) made into a paint. From the viewpoint of imparting stain resistance by adding the component (B), it is preferable to add it to the emulsion (A) which is made into a paint,
It is more preferable to mix it just before coating.

The silicon compound having at least one amino group and / or its derivative and at least one hydrolyzable silyl group in one molecule in the component (C) is not particularly limited and may be, for example, a compound represented by the general formula: Examples thereof include compounds represented by (III) and general formula (IV) and / or salts thereof.

[0038]

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(In the formula, R ⁴ , R ⁵ and R ⁶ are the same or different, and are an alkyl group having 1 to 10 carbon atoms and ^{6 to} 1 carbon atoms.
0 aryl group, C 7-10 aralkyl group, X ²
Is at least one selected from the group consisting of a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group.
Seed group, A is an alkylene group having 1 to 10 carbon atoms, 1 carbon atom
~ 100 polyalkylene oxide groups, c and e are 0
Is an integer of 2; d is an integer of 0 to 1; m is an integer of 0 to 5. )

[0040]

[Chemical 6]

(In the formula, R ⁴ , R ⁵ , X ² , c and d are the same as above, and f is an integer of 1 to 6.)

Silicon compounds having at least one amino group and / or derivative thereof and at least one hydrolyzable silyl group in one molecule represented by the general formulas (III) and (IV) and salts thereof. As a specific example of, for example,

[0043]

[Chemical 7]

Amino group-containing silanetriols such as;

[0045]

Embedded image

[0046]

[Chemical 9]

[0047]

[Chemical 10]

Monoaminosilanes such as;

[0049]

[Chemical 11]

[0050]

[Chemical 12]

Diaminosilanes such as;

[0052]

[Chemical 13]

Triaminosilanes such as; X-12-5
204, X-12-633AT, X-12-734, X
-12-575, X-12-577, X-12-563
B, X-12-565, X-12-730, X-12-
562, CF-136, KBE-9703, KBM-5
76 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), A-1100,
A-1110, A-1122, A-1106, A-11
26, A-1160, Y-9138, Y-5823, Y
-5987, AZ-6131, AZ-6160 (above,
Made by Nippon Unicar Co., Ltd., SH6020, SH602
6, SZ6023, SZ6032, SZ6050, SZ
6079, SZ6083, AY43-021 (all manufactured by Toray Silicone Co., Ltd.), TSL8331, TSL8.
340, TSL8345 (above, Toshiba Silicone Co., Ltd.)
Made) etc.

The component (C) may be used alone or in combination of two or more. It is preferable to add 1 to 70 parts by weight, more preferably 2 to 50 parts by weight, to 100 parts by weight of the resin solid content of the component (A). When the amount is less than 1 part by weight, there is almost no stain resistance imparting effect, and when it exceeds 70 parts by weight, the emulsion stability is lowered and the storage stability is also lowered.

The component (C) may be blended with the emulsion (A) in advance and then made into a paint, or may be blended with the emulsion (A) made into a paint.

Further, it is also possible to blend and use one kind or two or more kinds of the component (B) and one kind or two or more kinds of the component (C). When (B) and (C) are blended and used, (B) is added to 100 parts by weight of (A).
And the total amount of (C) is 1 to 70 parts by weight.

Specific examples of the curing catalyst as the component (D) include, for example, dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, dioctyltin malate, tin octylate and other organotin compounds; phosphoric acid, monomethyl phosphate, Phosphoric acid or phosphates such as monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, Glycidyl methacrylate, glycidol, acrylic glycidyl ether,
3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, Cardura (E) manufactured by Yuka Shell Epoxy Co., Ltd.,
Addition reaction products of epoxy compounds such as Epikote 828 and Epikote 1001 with phosphoric acid and / or acidic monophosphoric acid ester; organic titanate compounds; organoaluminum compounds; organozirconium compounds; maleic acid, adipic acid, azelaic acid, sebacic acid, itacone Acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid,
These acid anhydrides, acidic compounds such as p-toluenesulfonic acid; amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, dodecylamine; Mixtures or reactants; alkaline compounds such as sodium hydroxide and potassium hydroxide.

