JPH0718149A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition excellent in preservability, capable of giving coating films of excellent adhesion, high water resistance and high hardness, comprising a specific silanol group-contg. compound and an emulsion containing a specific silyl group-bearing polymer. CONSTITUTION:This resin composition comprises (A) an emulsion containing a polymer having silyl group of formula I (R<1> is a 1-10C alkyl, aryl, etc.; X<1> is halogen, amino, etc.; (a) is 0-2) and (B) a silanol compound of formula II (R<5> is the same as R<1>; Y is a functional group-contg. monovalent hydrocarbon; (b) is 0-2). The silyl group-contg. polymer in the component A is pref. a polymer prepared by emulsion polymerization of an alkoxysilyl group-contg. vinyl monomer and a hydrophilic vinyl monomer having polyoxyethylene chain through monomer dripping polymerization technique. The component B can be prepared, for example, by hydrolyzing in water a hydrolyzable silyl group-contg. silane coupling agent such as gamma-aminopropyltriethoxysilane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more specifically, it has excellent coating performance for interior / exterior buildings, automobiles, home appliances, etc., which are required to have weather resistance and durability. It relates to a curable resin composition that can be applied.

[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, it has been attempted to switch from using an organic solvent to using an aqueous solvent. .

However, as a conventional aqueous resin, a water-dispersible resin is generally used, but this water-dispersible resin does not have a crosslinkable functional group, and as a result,
Strongly affected by the surfactant used during emulsion polymerization,
There is a drawback that physical properties such as weather resistance, water resistance, and stain resistance of a cured product (coating film) formed by comparison with those using an organic solvent are remarkably deteriorated.

Various attempts have been proposed to improve this drawback, and one of them has been proposed to apply an emulsion of a polymer having an alkoxysilyl group as a crosslinkable functional group to a coating material. (See JP-A-3-227312).

However, the above-mentioned emulsion has a problem that it is inferior in adhesiveness to the base, particularly to organic substances.

Therefore, the present inventor has conducted extensive studies in view of the above-mentioned prior art, and as a result, a resin composition containing an emulsion of a polymer containing a specific silyl group and a silanol group-containing compound has a storage stability. It was finally found that a coating film excellent in durability, water resistance, hardness and adhesion to an object to be coated can be formed from the resin composition, and the present invention has been completed.

[0007]

That is, the curable resin composition of the present invention has the general formula

[Chemical 3] (In the formula, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group,
X ¹ is a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group or an amino group, and a is an integer of 0 to 2 (provided that R ¹ and X ¹ are each 2 or more. In some cases, they are the same or different)) and an emulsion (A) containing a polymer having a silyl group represented by the following (hereinafter referred to as "silyl group-containing polymer" or "polymer (a)"), and General formula

[Chemical 4] (In the formula, R ⁵ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group;
Y contains a monovalent hydrocarbon group containing a functional group, and b contains a silanol group-containing compound (B) represented by 0).

The silyl group-containing polymer for obtaining the emulsion (A) used in the present invention is not particularly limited, and contains, for example, a silyl group represented by the general formula (I).
Epoxy resins, polyester resins, polyether resins, acrylic resins, fluororesins, etc. can be mentioned,
Among these, the acrylic resin is preferable because the coating film formed by using the obtained curable resin composition has excellent weather resistance and chemical resistance, has a wide range of resin designs, and is inexpensive. preferable.

The method for preparing the polymer (a) is not particularly limited, and for example, a vinyl monomer containing a silyl group represented by the general formula (I) (hereinafter referred to as "monomer (a-
1) ”) and another vinyl-based monomer copolymerizable therewith (hereinafter referred to as“ monomer (a-2) ”) can be easily obtained to obtain the polymer (a). It is preferable from the point.

In the general formula (I), the aryl group represented by R ¹ preferably has 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 15 carbon atoms. preferable.

Specific examples of the monomer (a-1) include the following compounds.

[Chemical 5] Such as the general formula (III)

[Chemical 6] (In the formula, R ¹ and a are the same as the above, R ² is a hydrogen atom or a methyl group, and X ² is a halogen atom).

[0012]

[Chemical 7] Such as the general formula (IV)

[Chemical 8] (In the formula, R ¹ , R ² , X ² and a are the same as described above, and n is an integer of 1 to 12).

