JP3291635B2 - 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 providing a coating film having excellent performance to interior and exterior buildings, automobiles, home electric appliances, and the like, which require weather resistance and durability.

[0002]

2. Description of the Related Art In recent years, from the viewpoints of pollution prevention and resource saving, attempts have been made to convert paints and adhesives from those using organic solvents to aqueous ones.

However, a water-dispersible resin is generally used for the conventional water-based resin, and the water-dispersible resin does not have a crosslinkable functional group. As a result, when a surfactant is used during the emulsion polymerization, it is strongly affected by the surfactant, so that the weather resistance and water resistance of the formed coating film are compared with those in which an organic solvent is used. And the physical properties of the coating film such as stain resistance are remarkably poor.

[0004] Various attempts have been proposed to improve this drawback, one of which is to apply an emulsion of a polymer having an alkoxysilyl group, which is a crosslinkable functional group, to a paint, and to use an organic solvent as a curing agent. It has been proposed to use a tin compound for curing (JP-A-3-22712).

[0005]

However, when the organotin compound is used alone, the balance between pot life, appearance, and curability is poor, and there are many practical problems.
That is, if the use amount of the organotin compound is reduced, the pot life and appearance are improved, but the curability is deteriorated,
On the other hand, when the amount of the organotin compound used is large, the curability is not a problem, but the pot life and appearance are extremely reduced, so that it has been a large barrier in practical use.

[0006]

Means for Solving the Problems As a result of intensive studies on this problem, the present inventors have found that when a mercapto group-containing compound is added to an organotin compound, the catalyst activity is hardly reduced, while the pot life is reduced. In addition, the present inventors have discovered that the appearance is improved, which is extremely important in practical use, and have completed the present invention.

That is, the present invention provides a curable resin comprising a silyl group-containing polymer emulsion (A), an organotin compound (B) and a mercapto group-containing compound (C) represented by the following general formula (I): A composition.

[0008]

Embedded image (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. However, when each of R ¹ and X ¹ is 2 or more, they are the same or different. )

The polymer containing a silyl group represented by the above formula (I) for obtaining the emulsion (A) used in the present invention (hereinafter referred to as polymer (A)) is not particularly limited. For example, an epoxy resin, a polyester resin, a polyether resin, an acrylic resin, a fluororesin, etc. containing a silyl group represented by the general formula (I) can be mentioned. Among these, the curable resin composition obtained is Acrylic resins are preferred from the viewpoint that the coating film formed using the product is excellent in weather resistance and chemical resistance, has a wide range of resin designs, and is inexpensive.

The method for preparing the polymer (A) is not particularly limited. For example, a vinyl monomer containing a silyl group represented by the general formula (I) (hereinafter referred to as monomer (a-1)) ) And a method of polymerizing another vinyl monomer copolymerizable with the monomer (hereinafter, referred to as monomer (a-2)) are preferable in that the polymer (A) can be easily obtained.

[0011] In the above formula (I), the aryl group represented by ^{R 1,} for example, preferably has a carbon number of 6-10, and as the aralkyl groups, for example those having a carbon number of 7 to 10 preferable.

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

[0013]

Embedded image General formula (II) such as

Embedded image (Wherein R ¹ and a are the same as above, R ² represents a hydrogen atom or a methyl group, and X ² represents a halogen atom);

[0014]

Embedded image General formula (III) such as

Embedded image (Wherein, R ¹ , R ² , X ² and a are the same as described above, and n represents an integer of 1 to 12);

[0015]

Embedded image General formula (IV) such as

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

[0016]

Embedded image General formula (V) such as

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

[0017]

Embedded image General formula (VI) such as

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

[0018]

Embedded image General formula (VII) such as

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

[0019]

Embedded image General formula (VIII) such as

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

[0020]

Embedded image General formula (IX) such as

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

[0021]

Embedded image General formula (X) such as

Embedded image (Wherein, R ¹ , R ² , R ³ , a and n are the same as described above;
R ⁴ represents —CH ₂ O— or —CH ₂ OCO—. )
A compound represented by the formula:

[0022]

Embedded image General formula (XI) such as

Embedded image (Wherein, R ¹ , R ² , R ³ , a and n are the same as described above;
p shows the integer of 1-12. A compound represented by);

[0023]

Embedded image General formula (XII) such as

Embedded image (Wherein R ¹ , R ³ , a and n are the same as those described above). These can be used alone or in combination of two or more. Among these, an alkoxysilyl group-containing vinyl monomer is preferred from the viewpoint of ease of handling, cost, and no reaction by-product.

