JPH05331408A - Curing composition for aqueous dispersion-type coating and its production - Google Patents

Abstract

PURPOSE:To obtain a curing composition for aqueous dispersion-type coating excellent in workability, water resistance, weatherability and durability, useful for the inner trimming and/or cladding for buildings automobiles, etc., by dispersion polymerization of a hydrolyzable silyl group-contg. vinyl copolymer in the presence of a specific water-soluble resin in an aqueous medium. CONSTITUTION:The composition can be obtained by dispersion polymerization, (A) in an aqueous medium in the presence of, as dispersion stabilizer, a water-soluble resin prepared by neutralizing with ammonia or an organic amine a vinyl copolymer having in one molecule hydrolyzable silyl functional group of the formula [R<1> is H or methyl; R<2> is CO-O(CH2)n (n is 1-10), phenylene, etc.; R3 is H, 1-10C alkyl, aryl, etc.; X is hydrolyzable group; a is 0-2] and carboxyl group, of (B) the above copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to various interior and exterior coatings, automobiles, household appliances, various coatings for plastics, etc.
In particular, the present invention relates to a curable composition for an aqueous dispersion type coating composition having a good coating film performance, which is used for coating requiring weather resistance and durability, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, from the viewpoint of pollution control and resource saving, conversion from organic solvent to water-soluble or water-dispersible resin. Is being attempted. However, the conventional aqueous dispersion type resin is produced by an emulsion polymerization method using an ionic or nonionic surfactant, and as a result, a coating formed by the influence of the surfactant used for the polymerization is formed. It has the drawbacks that the weather resistance, water resistance, and stain resistance of the film are poor, and the gloss of the coating film is inferior to that of the solvent system due to the difference in the film forming mechanism.

Various attempts have been proposed to improve this drawback. One of them is to use a water-soluble polymer compound such as a maleinized polybutadiene, a maleinized alkyd resin or a water-soluble acrylic resin as a dispersion stabilizer. Then, a polymerization reaction is performed in an aqueous medium to obtain a desired aqueous dispersion-type resin.

According to this method, the particle diameter of the resulting aqueous dispersion type resin is 0.1 μm or less, generally 0.02 to 0.0.
It is about 5 μm, which is significantly finer than the particles obtained by the conventional emulsion polymerization method of about 0.1 to 0.3 μm, and thus the gloss of the formed coating film is close to that of the solvent type. Has been obtained. Further, since the dispersion stabilizer for polymerization is a polymer compound and the resin produced during the polymerization has a strong interaction such as graft-bonding, an improvement effect is recognized in terms of water resistance and stain resistance.

On the other hand, while having the above-mentioned advantages, a resin using a maleinized polybutadiene or a maleinized alkyd resin as a dispersion stabilizer shows a peculiar aqueous solution behavior from the viewpoint of physical properties, and is practically suitable for coating workability and storage stability. However, it has a very limited range of uses. Further, when polymerizing a water-soluble acrylic resin as a dispersion stabilizer, there is a drawback that the polymerization stability is poor because the protective power of particles depends on the affinity of the dispersion resin and the produced polymer, and in order to overcome this drawback. It is necessary to introduce an unsaturated group into the side chain of the water-soluble acrylic resin and graft-polymerize it to increase the polymerization stability.

Further, since the water-soluble resin such as maleated polybutadiene, maleated alkyd resin, and water-soluble acrylic resin is used in a large amount as compared with the emulsifier used in ordinary emulsion polymerization, the water-dispersed resin composition thus produced contains The water-soluble component increases, and as a result, the water resistance of the coating film decreases. Furthermore, the weather resistance and the stain resistance are deteriorated.

To solve these problems, various methods such as graft polymerization of a water-soluble polymer and introduction of crosslinking reaction points have been adopted, but they have not been improved to a satisfactory level.

