JP3333289B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition capable of imparting excellent coating performance to interior and exterior buildings, automobiles, home electric appliances, and the like that require excellent weather resistance.

[0002]

2. Description of the Related Art In recent years, from the viewpoints of pollution prevention and resource saving, attempts have been made to switch from an organic solvent-based paint or adhesive to an aqueous paint or adhesive.

However, a water-dispersible resin is generally used in the conventional water-based resin, and the water-dispersible resin does not have a crosslinkable functional group. When an activator is used, it is strongly affected by the effect, and the coating performance such as weather resistance, water resistance, and stain resistance of a coating film formed in comparison with the case where an organic solvent is used is improved. There was a drawback that it was very bad.

Various attempts have been made to remedy this drawback, and one of the proposals is to apply a polymer emulsion having a alkoxysilyl group, which is a crosslinkable functional group, to a paint. JP-A-3-227312).

However, even when the above emulsion is used, the weather resistance of the formed coating film is not practically satisfactory, so that ordinary solid ultraviolet absorbers and light stabilizers are not used. Attempts have been made to improve the weather resistance by blending them, but such solid UV absorbers and light stabilizers have the problem that they are inferior in dispersibility in emulsions and that uniform coatings cannot be obtained.

[0006]

Therefore, the present inventor has proposed:
As a result of intensive studies in view of the above prior art, as a result of using a resin emulsion containing a polymer emulsion containing a specific silyl group and a liquid ultraviolet absorber and / or a liquid light stabilizer, Has finally found that a coating film having particularly improved weather resistance can be formed, and completed the present invention.

[0007]

That is, the present invention provides a compound represented by the general formula (I):

[0008]

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[0009] (In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, a monovalent hydrocarbon group selected from aryl and aralkyl groups, X ¹ is an alkoxy group, a is an integer of 0 to 2 (However, when R ¹ and X ¹ are each 2 or more, they are the same or different.) 1 to 30% by weight of an alkoxysilyl group-containing vinyl monomer represented by the following formula:
%, Hydrophilic vinyl monomer having a polyoxyethylene chain
0.1 to 10% by weight and the balance of other vinyl monomers
Emulsion copolymers obtained by copolymerization of
And a curable resin composition comprising an emulsion (A) excluding a fluorinated copolymer ) and a liquid ultraviolet absorber (B) and / or a liquid light stabilizer (C).

[0010]

The curable resin composition of the present invention has the general formula (I) as described above:

[0011]

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[0012] (In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, a monovalent hydrocarbon group selected from aryl and aralkyl groups, X ¹ is an alkoxy group, a is an integer of 0 to 2 (However, when R ¹ and X ¹ are each 2 or more, they are the same or different.) 1 to 30% by weight of an alkoxysilyl group-containing vinyl monomer represented by the following formula:
%, Hydrophilic vinyl monomer having a polyoxyethylene chain
0.1 to 10% by weight and the balance of other vinyl monomers
Emulsion copolymers obtained by copolymerization of
Excluding a fluorocopolymer) (A) and a liquid ultraviolet absorber (B) and / or a liquid light stabilizer (C).

[0013] The present invention said emulsion copolymerization polymer to sell an emulsion (A) used in (hereinafter, the polymer (A) trough <br/> U) is formed by using the curable resin composition to be e Acrylic resins are preferred from the viewpoint that the resulting coating film has excellent weather resistance and chemical resistance, has a wide range of resin designs, and is inexpensive.

[0014] wherein the polymer (A) a method for preparing, in particular no limitation, for example, the general formula (I) alkoxy silyl group-containing vinyl-based monomer represented by (hereinafter, the monomer (A-1) ) and copolymerizable therewith poly that
The method of polymerizing another vinyl monomer including a hydrophilic vinyl monomer having an oxyethylene chain (hereinafter, referred to as monomer (A-2)) can easily produce the polymer (A). It is preferable in that it can be obtained.