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 acrylate, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, and pentafluoropropylene; styrene, α
-Aromatic hydrocarbon-based 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 Α, β-ethylenically unsaturated carboxylic acids such as acid and citraconic acid; acids having a polymerizable carbon-carbon double bond such as styrene sulfonic acid and vinyl sulfonic acid, or alkali metal salts, ammonium salts and amines thereof Salts such as salts; acid anhydrides such as maleic anhydride or half esters thereof 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 hydrochloric acid or acetate thereof; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and 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 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), Pl
accelFA-1, PlacelFA-3, Pla
ccelFA-4, PlacelFM-1, Plac
celFM-4 (manufactured by Daicel Chemical Industries, Ltd.),
HE-10, HE-20, HP-10, HP-20 (all manufactured by Nippon Shokubai Chemical Co., Ltd.), Blemmer PP series, Blemmer PEP series, Blemmer AP-4
00, Blemmer NKH-5050, Blemmer GLM
(Nippon Oil & Fats Co., Ltd.), hydroxyl-containing vinyl monomers such as hydroxyl-modified vinyl-modified hydroxyalkyl vinyl monomers; Blenmer PE-90, PE-20
0, Blemmer PE series such as PE-350, Blemmer PME-100, PME-200, PME-40
0 and other Blemmer PME series, Blemmer AE-
Blemmer AE series such as 350 (all manufactured by NOF Corporation), MA-30, MA-50, MA-100,
MA-150, RA-1120, RA-2614, RM
A-564, RMA-568, RMA-1114, MP
Hydrophilic vinyl monomers having a polyoxyethylene chain, such as G130-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
A22, such as a polymerizable light stabilizer and a polymerizable ultraviolet absorber.

The type of the monomer (a-2) may be selected according to the desired physical properties of the curable resin composition to be 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 monomer or a siloxane-containing vinyl monomer is used. It is preferable 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. When an acidic vinyl monomer is used, the mechanical stability of the emulsion (A) is improved. Also, n-
Butyl methacrylate, i-butyl methacrylate, t
Stabilization of silyl group by copolymerizing 60 parts or more of methacrylate having alkyl group having 4 or more carbon atoms or cycloalkyl group such as butyl methacrylate, cyclohexyl methacrylate or cycloalkyl group with respect to 100 parts by weight of total polymerization components (parts by weight, same hereafter) Sex is improved.

When a hydrophilic monomer having a polyoxyethylene chain is used in the monomer (a-2), the stability of the silyl group in the monomer (a-1) decreases. It is preferable because the mechanical stability of the emulsion (A) and the water resistance and gloss of a coating film formed using the obtained curable resin composition are improved. In addition, when using such a hydrophilic monomer having a polyoxyethylene chain, the compounding amount is 0.1 to 100 parts of the total amount of the polymerization component.
It is preferable to adjust so as to be 10 parts. 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 curable resin composition may be reduced. When the amount exceeds 10 parts, the coating film tends to be softened and stain tends to adhere.

In the present invention, the monomer (a-2) has at least two polymerizable unsaturated double bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate and the like. By using a monomer, 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 2 to 2 parts, based on 100 parts of the total amount of the polymerization components.
0 parts, that is, the amount of the monomer (a-2) is 70 to 9
Adjust to 9 parts, preferably 80 to 98 parts.
When the amount of the monomer (a-1) is less than 1 part, water resistance and weather resistance of a coating film formed using the obtained resin composition tend to be poor, and when the amount exceeds 30 parts. Has a tendency that the stability of the emulsion (A) decreases.

In the present invention, the alkoxysilyl group in water is stable and inexpensive, and 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-
The 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. Above all, 1 to 30% (wt%, the same applies hereinafter) of an alkoxysilyl group-containing vinyl monomer, preferably 2 to 25%, 0.1 to 10% of a hydrophilic vinyl monomer having a polyoxyethylene chain, Preferably 0.5 to 1
An emulsion copolymer obtained by copolymerizing a polymerization component containing 0% and a balance of another vinyl monomer provides stability of an alkoxysilyl group, mechanical stability of an emulsion (A), and a resin composition obtained. It is particularly preferable from the viewpoint that the coating film formed using the product has excellent water resistance and gloss.