[0013]

[Chemical 9] Such as general formula (V)

[Chemical 10] (In the formula, R ¹ , R ² and a are the same as above, and R ³ is 1 to 1.
6 represents an alkyl group of 6).

[0014]

[Chemical 11] , General formula (VI)

[Chemical 12] (In the formula, R ¹ , R ² , R ³ , a and n are the same as above)
A compound represented by.

[0015]

[Chemical 13] Such as the general formula (VII)

[Chemical 14] (In the formula, R ¹ , R ² , R ³ , a and n are the same as above)
A compound represented by.

[0016]

[Chemical 15] Such as the general formula (VIII)

[Chemical 16] (In the formula, R ¹ , R ² , R ³ , a and n are the same as above)
A compound represented by.

[0017]

[Chemical 17] , General formula (IX)

[Chemical 18] (Wherein R ¹ , R ² , R ³ and a are the same as defined above).

[0018]

[Chemical 19] Such as general formula (X)

[Chemical 20] (In the formula, R ¹ , R ² , R ³ , a and n are the same as above)
A compound represented by.

[0019]

[Chemical 21] , General formula (XI)

[Chemical formula 22] (In the formula, R ¹ , R ² , R ³ , a and n are the same as above,
Compounds represented by R ⁴ is a _-CH 2 O-or _-CH 2 OCO-).

[0020]

[Chemical formula 23] Such as the general formula (XII)

[Chemical formula 24] (Wherein R ¹ , R ² , R ³ , a and n are the same as above, and p is an integer of 1 to 12).

[0021]

[Chemical 25] Such as the general formula (XIII)

[Chemical formula 26] (In the formula, R ¹ , R ³ , a and n are the same as the above) and the like.

These may be used alone or in admixture of two or more. Among these, the alkoxysilyl group-containing vinyl monomer is preferable because it is easy to handle, is inexpensive, and produces no reaction by-products.

The monomer (a-2) is not particularly limited and includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and t-butyl. (Meth) acrylate-based monomers such as (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate , 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth)
Fluorine-containing vinyl monomers such as acrylate, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoropropylene; styrene, α
-Aromatic hydrocarbon vinyl monomers such as methylstyrene, chlorostyrene, 4-hydroxystyrene and vinyltoluene; (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid Acids, α, β-ethylenically unsaturated carboxylic acids such as citraconic acid; acids having a polymerizable carbon-carbon double bond such as styrene sulfonic acid and vinyl sulfonic acid, or their alkali metal salts, ammonium salts, amines Salts such as salts; acid anhydrides such as maleic anhydride or half esters of these with alcohols having a straight or branched chain having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate , Having an amino group such as diethylaminoethyl (meth) acrylate ( (Meth) acrylate: (meth) acrylamide, α-ethyl (meth) acrylamide, N-
Butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine, or their hydrochloric acid and acetate salts; vinyl acetate, vinyl propionate, diallyl phthalate and other vinyl esters and allyl compounds; (meth) Nitrile group-containing vinyl monomers such as acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Aronix M-5700 (manufactured by Toagosei Chemical Industry Co., Ltd.), Pl
accelFA-1, PlaccelFA-3, Pla
ccelFA-4, PlaccelFM-1, Plac
celFM-4 (all manufactured by Daicel Chemical Industries, Ltd.),
HE-10, HE-20, HP-10, HP-20 (above, Nippon Shokubai Co., Ltd.), Bremmer PP series, Bremmer PEP series, Bremmer AP-400, Bremmer NKH-5050, Bremmer GLM (above,
Nippon Oil & Fats Co., Ltd.), hydroxyl group-containing vinyl monomers such as hydroxyl group-containing vinyl-modified hydroxyalkyl vinyl monomer; Bremmer PE-90, PE-200, PE-
Bremmer PE series such as 350, Bremmer PM
Bremmer PME series such as E-100, PME-200, and PME-400, Bremmer AE series such as Bremmer AE-350 (above, NOF Corporation)
Manufactured), MA-30, MA-50, MA-100, MA-
150, RA-1120, RA-2614, RMA-5
64, RMA-568, RMA-1114, MPG13
Hydrophilic vinyl-based monomer having polyoxyethylene chain such as 0-MA (manufactured by Nippon Emulsifier Co., Ltd.); (meth)
Α, such as hydroxyalkyl esters of acrylic acid,
Phosphate ester group-containing vinyl compounds such as condensation products of hydroxyalkyl esters of β-ethylenically unsaturated carboxylic acids with phosphoric acid or phosphoric acid esters or vinyls such as (meth) acrylates containing urethane bond or siloxane bond Compounds; vinyl group-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; amide group-containing vinyl compounds such as itaconic acid diamide, crotonamide, maleic acid diamide, fumaric acid diamide and N-vinylpyrrolidone; Toagosei Chemical Industry ( Co., Ltd. macromonomers AS-6, AN-6, AA-
6, compounds such as AB-6, AK-5, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinyl imidazole, vinyl sulfone Other vinylic monomers such as acids; LA87, LA82, LA2 manufactured by Asahi Denka Co., Ltd.
Polymerization type light stabilizers such as 2 and polymerization type ultraviolet absorbers can be used.