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

Specific examples of the monomer (A-1) include, for example,

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

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General formula (IV) such as:

[0027]

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(Wherein R ¹ , R ² and a are the same as above, and R ³ is an alkyl group having 1 to 16 carbon atoms);

[0029]

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General formula (V) such as:

[0031]

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Wherein R ¹ , R ² , R ³ , a and n are the same as defined above;

[0033]

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General formula (VI) such as:

[0035]

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Wherein R ¹ , R ² , R ³ , a and n are the same as defined above;

[0037]

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Formula (VII) such as:

[0039]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as described above);

[0041]

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General formula (VIII) such as:

[0043]

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(Wherein R ¹ , R ² , R ³ and a are as defined above);

[0045]

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General formula (IX) such as:

[0047]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as described above);

[0049]

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General formula (X) such as:

[0051]

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(Wherein R ¹ , R ² , R ³ , a and n are the same as above, and R ⁴ is —CH ₂ O— or —CH ₂ OCO
A compound represented by-);

[0053]

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General formula (XI) such as:

[0055]

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Wherein R ¹ , R ² , R ³ , a and n are the same as described above, and p is an integer of 1 to 12, and the like. These can be used in combination. These alkoxysilicons
Le-containing vinyl monomers, ease of handling, RaYoshimi preferable either that point and reaction by-products of the price does not occur.

[0057] Examples of the monomer (A-2), if other example <br/> methyl (meth) acrylate, ethyl (meth) acrylate, n- butyl (meth) acrylate, i- butyl (meth) acrylate, t - butyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylate monomers such as cyclohexyl (meth) acrylate; scan styrene, alpha-methyl styrene, chlorostyrene, 4-hydroxystyrene, aromatic such as vinyl toluene Aromatic hydrocarbon vinyl monomer; α, β such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid, etc.
-Ethylenically unsaturated carboxylic acids; styrene sulfonic acid,
Acids having a polymerizable carbon-carbon double bond such as vinyl sulfonic acid or salts thereof such as alkali metal salts, ammonium salts and amine salts; acid anhydrides such as maleic anhydride or those having 1 to 20 carbon atoms (Meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; (meth) Acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine, or hydrochloric acid or acetate thereof; vinyl acetate, vinyl propionate, diallyl phthalate Any vinyl ester or allyl compound; vinyl monomer containing a nitrile group such as (meth) acrylonitrile; vinyl monomer containing an epoxy group such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Alonix M-5700 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), Placel FA-1, Pla
ccel FA-3, Placel FA-4, Pla
ccel FM-1, Placel FM-4 (or more,
Daicel Chemical Industries Ltd.), HE-10, HE-2
0, HP-10, HP-20 (all manufactured by Nippon Shokubai Co., Ltd.), Blemmer PP series, Blemmer PEP series, Blemmer AP-400, Blemmer NKH-5
050, Blemmer GLM (Nippon Oil & Fats Co., Ltd.)
), Hydroxyl-containing vinyl-based monomers such as hydroxyl-containing vinyl-modified hydroxyalkylvinyl-based monomers; Blemmer PE series such as Blemmer PE-90, PE-200, PE-350, Blemmer PME-100, P
Blemmer PME such as ME-200, PME-400
Series, Blemmer A such as Blemmer AE-350
E series (all manufactured by NOF Corporation), MA-30,
MA-50, MA-100, MA-150, RA-11
20, RA-2614, RMA-564, RMA-56
8, hydrophilic vinyl monomers having a polyoxyethylene chain such as RMA-1114 and MPG130-MA (all manufactured by Nippon Emulsifier Co., Ltd.); α, β such as hydroxyalkyl esters of (meth) acrylic acid A vinyl compound containing a phosphate ester group such as a condensation product of a hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid and phosphoric acid or a phosphoric acid ester, or a vinyl compound such as a (meth) acrylate containing a urethane bond or a siloxane bond; An amino group-containing vinyl compound such as vinylpyridine and aminoethyl vinyl ether; itaconic acid diamide;
Amide group-containing vinyl compounds such as crotonamide, maleic diamide, fumaric diamide, and N-vinylpyrrolidone; AS-6, AN-6, AA-6, and AB-6, macromonomers manufactured by Toagosei Chemical Industry Co., Ltd. -6, AK-
Compounds such as 5, 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinyl imidazole, and other vinyl monomers such as vinyl sulfonic acid And body.