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 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 a batch polymerization method, a monomer drop polymerization method, and an emulsion monomer drop polymerization method. In the present invention, a monomer drop polymerization method and an emulsion monomer drop polymerization method are particularly preferable for ensuring the stability of the emulsion during production. Particles having a multilayer structure can also be obtained by multi-stage polymerization of monomers having different compositions or emulsified monomer liquids. 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-560S.
F (all manufactured by Nippon Emulsifier Co., Ltd.), Emar NC-3
5. Polyoxyethylene nonyl phenyl ether sulfate such as Revel WZ (all manufactured by Kao Corporation), N
ewcol-707SN, Newcol-707SF,
Newcol-723SF, Newcol-740SF
(Above, manufactured by Nippon Emulsifier Co., Ltd.), such as polyoxyethylene allyl ether sulfate, Newcol-861
Octylphenoxyethoxyethylsulfonate such as SE (manufactured by Nippon Emulsifier Co., Ltd.), Newcol-1305
Anionic surfactant having a polyoxyethylene chain such as polyoxyethylene tridecyl ether sulfate such as SN (manufactured by Nippon Emulsifier Co., Ltd.); sodium lauryl sulfonate, sodium dodecylbenzene sulfonate, sodium isooctylbenzene sulfonate, etc. Representative examples thereof include ammonium salts such as imidaline laurate and ammonium hydroxide. Among these, among these, the monomer (a)
The anionic surfactant having a polyoxyethylene chain is preferred from the viewpoint that the polymerization reaction proceeds in a state where the silyl group in -1) is stabilized.

Examples of the nonionic surfactant include polyethylene glycol nonyl phenyl ether; polyoxyethylene nonyl phenyl ether,
Polyoxyethylenes such as polyoxyethylene lauryl ether; L-77, L-720, L-5410, L
Non-ionic surfactants containing silicone such as -7602 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 in particular, when a reactive surfactant having a polyoxyethylene group in the molecule is used, the resulting curable resin composition is obtained. The water resistance of the coating film formed by using is improved.

Specific examples of such a reactive surfactant include, for example, Adecaria soap NE-10 and 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 in combination of two or more. The amount of the surfactants used is 10 parts or less, preferably 0.5 to 10 parts, based on 100 parts of the total amount of the polymerization components.
8 parts. When the use amount of such a surfactant exceeds 10 parts, 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 polyoxyethylene is used as an emulsifier. It is preferable to use 0.2 to 10 parts, and preferably 0.5 to 8 parts, of the anionic surfactant having a chain based on 100 parts of the total amount of the polymerization components, from the viewpoint of stability against the alkoxysilyl group.

In order to further improve the water resistance of the coating film, instead of using such a surfactant, a water-soluble resin having a silyl group represented by the general formula (I) introduced therein 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. In order to maintain the stability of the mixed solution during the polymerization and stably perform the polymerization, the temperature is 70 ° C. or lower, preferably 40 to 65 ° C., and the pH is 5 to stabilize the silyl group. -8, preferably 5-7.

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

The polymerization initiator is used in an amount of 0.01 to 10 parts, preferably 0.0 to 10 parts, based on 100 parts of the total amount of the polymerization components.
5 to 5 parts. When the amount of the polymerization initiator used is 0.01
If the amount is less than 10 parts, polymerization may be difficult to proceed, and if the amount is more than 10 parts, the molecular weight of the resulting polymer is reduced, and the coating film formed using the obtained resin composition Durability tends to decrease.

In order to stably obtain 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 0.0001 to 1 part, preferably 0.001 to 0.5 part, based on 100 parts of the total amount of the polymerization components.

The polymer (A) thus obtained is
For example, an emulsion (A) can be obtained by adding a desired amount of deionized water or the like and dispersing the polymer (A).

The resin solid content concentration in the emulsion (A) is preferably 20 to 70%, more preferably 30 to 70%.
Adjust so as to be ~ 60%. When the resin solids concentration exceeds 70%, the concentration of the system is significantly increased, so that it is difficult to remove the heat generated by the polymerization reaction, and it takes a long time to remove the resin from the polymerization vessel. Tend to be. Further, when the resin solid content concentration is less than 20%, although there is no problem in terms of polymerization operation, the amount of resin generated by one polymerization operation is small,
In addition to being economically disadvantageous, there is a tendency for the film thickness to be reduced during the formation of the coating film, resulting in performance deterioration and disadvantageous 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 1.0 μm, it has excellent film forming ability.

