JP3226375B2 - Acrylic curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an acrylic curable resin composition. More specifically, for interior and exterior buildings, automobiles, home appliances, etc., where weather resistance and durability are required,
The present invention relates to an acrylic curable resin composition capable of providing excellent coating performance.

[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 of the activator, and the coating film properties such as weather resistance, water resistance, and stain resistance of the coating film formed in comparison with those using an organic solvent are reduced. 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).

[0005] However, even in the above emulsion, the stability of the alkoxysilyl group is insufficient.
The emulsion is not excellent in storage stability, and there is a problem that a coating film formed using the emulsion has insufficient durability, hardness, and adhesion to an object to be coated.

[0006]

Therefore, the present inventor has proposed:
As a result of intensive studies in view of the prior art, a resin composition containing a specific silyl group-containing polymer emulsion and a specific water-absorbing agent has excellent storage stability, and from the resin composition, durability, The inventors have finally found that a coating film having significantly improved water resistance, hardness, and adhesion to an object to be coated can be formed, and have completed the present invention.

[0007]

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

[0008]

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(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 a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, An aminooxy group, a phenoxy group, a thioalkoxy group or an amino group, a represents an integer of 0 to 2 (however, when R ¹ and X ¹ each are 2 or more, they are the same or different); Comprising an emulsion of a silyl group-containing polymer (A) and an aqueous silane-based osmotic water-absorbing agent (B),
The silyl group-containing polymer represented by the general formula (I) contains 1 to 30% by weight of an alkoxysilyl group-containing vinyl monomer, and a hydrophilic vinyl monomer having a polyoxyethylene chain.
About 1 to 10 wt% and the balance other vinyl acrylic curable resin composition is an acrylic emulsion copolymer polymerized moieties consisting of monomers by copolymerizing.

[0010]

Function and Examples The acrylic curable resin composition of the present invention has the general formula (I):

[0011]

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(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 a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, An aminooxy group, a phenoxy group, a thioalkoxy group or an amino group, a represents an integer of 0 to 2 (however, when R ¹ and X ¹ each are 2 or more, they are the same or different); The emulsion contains a silyl group-containing polymer emulsion (A) and an aqueous silane-based osmotic water-absorbing agent (B), and the silyl group-containing polymer represented by the general formula (I) contains an alkoxysilyl group-containing polymer. A polymerization component comprising 1 to 30% by weight of a vinyl monomer, 0.1 to 10% by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain and the balance of other vinyl monomers is used. Those which are acrylic emulsion copolymer combined composed.

The silyl group-containing polymer represented by the general formula (I) (hereinafter referred to as polymer (A)) for obtaining the emulsion (A) used in the present invention is represented by the general formula (I)
An acrylic resin containing a silyl group represented by the formula: In the acrylic resin , a coating film formed by using the obtained acrylic curable resin composition has weather resistance and chemical resistance It is advantageous in that it is excellent in resin design, has a wide range of resin designs, and is inexpensive.

[0014] prepare the polymer (A), Arco
A vinyl monomer containing a silyl group represented by the general formula (I), which is a vinyl monomer containing a xylsilyl group (hereinafter, referred to as monomer (A-1)) ;
Hydrophilic vinyl monomer having ethylene chain and other vinyl
A method of polymerizing another vinyl monomer (hereinafter, referred to as monomer (A-2)) copolymerizable with monomer (A-1), which is a monomer (A-1) ) Can be obtained.

In the general formula (I), the aryl group representing R ¹ is preferably one having 6 to 10 carbon atoms, and the aralkyl group is preferably one having 7 to 15 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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[0028] (In the formula, R ¹ us and a are the same as defined above, R ² is
A hydrogen atom or a methyl group; R ³ represents 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 and a are the same as above, and n is an integer of 1 to 12 ;

[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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[0056] ^{(wherein, R 1, R 2, R} 3, a and n are the same, p is an integer of 1 to 12) alkoxysilyl group-containing vinyl monomers such as the compound represented by the These can be used alone or in combination of two or more. These alkoxysilyl group-containing vinyls
Systems monomers, ease of handling, RaYoshimi preferable either that point and reaction by-products of the price does not occur.