The type of the monomer (A-2) may be selected according to the desired properties of the obtained curable resin composition. For example, in order to impart water repellency to a coating film formed using the obtained resin composition and to improve water resistance and durability, a fluorine-containing vinyl monomer or a siloxane-containing vinyl monomer is used. In order to improve the stability of the obtained 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, and polypropylene glycol methacrylate. In addition, when an acidic vinyl monomer is used, the mechanical stability of the emulsion (A) is improved. further,
For example, when a methacrylate having an alkyl group having 4 or more carbon atoms or a cycloalkyl group such as n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, and cyclohexyl methacrylate is used, silyl in the polymer (A) is used. It is preferable because the stability of the group is improved.

[0059] Among the monomers (A-2)ofPolio
Using a hydrophilic monomer having a ethylene chainBy doing
RLow stability of the silyl group in the monomer (A-1)
Without lowering the mechanical stability of the emulsion (A)
Resistance of the coating film formed using the obtained curable resin composition
It is preferable because the aqueous property and glossiness are improved. In addition,
When a hydrophilic monomer having a polyoxyethylene chain is used
The amount of the mixture was 0.1 parts with respect to 100 parts of the total amount of the polymerization components.
It is preferable to adjust so as to be 10 to 10 parts. Take
If the amount is less than 0.1 part, the emulsion
The mechanical stability of (A) and the resulting curable resin composition
The water resistance and gloss of the coating film formed by using
If you have more than 10 copies,
There is a tendency that the coating film softens and stains easily adhere.

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

The monomer (A-1) and the monomer (A-
The compounding amount of 2) is such that the compounding amount of the monomer (A-1) is 1 to 30 parts, preferably 1.1 to 100 parts of the total amount of the polymerization components.
To 30 parts, more preferably 2 to 25 parts, that is, the amount of the monomer (A-2) is 70 to 99 parts, preferably 7 to 99 parts.
It is desirable to adjust so as to be 0 to 98.9 parts, more preferably 75 to 98 parts. The amount of the monomer (A-1) is less than the lower limit, that is, the monomer (A-2)
When the amount exceeds the upper limit, the water resistance and weather resistance of a coating film formed using the obtained resin composition tend to be inferior, and the amount of the monomer (A-1) decreases. If the upper limit is exceeded, that is, if the amount of the monomer (A-2) is less than the lower limit, the stability of the emulsion (A) tends to decrease.

In the present invention, the alkoxysilyl groups in water are stable, inexpensive, and the by-products when forming a coating film using the obtained resin composition have an adverse effect on the coating film. From the viewpoint that the monomer (A-
A polymer (A) obtained 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. 1 to 30% by weight of a silyl group-containing vinyl monomer, preferably 2 to 25% by weight,
Hydrophilic vinyl monomer having a polyoxyethylene chain 0.
An emulsion copolymer obtained by copolymerizing 1 to 10% by weight, preferably 0.5 to 10% by weight, and the balance of a polymerization component comprising a vinyl monomer, has a stability of alkoxysilyl group and a mechanical property of the emulsion (A). This is particularly preferred in terms of excellent thermal stability and excellent water resistance and gloss of a coating film formed using the obtained resin composition.

The monomer (A-1) and the monomer (A-
The polymer (A) can be obtained by polymerizing 2) with an ordinary method.
The emulsion polymerization method is preferred in consideration of the particle size and stability of the emulsion (A).

The emulsion polymerization method is not particularly limited.
For example, a batch polymerization method, a monomer dropping polymerization method, an emulsion monomer dropping polymerization method and the like can be appropriately selected and employed from among various emulsion polymerization methods.In the present invention, particularly, the stability of the emulsion during production is improved. In order to ensure the above, a monomer drop polymerization method and an emulsion monomer drop polymerization method are preferable. Further, particles having a multilayer structure can be obtained by subjecting monomers having different compositions or emulsified monomer liquids to multistage polymerization.

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 for ordinary emulsion polymerization, and examples thereof include ionic and nonionic surfactants.

