JPH1017817A - Resin composition for water-base paint having excellent stain resistant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. for a water-base paint which can yield a coating having excellent stain resistance, weather resistance, and water resistance comparable with solvent type paints. SOLUTION: This resin compsn. comprises: 100 pts.wt. (on a resin solid content) emulsion A of a polymer prepd. by copolymerizing an epoxy-contg. vinyl monomer with other vinyl monomer; and 1 to 30 pts.wt. silicone compd. B having in one molecule at least one amino group and at least one hydrolyzable silyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various kinds of coatings on, for example, interior and exterior of buildings, automobiles, household appliances, plastics, and the like, particularly in applications requiring weather resistance and durability.
The present invention relates to a resin composition for a water-based paint exhibiting good film performance.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, from the point of view of pollution control and resource saving, from those using organic solvents to those using no organic solvents, Attempts have been made to switch to those using dispersible resins and powder resins. In the field of paints, the transition to water-based paints rather than powder paints has been vigorous. However, conventional water-based paints are strongly affected by surfactants used for polymerization because the resin does not have a crosslinkable functional group in the molecule, and as a result, the weather resistance and water resistance of the formed coating film are increased. The properties and stain resistance were remarkably deteriorated, and the film properties were inferior to those of the solvent-based paint.

Various attempts have been made to improve this drawback. For example, a proposal has been made to apply a polymer emulsion having a hydrolyzable silyl group as a crosslinkable functional group to an aqueous paint (see JP-A-3-22712). ) And a proposal of an aqueous emulsion paint in which cross-linking between particles is introduced by a reaction between a carboxyl group and a hydrazyl group (Japanese Patent Application Laid-Open No. H5-205).
No. 59305). Further, there has been proposed a water-dispersed fluororesin paint in which a fluororesin having a high performance in a solvent system is converted to an aqueous solution (see JP-A-5-25421).

[0004] As a result, in terms of weather resistance and water resistance,
Although some improvements have been made, problems have arisen due to the water-based treatment, which is not sufficient. There is also a problem that the stain resistance is considerably inferior to that of the solvent type. In particular, in recent years, requirements for stain resistance have been increasing in various fields, and a level close to that of solvent-based low-stain paints has been demanded.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve these problems, and as a result, it has been found that a polymer containing an epoxy group has at least one amino group per molecule and at least one amino group per molecule. By mixing a silicon compound having one hydrolyzable silyl group at a specific ratio, it is possible to obtain a coating film having stain resistance that cannot be obtained with a conventional water-based paint, and having excellent weather resistance and water resistance. It has finally been found that it can be formed and has completed the present invention.

That is, in order to solve the above-mentioned problems, the resin composition for water-based paint according to claim 1 is obtained by copolymerizing a vinyl-based monomer containing an epoxy group with another vinyl-based monomer. The resulting polymer emulsion (A) and 1
A silicon compound having at least one amino group and at least one hydrolyzable silyl group in the molecule,
Component (B) is contained in an amount of 1 to 30 parts by weight with respect to 100 parts by weight of resin solid content of component (A).

In the resin composition for a water-based paint according to claim 2, the vinyl monomer having an epoxy group which is a component of the polymer in the component (A) is glycidyl (meth) acrylate or methyl glycidyl (meth). One or more selected from the group consisting of acrylates and 3,4-epoxycyclohexylmethyl (meth) acrylate, wherein the polymer in component (A) has at least one epoxy group in one molecule And

According to a third aspect of the present invention, the polymer in the component (A) contains a silyl group represented by the general formula (I).

[0009]

Embedded image (In the formula, R ₁ represents 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 X ₁ represents 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; In the composition according to the fourth aspect, the polymer having a silyl group represented by the general formula (I) in the component (A) of the resin composition for an aqueous coating composition according to the third aspect is used in an amount of 100 parts by weight as a total of the polymerization component. 1 ~
30 parts by weight of an alkoxysilyl group-containing vinyl monomer,
Emulsion copolymer obtained by copolymerizing a polymerization component containing 0.1 to 10 parts by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain using an anionic surfactant having a polyoxyethylene chain According to the fifth aspect, the polymer containing a silyl group represented by the general formula (I) in the resin composition for a water-based coating according to the third aspect is obtained by converting an alkyl methacrylate having an alkyl group having 4 or more carbon atoms into an alkyl methacrylate. A polymer obtained by copolymerizing at least 60 parts by weight of one or more members of the group consisting of cycloalkyl methacrylates having a cycloalkyl group having 4 or more carbon atoms with respect to 100 parts by weight of the total amount of the polymerization components. .

In a sixth aspect of the present invention, the silicone compound as the component (B) in each of the resin compositions for water-based paints according to the first to fifth aspects is replaced with 3-aminopropyltrimethoxysilane,
-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-
One or more selected from the group consisting of aminopropyltrimethoxysilane.