[0008]

Means and Actions for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have neutralized hydrolyzable silyl functional groups and carboxyl groups with amines as essential components. A water-soluble acrylic resin having both groups is used as a dispersion stabilizer, and a vinyl-based copolymer containing a hydrolyzable silyl group is dispersion-polymerized in an aqueous medium in the presence of the resin to obtain a stable and reactive aqueous solution. A dispersion type resin could be synthesized. To this aqueous dispersion-type resin, a solvent is added as a film-forming aid to accelerate the crosslinking reaction,
By adding a curing catalyst, it was possible to obtain a curable composition for an aqueous dispersion type coating which was excellent in weather resistance, water resistance, durability and workability. Thus, a curable composition for an aqueous dispersion type coating having excellent weather resistance, water resistance and stain resistance was found, and the present invention was completed. That is, the curable composition for aqueous dispersion-type coating material of the present invention is (A) a vinyl-based copolymer having both a hydrolyzable silyl functional group and a carboxyl group in one molecule, and is composed of ammonia or an organic amine compound. A water-soluble resin obtained by neutralization, (B) a hydrolyzable silyl group-containing vinyl copolymer which is dispersion-polymerized in an aqueous medium in the presence of the resin, using (A) as a dispersion stabilizer, and (C ) A solvent is blended.

The second aspect of the present invention is a method for producing a curable resin for an aqueous dispersion type coating composition, which is a vinyl-based copolymer having both a hydrolyzable silyl functional group and a carboxyl group in the molecule, such as ammonia or Dispersion polymerization of a hydrolyzable silyl group-containing vinyl copolymer (B) in an aqueous medium in the presence of the resin, using a water-soluble resin (A) obtained by neutralization with an organic amine compound as a dispersion stabilizer. Is a method characterized by.

Component (A) of the present invention, which is a vinyl-based copolymer containing a hydrolyzable silyl functional group and having a carboxyl group neutralized with an amine to be water-soluble, has a substantially vinyl-based main chain. It consists of a polymer chain and has at least one silicon atom bonded to the main chain and / or side chain with a hydrolyzable group in one molecule.
It is a copolymer having one, preferably 2 to 30, more preferably 2 to 10, and is generally obtained by copolymerizing a vinyl-based monomer and a hydrolyzable silyl group-containing monomer. The main chain or side chain of the copolymer may partially contain a urethane bond or a siloxane bond. In addition, in order to make the vinyl-based copolymer water-soluble, a vinyl-based monomer having a carboxyl group is added to
0 parts by weight (total amount of monomers is 100 parts by weight (hereinafter, simply referred to as "part")), preferably 2 to 25 parts, more preferably 3 to 15 parts by copolymerization, before polymerization, during polymerization or It may be neutralized with ammonia or an organic amine compound after the polymerization.

Examples of the hydrolyzable silyl group-containing vinyl monomer, which is an essential component of the water-soluble vinyl copolymer as the component (A), include those represented by the general formula:

[Chemical 3] (In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is —CO.
_{-O- (CH 2) n - (} n = 1~10), a phenylene group, (which may or may not be specifically included) alkenylene group or a single bond. R ³ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group and a thioalkoxy group. , A hydrolyzable group selected from amino groups, a is an integer of 0 to 2, and when X and R ³ bonded to Si are each 2 or more, they may be the same group or different groups. Good. ), Which is a monomer having a hydrolyzable silyl group and having a polymerizable carbon-carbon double bond, such as an alkoxysilyl group-containing vinyl monomer.

Specific examples of the alkoxysilyl group-containing vinyl monomer include, for example,

[Chemical 4]

[Chemical 5] Etc.

These hydrolyzable silyl group-containing monomers such as alkoxysilyl groups may be used either individually or in combination of two or more, preferably 1 to 50 parts, more preferably 2 to 20 parts. Copolymerization is preferable (100 parts of all monomers are used, the same applies hereinafter).

Examples of the carboxyl group-containing vinyl monomer which is another essential component of the water-soluble vinyl copolymer as the component (A) include, for example, acrylic acid, methacrylic acid, maleic acid and maleic anhydride. Α, β-ethylenically unsaturated carboxylic acids such as itaconic acid, itaconic anhydride, crotonic acid, fumaric acid and citraconic acid. Among these, acrylic acid and methacrylic acid are preferable in terms of polymerizability, water solubility, and function as a dispersant.

These carboxyl group-containing vinyl monomers may be used either individually or in combination of two or more.
Part is preferably copolymerized, more preferably 2 to 2
It is preferred that 5 parts are copolymerized, more preferably 3 to 15 parts.