The type of the monomer (a-2) may be selected according to the desired physical properties of the curable resin composition obtained. For example, in order to impart water repellency to a coating film formed using the obtained resin composition and improve water resistance and durability, a fluorine-containing vinyl-based monomer or a siloxane-containing vinyl-based monomer is used. Preferably, in order to improve the stability of the obtained emulsion (A),
It is preferable to use a hydrophilic monomer such as (meth) acrylic acid, maleic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide, a hydroxyl group-containing vinyl monomer, or polypropylene glycol methacrylate. Moreover, when an acidic vinyl-based monomer is used, the mechanical stability of the emulsion (A) is improved. A total of 100 parts by weight of a polymerization component of a methacrylate having an alkyl group or a cycloalkyl group having 4 or more carbon atoms such as n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, and cyclohexyl methacrylate (hereinafter, simply referred to as “part”). The copolymerization of 60 parts or more with respect to (1) improves the stability of the silyl group.

When a hydrophilic monomer having a polyoxyethylene chain is used as the monomer (a-2), the stability of the silyl group in the monomer (a-1) decreases. However, the mechanical stability of the emulsion (A) and the water resistance and gloss of the coating film formed using the resulting curable resin composition are improved, which is preferable.

The repeating number of oxyethylene in the chain of the hydrophilic monomer is not particularly limited, but it is 3 to 30.
Is preferred.

When the hydrophilic monomer having a polyoxyethylene chain is used, the compounding amount is 100 in total of the polymerization components.
It is preferable to prepare 0.1 to 10 parts per part. When the blending amount is less than 0.1 part, the mechanical stability of the emulsion (A) and the water resistance and gloss of the coating film formed by using the curable resin composition obtained may deteriorate. If it exceeds 10 parts, the coating film tends to soften and stains tend to adhere.

In the present invention, the monomer (a-2) has two or more polymerizable unsaturated double bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate and triallyl cyanurate. By using a monomer, the resulting polymer can be made to have a crosslinked structure.

The monomer (a-1) and the monomer (a-
The blending amount of 2) is such that the blending amount of the monomer (a-1) is 1 to 30 parts, preferably 2 to 2 with respect to 100 parts of the total amount of the polymerization components.
0 part, that is, the amount of the monomer (a-2) compounded is 70 to 9
It is prepared to be 9 parts, preferably 80 to 98 parts.
When the compounding amount of the monomer (a-1) is less than 1 part, the water resistance and weather resistance of the coating film formed using the obtained resin composition tend to be poor, and when it exceeds 30 parts. , The stability of the emulsion (A) tends to decrease.

In the present invention, the alkoxysilyl group in water is stable and the price is low, and by-products when forming a coating film using the resulting resin composition adversely affect the coating film. From the viewpoint of not giving
A polymer (a) obtained by using an alkoxysilyl group-containing vinyl monomer as 1) and a hydrophilic vinyl monomer having a polyoxyethylene chain as the monomer (a-2) is preferable, and among them, alkoxysilyl Group-containing vinyl-based monomer 1 to 30% by weight, preferably 2 to 25% by weight, polyoxyethylene chain-containing hydrophilic vinyl-based monomer 0.1 to 10% by weight, preferably 0.5 to 10% by weight %
And an emulsion copolymer obtained by copolymerizing the rest with other vinyl-based monomer, using the obtained resin composition and the stability of the alkoxysilyl group, the mechanical stability of the emulsion (A). It is particularly preferable in that the formed coating film has excellent water resistance and gloss.