The component (D) may be used alone,
Two or more kinds may be used in combination. The amount of the curing catalyst used is not particularly limited, but is 0 to 20 parts by weight, usually 0.1 to 20 parts by weight, and preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the component (B) or (C). Use parts by weight. Usage is 20
If it exceeds the weight part, the appearance of the coating film tends to deteriorate.

The resin composition for an aqueous coating composition comprising the component (A), the component (B) and the component (C) has good film-forming ability as it is, but a co-solvent is used to further improve the film-forming ability. Can be increased. Specific examples of the cosolvent include, for example, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, hexyl alcohol, and octyl alcohol; cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, tripropylene glycol monoethyl ether, tripropylene glycol Monobuchi Ethers, ethers such as tripropylene glycol monoisobutyl ether; butyl cellosolve acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monobutyl ether acetate, glycol ether esters such as tripropylene glycol monoisobutyl ether acetate can give.

These solvents may be added during the polymerization of the emulsion copolymer (1) or after the polymerization.

In the obtained resin composition for water-based paints, pigments (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, etc., carbon dioxide, red iron oxide, cyanine blue) that are usually used in paints as an additive are added as necessary. Additives such as colored pigments) and plasticizers, solvents, dispersants, thickeners, defoamers, antiseptics, antisettling agents, leveling agents, UV absorbers, etc. It is also possible to mix and use. When adding titanium dioxide to the resin composition for water-based paint, the isoelectric point is 7
Gloss and weather resistance are improved by using the above titanium dioxide. Specifically, JR901, JR603, J
R602 (above, manufactured by Teika Co., Ltd.) and the like.

The effect of imparting the stain resistance of the present invention is that the general formula (I) is added to 100 parts by weight of the synthetic resin emulsion (A).
And / or a partial hydrolyzed condensate thereof (B) and / or a silicon compound having at least one amino group and / or its derivative and at least one hydrolyzable silyl group in one molecule. It is developed by applying 1 to 70 parts by weight of (C) and 0 to 20 parts by weight of the curing catalyst (D) to the object to be treated, particularly by mixing and applying immediately before coating. The mechanism of manifesting the effect is that the component (B) and / or the component (C) is localized on the surface of the coating film during the cross-linking reaction, whereby the coating surface hardness and hydrophilicity are imparted. Since the surface hardness of the coating film is high, scratches are less likely to occur and contamination is prevented. At the same time, since the coating film is hydrophilic, a cleaning effect against rain or the like is exhibited, and a coating film having further excellent stain resistance is formed.

As described above, (A), (B) and /
Alternatively, after the composition comprising the components (C) and (D) is applied to an object to be coated by a conventional method, the composition is usually cured at 10 ° C. or higher to give stain resistance, weather resistance, and adhesion to the surface of the object to be coated. sex,
A cured product (coating film) having excellent physical properties such as durability can be formed.

The composition of the present invention is used, for example, for building interiors,
For automobiles such as metallic base or clear on metallic base, for direct coating of metal such as aluminum, stainless steel, silver, slate, concrete, roof tile, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, silicic acid It is used as a paint or top treatment agent for direct coating of ceramics such as calcium plate, tile, brick, etc., for glass, stone material such as natural marble and granite. In addition to direct coating, it is also used for coating on water-based or solvent-based primer, acrylic rubber, topcoat with multiple finishes, inorganic base materials such as concrete, and water-based or solvent-based water-absorption inhibitor. To be

[0065]

EXAMPLES Next, a method for preparing the composition of the present invention and a method for producing the composition will be described based on examples.