According to a seventh aspect of the present invention, in each of the resin compositions for an aqueous coating composition according to the first to sixth aspects, a curing catalyst (C) is used at the time of coating.
0.1 to 20 parts by weight is further blended.

According to an eighth aspect of the present invention, the component (C) in the resin composition for an aqueous paint according to the seventh aspect is obtained by emulsifying an organic aluminum compound or an organic tin compound with a surfactant mainly composed of an alkyl ether type surfactant. It shall be done.

In the ninth aspect, the component (C) is an acidic phosphoric acid ester, a mixture or a reaction product of an organic carboxylic acid and an organic amine.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The type of resin of an epoxy group-containing polymer (hereinafter referred to as polymer (A)) for obtaining emulsion (A) used in the present invention is not particularly limited. Epoxy resins, polyester resins containing epoxy groups, polyether resins, acrylic resins, fluororesins and the like, among these,
A coating film formed using the obtained curable resin composition is excellent in weather resistance and chemical resistance, and also has a wide range of resin designs, so that acrylic resins, urethane resins, fluororesins, and the like are preferable, and further, Acrylic resins are particularly preferred from the viewpoint of low cost.

The polymer (A) preferably contains a silyl group represented by the general formula (I) in order to enhance weather resistance. Examples of such a polymer include a vinyl-based monomer containing an epoxy group (hereinafter, referred to as a monomer (a-1)) and a vinyl-based polymer containing a silyl group represented by the general formula (I) (hereinafter, referred to as a monomer). , Monomer (a-2)) and another vinyl monomer copolymerizable therewith (hereinafter, referred to as monomer (a-3)).

Specific examples of the monomer (a-1) include, for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the following general formula: Compounds to be used.

[0017]

Embedded image

Embedded image (Wherein R ₂ represents a hydrogen atom or a methyl group;
₃ represents a divalent aliphatic hydrocarbon group of 1 to 6; These epoxy group-containing vinyl monomers may be used alone or in combination of two or more, and are preferably copolymerized at 1 to 30 parts by weight, more preferably at 2 to 20 parts by weight. Is more preferred. If the copolymerization amount is less than 1 part by weight, the reaction with the above-mentioned component (B) becomes insufficient, and the stain resistance becomes insufficient. If the amount exceeds 30 parts by weight, the stability of the emulsion decreases, and the storage stability increases. Also decrease.

Specific examples of the monomer (a-2) include the following compounds.

[0019]

Embedded image

Embedded image .

These silyl group-containing vinyl monomers include:
One type may be used alone, or two or more types may be used in combination.
It is preferably copolymerized by weight, more preferably 2 to 20 parts by weight. If the copolymerization amount is less than 1 part by weight, the water resistance and weather resistance are poor, and if it exceeds 30 parts by weight, the stability of the emulsion decreases, and the storage stability also decreases.

The type of the monomer (a-3) is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, Vinyl monomers such as cyclohexyl (meth) acrylate; trifluoroethyl (meth)
Acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, hexafluoropropylene ,
Fluorine-containing vinyl monomers such as chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, and pentafluoropropylene; aromatics such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene Aromatic hydrocarbon-based vinyl monomers; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride,
Acids having a polymerizable carbon-carbon double bond, such as α, β-ethylenically unsaturated carboxylic acids such as crotonic acid, fumaric acid, and citraconic acid; styrenesulfonic acid, vinylsulfonic acid; and salts thereof (alkali Metal salts, ammonium salts, amine salts, etc.); acid anhydrides such as maleic anhydride or half esters thereof with linear or branched alcohols having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (Meth) acrylates having an amino group such as (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide , N-methylacrylamide, acrylo Rumorpholine or hydrochloric acid and acetate thereof; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl monomers containing a nitrile group such as (meth) acrylonitrile; 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate,
2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Alonix 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), Placec
lFA-1, PlacelFA-4, Placel
FM-1, PlacelFM-4 (all manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-20, HP-10,
HP-20 (manufactured by Nippon Shokubai Chemical Co., Ltd.), Blemmer PP series, Blemmer PE series, Blemmer PEP series, Blemmer AP-400, Blemmer AE-350, Blemmer NKH-5050, Blemmer GLM (More than MA-30, M
A-50, MA-100, MA-150, RA-112
0, RA-2614, RMA-564, RMA-56
8, RMA-1114, MPG130-MA (Nippon Emulsifier Co., Ltd.), hydroxyl-containing vinyl monomers such as hydroxyl-modified vinyl-modified hydroxyalkylvinyl monomers, hydroxyalkyl esters of (meth) acrylic acid, etc. Α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters and phosphate ester group-containing vinyl compounds or vinyl compounds such as (meth) acrylates containing urethane bonds or siloxane bonds; Macros manufactured by Toa Gosei Chemical Co., Ltd. AS-6 and AN- which are monomers
6, AA-6, AB-6, and AK-5; other vinyl monomers such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, N-vinylimidazole, and vinyl sulfonic acid LA87, LA82, LA2 manufactured by Asahi Denka Kogyo KK
And a polymerization type light stabilizer, a polymerization type ultraviolet absorber and the like.