The monomer (A-2) is not particularly restricted but includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and t-butyl. (Meth) acrylate monomers such as (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, and perfluorocyclohexyl (meth) acrylate , 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth)
Fluorine-containing vinyl monomers such as acrylates; aromatic hydrocarbon-based vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene; (meth) acrylic acid, maleic acid, and anhydride Α, β-ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, citraconic acid; polymerizable carbon-carbon double bonds such as styrenesulfonic acid and vinylsulfonic acid; Having acid,
Or a salt thereof such as an alkali metal salt, an ammonium salt or an amine salt; an acid anhydride such as maleic anhydride or a half ester thereof with an alcohol having a linear or branched chain having 1 to 20 carbon atoms; dimethylaminoethyl ( (Meth) acrylates having an amino group such as 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 or vinyl ester such as vinyl acetate, vinyl propionate or diallyl phthalate; (meth)
Vinyl monomers containing a nitrile group such as acrylonitrile; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl Vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene,
Alonix M-5700 (Toa Gosei Chemical Industry Co., Ltd.), Plac
celFA-1, PlaccelFA-3, PlaccelFA-4, PlaccelFM-1
, PlaccelFM-4 (Daicel Chemical Industries, Ltd.)
HE-10, HE-20, HP-10, HP-2
0 (all manufactured by Nippon Shokubai Co., Ltd.), Blemmer PP series, Blemmer PEP series, Blemmer AP-400,
Hydroxyl-containing vinyl monomers such as Blemmer NKH-5050, Blemmer GLM (both manufactured by NOF Corporation) and hydroxyl-containing vinyl-modified hydroxyalkylvinyl monomers; Blemmer PE-90, PE-200, PE-350 Such as Blemmer PE series, Blemmer PME-100
, PME-200, PME-400 etc.
Blemmer A such as E series, Blemmer AE-350
E series (above, manufactured by NOF Corporation), MA-30, M
A-50, MA-100, MA-150, RA-1120, RA-
2614, RMA-564, RMA-568, RMA-1114, M
Hydrophilic vinyl monomers having a polyoxyethylene chain, such as PG130-MA (all manufactured by Nippon Emulsifier Co., Ltd.);
Vinyl compounds containing a phosphate ester group, such as condensation products of hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, such as hydroxyalkyl esters of (meth) acrylic acid, and phosphoric acid or phosphoric acid esters; Vinyl compounds such as (meth) acrylates containing urethane bonds and siloxane bonds; vinyl compounds containing amino groups such as vinylpyridine and aminoethyl vinyl ether; itaconic diamide, crotonamide, maleic diamide, fumaric diamide, N-vinylpyrrolidone Amide group-containing vinyl compounds such as AS-6 and AN-6, which are macromonomers manufactured by Toa Gosei Chemical Industry Co., Ltd.
Compounds such as AA-6, AB-6, and AK-5, 2-hydroxyethyl vinyl ether, methyl vinyl ether,
Other vinyl monomers such as cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, vinylsulfonic acid; LA87, LA82 manufactured by Asahi Denka Kogyo KK , L
Polymerized light stabilizers such as A22, and polymerized ultraviolet absorbers.

As the monomer (A-2), a hydrophilic vinyl monomer having a polyoxyethylene chain and another vinyl monomer are used. May be selected according to the desired physical properties of the obtained acrylic curable resin composition. For example, in order to impart water repellency to a coating film formed using the obtained acrylic curable resin composition and to improve water resistance and durability, a fluorine-containing vinyl monomer or a siloxane-containing vinyl monomer may be used. In order to improve the stability of the obtained emulsion (A), (meth) acrylic acid, maleic acid, dimethylaminoethyl (meth) acrylate, (meth) acrylamide, a hydroxyl group-containing vinyl It is preferable to use a hydrophilic monomer such as a monomer or polypropylene glycol methacrylate. When an acidic vinyl monomer is used, the mechanical stability of the emulsion (A) is improved.