Production Examples 1 to 4 In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introducing tube and a dropping funnel, 40 parts of deionized water (parts by weight, hereinafter the same), 1 part of sodium dodecylbenzenesulfonate ( Production Examples 1, 3, 4) or 1 part of polyoxyethylene nonylphenyl ether sulfate (Production Example 2), 1 part of polyoxyethylene nonylphenyl ether, 0.5 part of ammonium acetate, 0.3 part of rongalite, t-butyl. 0.1 part of hydroperoxide was charged and the temperature was raised to 50 ° C. while introducing nitrogen gas. 20 parts of 158 parts of the mixture having the composition shown in Table 1 were added dropwise using a dropping funnel over 30 minutes to carry out initial polymerization. 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 by a dropping funnel. After this, post-polymerization is carried out for 1 hour,
Deionized water was added to obtain emulsions (A-1) to (A-4) having a resin solid content of 50% by weight.

[0067]

[Table 1]

Production Example 5 A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introducing tube and a dropping funnel was charged with 45 parts of deionized water, 1 part of dodecylbenzenesulfonic acid and 1 part of sodium dodecylbenzenesulfonate. The temperature was raised to 50 ° C. while introducing nitrogen gas. 50 parts of octamethylcyclotetrasiloxane was added dropwise using a dropping funnel over 1 hour. After polymerizing for 3 hours, it was neutralized with sodium carbonate, and deionized water was added to the emulsion to form a dimethylpolysiloxane (A-5) in which both ends of the molecular chain having a resin solid content of 50% by weight were blocked with hydroxyl groups. ).

Production Examples 6 to 7 Commercially available epoxy resin (Okaka Shell Epoxy Co., Ltd .: Epicoat 1001, Production Example 6) or commercial melamine resin (Mitsui Toatsu Chemical Co., Ltd .: Uban 2028, Production Example 7) 50 Parts, 1 part of polyoxyethylene nonylphenyl ether sulfate and 1 part of polyoxyethylene nonyl phenyl ether were mixed while heating to 50 ° C., and 48 parts of deionized water was mixed at room temperature, followed by emulsification using a homogenizer. , Epoxy resin emulsion (A-
6), an emulsion of melamine resin (A-7) was obtained.

Example 1 To 100 parts of titanium oxide (CR97, manufactured by Ishihara Sangyo Co., Ltd.), 3 parts of SMA1440 (manufactured by ATOCHEM),
Emulgen A-60 (manufactured by Kao Corporation) 1 part, Tyrose H
-4000P (Hoechst Synthetic Co., Ltd.) 2% aqueous solution 1
No. 0, SN Deformer 247 (San Nopco Ltd.)
0.5 parts, 0.5% 15% ammonia water, and 25 parts deionized water were added, glass beads having a particle size of 2 mm were added in the required amount, and the mixture was stirred at 1000 rpm for 1 hour using a sand mill to give a pigment paste. Prepared.

With respect to 60 parts of emulsion (A-1),
After adding 3 parts of CS-12 (manufactured by Chisso Co., Ltd.) and stirring the mixture sufficiently, 30 parts of pigment paste and Chirose H-4000.
2 parts of 2% aqueous solution of P (manufactured by Hoechst Synthetic Co., Ltd.), 2 parts of 20% aqueous solution of Adecanol UH-420 (manufactured by Asahi Denka Co., Ltd.), 2.9 parts of propylene glycol, SN deformer 247 (San Nopco ( Co., Ltd.) 0.1 part,
The mixture was stirred at 500 rpm for 10 minutes, and white enamel (a-
I got 1).

To 100 parts of this white enamel (a-1), 6 parts of ESI40 (Tetraethylsilicate partially hydrolyzed condensate manufactured by Colcoat Co., Ltd.) and 5 parts of an emulsion of dibutyltin dilaurate (tin) were added to 100 parts of white enamel. A compound content of 10%) was blended and diluted with deionized water to an appropriate coating viscosity, and then coated on the slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Examples 2 to 4 White enamel (a-2) was obtained using the emulsion (A-2) in the same manner as in Example 1.