The organotin compound (B) used in the present invention
Examples include carboxylic acid-type organic tin compounds such as tin octylate, dibutyltin dilaurate, and dioctyltin dimaleate; sulfide-type and mercaptide-type organic tin compounds such as monobutyltin sulfide and dioctyltin mercaptide; dioctyltin oxide and the like Organic tin oxide; a compound obtained by reacting an organic tin oxide with an ester compound such as ethyl silicate, ethyl silicate 40, dimethyl maleate, or dioctyl phthalate is effective. The organotin compound (B) is used in an amount of 0.0001 to 50 parts, preferably 0.001 to 30 parts, per 100 parts of the resin solid content of the silyl group-containing emulsion (A).

The mercapto group-containing compound (C) used in the present invention includes n-dodecyl mercaptan and ter
alkyl mercaptans such as t-butyl mercaptan;
mercaptosilanes such as γ-mercaptopropyltrimethoxysilane; mercapto group-containing carboxylic acids such as 2-mercaptopropionic acid and thiosalicylic acid; mercapto group-containing ester compounds such as 2-ethylhexyl thioglycolate; Capcure 3-800 (Diamond Shamrock) And a mercapto group-containing polymer such as a polyether having a mercapto group at both terminals (manufactured by Chemicals Co., Ltd.), thiophenol, and thiobenzoic acid. The amount of use of these mercapto group-containing compounds is in the range of 0.05 to 20, preferably 0.1 to 10, by weight based on the organotin compound (B).

The organotin compound (B) and the mercapto group-containing compound (C) may be added to the silyl group-containing emulsion (A) in a predetermined mixture, or may be added separately.

The composition of the present invention may also be prepared by mixing the emulsion containing a silyl group (A) with the organotin compound (B) and the compound containing a mercapto group (C) (two-pack type) before use. Either a mode of mixing and using it as it is (one-pack type) or either type may be used.

When the organotin compound (B) and the mercapto group-containing compound (C) are emulsified in advance or dissolved in a film-forming aid, the curing activity is high and even when mixed with the emulsion (A). The generation of aggregates can be suppressed.

In order to emulsify the components (B) and (C), a method of mixing the components (B), (C), the surfactant and deionized water with a surfactant and dispersing the mixture with a homogenizer is used. Is simple and preferred.

Examples of such surfactants include alkyl ether type nonions such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether. If the anionic surfactant is used in an amount of 50% or more of all the surfactants, there is no problem even if other surfactants are used in combination. The surfactants that can be used in combination are not particularly limited, and specific examples thereof include alkylaryl ether types such as polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether; polyoxyethylene laurate, polyoxyethylene oleate, and polyoxyethylene. Alkyl ester type such as ethylene stearate;
Alkylamine types such as polyoxyethylene laurylamine; sorbitan types such as sorbitan laurate, sorbitan stearate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate; ammonium alkyl benzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium dialkyl sulfo Sulfonate type such as succinate; sulfate type such as sodium polyoxyethylene nonyl phenyl ether sulfate and ammonium polyoxyethylene allyl ether sulfate;
Phosphate types such as alkoxyalkyl phosphate and alkyl phosphate are exemplified. One of these surfactants may be used alone, or two or more thereof may be used in combination. When the content of the alkyl ether surfactant is less than 50%, the components (B) and (C) may be emulsified immediately after the emulsification, but separated after a lapse of time.

The method for preparing the curing agent emulsion used in the present invention is not particularly limited, but the component (B) and the component (C)
A total of 5 to 20 parts of components, 5 to 20 parts of a surfactant, and 60 to 90 parts of deionized water were mixed to obtain 100 parts of an emulsion,
This was homogenized using a homogenizer at 5,000 to 20,000.
A method of stirring at 0 rpm for 5 to 15 minutes is preferred. If the stirring is insufficient, the gloss of the coating film may be reduced.

It is to be noted that 5 to 20 parts of ethylene glycol and propylene glycol can be added as an antifreezing agent.

When the components (B) and (C) are dissolved in a film-forming aid, the film-forming aid is not particularly limited.