The monomer (a-1) and the monomer (a-
The polymer (a) can be obtained by polymerizing 2) and 2 by a conventional method.
The emulsion polymerization method is preferable in consideration of the particle size and stability of the emulsion (A).

The emulsion polymerization method is not particularly limited and may be appropriately selected from various emulsion polymerization methods such as batch polymerization method, monomer dropping polymerization method and emulsion monomer dropping polymerization method. In the invention, the monomer dropping polymerization method and the emulsion monomer dropping polymerization method are particularly preferable in order to ensure the stability of the emulsion during the production. It is also possible to obtain particles having a multi-layer structure by carrying out multi-stage polymerization of monomers or emulsion monomer liquids having different compositions. In addition, in order to further improve the stability of the obtained polymer, it is preferable to use a surfactant as an emulsifier.

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

Examples of the ionic surfactants include Newcol-560SN and Newcol-560S.
F (above, manufactured by Nippon Emulsifier Co., Ltd.), Emal NC-3
5, Polyoxyethylene nonylphenyl ether sulfate such as Revere WZ (all manufactured by Kao Corporation), N
ewcol-707SN, Newcol-707SF,
Newcol-723SE, Newcol-740SF
(Above, manufactured by Nippon Emulsifier Co., Ltd.), polyoxyethylene allyl ether sulfate, Newcol-861
Octylphenoxyethoxyethyl sulfonate such as SE (manufactured by Nippon Emulsifier Co., Ltd.), Newcol-1305
Anionic surfactants having a polyoxyethylene chain such as polyoxyethylene tridecyl ether sulfate such as SN (manufactured by Nippon Emulsifier Co., Ltd.); sodium laurylsulfonate, sodium dodecylbenzenesulfonate, sodium isooctylbenzenesulfonate, etc. Typical examples thereof include ammonium salts such as imidazole laurate and ammonium hydroxide, among which the monomer (a)
The anionic surfactant having a polyoxyethylene chain is preferable from the viewpoint that the polymerization reaction proceeds with the silyl group in -1) being stabilized.

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

In the present invention, 1 is used as an emulsifier.
A curable resin composition obtained by using a reactive surfactant having a polymerizable double bond in the molecule, particularly when a reactive surfactant having a polyoxyethylene group in the molecule is used The water resistance of the coating film formed by using is improved.

Specific examples of such a reactive surfactant include, for example, ADEKA REASOAP NE-10 and NE-2.
0, NE-30, NE-40, SE-10N (all manufactured by Asahi Denka Co., Ltd.), Antox-MS-60 (manufactured by Nippon Emulsifier Co., Ltd.), Aqualon RN-20, RN-30,
RN-50, HS-10, HS-20, HS-1025
(The above are manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

The above surfactants may be used alone or in admixture of two or more, and the amount thereof used is 10 parts or less, preferably 0.5 to 10 parts, based on 100 parts of the total amount of the polymerization components.
Eight copies. When the amount of such a surfactant used exceeds 10 parts, the water resistance of the coating film formed using the obtained resin composition tends to decrease.

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

In order to further improve the water resistance of the coating film, a water-soluble resin having a silyl group represented by the general formula (I) introduced therein may be used instead of using such a surfactant. Good.

The monomer (a-1) and the monomer (a-
In order to carry out the polymerization with 2) more stably, a redox catalyst can be used as a polymerization initiator. The temperature is 70 ° C. or lower, preferably 40 to 65 ° C. in order to maintain the stability of the mixed solution during the polymerization and to carry out the polymerization stably, and the pH is 5 to stabilize the silyl group. -8, preferably 5-7.

Examples of the redox catalysts include a combination of potassium or ammonium persulfate with sodium acid sulfite or rongalite, a combination of hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydro. Examples thereof include a combination of an organic peroxide such as peroxide and acidic sodium sulfite, Rongalit, or the like. In particular, a combination of an organic peroxide and a reducing agent is preferable because polymerization can be stably performed.