The type of the monomer (a-3) may be selected according to the desired physical properties of the curable resin composition to be obtained. 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, a vinyl monomer having a hydroxyl group, polyethylene glycol methacrylate, and polypropylene glycol methacrylate. Further, in order to improve the water resistance and durability of a coating film formed using the obtained resin composition, a functional group for crosslinking inside and between particles of the emulsion may be introduced, or a fluorine-containing vinyl may be introduced. It is preferable to use a monomer or a siloxane-containing vinyl monomer. When an acidic vinyl monomer is used, the mechanical stability of the emulsion (A) is improved.

In addition, monomers having two or more polymerizable unsaturated bonds, such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, and triallyl cyanurate, may be used to form a polymer. It is also possible to have a crosslinked structure.

Further, for example, a compound having 4 carbon atoms such as n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, etc.
The use of the above methacrylate having an alkyl group or a cycloalkyl group is preferable because the stability of the silyl group in the polymer (A) is improved.

The monomer (a-1) and the monomer (a-
The mixing ratio of 2) and the monomer (a-3) is 1 to 100 parts by weight of the total amount of the polymerization components for the monomer (a-1).
30 parts by weight, preferably 1.1 to 25 parts by weight, more preferably 2 to 20 parts by weight, and the monomer (a-2) is 1 part by weight.
To 30 parts by weight, preferably 1.1 to 25 parts by weight, more preferably 2 to 20 parts by weight, so that the monomer (a-
The compounding amount of 3) is 40 to 98 parts by weight, preferably 50 to 9 parts by weight.
It is adjusted to 7.8 parts by weight, more preferably 60 to 96 parts by weight. If the amount of the monomer (a-1) is less than the above lower limit, the coating film formed using the polymer (A) obtained has insufficient stain resistance and the monomer (a-
When the blending amount of 2) is less than the above lower limit, the water resistance and weather resistance of a coating film formed using the obtained polymer (A) tend to be poor, and the monomer (a-1) When the amount of the monomer (a-2) exceeds each of the above upper limits, the stability of the emulsion (A) tends to decrease.

When a hydrophilic vinyl monomer having a polyoxyethylene chain is used as the monomer (a-3) as described above, the stability of the silyl group in the monomer does not decrease. In addition, the stability of the emulsion in the step of converting the copolymer into a coating is ensured, and the mechanical stability and chemical stability of the emulsion (A) and the coating film formed by using the obtained curable resin composition. It is preferable because water resistance and gloss are improved. When such a hydrophilic monomer having a polyoxyethylene chain is used, the compounding amount is preferably adjusted to be 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the polymerization components, and is preferably 0.5 to 10 parts by weight. 10 parts by weight is more preferred. When the amount is less than 0.1 part by weight, the mechanical stability of the emulsion (A) and the water resistance and gloss of a coating film formed using the obtained curable resin composition tend to decrease. If the amount exceeds 10 parts by weight, the coating film tends to be softened and dirt tends to adhere.

Next, a method for producing the emulsion (A) will be described. As the polymerization method, means for emulsion polymerization such as batch polymerization, monomer drop polymerization, and emulsion monomer drop polymerization can be appropriately selected.In particular, monomer drop polymerization and emulsion monomer drop polymerization ensure stability during production. Suitable above.

The emulsifier used for the emulsion polymerization is not particularly limited, and a commonly used one such as an ionic or nonionic surfactant can be used. Examples of the ionic surfactant include sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; Newcol-72
3SF, Newcol-707SN, Newcol-7
07SF, Newcol-740SF, Newcol-
Anionic emulsifiers containing (poly) oxyethylene groups such as 560SN (all manufactured by Nippon Emulsifier Co., Ltd.); ammonium salts such as imidaline laurate and ammonium hydroxide; polyoxyethylene as a nonionic surfactant Polyoxyethylenes such as nonylphenyl ether and polyoxyethylene lauryl ether; L-77, L-720, L-5410, L-760
2. Nonionic emulsifiers containing silicon, such as L-7607 (all manufactured by Union Carbide), are typical. Further, as an emulsifier, Adecaria soap NE-10, NE-20, NE-30, which has polymerization reactivity,
NE-40, SE-10N (above, Asahi Denka Kogyo Co., Ltd.)
), Antox-MS-60, Antox-MS-2
N, RMA-653, (all manufactured by Nippon Emulsifier Co., Ltd.),
Aqualon RN20, RN30, RN50, HS05,
Use of HS10, HS20, and HS1025 (both manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can improve water resistance.