As a film forming aid, for example, HO- (CH
₂ CH _{2 O)} n -R represented by ⁵ (poly) ethylene glycol or (poly) ethylene glycol monoalkyl ether ^{(R 5} is an alkyl group having a linear and / or branched C1-10 hydrogen or carbon, n Represents an integer of 1 to 5.), R ⁶ CO—O— (CH ₂ CH ₂ O) _n −
Represented by R ⁵ (poly) ethylene glycol ester or (poly) ethylene glycol ether esters (R ⁵ represents a linear and / or alkyl groups with branched C1-10 hydrogen or carbon, n represents an integer of 1 to 5, R ⁶ represents a straight-chain and / or branched alkyl group having 1 to 10 carbon atoms), HO- (C ₃ H ₆ O) _n -R ⁵ , and (poly) propylene glycol or (poly) propylene. Glycol monoalkyl ether (R ⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms and having a straight chain and / or branch; n is an integer of 1 to 5); R ⁶ CO
-O- and _{(C 3 H 6 O) n} -R 5 shown by (poly) propylene glycol esters or (poly) glycol ether esters ^{(R 5} represents a linear and / or branched C1-10 hydrogen or carbon in An alkyl group having n, n is an integer of 1 to 5, R ⁶ represents a linear and / or branched alkyl group having 1 to 10 carbon atoms), and the like. Specifically, for example, cellosolve, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene Glycol methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, tripropylene glycol methyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol isobutyl ether, etc. Ethers: ethyl cellosolve acetate, butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monoethyl ether acetate, There are ether esters such as tripropylene glycol monobutyl ether acetate and tripropylene glycol monoisobutyl ether acetate. Further, propylene glycol phenyl ether, propylene glycol diacetate, 2,2,4-trimethylpentanediol-1,3-monoisobutyrate and the like can be used. In particular, 2,2,4-trimethylpentanediol-1,3-monoisobutyrate is preferable since it has good stability with respect to the component (A).

These film-forming assistants can be used alone or in combination of two or more.

In dissolving the components (B) and (C), a film-forming auxiliary is used in an amount of 1% or more, preferably 2% or more, based on the resin solid content of the silyl group-containing emulsion (A). , A solvent other than the film-forming aid can be used. Examples of such solvents include, but are not limited to, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic solvents such as xylene and toluene; esters such as butyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone. And the like.

(B) in a solution dissolved in a film-forming auxiliary or the like
The concentrations of the component and the component (C) are not particularly limited, but are adjusted to 0.5 to 50% for ease of handling.

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 Adding a silane coupling agent such as an additive such as a film forming aid, ethyl silicate, methyl silicate or a partial hydrolyzed condensate thereof, aminosilane, or epoxysilane to the curable resin composition as necessary. Can be.

Further, a commercially available water-based paint can be blended with the curable resin composition of the present invention. Such water-based paints include, for example, acrylic paints, thermosetting acrylic paints such as acrylic melamine paints, alkyd paints, epoxy paints, fluororesin paints, and the like. Weather resistance, acid resistance, solvent resistance, etc. can be improved. Further, by adding an additive such as a thickener, the curable resin composition of the present invention can 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 an ordinary method such as dipping, spraying, application using a brush, or the like.
It can be baked and cured at about 200 ° 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 base or clear on metallic base, for direct application of metal such as aluminum and stainless steel, for direct application of glass, natural marble, granite and the like. It can be suitably used as a surface treatment agent, including paints for direct application to stone materials, such as slate, concrete, and tile.

[0066]

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 these Examples.

Production Examples 1 to 3 (Emulsion (A-1))
(Production of (A-3)) 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 (Production Example 1) Or 0.9 parts of polyoxyethylene nonyl phenyl ether sulfate (Newcol-560SN) (Production Examples 2 and 3), 1 part of polyoxyethylene nonyl phenyl ether, 0.35 part of Rongalite, and 0.1 part of ammonium acetate.
5 parts, 0.2 part of t-butyl hydroperoxide and 20 parts of 158 parts of the mixture having the composition shown in Table 1 were added to perform initial charging. Thereafter, the temperature was raised to 50 ° C. while introducing nitrogen gas, and after heating for 1 hour, a mixture of 0.5 part of t-butyl hydroperoxide and 138 parts of the remaining 158 parts of the mixture was dropped into a dropping funnel. For 3 hours. Thereafter, after 1 hour of polymerization, the emulsion (A-1) (Production Example 1), (A-2) (Production Example 2) and (A-2) having a resin solid content concentration of 40% by adding deionized water were added. -3) (Production Example 3) was obtained.