The amount of the polymerization initiator used is 0.01 to 10 parts, preferably 0.0 to 100 parts by weight of the total amount of the polymerization components.
5 to 5 parts. The amount of such a polymerization initiator used is 0.01
When it is less than 10 parts by weight, the polymerization may be difficult to proceed, and when it is more than 10 parts by weight, the molecular weight of the polymer to be produced is lowered, and the coating film formed by using the obtained resin composition is Durability tends to decrease.

Further, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used in order to stably impart the catalytic activity of the polymerization initiator. The amount of such chelating agent used is
It is 0.0001 to 1 part, preferably 0.001 to 0.5 part, relative to 100 parts of the total amount of the polymerization component.

The viscosity of the obtained silyl group-containing polymer is preferably 10 to 40 cp in terms of solid content of 40% by weight.

An emulsion (A) can be obtained by adding a desired amount of deionized water or the like to the polymer (a) and dispersing the polymer (a).

The resin solid content concentration in the emulsion (A) is 20 to 70% by weight, preferably 30 to 60% by weight.
To be prepared. When the resin solid content concentration exceeds 70% by weight, the concentration of the system increases remarkably, which makes it difficult to remove the heat generated by the polymerization reaction or takes a long time to remove from the polymerization vessel. Tends to cost. Further, when the resin solid content concentration is less than 20% by weight, there is no problem in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is economically disadvantageous. When the film is formed, the film thickness becomes thin, which may cause performance deterioration and disadvantage in terms of coating workability.

The emulsion (A) in the present invention
Since is composed of ultrafine particles having an average particle diameter of about 0.02 to 1.0 μm, it has excellent film forming ability.

The component (B) represented by the general formula (II) is not particularly limited, and commercially available X-12-843 (γ-
Hydrolyzate of aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), Hydrosil 2627, 26
28, 2776, 2774, 2775, 2759, 27
88, 2810, 2781 (above, manufactured by Huls) or the like may be used, and can be easily obtained by hydrolyzing a silane coupling agent having a hydrolyzable silyl group in water.

Examples of the silane coupling agent having a hydrolyzable silyl group as the raw material of the component (B) include γ-
Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N
-Β- (N-vinylbenzylamino) ethyl-γ-aminopropyltrimethoxysilane; γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane Methoxysilane; structural formula (II)
Vinyl group-containing compounds represented by I) to (XII); and their partial hydrolysis-condensation products; reaction products of aminosilane and epoxysilane; reaction products of aminosilane and epoxy compound.

The component (B) can be obtained by slowly dropping the above silane coupling agent into water at room temperature for hydrolysis.

When the silane coupling agent as a raw material is directly added to the emulsion (A), it may aggregate.
By using a compound having a silanol group, the hydrophilicity is increased and the compound becomes stable even when added to the emulsion (A) component.

By stirring and mixing the emulsion (A) and the silanol group-containing compound (B) with a homogenizer or the like so as to obtain a uniform composition,
The curable resin composition of the present invention can be obtained. (A)
The component and the component (B) may be mixed in advance, or may be mixed at the time of use.

The blending ratio of the emulsion (A) and the silanol group-containing compound (B) is such that the blending amount of the silanol group-containing compound (B) is 0.05 to 50 relative to 100 parts of the resin solid content of the emulsion (A). Part, preferably 0.1
Prepare to be ~ 20 parts. When the compounding amount of the silanol group-containing compound (B) is less than 0.05 part, the curability of the obtained resin composition and the coating film formed by using the resin composition on an article to be coated Adhesion tends to be insufficient, and if it exceeds 50 parts, the coating film tends to be brittle and the emulsion tends to aggregate.

When it is desired to accelerate the effect of crosslinking of the curable resin composition of the present invention, a curing agent can be added, if necessary, at the time of application to the article to be coated.

Examples of the curing agent include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, dibutyltin diacetate, dibutyltin dimethoxide, tributyltin sulfite, dibutyltin thioglycolate, tin octylate. Organotin compounds, aluminum isopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate Aluminum diisopropylate, other organoaluminum compounds such as organometallic compounds, paratoluene sulfonic acid, etc. Compounds, basic compounds such as sodium hydroxide and potassium hydroxide, and mixtures or reaction products of acidic phosphoric acid esters and amines. Is, it can be used alone or in admixture of two or more organotin compounds in terms of high curing activity among these and organic aluminum compounds are preferred.