There are no particular restrictions on the vinyl monomer that is copolymerized with these hydrolyzable silyl group-containing vinyl monomer and carboxyl group-containing vinyl monomer.
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, diester or half ester of unsaturated polycarboxylic acid and a straight or branched alcohol having 1 to 20 carbon atoms. Unsaturated polycarboxylic acid ester; aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, chlorostyrene, styrenesulfonic acid, 4-hydroxystyrene, vinyltoluene; vinyl acetate Vinyl esters such as vinyl propionate and diallyl phthalate, and allyl compounds; vinyl compounds containing nitrile groups such as (meth) acrylonitrile; vinyl compounds containing epoxy groups such as glycidyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate,
Basic nitrogen atom-containing vinyl compounds such as vinyl pyridine and aminoethyl vinyl ether; (meth) acrylamide, itaconic acid diamide, α-ethyl (meth) acrylamide, crotonamide, maleic acid diamide, fumaric acid diamide, N-vinylpyrrolidone, N Amide group-containing vinyl compounds such as butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, Aronix 5700 (manufactured by Toagosei Co., Ltd.), Placc
elFA-1, PlaccelFA-4, Placce
hydroxyl group-containing vinyl compounds such as 1FM-1, Placcel FM-4 (all manufactured by Daicel Chemical Industries, Ltd.); α, β-, such as hydroxyalkyl esters of (meth) acrylic acid.
Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids and phosphoric acid ester group-containing vinyl compounds or vinyl compounds such as (meth) acrylates containing urethane bond or siloxane bond; AS- which is a micromonomer manufactured by Toagosei Co., Ltd. 6, AN-6, AA-6, AB-
6, compounds such as AK-5; vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene,
Other vinyl compounds such as butadiene, N-vinyl imidazole, vinyl sulfonic acid and the like can be mentioned.

The above-mentioned monomers can be copolymerized by any of the commonly used polymerization methods, such as emulsion polymerization method, suspension polymerization method and solution polymerization method. The solution polymerization method is preferably used because of the ease of operation.

In carrying out the solution polymerization, the solvent used is not particularly limited as long as it can dissolve the copolymerization reaction product, but the polymer is dissolved in an aqueous medium and used as a dispersion stabilizer for the polymerization. At this time, it is preferable to use a water-soluble organic solvent because the operation is easier if the solvent does not have to be recovered. Alternatively, the solvent may be recovered and the isolated copolymerization may be used as a dispersion stabilizer for polymerization.

As the solvent to be used, a linear and / or branched alcohol solvent having 1 to 10 carbon atoms, HO
- _{(CH 2} CH ₂₎ represented by n -OR ⁴ (poly) ethylene glycol monoalkyl ether ^{(R 4} is C 1 -C
An alkyl group having 10 to 10 straight and / or branched, n
Is an integer of from 1 to _{^{5), R 5 CO-O- (}} CH 2 CH 2) n
(Poly) ethylene glycol ether ester represented by —OR ⁴ (R ⁴ is a linear and / or branched alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 5 and R ⁵ is 1 to 1 carbon atoms. 10 linear and (or) an alkyl group having a _{branch), HO- (CH 2 CH 2} CH 2) represented by n -OR ⁴ (poly) propylene glycol monoalkyl ether ^{(R 4} is from 1 to 10 carbon atoms An alkyl group having a straight chain and / or a branch, n is an integer of 1 to 5), R ⁵ CO—O
_{- (CH 2 CH 2 CH 2} ) n represented by -OR ⁴ (poly) propylene glycol ether ester ^{(R 4} is an alkyl group having a straight chain and (or) branched having 1 to 10 carbon atoms, n represents 1 to 5 integer, R ⁵ can be used an alkyl group) or the like having a straight-chain and (or) branched having 1 to 10 carbon atoms.
Specifically, for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol,
Alcohols such as n-butyl alcohol, isobutyl alcohol, hexyl alcohol and octyl alcohol;
Cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl Ethers such as ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol isobutyl ether; butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, ether esters, such as tripropylene glycol mono isobutyl ether acetate, and the like.

The polymerization initiator is not particularly limited as long as it is a commonly used initiator, and redox type initiators, azo type initiators, and peroxides may be used. Among these initiators, azo-based initiators are preferable, and specific examples include:
For example, azo-based nitriles such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobismethylbutyronitrile, azobisdimethylmethoxyvaleronitrile; V-5
Azoamidines such as 0, VA-041, VA-044, VA-061 (all manufactured by Wako Pure Chemical Industries, Ltd.); VA-08
0, VA-086, VA-088 (above Wako Pure Chemical Industries, Ltd.
Azoamides; azodi-tert-octane,
Azoalkyls such as azodi-tert-butane; cyanopropylazoformamide, azobiscyanovaleroleic acid, dimethylazobismethylpropionate, azobishydroxymethylpropionitrile and the like.
Also, if necessary, n-dodecyl mercaptan, t-
Dodecyl mercaptan, n-butyl mercaptan, γ-
Mercaptopropyltrimethoxysilane, .gamma.-mercaptopropyl triethoxysilane, .gamma.-mercaptopropyl methyl dimethoxy _{silane, (CH 3 O) 3 Si} -S-
_{S-Si (OCH 3) 3} , (CH 3 O) 3 Si- (CH
_{2) 3 -S-S- (CH} 2) 3 -Si (OCH 3) 3,
_{(CH 3 O) 3 Si-} S 8 -Si (OCH 3) using a chain transfer agent ₃ or the like may be the molecular weight regulator.