Into this white enamel (a-2), 6 parts of ESI40 (produced by Colcoat Co., Ltd .: tetraethyl silicate partially hydrolyzed condensate) per 100 parts of white enamel (Example 2) or MSI51 (Colcoat (stock) was used. ): Tetramethylsilicate partially hydrolyzed condensate) 3 parts and ESI
40.3 parts (Example 3) or ESI 40. 3 parts (Example 4) and 5 parts of dibutyltin dilaurate emulsion (10% tin compound content) were mixed, and a suitable coating viscosity was obtained using deionized water. After diluting to 1, the slate plate was painted with air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Example 5 White enamel (a-3) was obtained using the emulsion (A-3) in the same manner as in Example 1.

To this white enamel (a-3), 100 parts of white enamel was added to a blocked isocyanate compound (Death Module BL317 manufactured by Sumitomo Bayer Urethane Co., Ltd.).
5) 10 parts were added, and 6 parts of BSI20 (produced by Colcoat Co., Ltd .: tetra-n-butyl silicate partially hydrolyzed condensate) and 5 parts of an emulsion of dibutyltin malate (tin compound content 10%) were added. It was blended and diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Example 6 White enamel (a-4) was obtained using the emulsion (A-4) in the same manner as in Example 1.

To this white enamel (a-4), 10 parts of adipic acid dihydrazide was added to 100 parts of white enamel, and further, BSI20 (manufactured by Colcoat Co., Ltd .: tetra-n-butyl silicate partially hydrolyzed condensate). ) And 5 parts of an emulsion of dibutyltin malate (tin compound content 1
0%) was mixed and diluted with deionized water to an appropriate coating viscosity, and then coated on the slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Example 7 White enamel (a-5) was obtained using the emulsion (A-5) in the same manner as in Example 1.

To this white enamel (a-5), an emulsion of 6 parts of PSI40 (Tetra-n-propyl silicate partially hydrolyzed condensate manufactured by Colcoat Co., Ltd.) and 100 parts of white enamel and dibutyltin dilaurate was prepared. 5 parts (tin compound content of 10%) was blended, diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Example 8 In the same manner as in Example 1, 30 parts of emulsion (A-6) and 30 parts of emulsion (A7) were used to prepare white enamel (a).
-6) was obtained.

An emulsion of 6 parts of PSI40 (produced by Colcoat Co., Ltd .: tetra-n-propyl silicate partially hydrolyzed condensate) with 100 parts of white enamel and dibutyltin dilaurate was added to the white enamel (a-6). 5 parts (tin compound content of 10%) was blended, diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Examples 9 to 11 Commercially available water-based fluoro paints (Asahi Glass C & R Co., Ltd .: Bonflon water-based) (Example 9) or water-based silicone paints (SK Kaken Co., Ltd .: Compo Silicon) (Examples) 10)
Or water-based acrylic urethane paint (Kansai Paint Co., Ltd.)
Manufactured by: Aquaretane) (Example 11), white enamel 10
To 0 parts, 10 parts of ESI40 (manufactured by Colcoat Co., Ltd .: tetraethyl silicate partially hydrolyzed condensate) and 10 parts of an emulsion of dibutyltin dilaurate (10% tin compound content) were mixed, and deionized water was used. After diluting to an appropriate coating viscosity, the slate plate was coated with air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Example 12 60 parts of emulsion (A-1) was added to CS-12.
After adding 3 parts (manufactured by Chisso Corporation) and stirring sufficiently,
3 parts of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 30 parts of pigment paste and Tyrose H-
4000P (Hoechst Synthetic Co., Ltd.) 2% aqueous solution 2
2 of ADEKA NOL UH-420 (manufactured by Asahi Denka Co., Ltd.)
0% aqueous solution 2 parts, propylene glycol 2.9 parts, SN
0.1 part of Deformer 247 (manufactured by San Nopco Ltd.) was mixed and stirred at 500 rpm for 10 minutes to obtain white enamel (a-7).