The above surfactants can be used alone or in admixture of two or more. The amount of the surfactants used is preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the polymerization components.
0.5 to 8 parts by weight is more preferred. If the amount of such a surfactant exceeds the above upper limit, the water resistance of a coating film formed using the obtained resin composition tends to decrease.

When an emulsion polymer is obtained using the above-mentioned vinyl polymer having an alkoxysilyl group and a hydrophilic vinyl monomer having a polyoxyethylene chain as a polymerization component, the above polyoxyethylene chain is used as an emulsifier. It is preferable to use 0.2 to 10 parts by weight of the anionic surfactant having the formula (1) based on 100 parts by weight of the total amount of the polymerization component from the viewpoint of the stability of the emulsion, and it is more preferable to use 0.5 to 8 parts by weight.

The monomer (a-1) and the monomer (a-
In the polymerization of 2) and the monomer (a-3), the temperature is preferably maintained at 70 ° C. or lower in order to maintain the stability of the mixed solution during the polymerization and to stably perform the polymerization.
65 ° C. is more preferred. To stabilize the silyl group,
The pH is preferably from 5 to 8, and more preferably from 5 to 7.

As the above-mentioned polymerization initiator, those usually used are used. From the viewpoint of the stability of polymerization and the like, redox catalysts are preferable. Specifically, for example, potassium persulfate, ammonium persulfate and acidic sulfite are used. Combination of sodium and Rongalite, combination of hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, organic peroxide such as p-menthane hydroperoxide and sodium acid sulfite, Rongalite, etc. And the like are used. In particular, a combination of an organic peroxide and a reducing agent is preferred.

The amount of the polymerization initiator used is preferably from 0.01 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the polymerization components. When the amount of the polymerization initiator is less than the lower limit, the polymerization may be difficult to proceed, and when the amount exceeds the upper limit, the molecular weight of the produced polymer is reduced, and the obtained resin composition is used. The durability of the formed coating film tends to decrease.

In order to stably impart the catalytic activity of the polymerization initiator, it is preferable to use a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate in combination. The amount of the chelating agent to be used is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.
5 parts by weight is more preferred.

The solid concentration of the emulsion (A) is 20
The range is preferably from 70 to 70% by weight, more preferably from 30 to 60% by weight.

If the solids concentration exceeds 70% by weight, the viscosity of the system will increase significantly, making it difficult to remove the heat generated by the polymerization reaction, and it will take a long time to take out from the polymerization machine. Occurs. In addition, when the solid concentration is 2
When the amount is less than 0% by weight, there is no problem in terms of the polymerization operation, but the amount of resin produced by one polymerization operation is small, so that it is extremely disadvantageous from the economical point of view, and also 20% in weight from the demands of applications. If it is less than%, the film thickness of the coating film becomes too thin, which is disadvantageous in that performance is deteriorated and coating workability is deteriorated.

The emulsion (A) thus obtained is composed of ultrafine particles having an average particle size of about 0.02 to 1.0 μm, and as a result, has an excellent film forming ability.

The component (B) used in the present invention is a silicon compound having at least one amino group and / or a derivative thereof and at least one hydrolyzable silyl group in one molecule. The following general formula (XV
Examples include the compounds represented by I) and the general formula (XVII), but are not limited thereto.

[0039]

Embedded image (Wherein R ₄ , R ₅ and R ₆ are an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,
0 represents an aralkyl group, and when there are two or more aralkyl groups, they may be the same or different; X ₂ represents a halogen atom,
A represents at least one group selected from the group consisting of an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group and an amino group;
Represents an alkylene group having 1 to 10 carbon atoms and a polyalkylene oxide group having 1 to 100 carbon atoms, and b and d represent 0 to 2
Is an integer of 0 to 1, and m is an integer of 0 to 5. )

Embedded image (In the formula, R ₄ , R ₅ , X ₂ , b and c are the same as above, and 1 is an integer of 1 to 6.) 1 represented by the general formula (XVI) and the general formula (XVII) Specific examples of a silicon compound having at least one amino group and / or a derivative thereof and at least one hydrolyzable silyl group in a molecule and salts thereof include, for example,

Embedded image

Embedded image

Embedded image Etc., X-12-5204, X-12-633AT, X
-12-734, X-12-575, X-12-57
7, X-12-563B, X-12-565, X-12
-730, X-12-562, CF-136, KBE-
9703, KBM-576 (Shin-Etsu Chemical Co., Ltd.)
A-1100, A-1110, A-1122, A
-1106, A-1126, A-1160, Y-913
8, Y-5823, Y-5987, AZ-6131, A
Z-6160 (all manufactured by Nippon Unicar Co., Ltd.), SH6
020, SH6026, SZ6023, SZ6032,
SZ6050, SZ6079, SZ6083, AY43
-021 (all made by Toray Silicone Co., Ltd.), TSL
8331, TSL8340, and TSL8345 (all manufactured by Toshiba Silicone Co., Ltd.).