In the present invention, the monomer (A-2)
Among them, since a hydrophilic monomer having a polyoxyethylene chain is used, the mechanical stability of the emulsion (A) can be reduced without lowering the stability of the silyl group in the monomer (A-1). The water resistance, gloss, and the like of a coating film formed using the acrylic curable resin composition are improved. The compounding amount of the hydrophilic monomer having a polyoxyethylene chain is 0.1 to 10 parts based on 100 parts (parts by weight, hereinafter the same) of the total amount of the polymerization components. When the amount is less than 0.1 part, the mechanical stability of the emulsion (A) and the water resistance and gloss of a coating film formed using the obtained acrylic curable resin composition are reduced. If the amount is lowered and exceeds 10 parts, the coating film is softened and stains are easily attached.

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) which is an alkoxysilyl group-containing vinyl monomer and the monomer (A-2) which is a hydrophilic vinyl monomer having a polyoxyethylene chain and another vinyl monomer )), The total amount of the polymerization components is 10
The amount of the monomer (A-1) is from 1 to 30 based on 0 parts.
Parts, that is, the amount of the monomer (A-2) is 70 to 99.
Adjust to be a part. When the amount of the monomer (A-1) is less than 1 part, the obtained acrylic curing
The water resistance and weather resistance of the coating film formed using the conductive resin composition are poor, and when the amount exceeds 30 parts, the stability of the emulsion (A) is reduced.

In the present invention, 1 to 30% by weight of an alkoxysilyl group-containing vinyl monomer, preferably 2 to 25%
% By weight, 0.1 to 10% by weight of a hydrophilic vinyl-based monomer having a polyoxyethylene chain, preferably 0.5 to 10% by weight, and the remaining vinyl-based monomer being copolymerized. Since the acrylic emulsion copolymer is used, the alkoxysilyl group in water is stable, inexpensive, and produces by-products when forming a coating film using the obtained acrylic curable resin composition. The product does not adversely affect the coating film, especially the stability of the alkoxysilyl group, the mechanical stability of the emulsion (A) and the resulting acrylic curing
There is an advantage that the water resistance and gloss of the coating film formed using the conductive resin composition are excellent.

The monomer (A-1) and the monomer (A-
2) and can be ur polymer by polymerizing in a conventional manner with (A), emulsion polymerization method considering the particle diameter and stability of ET Marujon (A) is used.

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. 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 and Newcol-560SF (all manufactured by Nippon Emulsifier Co., Ltd.), Emar NC-35, and Reveil WZ (all described above).
Polyoxyethylene nonyl phenyl ether sulfate (New Kao Corp.), Newcol-707SN, Newcol-707S
F, polyoxyethylene allyl ether sulfate such as Newcol-723SF, 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 with a polymerizable double bond in the molecule can be used, especially when a reactive surfactant with a polyoxyethylene group in the molecule is used, the resulting acrylic curable The water resistance of the coating film formed using the resin composition is improved.

Specific examples of such a reactive surfactant 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 surfactants can be used alone or as a mixture of two or more kinds. The amount of the surfactants to be used is 10 parts or less, preferably 0.5 to 50 parts per 100 parts of the total amount of the polymerization components.
8 parts are preferred. If the amount of the surfactant exceeds 10 parts, the water resistance of the coating film formed using the obtained acrylic curable resin composition tends to decrease.

[0071] In the present invention, since selling emulsion polymer with a hydrophilic vinyl monomer having the alkoxysilyl group-containing vinyl monomers and polyoxyethylene chains as a polymerization component, wherein the emulsifier Anionic surfactant having a polyoxyethylene chain is used in an amount of 0.2 to 10 parts, preferably 0.5 to 100 parts of the total amount of the polymerization components.
From 8 to 8 parts is preferable from the viewpoint of stability against the alkoxysilyl group.

Further, 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 carry out the polymerization, the temperature is preferably 70 ° C. or lower, particularly preferably 40 to 65 ° C. Is 5
8, it is preferable to adjust so as to be 6 to 7, especially.