Regarding the polymerization conditions, it is usually 40 to 170.
Polymerization at a polymerization temperature of 50 ° C., preferably 50 to 150 ° C. for 3 to 24 hours, preferably 4 to 20 hours is desirable.

When carrying out aqueous dispersion polymerization using the copolymer thus obtained, it is necessary to first dissolve the polymer in an aqueous medium. The aqueous medium here means water or water in which a water-soluble organic solvent is dissolved. Water solubilization can be achieved by neutralizing the carboxyl group with ammonia or an organic amine compound. Specific examples of the amine compound used for the neutralization treatment include:
For example, ammonia, methylamine, dimethylamine,
Examples thereof include trimethylamine, ethylamine, diethylamine, triethylamine, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine and the like. The amount of the amine compound used for neutralization may be less than the equivalent of the carboxyl group or may be used in an equivalent amount or in a small excess, but it is preferable to use the equivalent amount or a small excess, if anything, polymerization rate, polymerization stability, hydrolysis From the viewpoint of the stability of the functional silyl functional group, pH 6 to 1 is obtained by neutralization.
The pH is preferably adjusted to 0, preferably 7 to 9.

Further, upon water-solubilization, the copolymer may be mixed with an aqueous medium while being dissolved in a water-soluble organic solvent, or the polymer may be recovered by a method such as distillation or reprecipitation and then added to the aqueous medium. You can add it.

The thus obtained copolymer is used as a dispersion stabilizer to carry out a polymerization reaction in an aqueous medium to obtain the desired curable composition for an aqueous dispersion type coating composition. Regarding the polymerization operation, a usual emulsion polymerization polymerization operation can be adopted.

Examples of the hydrolyzable silyl group-containing vinyl monomer, which is an essential component of the hydrolyzable silyl group-containing vinyl copolymer as the component (B), include those represented by the general formula:

[Chemical 6] (In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is —CO.
_{-O- (CH 2) n - (} n = 1~10), a phenylene group, (may not be included in particular) alkenylene group or a single bond. R ³ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group and a thioalkoxy group. , A hydrolyzable group selected from an amino group, and a is 0 to 2
When X and R ³ bonded to Si are each 2 or more, they may be the same group or different groups. ), Which is a monomer having a hydrolyzable silyl group and having a polymerizable carbon-carbon double bond, such as an alkoxysilyl group-containing vinyl monomer.

Specific examples of the alkoxysilyl group-containing vinyl monomer include those described in the detailed description of the water-soluble vinyl copolymer as the component (A).

There is no particular limitation on the vinyl monomer copolymerizable with the hydrolyzable silyl group-containing vinyl monomer and the carboxyl group-containing vinyl monomer, and a specific example of the vinyl monomer is the component (A). Any of those described in the detailed description of the water-soluble vinyl-based copolymer can be used. In addition to that, for example, a polymer produced by using a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, and triallyl cyanurate has a crosslinked structure. It is also possible to have one.

These monomers can be appropriately selected from one type or two or more types depending on the quality of the final product.

The amount of the water-soluble resin used as the dispersion stabilizer is 1/20 to 1 / in weight ratio with respect to the monomers to be polymerized.
The ratio is 0.3, preferably 1/10 to 1/1.

Water is usually used as the aqueous medium in which the dispersion stabilizer is dissolved. However, when the dispersant resin is used in a state of being dissolved in an organic solvent, as a result, an amount of the organic solvent corresponding to the amount of the dispersant resin is used. Will be included in the system. In addition to the above, it is also possible to add a water-soluble organic solvent in an amount of ½ or less with respect to water for the purpose of increasing the solubility of the dispersant resin.