To this white enamel (a-7), 100 parts of white enamel was mixed with 3 parts of an emulsion of dibutyltin dilaurate (tin compound content: 10%), and deionized water was used to obtain an appropriate coating viscosity. After diluting to 1, the slate plate was painted with air spray. Then, the coated plate at 20 ℃ 10
I was cured for a day.

Examples 13 to 15 In the same manner as in Example 12, emulsion (A-2) 60
3 parts of 3-aminopropylsilanetriol (Example 13), 3 parts of 3-aminopropyltriethoxysilane (Example 14), and 1.5 parts (Example 15) were added to each part, and white enamel ( a-8) to (a-10) were obtained.

These white enamel (a-8) to (a-1)
0) was mixed with 100 parts of white enamel and 3 parts of an emulsion of dibutyltin dilaurate (content of tin compound: 10%), diluted with deionized water to an appropriate coating viscosity, and then aired on a slate plate. Painted with spray. afterwards,
The coated plate was cured at 20 ° C. for 10 days.

Example 16 Emulsion (A-3) 60 was prepared in the same manner as in Example 12.
Y-9138 (manufactured by Nippon Unicar Co., Ltd.) 3
Parts were added to obtain white enamel (a-11).

With respect to 100 parts of white enamel, a blocked isocyanate compound (manufactured by Sumitomo Bayer Urethane Co., Ltd .: Death Module BL31) was added to this white enamel (a-11).
75) Add 10 parts, and further mix 3 parts of an emulsion of dibutyltin dilaurate (tin compound content 10%),
After diluting to an appropriate coating viscosity with deionized water, the slate plate was coated with air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Example 17 Emulsion (A-4) 60 was prepared in the same manner as in Example 12.
A-1160 (manufactured by Nippon Unicar Co., Ltd.) 3
Parts were added to obtain white enamel (a-12).

To 100 parts of white enamel, 10 parts of adipic acid dihydrazito was added to this white enamel (a-12), and further 3 parts of dibutyltin dilaurate emulsion (10% tin compound content) was added. After being diluted with deionized water to an appropriate coating viscosity, the slate plate was coated with air spray. Then, the coated plate at 20 ℃ 10
I was cured for a day.

Example 18 Emulsion (A-5) 60 was prepared in the same manner as in Example 12.
3 parts of 3-aminopropyltriethoxysilane 3
Parts were added to obtain white enamel (a-13).

To this white enamel (a-13), dibutyltin dilaurate emulsion 3 was added to 100 parts of white enamel.
Parts (tin compound content 10%) were mixed, diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. After that, the coated plate at 20 ℃ 1
I was cured for 0 days.

Example 19 Emulsion (A-6) 30 was prepared in the same manner as in Example 12.
Parts and 30 parts of emulsion (A-7), 3 parts of 3-aminopropylsilanetriol was added to obtain white enamel (a-14).

To this white enamel (a-14), dibutyltin dilaurate emulsion 3 was added to 100 parts of white enamel.
Parts (tin compound content 10%) were mixed, diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. After that, the coated plate at 20 ℃ 1
I was cured for 0 days.

Examples 20 to 22 Commercially available water-based fluorine paint (Asahi Glass C & R Co., Ltd .: Bonflon water-based) (Example 20) or water-based silicone paint (SK Kaken Co., Ltd .: Composilicon) (Example) 21)
Or water-based acrylic urethane paint (Kansai Paint Co., Ltd.)
(Manufactured by: Aqualene) (Example 22), white enamel 10
3-aminopropyltrimethoxysilane 5 against 0 part
Parts and 5 parts of an emulsion of dibutyltin dilaurate (content of tin compound: 10%) were mixed and diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Comparative Examples 1, 2 and 5 White enamel (a-1), (a-2) and (a-5) were diluted with deionized water to an appropriate coating viscosity and then air sprayed onto a slate plate. I painted it. Then, the coated plate was cured at 20 ° C. for 10 days.