The above component (B) may be used alone or in combination of two or more. It is preferable that the component (B) is used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin solid content of the component (A). ,
It is more preferable to mix 2 to 20 parts by weight. When the amount is less than 1 part by weight, there is almost no effect of imparting stain resistance, and when the amount exceeds 30 parts by weight, the stability of the emulsion decreases, and the storage stability also decreases.

The component (B) may be previously blended with the emulsion (A) and then made into a paint, or may be later blended into the previously made emulsion (A).

Specific examples of the curing catalyst of the component (C) suitably used in the present invention include organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, dioctyltin malate, tin octylate; Phosphoric acid or phosphates such as acid, monomethyl phosphate, 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- Licid propyl methyl dimethoxy silane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Yuka Shell Epoxy Co., Ltd. Kadeyura (E), Epikote 828, Epikote 1
Addition products of epoxy compounds such as 001 with phosphoric acid and / or acidic monophosphate; organic titanate compounds; organic aluminum compounds; organic zirconium compounds; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid Succinic acid, trimellitic acid, pyromellitic acid, acid anhydrides thereof, acidic compounds such as paratoluenesulfonic acid; hexylamine, di-2
Amines such as -ethylhexylamine, N, N-dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; and alkaline compounds such as sodium hydroxide and potassium hydroxide.

When an organometallic compound is used as a curing catalyst, a composition emulsified in advance using an alkyl ether-type surfactant is added to the resin composition at the time of application to an object to be coated. It is preferable because it has excellent curability and storage stability. The mixing ratio of such an organic metal compound emulsion is preferably 10 to 200 parts by weight, more preferably 20 to 100 parts by weight, and more preferably 20 to 100 parts by weight, based on 100 parts by weight of the organic metal compound. Is preferably 80 to 1500 parts by weight, and 200 to
1200 parts by weight is more preferable, and the antifreezing agent such as polyethylene glycol is preferably 10 to 200 parts by weight,
20 to 100 parts by weight are more preferred. The content of the organometallic compound in the emulsion is preferably 5 to 50%, and 7 to 30%.
Is more preferred.

The above component (C) may be used alone or in combination of two or more. The amount of the component (C) is not particularly limited, but is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the resin solid content of the component (A). Use parts by weight. If the amount is less than 0.1 part by weight, the curability of the composition tends to decrease,
If the amount exceeds the weight part, the appearance of the coating film tends to decrease.

The above components (A), (B) and (C)
The resin composition for water-based paint composed of the components has good coating film forming ability as it is, but the coating film forming ability can be further enhanced by using a cosolvent. Specific examples of the co-solvent include, for example, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, hexyl alcohol, and octyl alcohol; cellosolve, ethyl cellosolve, butyl cellosolve, and 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 Propylene glycol monob Ethers such as butyl ether and tripropylene glycol monoisobutyl ether; glycol ether esters such as butyl cellosolve acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monobutyl ether acetate, and tripropylene glycol monoisobutyl ether acetate. No.

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

Further, in order to further enhance the weather resistance of a coating film formed from the resin composition of the present invention, an ultraviolet absorber or a light stabilizer may be added. The ultraviolet absorber is not particularly limited, but is preferably a liquid in view of ease of handling. Specifically, for example, i-octyl-3-
(3- (2H-benzotriazol-2-yl) -5-
t-butyl-4-hydroxyphenyl) propionate (registered trademark TINUVIN 384), methyl-3- (3
-(2H-benzotriazol-2-yl) -5-t-
Reaction product of butyl-4-hydroxyphenyl) propionate with polyethylene glycol (TIN®
UVIN1130) (Nippon Ciba Geigy Co., Ltd.)
And benzotriazole-based ultraviolet absorbers such as benzotriazole-based UV absorbers at room temperature. These may be used alone or in combination of two or more. Also, the light stabilizer is not particularly limited, but is preferably a liquid in view of ease of handling. Specifically, for example, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) Hindered amine light stabilizers such as sebacate (registered trademark TINUVIN 123) and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (registered trademark TINUVIN 292) (all manufactured by Nippon Ciba Geigy Co., Ltd.) And the like, and these can be used alone or as a mixture of two or more.

These UV absorbers and light stabilizers can be used in combination.

In the present invention, from the viewpoint of the stability of the emulsion (A), those having no imino group in the structure are preferred.

The resin composition for water-based paints of the present invention may further contain, as additives, pigments (white pigments such as titanium dioxide, calcium carbonate, barium carbonate and kaolin, carbon, red iron, It is used as an ordinary paint composition such as a colored pigment such as cyanine blue), a plasticizer, a solvent, a dispersant, a thickener, an antifoaming agent, a preservative, an anti-settling agent, a leveling agent, and an ultraviolet absorber. Additives can be used as a mixture. When blending titanium dioxide with the resin composition for water-based paint, the isoelectric point is 7
By using the above titanium dioxide, gloss and weather resistance are improved. Specifically, JR901, JR603, J
R602 (all manufactured by Teica Co., Ltd.) and the like.