Examples of the ionic surfactant include Newcol-560SN, Newcol-560SF (all manufactured by Nippon Emulsifier Co., Ltd.), Emal NC-35, and Reveil WZ (all;
Polyoxyethylene nonyl phenyl ether sulfate (New Kao Corp.), Newcol-707SN, Newcol-707S
F, polyoxyethylene allyl ether sulfate such as Newcol-723SF and Newcol-740SF (all manufactured by Nippon Emulsifier Co., Ltd.), octylphenoxyethoxyethyl sulfonate such as Newcol-861SE (Nippon Emulsifier Co., Ltd.), Ne
Anionic surfactant having a polyoxyethylene chain such as polyoxyethylene tridecyl ether sulfate such as wcol-1305SN (manufactured by Nippon Emulsifier Co., Ltd.); sodium lauryl sulfonate, sodium dodecyl benzene sulfonate, isooctyl benzene sulfonic acid Representative examples include sulfonates such as sodium; and ammonium salts such as imidaline laurate and ammonium hydroxide. Among these, a state in which the silyl group in the monomer (A-1) is stabilized The anionic surfactant having a polyoxyethylene chain is preferable from the viewpoint that the polymerization reaction proceeds.

The nonionic surfactants include:
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
Non-ionic surfactants containing silicone such as 602 and L-7607 (all manufactured by Union Carbide Co., Ltd.) are typical examples.

In the present invention, one emulsifier is used.
A reactive surfactant having a polymerizable double bond in the molecule can be used, and especially when a reactive surfactant having a polyoxyethylene group in the molecule is used, the curable resin composition obtained can be used. The water resistance of the coating film formed using the product is improved.

Specific examples of such reactive surfactants include, for example, Adecaria Soap NE-10, NE-2
0, NE-30, NE-40, SE-10N (all manufactured by Asahi Denka Kogyo Co., Ltd.), Antox-MS-60 (Nippon Emulsifier Co., Ltd.), Aqualon RN-20, RN-30,
RN-50, HS-10, HS-20, HS-1025
(Above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

The above-mentioned surfactants can be used alone or as a mixture of two or more kinds. The amount used is 10 parts or less, preferably 0.5 to 8 parts, based on 100 parts of the total amount of the polymerization components. preferable. When the amount of the surfactant exceeds the upper limit, the water resistance of a coating film formed using the obtained resin composition tends to decrease.

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

In order to further improve the water resistance of the coating film, instead of using such a surfactant, a water-soluble resin obtained by introducing a silyl group represented by the above general formula (I) may be used. 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. Further, in order to maintain the stability of the mixed solution during the polymerization and stably perform the polymerization, the temperature is preferably 70 ° C. or less, particularly preferably 40 to 65 ° C., and for stabilizing the silyl group, pH 5
It is preferable to adjust so as to be ８8, especially 5７7.

Examples of the redox catalyst include a combination of potassium persulfate or ammonium persulfate and sodium acid sulfite or Rongalite, a combination of hydrogen peroxide and ascorbic acid, t-butyl hydroperoxide, benzoyl peroxide, cumene hydrochloride. Examples include a combination of an organic peroxide such as peroxide with sodium acid 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 based on the total amount of the polymerization components.
It is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts. If the amount of such a polymerization initiator is less than the lower limit, the polymerization may be difficult to proceed.If the amount exceeds the upper limit, the molecular weight of the produced polymer is reduced, The durability of a coating film formed using the obtained resin composition tends to decrease.

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

By adding, for example, a desired amount of deionized water or the like to the polymer emulsion (A) thus obtained, the resin solids concentration in the emulsion (A) is reduced to 20%.
It is preferably adjusted to be 70% by weight, especially 30-60% by weight. If the resin solids concentration exceeds the upper limit, the concentration of the system rises remarkably, making it difficult to remove the heat generated by the polymerization reaction, or taking a long time to remove from the polymerization vessel. Tends to be required. Further, when the resin solids concentration is less than the lower limit, although there is no problem in terms of polymerization operation, the amount of resin generated by one polymerization operation is small, and disadvantageous in terms of economy, When the coating film is formed, the film thickness becomes thin, which tends to cause performance deterioration or disadvantage in terms of coating workability.