As the polymerization initiator, any of water-soluble or oil-soluble peroxides, azo initiators, redox initiators and the like which are usually used in radical polymerization can be used, but water-soluble initiators are preferable. used. Specific examples of the water-soluble initiator include, for example, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, and tert.
-Butyl peroxide, cumene hydroperoxide, peroxides such as azodiisobutyric acid diamide, persulfates, and azo compounds and redox initiators activated by a water-soluble reducing agent in the aqueous phase.

The amount of such an initiator used is 0.01 to 10 parts, preferably 0.05 to 5 parts, based on the weight of the monomer.

The ionic property usually used for emulsion polymerization,
It is possible to use a nonionic surfactant together, but it is preferable to use only a small amount from the viewpoint of water resistance, weather resistance and the like. Specific examples of the ionic and nonionic surfactants include potassium n-dodecyl sulfonate, sodium isooctylbenzene sulfonate, sodium laurate, polyethylene glycol nonyl phenyl ether and the like.

The polymerization conditions are such that the polymerization temperature is 30 to 90 ° C., preferably 40 to 80 ° C.

The solid content concentration in the aqueous dispersion type resin composition is
According to the method of the present invention, the range is 20 to 70% by weight.

When the solid content concentration exceeds 70% by weight, the viscosity of the system remarkably increases and it is difficult to remove the heat generated by the polymerization reaction, and it takes a long time to take it out from the polymerization machine. Occurs. In addition, the solid content concentration is 20
When the amount is less than 10% by weight, no problem occurs in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is extremely disadvantageous from an economical point of view, and is 20 from the viewpoint of application. If the concentration is less than wt%, the film thickness of the coating film becomes thin, resulting in performance deterioration and disadvantage in coating workability.

The aqueous dispersion-type resin composition thus obtained is composed of ultrafine particles having a particle size of 0.02 to 0.1 μm, and as a result, has an excellent film forming ability.

The addition of the solvent which is the component (C) used in the present invention is mainly aimed at assisting the film formation of the aqueous dispersion type resin composition, and the addition of a trace amount of stability of the composition and the coating film Solvents that act effectively on the formation and development of coating properties are preferred. The amount of such a solvent added is 0.1 to 15 parts, preferably 0.5 to 1 with respect to the aqueous dispersion type resin composition.
It is 0. Specific examples of such a solvent include, for example,
Cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl Ethers such as ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol isobutyl ether; butyl cellosolve acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol Monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, ether esters, such as tripropylene glycol mono isobutyl ether acetate, and the like.

The solvent as the component (C) may be added during the polymerization of the aqueous dispersion type resin, or immediately after the completion of the polymerization or after cooling.

The curable composition for water-dispersed paints thus obtained may or may not use a curing catalyst, but a catalyst may be used in order to accelerate the curability and bring out the required physical properties. Can be used. Specific examples of such a curing catalyst include, for example, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, organotin compounds such as tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl. Phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate,
Phosphoric acid or phosphoric acid esters such as diethyl phosphate, dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, acrylic glycidyl ether, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane,
Addition of (3,4-epoxycyclohexyl) ethyltrimethoxysilane, an epoxy compound such as Cardura (E) manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 828, Epicoat 1001 and phosphoric acid and / or acidic monophosphate ester Reaction product; Organic titanate compound; Organoaluminum compound; Organozirconium compound; Maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid, their acid anhydrides, Acidic compounds such as paratoluenesulfonic acid; amines such as hexylamine, di-2-ethylhexylamine, N, N-dimethyldodecylamine, dodecylamine; mixtures or reaction products of these amines and acidic phosphoric acid ester; water Al such as sodium oxide and potassium hydroxide Li compound, and the like.

Among these curing catalysts, organotin compounds,
A mixture or reaction product of an acidic phosphoric acid ester and an amine,
Saturated or unsaturated polycarboxylic acid or its anhydride,
A reactive silicon compound, an organic titanate compound, an organic aluminum compound or a mixture thereof is preferable because of its high activity. More preferably, it is an organic tin compound, an acidic phosphoric acid ester, or a mixture or reaction product of an acidic phosphoric acid ester and an amine.

Such a curing catalyst may be used alone or in combination of two or more kinds. The amount of the curing catalyst used is not particularly limited, but is usually 0.01 to 20 parts, more preferably 0.1 to 10 parts, relative to 100 parts of the solid content of the curable composition for aqueous dispersion type coating material. . When the amount of the curing catalyst used exceeds 20 parts, the appearance of the coating film tends to deteriorate.