Comparative Example 3 White enamel (a-3) was added to 100 parts of white enamel.
10 parts of a blocked isocyanate compound (Desmodur BL3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added, diluted with deionized water to an appropriate coating viscosity, and then coated on a slate plate by air spray. afterwards,
The coated plate was cured at 20 ° C. for 10 days.

Comparative Example 4 Adipic acid dihydrazide 10 was added to white enamel (a-4).
Parts were added and diluted to an appropriate coating viscosity with deionized water, and then coated on the slate plate with air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Comparative Example 6 White enamel (a-6) was diluted with deionized water to an appropriate coating viscosity and then coated on a slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Comparative Examples 7 to 9 Commercially available water-based fluorine paint (Asahi Glass C & R Co., Ltd .: Bonflon water-based) or water-based silicone paint (SK Kaken Co., Ltd .: Composilicon) or water-based acrylic urethane paint (Kansai Paint). Each of Aquaretane manufactured by Co., Ltd. was diluted with deionized water to an appropriate coating viscosity, and then coated on the slate plate by air spray. Then, the coated plate was cured at 20 ° C. for 10 days.

Examples 1 to 22 and Comparative Example 1 described above
Each of the coating films obtained in No. 9 was examined for stain resistance, hydrophilicity and hardness. The methods for measuring and evaluating the respective physical properties are as follows, and the results are shown in Tables 2 to 6.

(Staining resistance) The lightness represented by the L ^* a ^* b ^* color system at the early stage of exposure was measured by a color difference meter (CR manufactured by Minolta Co., Ltd .: CR).
300), and the outdoor exposure at 30 ° on the south side was carried out for 3 months in Settsu City, Osaka Prefecture. The absolute value (ΔL value) of the difference in brightness after exposure and the brightness before exposure was used as a measure of contamination. In addition, the smaller the numerical value is, the better the stain resistance is, and the larger the numerical value is, the dirty.

(Hydrophilicity) Hydrophilicity was measured by using a contact angle measuring device (CA-S150 type manufactured by Kyowa Interface Science Co., Ltd.) in Settsu City, Osaka Prefecture, with water after 3 months of outdoor exposure at 30 ° south surface. It was evaluated by measuring the contact angle. The smaller the value, the higher the hydrophilicity.

(Hardness) Pendulum hardness meter (Erichsen Co., Ltd.)
(Manufactured by: PERSOZ hardness meter), the hardness was measured after 3 months of outdoor exposure at 30 ° on the south surface in Settsu City, Osaka Prefecture (Perozos hardness). The higher the value, the higher the hardness.

[0106]

[Table 2]

[0107]

[Table 3]

[0108]

[Table 4]

[0109]

[Table 5]

[0110]

[Table 6]

[0111]

EFFECT OF THE INVENTION The resin composition for water-based paint of the present invention is a coating film having excellent weather resistance and durability on the surface of the object to be treated, and excellent stain resistance when applied to the object to be treated. Is formed. Further, the coating film forming method of the present invention, that is, in the resin composition, the silicon compound represented by the general formula (I) and / or its partial hydrolysis-condensation product and / or at least one amino in one molecule. A group and / or a derivative thereof, a silicon compound having at least one hydrolyzable silyl group, and a curing catalyst are mixed and then applied to an object to be treated so that the surface of the object is resistant to contamination by outdoor exposure. An excellent coating film is formed.

Claims (16)