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

Representative examples of the liquid ultraviolet absorber (B) (hereinafter referred to as ultraviolet absorber (B)) used in the present invention include, for example, i-octyl-3- [3- (2H-benzotriazole-2). -Yl) -5-t-butyl-4-
Hydroxyphenyl] propionate (registered trademark TINUVI
N384), a reaction product of methyl-3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate and polyethylene glycol (registered trademark TINUVIN1130) (Japanese) Benzotriazole-based ultraviolet absorbers such as Ciba-Geigy Co., Ltd.) may be used at room temperature and may be used alone or in combination of two or more.

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

Liquid light stabilizer (C) used in the present invention
Representative examples of the light stabilizer (C) are, for example, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (registered trademark TINU)
VIN123), bis (1,2,2,6,6-pentamethyl-
4-Piperidyl) sebacate (registered trademark TINUVIN292)
(Above, manufactured by Nippon Ciba Geigy Co., Ltd.) such as hindered amine light stabilizers and the like, which are liquid at room temperature, and these can be used alone or in combination of two or more.

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 curable resin of the present invention is obtained by stirring and mixing the emulsion (A) and the ultraviolet absorber (B) and / or the light stabilizer (C) with a homogenizer or the like so as to have a uniform composition. A composition can be obtained. In the present invention, the emulsion (A) and the ultraviolet absorber (B) and / or the light stabilizer (C) may be prepared in advance or may be prepared at the time of use.

The mixing ratio of the emulsion (A) and the ultraviolet absorber (B) and / or the light stabilizer (C) is such that the ultraviolet absorber (B) and / or the light stabilizer (C)
Is preferably adjusted so as to be 0.05 to 10 parts, more preferably 0.1 to 5 parts, per 100 parts of the resin solid content of the emulsion (A). When the amount of the ultraviolet absorber (B) and / or light stabilizer (C) is less than the lower limit, the weather resistance of the coating film formed using the obtained resin composition is improved. When the content exceeds the upper limit, the coating tends to be colored.

In order to accelerate the curing of the curable resin composition of the present invention by cross-linking, a curing agent may be blended, if necessary, at the time of application to an object to be coated.

Examples of the curing agent include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, dibutyltin diacetate, dibutyltin dimethoxide, tributyltin sulphite, dibutyltin thioglycolate, tin octylate and the like. Organic metal compounds such as organotin compounds, aluminum isopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate, etc., and acidity such as p-toluenesulfonic acid Compounds, basic compounds such as sodium hydroxide and potassium hydroxide, and mixtures or reactants of acidic phosphate 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 the curing agent, a resin emulsified in advance using, for example, an alkyl ether type surfactant is added to the resin composition at the time of application to the object to be coated. The composition is preferable because it has excellent curability and storage stability.

The amount of the curing agent is preferably 0.01 to 10 parts, more preferably 0.1 to 5 parts, per 100 parts of the resin solid content of the emulsion (A). If the amount is less than the lower limit, there is a tendency that the effect of expressing the curing activity by using a curing agent becomes insufficient,
When the upper limit is exceeded, the water resistance of a coating film formed using the obtained resin composition tends to decrease.

In the present invention, for example, titanium dioxide, calcium carbonate,
Pigments such as white pigments such as barium carbonate and kaolin, colored pigments such as carbon black, red iron and cyanine blue, colloidal silica, plasticizers, solvents, dispersants, thickeners, defoamers, preservatives, and film-forming aids An additive such as an agent, a silicate such as methyl silicate or ethyl silicate, or a partially hydrolyzed condensate thereof can be blended into the curable resin composition as needed.

Further, a commercially available water-based paint can be blended with 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 paints, alkyd paints, epoxy paints, fluororesin paints, and the like. It is possible to improve the weather resistance, acid resistance, solvent resistance, etc. of the coating film formed using the product. By adding an additive such as a thickener, the curable resin composition of the present invention can also be used for applications such as adhesives and pressure-sensitive adhesives.

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

The curable resin composition of the present invention is applied to an object to be coated by a usual method such as immersion, spraying, application using a brush, etc.
It can be baked and cured at about 0 ° C. to obtain a coating film.

The curable resin composition of the present invention can be used, for example, for interior and exterior of buildings, for automobiles such as metallic bases and 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 paints for direct application to stone materials such as stones, slate, concrete, and tiles.

