JP3357929B2 - 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 a curable resin composition and, more particularly, to imparting excellent coating performance to interior and exterior buildings, automobiles, and household appliances for which weather resistance and durability are required. And a curable resin composition that can be used.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, attempts have been made to switch from using organic solvents to aqueous ones from the viewpoint of pollution control and resource saving. I have.

[0003] However, a water-dispersible resin is generally used as a conventional water-soluble resin. However, this water-dispersible resin does not have a crosslinkable functional group, and as a result, it is difficult to obtain a water-soluble resin during emulsion polymerization. Is strongly affected by the surfactant used in the coating, and the physical properties such as weather resistance, water resistance, and stain resistance of the cured product (coating film) formed in comparison with those using an organic solvent are significantly deteriorated. was there.

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. An application of a method of curing using a tin compound to a paint has been proposed (Japanese Patent Laid-Open No. Hei 3-
No. 227312).

However, when an organic tin compound is added to an emulsion and stored, agglomerates are liable to be generated, and during the storage, curing tends to proceed and the film-forming property tends to decrease.
It has proved impossible to use in liquids. Also,
Curing may not proceed sufficiently or may proceed unevenly, resulting in a decrease in gloss.

Accordingly, the present inventor has conducted intensive studies in view of the above-mentioned prior art, and as a result, the use of a water-soluble compound, which is a mixture or a reaction product of a water-soluble phosphate ester and an amine, as a curing agent makes it possible to form one liquid. It was found that the film-forming properties did not deteriorate even after storage, and the present invention was completed.

[0007]

The curable resin composition of the present invention has the general formula

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. )), An emulsion (A) containing a polymer having a silyl group (hereinafter, referred to as “silyl group-containing polymer” or “polymer (a)”), and a water-soluble acidic phosphate ester and an amine. Or a water-soluble compound (B) which is a reactant.

[0008] The silyl group-containing polymer for obtaining the emulsion (A) used in the present invention is not particularly limited. For example, epoxy resins and polyester resins containing a silyl group represented by the above general formula (I) , Polyether-based resins, acrylic resins, fluororesins, etc., among these, the coating film formed using the curable resin composition obtained is excellent in weather resistance and chemical resistance, and resin Acrylic resins are preferred because of their wide design and low cost.

The method for preparing the polymer (a) is not particularly limited. For example, a vinyl monomer containing a silyl group represented by the above general formula (I) (hereinafter referred to as monomer (a)
-1)) and the method of polymerizing another vinyl monomer copolymerizable therewith (hereinafter, referred to as monomer (a-2)) can easily obtain the polymer (a). Is preferred.

[0010] 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.

Embedded image General formula (II)

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

[0012]

Embedded image General formula (III)

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

[0013]

Embedded image General formula (IV)

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

[0014]

Embedded image General formula (V)

Embedded image (In the formula, R ¹ , R ² , R ³ , a and n are the same as described above.)
A compound represented by the formula:

[0015]

Embedded image General formula (VI)

Embedded image (In the formula, R ¹ , R ² , R ³ , a and n are the same as described above.)
A compound represented by the formula:

[0016]

Embedded image General formula (VII)

Embedded image (In the formula, R ¹ , R ² , R ³ , a and n are the same as described above.)
A compound represented by the formula:

[0017]

Embedded image General formula (VIII)

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

[0018]

Embedded image General formula (IX)

Embedded image (In the formula, R ¹ , R ² , R ³ , a and n are the same as described above.)
A compound represented by the formula:

[0019]

Embedded image General formula (X)

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:

[0020]

Embedded image General formula (XI)

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. And the like.

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
(The above are manufactured by NOF Corporation), hydroxyl-containing vinyl monomers such as hydroxyl-containing 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-
Blenmer 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 to 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
-Silyl is obtained by copolymerizing an alkyl group having 4 or more carbon atoms such as butyl methacrylate and cyclohexyl methacrylate or a methacrylate having a cycloalkyl group in an amount of 60 parts or more based on 100 parts by weight of the total amount of the polymerization components (hereinafter simply referred to as "parts"). The stability of the group 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. The number of oxyethylene repeats in the chain of the hydrophilic monomer is not particularly limited, but is preferably 3 to 30.

When such a hydrophilic monomer having a polyoxyethylene chain is used, the amount of the polymerizable component is 100%.
It is preferable to adjust the amount to be 0.1 to 10 parts with respect to the part. 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 are reduced. When the amount exceeds 10 parts, the coating film tends to be softened and stain tends to adhere.

In the present invention, as the monomer (a-2), for example, a monomer having two or more polymerizable unsaturated double bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate, etc. 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.
5 parts, that is, the compounding 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 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-
The polymer (a) obtained by using an alkoxysilyl group-containing vinyl monomer as 1) and a hydrophilic vinyl monomer having a polyoxyethylene chain as the monomer (a-2) is preferable. Among them, 1 to 30% by weight, preferably 2 to 25% by weight of an alkoxysilyl group-containing vinyl monomer, 0.1 to 10% by weight, preferably 0.1 to 10% by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain. 5-10% by weight
And an emulsion copolymer obtained by copolymerizing a polymerization component composed of the remaining vinyl monomer, and the stability of the alkoxysilyl group, the mechanical stability of the emulsion (A), and the obtained resin composition. Particularly preferred is that the formed coating film has excellent water resistance and gloss.