[Claims] 1. A synthetic resin emulsion (A) (100 parts by weight), a silicon compound represented by the general formula (I), and / or
Or its partial hydrolysis-condensation product (B) and / or 1
1 to 70 parts by weight of a silicon compound (C) containing at least one amino group and / or its derivative and at least one hydrolyzable silyl group in the molecule, and 0 to 20 parts by weight of a curing catalyst (D). A resin composition for water-based paints. (R ¹ O) _4-a —Si—R ² _a (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, R ² are the same or different,
C1-C10 alkyl group, C6-C10 aryl group, C7-C10 aralkyl group or C1-C1
10 alkoxy groups, a is an integer of 0-2. ) 2. The resin composition for an aqueous coating composition according to claim 1, wherein the synthetic resin emulsion (A) is mainly composed of an acrylic resin. 3. The component (A) is an acrylic resin emulsion and is obtained by copolymerizing a vinyl monomer having a silyl group represented by the general formula (II) with another vinyl monomer. The resin composition for water-based paints according to claim 1, which is the obtained silyl group-containing resin. Embedded image (In the formula, R ³ 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 to 7 carbon atoms.
10 aralkyl groups, X ¹ is the same or different, and is at least one group selected from the group consisting of a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group, b Is an integer from 0 to 2. ) 4. The resin composition for an aqueous coating composition according to claim 1, wherein the component (A) is an acrylic resin emulsion and comprises a resin having a urethane bond or a resin that undergoes urethane crosslinking. . 5. The resin according to claim 1, wherein the component (A) is an acrylic resin emulsion and comprises a carbonyl group-containing polymer emulsion and a compound containing a hydrazine and / or a hydrazyl group.
The resin composition for water-based paint as described above. 6. The component (A) contains a fluororesin made of another monomer copolymerizable with a fluoropolymerizable monomer such as tetrafluoroethylene, vinylidene fluoride or hexafluoropropylene. The resin composition for aqueous paints according to any one of claims 1 to 5. 7. The resin composition for water-based paints according to claim 1, wherein the component (A) contains a melamine resin. 8. The resin composition for an aqueous coating composition according to claim 1, wherein the component (A) contains a silicone resin. 9. The resin composition for an aqueous coating composition according to claim 1, wherein the component (A) contains an epoxy resin that is crosslinked with an acid or an amine. 10. The emulsion copolymer according to claim 1, wherein the component (A) is an emulsion copolymer obtained by copolymerizing 0.1 to 10 parts by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain. The resin composition for water-based paints according to any one of claims. 11. The component (A) comprises one or two or more of an alkyl methacrylate having an alkyl group having 4 or more carbon atoms and a cycloalkyl methacrylate having a cycloalkyl group having 4 or more carbon atoms, and a total amount of a polymerization component of 10.
The resin composition for aqueous paints according to any one of claims 1 to 10, which is obtained by copolymerizing 60 parts by weight or more with respect to 0 parts by weight. 12. The silicon compound and / or its partial hydrolyzed condensate in the component (B) is tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-. A butoxysilane, a tetra-i-butoxysilane, a tetra-t-butoxysilane and / or a partial hydrolyzed condensate thereof, which is characterized in that:
The resin composition for water-based paints according to any one of 1. 13. The silicon compound in the component (C) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-methyl-3-aminopropyltrimethoxysilane. , N-phenyl-3-aminopropyltrimethoxysilane, N, N-dimethyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-
(2-Aminoethyl) -3-aminopropyltriethoxysilane, N- (2- (N'-methyl) aminoethyl)
-3-Aminopropyltrimethoxysilane, N- (2-
(N ', N'-dimethyl) aminoethyl) -3-aminopropyltrimethoxysilane, The resin composition for water-based paints according to any one of claims 1 to 11, which is characterized in that. 14. The curing catalyst (D) is a product 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 according to any one of 1. 15. The aqueous coating composition according to claim 1, wherein the component (D) is an acidic phosphoric acid ester, a mixture or reaction product of organic carboxylic acids and organic amines. Resin composition. 16. The resin composition for water-based paints according to claim 1, wherein the silicone compound represented by the general formula (I) and / or 100 parts by weight of the synthetic resin emulsion (A). Alternatively, a partially hydrolyzed condensate thereof (B) and / or a silicon compound (C) 1 to 70 having at least one amino group and / or its derivative and at least one hydrolyzable silyl group in one molecule.
Parts by weight and 0 to 20 parts by weight of the curing catalyst (D) are blended,
A method for forming a coating film having excellent stain resistance, which is characterized in that it is applied to an object to be treated.