Examples of the redox catalyst include a combination of potassium 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 0.01 to 10 parts, preferably 0.0 to 10 parts, based on 100 parts of the total amount of the polymerization components.
Preferably it is 5 to 5 parts. When the amount of the polymerization initiator is less than 0.01 part, the polymerization may be difficult to proceed. When the amount is more than 10 parts, the molecular weight of the produced polymer may be reduced, Acrylic hard
Durability of the coating film formed by using a resistant 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 used is
0.0001 to 1 part, especially 100 parts of polymerization
It is preferably from 0.001 to 0.5 part.

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

The resin solid content concentration in the emulsion (A) is preferably adjusted so as to be 20 to 70% by weight, especially 30 to 60% by weight. Such resin solid content concentration
If the amount exceeds 70% by weight, the concentration of the system rises remarkably, so it becomes difficult to remove the heat generated by the polymerization reaction, and it takes a long time to take out from the polymerization vessel. There is. 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 generated by one polymerization operation is small, which is disadvantageous in economical terms. 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 0.7 μm, it has excellent film-forming ability.

Examples of the aqueous silane-based osmotic water-absorbing agent (B) (hereinafter referred to as water-absorbing agent (B)) used in the present invention include, for example, organoalkoxysilanes, organoacetoxysilanes, organohalogensilanes, organodisilanes, and organodisilanes. Silane carboxylic acid, organosilane thiol, organosilicon isocyanate, organosilicon isothiocyanate, these partial hydrolysates, etc. were emulsified using, for example, a surfactant, or forcedly emulsified by high-speed stirring to make aqueous. And the like. These can be used alone or as a mixture of two or more. In addition, an acrylic resin,
A mixture of a chlorinated resin, a fluorine-containing compound, or the like can also be used. Among these compounds, compounds obtained by converting organoalkoxysilane to an aqueous solution are preferable in view of the fact that the hydrolysis reaction by-product has low odor and harmfulness.

The above-mentioned organoalkoxysilanes include:
For example, the general formula (XII):

[0082]

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(Wherein R ⁵ and R ⁶ are each independently a monovalent hydrocarbon group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group and an aralkyl group, and b is an integer of 0 to 3) (However, when R ⁵ and OR ^{6 are} each 2 or more, they are the same or different.), A partial condensate of the compound, and the like. Specific examples of the compound represented by the general formula (XII) include, for example, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, ethoxytrimethylsilane, diethoxydimethylsilane,
Triethoxymethylsilane, methoxytriethylsilane, dimethoxydiethylsilane, trimethoxyethylsilane, ethoxytriethylsilane, diethoxydiethylsilane, triethoxyethylsilane, methoxytripropylsilane, dimethoxydipropylsilane, trimethoxypropylsilane, ethoxytripropyl Silane, diethoxydipropylsilane, triethoxypropylsilane, tetramethoxysilane, tetraethoxysilane, trimethoxyhexylsilane, dimethoxymethylhexylsilane, triethoxyhexylsilane, diethoxymethylhexylsilane, trimethoxyundecylsilane, dimethoxymethyl Undecylsilane, triethoxyundecylsilane, diethoxymethylundecylsilane, trimethoxyoctadecyl Orchid, dimethoxymethyloctadecylsilane, triethoxyoctadecylsilane, diethoxymethyloctadecylsilane, tripropoxymethylsilane, tripropoxyhexylsilane, tripropoxyundecylsilane, tripropoxyoctadecylsilane, tetrapropoxysilane, tri-n-butoxymethylsilane, Tri-n-butoxyhexylsilane, tri-n-
Butoxyundecylsilane, tetra-n-butoxysilane, tri-t-butoxymethylsilane, tri-t-butoxyhexylsilane, tri-t-butoxyundecylsilane,
Tri-t-butoxyoctadecylsilane, tetra-t-butoxysilane and the like can be mentioned.