The monomer (a-1) and the monomer (a-
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 invention, a monomer dropping polymerization method and an emulsion monomer dropping polymerization method are particularly preferable for securing 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, a reactive surfactant having a polymerizable double bond in one molecule can be used as an emulsifier, and in particular, a reactive surfactant having a polyoxyethylene group in a molecule is used. In this case, the water resistance of the coating film formed using the obtained curable 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-mentioned 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, 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 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 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 resin obtained by introducing a silyl group represented by the above general formula (I) into a water-soluble resin may be used.

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, the polymerization may be difficult to proceed, and if the amount exceeds 10 parts, the molecular weight of the resulting polymer decreases, and the coating film formed using the obtained resin composition Durability 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 with respect to 100 parts of the total amount of the polymerization components.
Parts, preferably 0.001 to 0.5 parts.

The viscosity of the thus obtained silyl group-containing polymer is preferably from 10 to 40 cp at a solid content of 40% by weight.

To the polymer (a), for example, a desired amount of deionized water or the like is added to disperse the polymer (a) to obtain an emulsion (A).

The solid content of the resin in the emulsion (A) is preferably adjusted to 20 to 70% by weight, more preferably 30 to 60% by weight. When the resin solids concentration exceeds 70% by weight, the concentration of the system rises remarkably, so that it is difficult to remove the heat generated by the polymerization reaction, or it takes a long time to take out from the polymerization vessel. Tends to be necessary. Further, when the resin solid content 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 terms of economy, and in addition to coating, When the film is formed, the film thickness becomes thin, which tends to cause performance deterioration and 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 1.0 μm, it has excellent film forming ability.

Examples of the water-soluble acidic phosphate which is a component of the component (B) include [(CH ₃ ) ₂ CHO] ₂ P (O) (OH) and [(CH
₃ ) ₂ CHO] P (O) (OH) ₂ , (C ₂ H ₅ O) ₂
P (O) (OH), (C ₂ H ₅ O) P (O) (O
H) ₂ , (CH ₃ O) ₂ P (O) (OH), (CH
_{3 O) P (O) (} OH) 2, (C 4 H 9 O) P (O)
_{(OH) 2, (C 2} H 5 O) P (O) (OH) 2, (C
Such as _{3 H 7 O) P (O} ) (OH) 2 and the like.

As the amine, if a water-soluble compound is produced by combining with a water-soluble acidic phosphoric acid ester, an aliphatic primary amine, an aliphatic secondary amine or an aliphatic tertiary amine is used.
Any of amines, aliphatic unsaturated amines, alicyclic amines, and aromatic amines may be used.

Specific examples of the amine include, for example, ethylamine, propylamine, n-butylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, aniline, triethanolamine, 3-amino-1-propanol, ethanolamine, morpholine,
Examples include diethylenetriamine, N, N-diethylhydroxylamine, piperidine, pyridine, trimethylaminoethylpiperazine, N, N, N ', N'-tetramethylethylenediamine and the like. Among them, n-butylamine, piperidine, triethanolamine, 3-amino-
When a water-soluble amine such as 1-propanol is used, one-pack stability is increased, and film formability is improved.

The amount of the acidic phosphate and the amine is determined by adjusting the amount of the amine according to the acid value of the acidic phosphate so that the amine is neutralized by the acidic phosphate. Is preferred.

The water-soluble acidic phosphoric acid ester and the amine can be used at an arbitrary concentration, for example, by mixing in water. When a water-soluble acidic phosphate and an amine are mixed, the two react with each other, and heat generation may be observed. In the present invention, it is also possible to use the above-mentioned reactants.

The mixing ratio of the components (A) and (B) is such that the resin solid content of the emulsion (A) of the silyl group-containing polymer is 1%.
0.0001 to 5 parts of acid phosphate ester per 100 parts
It is preferable to add the component (B) so that 0 part, preferably 0.001 to 30 parts is used. If it is less than 0.0001 part, the curing activity is insufficient, and if it exceeds 50 parts, the water resistance and the like decrease.

In the present invention, for example, white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, etc., carbon black,
Pigments such as colored pigments such as red iron and cyanine blue, colloidal silica, plasticizers, solvents, dispersants, thickeners, additives such as defoamers, preservatives, ultraviolet absorbers, film-forming aids, and ethyl silicate And a silane coupling agent such as methyl silicate or a partial hydrolyzed condensate thereof, aminosilane, or epoxysilane can be added to the curable resin composition as needed.

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 acrylic paints, thermosetting acrylic paints such as acrylic melamine paints, alkyd paints, epoxy paints, fluororesin paints, and the like.
When these are blended, the weather resistance, acid resistance, solvent resistance, and the like of the coating film formed using the resin composition 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.