[0043]

EXAMPLES Next, a method for preparing the composition of the present invention and a method for producing the composition will be described based on examples.

Production Example 1 (Combination of Water-Soluble Vinyl Copolymer)
Adult) stirrer, thermometer, reflux condenser, isopropyl alcohol 60 to a reaction vessel equipped with a nitrogen gas inlet tube and a dropping funnel
After charging up parts and raising the temperature to 75 ° C. while introducing nitrogen gas, the mixture (a) having the following composition was added dropwise at a constant rate over 5 hours using a dropping funnel.

[Mixture (a)] Acrylic acid 10 parts Butyl acrylate 20 parts Methyl methacrylate 70 parts 2,2′-Azobis-2,4-dimethylvaleronitrile 3 parts After the addition of the mixture (a) is completed, 75 ° C. After aging for 2 hours at room temperature, 8.5 parts of ammonia was added and then cooled, and isopropyl alcohol was added to the resin solution to adjust the solid content to 60%.
% Was prepared. The characteristics of the obtained resin solution (1) are shown in Table 1.

Production Example 2 (containing water-soluble hydrolyzable silyl group)
Synthesis of vinyl- containing copolymer (A)) Isopropyl alcohol 60 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
Then, the temperature was raised to 75 ° C. while introducing nitrogen gas, and then the mixture (b) having the following composition was added dropwise at a constant rate over 5 hours using a dropping funnel.

[Mixture (b)] Acrylic acid 10 parts Butyl acrylate 20 parts Methyl methacrylate 65 parts γ-methacryloxypropyltrimethoxysilane 5 parts 2,2′-azobis-2,4-dimethylvaleronitrile 3 parts Mixture After the addition of (b) was completed, the mixture was aged at 75 ° C. for 2 hours, 8.5 parts of ammonia was added and then cooled, and isopropyl alcohol was added to the resin solution to adjust the solid content concentration to 60.
% Was prepared. The characteristics of the obtained resin solution (2) are shown in Table 1.

Production Example 3 (containing water-soluble hydrolyzable silyl group)
Synthesis of vinyl- containing copolymer (A)) Isopropyl alcohol 60 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel.
After the temperature of the mixture was increased to 75 ° C. while introducing nitrogen gas, a mixture (c) having the following composition was added dropwise at a constant rate over 5 hours using a dropping funnel.

[Mixture (c)] Acrylic acid 10 parts Butyl acrylate 20 parts Methyl methacrylate 60 parts γ-methacryloxypropyltrimethoxysilane 10 parts 2,2′-azobis-2,4-dimethylvaleronitrile 3 parts Mixture After the dropping of (c) was completed, the mixture was aged at 75 ° C. for 2 hours, 8.5 parts of ammonia was added and then cooled, and isopropyl alcohol was added to the resin solution to adjust the solid content concentration to 60.
% Was prepared. The characteristics of the obtained resin solution (3) are shown in Table 1.

Production Example 4 (of aqueous dispersion type vinyl copolymer)
(Synthesis) 93 parts of deionized water was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solution (1) obtained in (Production Example 1) was further added to 18.5.
After parts were added and sufficiently stirred to dissolve, the temperature was raised to 70 ° C. while introducing nitrogen gas, and then the mixture (d) having the following composition was added dropwise at a constant rate over 5 hours by a dropping funnel.

[Mixture (d)] Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 60 parts Cumene hydroperoxide 1 part After the mixture (d) has been added dropwise, the mixture is aged at 70 ° C. for 2 hours and then cooled to obtain an aqueous dispersion. Deionized water was added to the liquid to prepare a solid content concentration of 50%. The properties of the obtained aqueous dispersion (1) are shown in Table 2.

Production Example 5 (Aqueous dispersion type hydrolyzable silyl group
Synthesis of vinyl-containing copolymer (B)) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel were charged with 93 parts of deionized water,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solution (1) obtained in (Production Example 1) was further added to 18.5.
After parts were added and sufficiently stirred to dissolve, the temperature was raised to 70 ° C. while introducing nitrogen gas, and then the mixture (e) having the following composition was added dropwise at a constant rate over 5 hours by a dropping funnel.