Further, a commercially available water-based paint can be blended with the resin composition for a 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. The weather resistance, acid resistance, solvent resistance, and the like of the coating film formed using the composition can be further improved.

The effect of imparting stain resistance in the present invention is based on 100 parts by weight of the emulsion (A), a silicone compound having at least one amino group and at least one hydrolyzable silyl group in one molecule. B) Appearing by applying 1 to 30 parts by weight of the composition to the object to be treated, more preferably by mixing and applying 0.1 to 20 parts by weight of the curing catalyst (C). The mechanism of the manifestation of the effect is
It is considered as follows. That is, when the component (B) is localized on the coating film surface during the crosslinking reaction, the coating film surface hardness and hydrophilicity are imparted. In addition, since the surface hardness of the coating film is increased, the coating is less likely to be scratched, thereby preventing contamination. Further, at the same time, since the coating film is hydrophilic, a cleaning effect against rain and the like is exhibited, and a coating film having more excellent stain resistance is formed.

According to the resin composition of the present invention, the above (A)
After the composition comprising the component (B) and the component (B) is applied to an object to be coated by a conventional method, it is usually cured at 10 ° C. or higher, so that the surface of the object to be coated is stain-resistant, weather-resistant, adherent, and durable. A cured product (coating film) having excellent physical properties can be formed. Therefore, for example, for building interior, automotive such as metallic base or clear on metallic base, aluminum, stainless steel, for direct coating of metal such as silver, slate,
Concrete, roof tile, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium silicate board, tile, brick, etc., ceramic coating, glass, natural marble, granite, etc. Alternatively, it is suitably used as an upper surface treatment agent. It is used not only for direct coating but also for coating on water-based or solvent-based permeable water-absorbing agents for inorganic equipment such as water-based or solvent-based primers, acrylic rubber, double-coated top coats, concrete, etc. Can be

[0054]

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

Production Examples 1 to 8 A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel was charged with 40 parts by weight of deionized water (hereinafter simply referred to as "parts") and polyoxyethylene nonylphenyl ether sulfonate. Charge 1 part of fate, 1 part of polyoxyethylene nonyl phenyl ether, 0.5 part of ammonium acetate, 0.3 part of Rongalite, 0.1 part of t-butyl hydroperoxide, and raise the temperature to 50 ° C. while introducing nitrogen gas. did. 20 parts of 158 parts of the mixture having the compositions shown in Tables 1 and 2 were dropped using a dropping funnel over 30 minutes to perform initial polymerization. One hour after the end of the dropping, the mixture 1
The remaining 138 parts out of 58 parts and 0.1 part of t-butyl hydroperoxide were dropped at a constant rate over 3 hours by a dropping funnel. Thereafter, polymerization was carried out for 1 hour, and deionized water was added to obtain emulsions (A-1) to (A-8) having a resin solid content of 50% by weight.

[0056]

[Table 1]

[Table 2] .

Example 1 For 100 parts of titanium oxide CR97 (manufactured by Ishihara Sangyo Co., Ltd.), 3 parts of SMA 1440 (manufactured by ATOCHEM), 1 part of Emulgen A-60 (manufactured by Kao Corporation), and 1 part of Tyrose H-
4000P (manufactured by Hoechst Gosei Co., Ltd.) 2% aqueous solution 10
, SN Deformer 247 (manufactured by San Nopco Co., Ltd.)
0.5 part, 0.5% 15% ammonia water, deionized water 2
Five parts were blended, a required amount of glass beads having a particle size of 2 mm was added, and the mixture was stirred for 1 hour at 1000 rpm using a sand mill to prepare a pigment paste.

For 60 parts of emulsion (A-1),
After adding 3 parts of CS-12 (manufactured by Chisso Corporation) and sufficiently stirring, 3-aminopropyltriethoxysilane 1.5 was added.
And 30 minutes of the pigment paste and 2% of Tyrose H-4000P (manufactured by Hoechst Gosei Co., Ltd.).
2 parts aqueous solution, Adekanol UH-420 (Asahi Denka Co., Ltd.)
2% aqueous solution of propylene glycol 2.9
, SN Deformer 247 (manufactured by San Nopco Co., Ltd.)
0.1 part was blended and stirred at 500 rpm for 10 minutes.
A white enamel (A-I) was obtained.

This white enamel was diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Example 2 In the same manner as in Example 1, a white enamel (A-II) was obtained using the emulsion (A-2).