In the present invention, for example, a melamine resin, an isocyanate compound or the like may be added to the curable resin composition as a cross-linking agent to impart quick curability or the like.

The curable resin composition of the present invention is applied to an object to be coated by a usual 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 bases or clear on metallic bases, for direct application to metals such as aluminum and stainless steel, for direct application to glass, natural marble, It can be suitably used as a surface treatment agent, including a paint for direct application to stone materials such as granite, and a direct application to ceramic base materials such as slate, concrete and tile.

[0058]

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 4 (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 parts of sodium dodecylbenzenesulfonate were added. .9 parts (Production Example 1) or polyoxyethylene nonylphenyl ether sulfate (Newcol-560SN, manufactured by Nippon Emulsifier Co., Ltd.)
0.9 part (Production Example 2, Production Example 3 and Production Example 4), 1 part of polyoxyethylene nonylphenyl ether, 0.35 part of Rongalit, 0.5 part of ammonium acetate, 0.2 part of t-butyl hydroperoxide 20 parts of 158 parts of a mixture having the composition shown in Table 1 were added to perform 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 158 parts of the remaining 13
Eight parts of the mixture was dropped at a constant speed over a period of 3 hours using a dropping funnel.

Thereafter, post-polymerization was carried out for 1 hour, deionized water was added, and emulsions (A-1), (A-2), (A-3) and (A-3) having a resin solids concentration of 40% by weight were obtained. −
4) was obtained. In addition, the emulsion (A-1) was produced in Production Example 1.
The emulsion (A-2) corresponds to Production Example 2, the emulsion (A-3) corresponds to Production Example 3, and the emulsion (A-4) corresponds to Production Example 4.

[0062]

[Table 1]

Production Examples 5 to 8 (Preparation of Water-Soluble Compound [Curing Agent] (B)) An acidic phosphoric acid ester, an amine and a solvent (pure water, butyl acetate) were mixed in the proportions shown in [Table 2]. A curing agent comprising the water-soluble compound (B) was prepared. Some heat generation was observed during mixing, and after the temperature reached room temperature, the above-mentioned curing agent was added to the emulsion and used.

[0064]

[Table 2]

The curability, appearance (gloss), storage stability and film formability of the obtained curable resin composition were examined according to the following methods. The results are shown in [Table 3].

Evaluation of Curability A predetermined amount of the obtained composition was applied to a polyethylene sheet, left at room temperature for 14 days, and then all of the coating film formed on the polyethylene sheet was peeled off. The 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 Further, 0.4 parts of CS-12 (film-forming aid: manufactured by Chisso Corporation) was added to the obtained composition, and 150 μm
The applicator was used to apply the composition, and one day later, the 60 ° gloss was measured.

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

Evaluation of Film Formability Emulsion (A) was added to the composition stored at 50 ° C. for one month.
CS-12 (see above) was added in a ratio of 0.4 part to 10 parts, applied to a glass plate with a 150 μm applicator, stored at 5 ° C., and observed for cracking.

[0070]

[Table 3]

From the results shown in [Table 3], Examples 1 to 6
The curable resin composition obtained in the above is excellent in storage stability, curability and film formability, and the coating film formed using this resin composition may be excellent in gloss. Understand.

[0072]

The cold-curable resin composition of the present invention does not deteriorate in film formability even after long-term storage, has good curability without generation of aggregates, and can be formed into one liquid. The cured product has excellent gloss. That is, the performance is greatly improved as compared with the conventional emulsion containing an alkoxysilyl group. Therefore, it can be suitably used, for example, for painting interior and exterior of buildings, automobiles, home electric appliances and the like.

Continuation of front page (56) References JP-A-5-25354 (JP, A) JP-A-59-124954 (JP, A) JP-A-4-63816 (JP, A) JP-A-3-227312 (JP) , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (4)

(57) [Claims] 1. A compound of the general formula (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 two or more,
They are the same or different. )), A curable resin composition containing an emulsion (A) containing a polymer having a silyl group, and a water-soluble compound (B) which is a mixture or a reaction product of a water-soluble acidic phosphate and an amine. . 2. The polymer according to claim 1, wherein the polymer comprises 1 to 30% by weight of a vinyl monomer containing an alkoxysilyl group, 0.1 to 10% by weight of a hydrophilic vinyl monomer having a polyoxyethylene chain, and the balance of other monomers. The curable resin composition according to claim 1, wherein the curable resin composition is an emulsion copolymer obtained by copolymerizing a polymerization component comprising a vinyl monomer with an anionic surfactant containing a polyoxyethylene chain. 3. The polymer according to claim 1, wherein at least one selected from the group consisting of an alkyl methacrylate having an alkyl group having 4 or more C atoms and a cycloalkyl methacrylate having a cycloalkyl group having 4 or more C atoms is added to 100 parts by weight of the total polymerization components. The curable resin composition according to claim 1 or 2, which is a copolymer obtained by copolymerization using at least 60 parts by weight of the curable resin composition. 4. The curable resin composition according to claim 1, wherein the amine of the water-soluble compound (B) is a water-soluble amine.