Next, the curable resin composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Production Examples 1 to 3 (Production of Emulsion (A)) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 40 parts of deionized water, 0.9 parts of sodium dodecylbenzenesulfonate were placed. Part (Production Example 1) or polyoxyethylene nonyl phenyl ether sulfate
(Newcol-560SN) 0.9 part (Production Examples 2 and 3), polyoxyethylene nonyl phenyl ether 1 part, Rongalit
0.35 parts, 0.5 parts of ammonium acetate, 0.2 parts of t-butyl hydroperoxide and a mixture 15 having the composition shown in Table 1.
20 parts out of 8 parts were added for initial preparation. Thereafter, 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 138 parts of the mixture of 158 parts of the above mixture were dropped by a dropping funnel for 3 hours. The solution was dropped at a constant speed. Thereafter, post-polymerization was performed for 1 hour, and deionized water was added to reduce the resin solids concentration.
40% by weight of emulsion (A) -1 (Production Example 1)
(A) -2 (Production Example 2) and (A) -3 (Production Example 3)
I got

[0097]

[Table 1]

Examples 1 to 6, Reference Examples 1 and 2 and Comparative Examples 1 to 4 Emulsions (A) obtained in Production Examples 1 to 3 were added to ultraviolet absorbers (B), light stabilizers (C), and film formation. Auxiliaries (CS-12,
Dibutyltin dilaurate as a curing agent was blended in the proportions shown in Tables 2 to 4 and stirred with a mechanical stirrer for 3 minutes to obtain a curable resin composition.

The weatherability of the obtained curable resin composition was examined according to the following method. Table 2 shows the results.
Are shown in FIGS.

(Weather resistance) A dry film thickness of 30 μm on a slate plate
m, dried for 2 weeks at room temperature and cured, and then accelerated for 1800 hours using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.). A weather resistance test was performed and the 60 ° gloss value was measured. From the gloss value of the coating film after the test and the gloss value of the coating film before the test, the gloss retention (%) after the test was determined based on the following equation. Gloss retention (%) = (gloss value after test / gloss value before test) × 100 The ultraviolet absorber (B) and light stabilizer (C) in Tables 2 to 4 are as shown below. .

(B) -1: TINUVIN384 (B) -2: TINUVIN1130 (B '): TINUVIN900 (manufactured by Nippon Ciba Geigy Co., Ltd.)
(C) -1: TINUVIN123 (C) -2: TINUVIN292 In Comparative Example 2, the gloss retention was 45 to 69% and varied depending on the measurement location.

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

From the results shown in Tables 2 to 4, Examples 1 to
It can be seen that the coating film formed using the curable resin composition obtained in No. 6 has a large gloss retention after the accelerated weathering test for 1800 hours and has excellent weather resistance.

Also, from the results shown in Table 2, Comparative Example 2
In the above, since a solid ultraviolet absorber is used, it can be seen that the gloss retention of the coating film varies greatly depending on the measurement location, and the dispersibility of the solid ultraviolet absorber is poor.

[0107]

The curable resin composition of the present invention forms a coating film having excellent weather resistance.

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/00-57/12 C08K 3/00-13/08 C08F 10/00-299/08

Claims (2)

(57) [Claims] 1. A compound of the general formula (I): (Wherein, 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 an alkoxy group, a is an integer of 0 to 2 (provided that when R ¹ and X ¹ is two or more, respectively,
These alkoxy is represented by the same or different))
1 to 30% by weight of a silyl group-containing vinyl monomer,
Hydrophilic vinyl monomer having a xyethylene chain 0.1 to
Polymerization consisting of 10% by weight and the balance of other vinyl monomers
Emulsion copolymer obtained by copolymerizing components (however, fluorine-containing
Curable resin composition containing an emulsion (A) of the present invention ( excluding a copolymer ) and a liquid ultraviolet absorber (B) and / or a liquid light stabilizer (C). Wherein the emulsion copolymer is a curable resin composition according to claim 1, wherein in which the polymerization components are E by copolymerizing in the presence of an anionic surfactant having a polyoxyethylene chain.