The white enamel was diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Examples 3 to 5 In the same manner as in Example 1, using the emulsion (A-3), 0.6 parts (Example 3) and 1.5 parts (Example 3) of 3-aminopropyltriethoxysilane were used. 4) 3 parts (Example 5) are blended, and white enamels (A-III) to (AV)
I got

These white enamels were diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Example 6 White enamel 10 was added to white enamel (AV) immediately before coating.
To 0 part, 3 parts of an emulsion of dibutyltin dimaleate (10% of tin compound content) was blended, diluted to an appropriate coating viscosity with deionized water, and applied to a slate plate by air spray. Thereafter, the coated plate was cured at 20 ° C. for 10 days.

Example 7 In the same manner as in Example 1, a white enamel (A-VI) was obtained using the emulsion (A-4).

The white enamel was diluted with deionized water to an appropriate coating viscosity, and then applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Examples 8 to 10 In the same manner as in Example 1, using emulsion (A-5), 0.6 parts of 3-aminopropyltriethoxysilane (Example 8), 1.5 parts (Example 8) 9) 3 parts (Example 1)
0) and white enamels (A-VII) to (AI)
X) was obtained.

These white enamels were diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Example 11 White enamel 1 (A-IX) was added to white enamel immediately before coating.
To 100 parts, 3 parts of an emulsion of dibutyltin dimaleate (10% of tin compound content) was mixed, diluted to an appropriate coating viscosity with deionized water, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Example 12 In the same manner as in Example 1, a white enamel (AX) was obtained using the emulsion (A-6).

The white enamel was diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Examples 13 and 14 In the same manner as in Example 1, using emulsion (A-3), 1.5 parts of N- (2-aminoethyl) -3-aminopropyltriethoxysilane (Example 13) ), 3 parts (Example 14), white enamel (A-XI), (AX)
II) was obtained.

These white enamels were diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Example 15 White enamel (A-XII) was mixed with 3 parts of an emulsified product of dibutyltin dimaleate (10% tin compound content) per 100 parts of white enamel immediately before coating, and deionized water was added. The resulting mixture was diluted to an appropriate coating viscosity using a slate plate, and then applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Examples 16 and 17 In the same manner as in Example 1, 1.5 parts of N, N-dimethyl-3-aminopropyltriethoxysilane (Example 16) and 3 parts of emulsion (A-3) were used. Part (Example 17)
, White enamel (A-XIII), (A-XI
V) was obtained.

These white enamels were diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Example 18 Immediately before coating, 3 parts of a dibutyltin dimaleate emulsion (10% tin compound content) was added to 100 parts of white enamel immediately before coating, and deionized water was added to white enamel (A-XIV). After diluting to an appropriate coating viscosity by using the slate plate, the slate plate was applied by air spray. The coated plate was cured at 20 ° C. for 10 days.

Examples 19 and 20 In the same manner as in Example 1, using emulsion (A-5), 1.5 parts of N- (2-aminoethyl) -3-aminopropyltriethoxysilane (Example 19) ), N, N-dimethyl-3-aminopropyltriethoxysilane 1.5
Parts (Example 20), white enamel (A-XV),
(A-XVI) was obtained.

These white enamels were diluted with deionized water to an appropriate coating viscosity, and coated on a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Comparative Example 1, 100 parts of titanium dioxide CR97 (manufactured by Ishihara Sangyo Co., Ltd.), 3 parts of SMA 1440 (manufactured by ATOCHEM), 1 part of Emulgen A-60 (manufactured by Kao Corporation), 1 part of Tyrose H −
4000P (manufactured by Hoechst Gosei Co., Ltd.) 2% aqueous solution 10
, SN Deformer 247 (manufactured by San Nopco Co., Ltd.)
0.5 part, 0.5% 15% ammonia water, deionized water 2
Five parts were blended, a required amount of glass beads having a particle size of 2 mm was added, and the mixture was stirred for 1 hour at 1000 rpm using a sand mill to prepare a pigment paste.

Emulsion (A-3) (Comparative Example 1) or (A-6) (Comparative Example 2) 60 parts of CS-12
After adding 3 parts (manufactured by Chisso Corporation) and sufficiently stirring, 30 parts of pigment paste and 2 parts of a 2% aqueous solution of Tyrose H-4000P (manufactured by Hoechst Gosei Co., Ltd.) were added.
420 (manufactured by Asahi Denka Co., Ltd.) 20% aqueous solution 2 parts, propylene glycol 2.9 parts, SN deformer 247
(Made by San Nopco Co., Ltd.) 0.1 part, 500 rpm
and stirred for 10 minutes at room temperature, white enamel (A-XVII),
(A-XVIII) was obtained.

This white enamel was diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Comparative Examples 3 and 4 , 1.5 parts of 3-aminopropyltriethoxysilane (Comparative Example 3) and 3 parts (Comparative Example 4) of emulsion (A-7) in the same manner as Comparative Example 1. Was blended to obtain white enamels (A-XIX) and (A-XX).