The solid content of the water absorption inhibitor (B) is
The stability of the water absorption inhibitor (B) and the emulsion (A)
Considering the concentration of the acrylic curable resin composition obtained by mixing with, about 2 to 80% by weight, preferably 5 to 50%
It is preferable that the amount is about weight%.

[0085] agitating the emulsion (A) and water-absorption inhibitor (B), for example so that such a uniform composition homogenizer, by mixing, accession of the present invention
A ril-based curable resin composition can be obtained.

The mixing ratio of the emulsion (A) and the water-absorbing agent (B) is such that the amount of the water-absorbing agent (B) is 0.3 to 50 per 100 parts of the resin solid content of the emulsion (A).
Parts, preferably 0.5 to 20 parts. When the amount of the water-absorbing agent (B) is less than 0.3 part, the curability of the obtained resin composition and the adhesion of the coating film formed using the resin composition to the object to be coated. Tends to be insufficient, and if it exceeds 50 parts, the coating film tends to be brittle.

In order to accelerate the curing of the acrylic curable resin composition of the present invention by crosslinking, a curing agent can 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 And basic compounds such as sodium hydroxide and potassium hydroxide. These may be used alone or in combination of two or more. Can, but organotin compound and an organoaluminum compound from the viewpoint of high curing activity Among these are preferred.

When an organometallic compound is used as a 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 an object to be coated. The composition is preferable because it 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 water-absorbing inhibitor (B). preferable. When the amount is less than 0.01 part, the effect of the curing activity by using the curing agent tends to be insufficient, and when the amount exceeds 10 parts, the obtained acrylic is used. The water resistance of the coating film formed using the system curable 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 ultraviolet absorbers Additives, such as a film-forming aid, can be added to the acrylic curable resin composition as needed.

Further, a commercially available water-based paint can be blended with the acrylic curable resin composition of the present invention. As, for example acrylic paints, thermosetting acrylic paints such as acrylic melamine paints, alkyd paints, epoxy paints, such as fluorine resin coating, and the like, when formulated with these coatings of such water-based, acrylic
The weather resistance, acid resistance, solvent resistance, etc. of the coating film formed using the phenol-based curable resin composition can be improved.
Further, by adding an additive such as a thickener, the acrylic curable resin composition of the present invention can be used for applications such as adhesives and pressure-sensitive adhesives.

In the present invention, as a crosslinking agent,
A such as melamine resins, isocyanate compounds, etc.
The curable resin composition may be added to the curable resin composition to impart quick-curing properties.

The acrylic curable resin composition of the present invention is
For example, the composition can be applied to an object to be coated by an ordinary method such as immersion, spraying, or application using a brush, and cured by baking at room temperature as it is or at about 60 to 200 ° C.

The acrylic curable resin composition of the present invention comprises:
For example, for automotive interiors and exteriors, clearing on metallic bases for repairs, etc. for automobiles, direct coating of metals such as aluminum and stainless steel, direct coating of glass, direct coating of stone materials, ceramic base materials such as slate, concrete, tile, etc. It can be suitably used as a surface treatment agent, including a coating material for coating.

Next, the acrylic 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 1-2 and Comparative Production Example 1 (Emulsion (A)
Preparation of) 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 and 0.9 parts of sodium dodecylbenzenesulfonate ( Comparative Production Example 1)
Or 0.9 parts of polyoxyethylene nonyl phenyl ether sulfate (Newcol-560SN) (Production Examples 1 and 2 ), 1 part of polyoxyethylene nonyl phenyl ether, 0.35 part of Rongalite, 0.5 part of ammonium acetate, t-butyl Hydroperoxide 0.2
Parts and 20 parts of 158 parts of the mixture having the composition shown in Table 1 were added to carry out 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 mixture 1
The remaining 138 parts of the mixture in 58 parts was dropped at a constant rate over 3 hours by a dropping funnel. Thereafter, after 1 hour, polymerization was carried out, and deionized water was added to the emulsion (A) -1 having a resin solid content concentration of 40% by weight ( Comparative Production Example 1).
(A) -2 (Production Example 1 ) and (A) -3 (Production Example 2 )
I got