When an organometallic compound is used as a curing agent, if it is added to the resin composition at the time of applying it to an object to be coated, it is emulsified with an alkyl ether type surfactant in advance. It is preferable because the product has excellent curability and storage stability.

The amount of the curing agent is 0.01 to 10 parts, preferably 0.1 to 5 parts, based on 100 parts of the total solid content of the emulsion (A) and the silanol group-containing compound (B). . When the amount is less than 0.01 part, the effect of exhibiting the curing activity due to the use of the curing agent tends to be insufficient, and when it exceeds 10 parts, the resin composition obtained. The water resistance of the coating film formed by using is likely to decrease.

In the present invention, white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, etc., pigments such as carbon black, red iron oxide, cyanine blue, etc., pigments and colloidal pigments, which are commonly used in paints, are also used. Additives such as silica, plasticizers, solvents, dispersants, thickeners, defoamers, preservatives, UV absorbers, film-forming auxiliaries, ethyl silicate, methyl silicate or their partial hydrolysis condensates are required. Can be added to the curable resin composition.

Further, a commercially available water-based paint can be added to the curable resin composition of the present invention. Examples of such water-based paints include thermosetting acrylic paints such as acrylic paints and acrylic melamine-based paints, alkyd paints, epoxy-based paints, and fluororesin paints. It is possible to improve the weather resistance, acid resistance, solvent resistance and the like of the coating film formed using. Further, by adding an additive such as a thickener, the curable resin composition of the present invention is an adhesive,
It can also be used for applications such as adhesives.

Further, in the present invention, as the crosslinking agent,
For example, a melamine resin, an isocyanate compound, or the like may be added to the curable resin composition to impart fast curability and the like.

The curable resin composition of the present invention is applied to an object to be coated by a conventional method such as dipping, spraying, coating using a brush, etc., and is applied at room temperature as it is, or at 60-
A coating film can be obtained by baking and curing at about 200 ° C.

The curable resin composition of the present invention is used, for example, for interior and exterior construction, for automobiles such as metallic bases or clears on metallic bases, for direct coating of metals such as aluminum and stainless steel, for direct coating of glass, natural marble and granite. It can be suitably used as a surface treatment agent including a coating material for direct coating of stone materials such as, and a coating material for ceramic base materials such as slate, concrete and roof tiles.

[0064]

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

Production Examples 1 to 3 (Production of Emulsion (A)) 40 parts of deionized water and sodium dodecylbenzenesulfonate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introducing pipe and a dropping funnel. .9 parts (Production Example 1) or 0.9 parts of polyoxyethylene nonylphenyl ether sulfate (Newcol-560SN) (Production Example 2,
3), polyoxyethylene nonyl phenyl ether 1
Parts, Rongalit 0.35 parts, ammonium acetate 0.5
Parts, 0.2 parts of t-butyl hydroperoxide and 20 parts of 158 parts of the mixture having the composition shown in [Table 1] were added to carry out initial charging.

Then, the temperature was raised to 50 ° C. while introducing nitrogen gas, and after heating for 1 hour, 0.5 part of t-butyl hydroperoxide and the remaining 13 parts in 158 parts of the mixture were added.
8 parts of the mixture was added dropwise at a constant rate by a dropping funnel over 3 hours.

Thereafter, polymerization was carried out for 1 hour, and deionized water was added to obtain emulsions (A-1), (A-2) and (A-3) having a resin solid content concentration of 40% by weight. It was

The emulsion (A-1) was prepared in Production Example 1
The emulsion (A-2) corresponds to Production Example 2 and the emulsion (A-3) corresponds to Production Example 3.

[0069]

[Table 1]

Examples 1 to 8 and Comparative Example 1 Emulsions (A-1) to (A) obtained in Production Examples 1 to 3
-3), any of the silanol group-containing compounds (B-1) to (B-3) shown in [Table 2] below is blended, and a film-forming auxiliary (CS12, Chisso Chemical Co., Ltd.). Made)
Then, dibutyltin dilaurate was added as a curing agent in a ratio shown in [Table 3], and stirred for 3 minutes using a mechanical stirrer to obtain a curable resin composition.