[Mixture (e)] Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 55 parts γ-methacryloxypropyltrimethoxysilane 5 parts Cumene hydroperoxide 1 part At 70 ° C. after the addition of the mixture (e) is completed. After aging for 2 hours, the mixture was cooled, and deionized water was added to the aqueous dispersion to prepare a solid content concentration of 50%. The characteristics of the obtained aqueous dispersion (2) are shown in Table 2.

Production Example 6 (Aqueous dispersion type hydrolyzable silyl group
Synthesis of vinyl-containing copolymer (B)) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel were charged with 93 parts of deionized water,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solution (1) obtained in (Production Example 1) was further added to 18.5.
After parts were added and sufficiently stirred to dissolve, the temperature was raised to 70 ° C. while introducing nitrogen gas, and then a mixture (f) having the following composition was added dropwise at a constant rate over 5 hours by a dropping funnel.

[Mixture (f)] Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 50 parts γ-methacryloxypropyltrimethoxysilane 10 parts Cumene hydroperoxide 1 part At 70 ° C. after the addition of the mixture (f) is completed. After aging for 2 hours, the mixture was cooled, and deionized water was added to the aqueous dispersion to prepare a solid content concentration of 50%. The properties of the obtained aqueous dispersion (3) are shown in Table 2.

Production Example 7 (Aqueous dispersion type hydrolyzable silyl group
Synthesis of vinyl-containing copolymer (B)) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel were charged with 93 parts of deionized water,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solution (2) obtained in (Production Example 2) was further added to 18.5.
After parts were added and sufficiently stirred to dissolve, the temperature was raised to 70 ° C. while introducing nitrogen gas, and then a mixture (g) having the following composition was added dropwise at a constant rate over 5 hours with a dropping funnel.

[Mixture (g)] Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 55 parts γ-methacryloxypropyltrimethoxysilane 5 parts Cumene hydroperoxide 1 part At 70 ° C. after the addition of the mixture (g) is completed. After aging for 2 hours, the mixture was cooled, and deionized water was added to the aqueous dispersion to prepare a solid content concentration of 50%. The properties of the obtained aqueous dispersion (4) are shown in Table 3.

Production Example 8 (Aqueous dispersion type hydrolyzable silyl group
Synthesis of vinyl-containing copolymer (B)) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel were charged with 93 parts of deionized water,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solution (2) obtained in (Production Example 2) was further added to 18.5.
After parts were added and sufficiently stirred to dissolve, the temperature was raised to 70 ° C. while introducing nitrogen gas, and then a mixture (h) having the following composition was added dropwise at a constant rate over 5 hours by a dropping funnel.

[Mixture (h)] Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 50 parts γ-methacryloxypropyltrimethoxysilane 10 parts Cumene hydroperoxide 1 part At 70 ° C. after the addition of the mixture (h) is completed. After aging for 2 hours, the mixture was cooled, and deionized water was added to the aqueous dispersion to prepare a solid content concentration of 50%. The properties of the obtained aqueous dispersion (5) are shown in Table 3.

Production Example 9 (Aqueous dispersion type hydrolyzable silyl group
Synthesis of vinyl-containing copolymer (B)) Stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel were charged with 93 parts of deionized water,
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solution (3) obtained in (Production Example 3) was further added to 18.5.
After parts were added and sufficiently stirred to dissolve, the temperature was raised to 70 ° C. while introducing nitrogen gas, and then the mixture (i) having the following composition was added dropwise at a constant rate over 5 hours using a dropping funnel.

[Mixture (i)] Styrene 20 parts Butyl acrylate 20 parts Methyl methacrylate 50 parts γ-methacryloxypropyltrimethoxysilane 10 parts Cumene hydroperoxide 1 part At 70 ° C. after the addition of the mixture (i) is completed. After aging for 2 hours, the mixture was cooled, and deionized water was added to the aqueous dispersion to prepare a solid content concentration of 50%. The properties of the obtained aqueous dispersion (6) are shown in Table 3.

[0062]

[Table 1]

[Table 2]

[Table 3]

Comparative Example 1 Aqueous dispersion type vinyl copolymer 100 obtained in Production Example 4
3 parts of diethylene glycol monobutyl ether acetate was added to each part, mixed well and then coated to prepare a film and a test plate.

Examples 1 to 5 To 100 parts of the aqueous dispersion-type hydrolyzable silyl group-containing vinyl copolymer (B) obtained in Production Examples 5 to 9, 3 parts of diethylene glycol monobutyl ether acetate was added and mixed well. After painting, a film and a test board were prepared.