[0098]

[Table 1]

Examples 1 to 5 and Comparative Examples 1 and 2 The emulsion (A) obtained in Production Examples 1 and 2 and Comparative Production Example 1 were added to the water-absorbing inhibitor (B) -1 (Aquaproof 40).
J, manufactured by Toa Gosei Chemical Industry Co., Ltd., solid content concentration 40% by weight) or (B) -2 (Aquaproof 20J, manufactured by Toa Gosei Chemical Industry Co., Ltd., solid content concentration 20% by weight), film forming aid (CS12, manufactured by Chisso Corp.) and dibutyltin dilaurate as a curing agent were blended in the proportions shown in Table 2 and stirred with a mechanical stirrer for 3 minutes to obtain a curable resin composition.

The storage stability as a physical property of the obtained curable resin composition was examined according to the following method. Table 2 shows the results.

(Storage stability) The viscosity (cP) of the composition comprising the emulsion (A) and the water-absorbing inhibitor (B) at the initial stage and after storage for one month in an atmosphere of 50 ° C. was measured using a B-type viscometer (25). ° C).

The state (appearance) of the composition at the beginning and after storage for one month in an atmosphere of 50 ° C. was visually observed.
The presence or absence of the change was examined and evaluated based on the following evaluation criteria. (Evaluation criteria) A: No change at all. B: A slight change is observed. C: The change is remarkable.

Next, the coating film formed using the above-mentioned curable resin composition comprising the emulsion (A), the water-absorbing inhibitor (B), the film-forming aid and the curing agent has properties such as water resistance, adhesion and water resistance. Hardness was determined according to the following method. Table 2 shows the results.

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

Immediately after the preparation of this test piece and in water at 40 ° C.
The state (appearance) after immersion for a week was visually observed, the presence or absence of the change was examined, and evaluated based on the following evaluation criteria. (Evaluation criteria) A: No change at all. B: The surface is slightly whitened. C: Whitening is remarkable.

(B) Adhesion The same test piece as used in the above (a) water resistance test was used. A 2 mm width knife was used on each of the test piece surfaces immediately after preparation and after immersion in 40 ° C. water for 2 weeks. Was cut off with a cellophane tape, the surface of the test piece was visually observed, and evaluated based on the following adhesion evaluation standard of the Japan Paint Inspection Association. (Adhesion evaluation criteria) 10 points: No peeling was observed. 8 points: about 80% of the coating film adhered. 6 points: about 60% of the coating film adhered. 0 point: a state where the entire surface is peeled off.

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

[0108]

[Table 2]

From the results shown in Table 2, the acrylic curable resin compositions obtained in Examples 1 to 5 have excellent storage stability, and are formed using the resin compositions. It can be seen that the resulting coating film has excellent water resistance and adhesion, and has high hardness.

[0110]

The acrylic curable resin composition of the present invention has excellent storage stability.
It is excellent in water resistance and adhesion to an object to be coated, and can form a coating film having high hardness.

Therefore, the acrylic curable resin composition of the present invention can be suitably used for coating 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 43/04 C08F 230/08 C08K 5/54-5/548 C09D 143/04

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 represents 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 represents an integer of 0 to 2 (provided that R ¹ and X ¹ each represent 2 or more; In some cases,
These contain the same or different)) silyl group-containing polymer emulsion (A) and an aqueous silane-based osmotic water-absorbing inhibitor (B), and contain a silyl group-containing polymer represented by the general formula (I). The polymer is an alkoxysilyl group-containing vinyl monomer in an amount of 1 to 30% by weight, a hydrophilic vinyl monomer having a polyoxyethylene chain.
1 to 10 wt% and the balance other vinyl acrylic curable resin composition is an acrylic emulsion copolymer polymerized moieties consisting of monomers by copolymerizing. Wherein the aqueous silane-based osmotic absorption inhibitor according to claim 1, wherein a 0.3 to 50 parts by weight based on the resin solid content of 100 parts by weight of (B) Emulsion (A) is the amount of Accession
Ril curable resin composition.