[0071]

[Table 2]

The storage stability of the obtained curable resin composition was examined according to the following method. The results are shown in [Table 3].

(Storage stability) The viscosity (cP) of the composition comprising the emulsion (A) and the silanol group-containing compound (B) after storage for 1 month in the atmosphere at 50 ° C.
It measured using the type | mold viscometer (25 degreeC). Further, the appearance of the above composition after storage for 1 month in the atmosphere at 50 ° C. was visually observed, and the presence or absence of the change was examined and evaluated based on the following evaluation criteria. [Storage Stability Evaluation Criteria] A: No change at all. B: A slight change is recognized. C: The change is remarkable.

Next, the water resistance, adhesion and hardness as the physical properties of the coating film formed by using the curable resin composition were examined according to the following methods. The results are shown in [Table 3].

(Water resistance) The dry film thickness was 30 on the slate plate.
The resin composition was applied so as to have a thickness of μm, dried at room temperature for 2 weeks and cured, and then a test piece (70 mm × 150 mm)
Was produced.

Immediately after the production of this test piece and after being immersed in water at 40 ° C. for 2 weeks, the state (appearance) was visually observed, and the presence or absence of the change was examined and evaluated based on the following evaluation criteria. [Water resistance evaluation criteria] A: No change at all. A ′: There is no change, or even if there is, it is negligible and can be ignored. B: The surface is slightly whitened. C: Significant whitening.

(Adhesion) The same test piece and slate plate as those used in the above-mentioned water resistance test were coated with an aqueous acrylic paint,
A water-based epoxy paint was applied to a slate plate, a resin composition was applied onto the slate plate so that the dry film thickness was 30 μm, and the test piece was cured by drying at room temperature for 2 weeks. After dipping the test piece surface in water for 2 weeks, a notch of 2 mm width was made with a knife, peeled with cellophane tape, and the condition of the test piece surface was visually observed. It was evaluated based on the adhesion evaluation standard of the inspection association. [Adhesion Evaluation Criteria] 10 points: No peeling is observed. 8 points: About 80% of the coating film adheres. 6 points: About 60% of the coating film adheres. 0 point: The front surface is peeled off.

(Hardness) The same test piece as used in the water resistance test was used, and the hardness of this test piece was measured using a pencil hardness meter.

[0079]

[Table 3]

From the results shown in [Table 3], Examples 1 to
The curable resin composition obtained in No. 8 has excellent storage stability, and the coating film formed using the resin composition has excellent water resistance and adhesion and high hardness. It can be seen that it is.

[0081]

EFFECT OF THE INVENTION The curable resin composition of the present invention is excellent in storage stability, and a coating film having excellent adhesion to organic substances, high water resistance and high hardness can be obtained from the resin composition. Can be formed.

Therefore, the curable resin composition of the present invention can be suitably used for coating interior and exterior of buildings, automobiles, household appliances and the like.

Claims (3)

[Claims] 1. A general formula: (In the formula, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group,
X ¹ is a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group or an amino group, and a is an integer of 0 to 2 (provided that each of R ¹ and X ¹ is 2 or more. In the case of, they are the same or different from each other)), and an emulsion (A) containing a polymer having a silyl group represented by the general formula: (In the formula, R ⁵ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group;
Y is a monovalent hydrocarbon group containing a functional group, b is a curable resin composition containing a silanol group-containing compound (B) represented by 0). 2. The polymer comprises 1 to 30% by weight of a vinyl monomer having an alkoxysilyl group, 0.1 to 10% by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain, and the balance other than The curable resin composition according to claim 1, which is a copolymer obtained by copolymerizing a polymerization component composed of a vinyl monomer with an anionic surfactant having a polyoxyethylene chain. 3. The polymer comprises at least one selected from an alkyl methacrylate having an alkyl group having a C number of 4 or more and a cycloalkyl methacrylate having a cycloalkyl group having a C number of 4 or more with respect to 100 parts by weight of the total amount of the polymerization components. The curable resin composition according to claim 1 or 2, which is a copolymer obtained by copolymerizing 60 parts by weight or more.