Example 6 To 100 parts of the aqueous dispersion-type hydrolyzable silyl group-containing vinyl copolymer (B) obtained in Production Example 7, 3 parts of diethylene glycol monobutyl ether acetate and 3 parts of dibutyltin dilaurate were added, After mixing well, coating was performed to prepare a film and a test plate.

Example 7 To 100 parts of the aqueous dispersion-type hydrolyzable silyl group-containing vinyl copolymer (B) obtained in Production Example 7, 3 parts of diethylene glycol monobutyl ether acetate and 20 parts of dibutyltin dilaurate were added, After mixing well, coating was performed to prepare a film and a test plate.

For Comparative Example 1 and Examples 1 to 7, film forming properties, gloss, water resistance, weather resistance, alkali resistance, acid resistance,
The gel fraction was evaluated and is shown in Tables 4-6.

[0068]

[Table 4]

[Table 5]

[Table 6]

From the evaluation results of Tables 4 to 6, the composition of the present invention is a composition excellent in durability such as water resistance, weather resistance, alkali resistance, and acid resistance, and is superior in performance to conventional water-based paints. It can be seen that it is a greatly improved one.

[0070]

EFFECTS OF THE INVENTION Conventional water-based paints are not always at satisfactory levels in terms of water resistance, weather resistance and durability due to various factors, but the curable composition for water-based dispersion paints of the present invention is , By having reactivity, water resistance, weather resistance,
It has excellent durability and workability.

Claims (6)

[Claims] 1. A water-soluble resin obtained by neutralizing (A) a vinyl-based copolymer having both a hydrolyzable silyl functional group and a carboxyl group in one molecule and neutralized with ammonia or an organic amine compound. B) An aqueous dispersion type in which (A) is used as a dispersion stabilizer, and a hydrolyzable silyl group-containing vinyl copolymer dispersed and polymerized in an aqueous medium in the presence of the resin, and (C) a solvent are blended. Curable composition for paints. 2. A vinyl copolymer having both a hydrolyzable silyl functional group and a carboxyl group in one molecule, wherein a water-soluble resin (A) obtained by neutralizing with ammonia or an organic amine compound is dispersed. A method for producing a curable resin for an aqueous dispersion type coating composition, comprising using as a stabilizer, dispersion-polymerizing a hydrolyzable silyl group-containing vinyl copolymer (B) in an aqueous medium in the presence of the resin. 3. The vinyl copolymer as the component (A) has the general formula: (In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is —CO.
_{-O- (CH 2) n - (} n = 1~10), a phenylene group, an alkenylene group or a single bond. R ³ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group and a thioalkoxy group. , A hydrolyzable group selected from amino groups, a is an integer of 0 to 2, and when X and R ³ bonded to Si are each 2 or more, they may be the same group or different groups. Good. ) A carboxyl group having a hydrolyzable silyl group and containing at least one unsaturated monomer having a polymerizable carbon-carbon double bond in at least one molecule, and used for imparting water solubility. The curability for an aqueous dispersion type coating composition according to claim 1, which is a vinyl-based copolymer containing at least 2 parts by weight of the α, β-ethylenically unsaturated monomer (100 parts by weight of all monomers). Composition. 4. The vinyl copolymer as the component (B) has the general formula: (In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is —CO.
_{-O- (CH 2) n - (} n = 1~10), a phenylene group, an alkenylene group or a single bond. R ³ is a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group and a thioalkoxy group. , A hydrolyzable group selected from amino groups, a is an integer of 0 to 2, and when X and R ³ bonded to Si are each 2 or more, they may be the same group or different groups. Good. 2. A vinyl-based copolymer having a hydrolyzable silyl group represented by the formula (1) and containing at least one unsaturated monomer having a polymerizable carbon-carbon double bond in at least one molecule. Curable composition for aqueous dispersion type paint. 5. The curable composition for an aqueous dispersion type coating composition according to claim 1, wherein the solvent as the component (C) has water solubility like alcohols. 6. When a curing catalyst is added, the curing catalyst is
Organic tin compounds, acidic phosphoric acid esters, mixtures or reactants of acidic phosphoric acid esters and amines, saturated or unsaturated polyvalent carboxylic acids, anhydrides of saturated or unsaturated polyvalent carboxylic acids, reactive silicon compounds, organic titanate compounds The curable composition for aqueous dispersion-type coatings according to claim 1, which is an organic zirconium compound, an organic aluminum compound, or a mixture thereof.