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[Table 1]

Production Example 4 (Components (B) and (C)
Preparation of solution (BC-1) 5 parts of dibutyltin dilaurate and 4 parts of n-dodecyl mercaptan were mixed with 91 parts of CS12 (manufactured by Chisso Corporation, 2,2,4-trimethylpentanediol-1,3-monoisobutyrate). And prepared by dissolving in

Production Example 5 (Components (B) and (C)
Preparation of Solution (BC-2)) A solution was prepared by dissolving 5 parts of dioctyltin dimaleate and 3 parts of γ-mercaptopropyltrimethoxysilane in 92 parts of ethyl cellosolve.

Production Example 6 (Components (B) and (C)
Preparation of emulsion (BC-3)) 5 parts of dibutyltin dilaurate, 4 parts of n-dodecyl mercaptan, 6 parts of TD-10014 (manufactured by Nippon Emulsifier Co., Ltd., alkyl ether surfactant), TD-1006
(Alkyl ether type surfactant manufactured by Nippon Emulsifier Co., Ltd.) 4 parts were previously placed in a homogenizer container, uniformly dispersed at 50 ° C., and then 71 parts of deionized water and 10 parts of propylene glycol were added, and the mixture was homogenized. The mixture was stirred at room temperature at 10,000 rpm for 15 minutes to prepare a curing agent emulsion (BC-3).

Examples 1 to 6 and Comparative Example 1 The silyl group-containing emulsions (A-1) to (A-3) obtained in Production Examples 1 to 3 were compared with the curing agents obtained in Production Examples 4 to 6. Solutions and emulsions (BC-1) to (BC
-3) was added at the ratio shown in Table 2 to obtain a curable composition.

Thereafter, the curability, appearance (gloss) and storage stability (pot life) of the curable composition
Was evaluated according to the following. The results are shown in Table 2.

Evaluation of Curability A predetermined amount of the obtained composition was applied to a polyethylene sheet, allowed to stand at room temperature for 7 days, and then all of the coating film formed on the polyethylene sheet was peeled off. The dried coating film was immersed in acetone for one day, and the residual ratio of the coating film after immersion in acetone was expressed as a gel fraction.

Evaluation of Appearance (Gloss) Further, 0.4 part of CS12 was added to the obtained composition, the composition was applied on a glass plate with a 150 μm applicator, and one day later, 60 ° gloss was measured. .

Evaluation of Storage Stability (Pot Life) The viscosity (cp) of the obtained composition was measured using a B-type viscometer (23 ° C.) at the initial stage and after storage at 50 ° C. for one month. . The state (appearance) of the liquid was visually observed.

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[Table 2]

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The curable resin composition of the present invention has a long pot life (pot life), can be made into one liquid, has no agglomerates, has good curability and gloss, and has a high viscosity. This is a drastically improved performance in comparison with the group-containing emulsion.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08F 30/08 C08F 130/08 C08F 230/08

Claims (7)

(57) [Claims] 1. A curable resin composition comprising a silyl group-containing polymer emulsion (A) represented by the following general formula (I), an organotin compound (B) and a mercapto group-containing compound (C). Embedded image (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. However, when each of R ¹ and X ¹ is 2 or more, they are the same or different. ) 2. A polymer having a silyl group represented by the general formula (I), wherein the vinyl monomer having an alkoxysilyl group is 1 to 30% by weight, and a hydrophilic vinyl monomer having a polyoxyethylene chain. An emulsion copolymer obtained by copolymerizing a polymerization component comprising 0.1 to 10% by weight and a balance of another vinyl monomer using an anionic surfactant having a polyoxyethylene chain. 2. The curable resin composition according to 1. 3. The curable resin composition according to claim 1, wherein the mercapto group-containing compound as the component (C) is n-dodecyl mercaptan. 4. The curable resin composition according to claim 1, wherein the mercapto group-containing compound as the component (C) is γ-mercaptopropyltrimethoxysilane. 5. An emulsion (A) of a polymer containing a silyl group represented by the general formula (I), comprising an alkyl methacrylate having an alkyl group having 4 or more carbon atoms and a cycloalkyl having a cycloalkyl group having 4 or more carbon atoms. One or more alkyl methacrylates are used in a total amount of 1
The curable resin composition according to claim 1, wherein the curable resin composition is obtained by copolymerizing at least 60 parts by weight with respect to 00 parts by weight. 6. The curable resin composition according to claim 1, wherein the organotin compound (B) and the mercapto group-containing compound (C) are emulsified in advance. 7. The curable resin composition according to claim 1, wherein the organotin compound as the component (B) and the mercapto group-containing compound as the component (C) are previously dissolved in a film-forming aid.