This white enamel was diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Comparative Example 5 White enamel 1 was added to white enamel (A-XX) immediately before coating.
To 100 parts, 3 parts of an emulsion of dibutyltin dimaleate (10% tin compound content) was mixed, diluted to an appropriate coating viscosity with deionized water, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

Comparative Example 6 In the same manner as in Comparative Example 1, 1.5 parts of 3-aminopropyltriethoxysilane (Comparative Example 6) were blended with the emulsion (A-8) to obtain a white enamel (A-XXI). ) Got.

The white enamel was diluted with deionized water to an appropriate coating viscosity, and applied to a slate plate by air spray. The coated plate was cured at 20 ° C. for 10 days.

The above Examples 1 to 20 and Comparative Examples 1 to
5 was examined for stain resistance, hydrophilicity, and hardness. The methods for measuring and evaluating the properties are as follows. [Table 3] to [Table 6] Emulsions, silicon compounds having an amino group and a hydrolyzable group, and a curing catalyst used in Examples and Comparative Examples, and evaluation results.
Shown in

The lightness represented by the L ^* a ^* b ^* color system at the initial stage of the exposure to contamination was measured with a colorimeter (CR300, manufactured by Minolta Co., Ltd.), and outdoors on Seto City, Osaka Prefecture on the south side of 30 km. Exposure was performed for 3 months. The absolute value (ΔL value) of the difference between the lightness after exposure and the lightness before exposure was used as a measure of contamination. The smaller the value, the better the stain resistance.

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

[0091] hardness pendulum hardness tester (Erichsen Co., Ltd.: PERSOZ hardness tester) was used to measure the hardness of three months after the south 30 ° outdoor exposure in Osaka Prefecture Settsu (Perozosu hardness). The higher the value, the higher the hardness.

[0092]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[0093]

As described above, according to the resin composition for a water-based coating of the present invention according to the first to ninth aspects, excellent weather resistance and durability which are not inferior to solvent-based coatings despite being water-based. A coating film having properties and stain resistance is obtained. In addition, the emulsion has excellent stability and storage stability. Therefore, the resin composition for a water-based paint of the present invention can be suitably used in various fields including architectural interiors, automobiles and the like.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08G 59/40 NLC C08G 59/40 NLC 59/68 NKM 59/68 NKM C08L 63/00 NJY C08L 63/00 NJY NKM NKM C09D 133/14 PGH C09D 133/14 PGH 157/00 PDE 157/00 PDE

Claims (9)

[Claims] An emulsion (A) of a polymer obtained by copolymerizing a vinyl monomer containing an epoxy group with another vinyl monomer, and at least one amino group in one molecule. And a silicon compound (B) having at least one hydrolyzable silyl group in an amount of 1 to 30 parts by weight of the component (B) based on 100 parts by weight of the resin solid content of the component (A). A resin composition for water-based paint comprising: 2. An epoxy group-containing vinyl monomer which is a polymer component in the component (A) is glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, or 3,4-epoxycyclohexylmethyl. The polymer according to claim 1, wherein the polymer (A) has at least one epoxy group in one molecule, which is one or more selected from the group consisting of (meth) acrylates. A resin composition for an aqueous paint. 3. The resin composition for water-based paint according to claim 1, wherein the polymer in the component (A) contains a silyl group represented by the general formula (I). Embedded image (In the formula, R ₁ represents 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 represents 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; Is an integer.) 4. A polymer containing a silyl group represented by the general formula (I) in the component (A), wherein the total amount of the polymer component is 10%.
A polymerization component containing 1 to 30 parts by weight of an alkoxysilyl group-containing vinyl monomer and 0.1 to 10 parts by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain in 0 part by weight is polyoxy The aqueous paint resin composition according to claim 3, wherein the resin composition is an emulsion copolymer obtained by copolymerization using an anionic surfactant having an ethylene chain. 5. A polymer containing a silyl group represented by the general formula (I), wherein the polymer comprises 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. One or more selected from the group consisting of a total of 10
The resin composition according to claim 3, which is a polymer obtained by using 60 parts by weight or more of 0 parts by weight. 6. The silicon compound as the component (B),
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-
1 selected from the group consisting of (N ′, N′-dimethyl) aminoethyl) -3-aminopropyltrimethoxysilane
6. One or two or more species.
The resin composition for a water-based paint according to any one of the above. 7. The method according to claim 1, wherein 0.1 to 20 parts by weight of the curing catalyst (C) is further added at the time of coating.
7. The resin composition for a water-based paint according to any one of items 1 to 6. 8. The method according to claim 7, wherein the component (C) is a product obtained by emulsifying an organic aluminum compound or an organic tin compound with a surfactant mainly composed of an alkyl ether type surfactant. A resin composition for aqueous paints. 9. The composition according to claim 1, wherein the component (C) is an acidic phosphate ester,
The resin composition for a water-based paint according to claim 7, which is a mixture or a reaction product of an organic carboxylic acid and an organic amine.