JP3359355B2 - Aqueous dispersion type composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to, for example,
The present invention relates to an aqueous dispersion composition having good coating performance in various coatings such as automobiles, home appliances, and plastics, particularly in applications requiring weather resistance and durability.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, the use of organic solvents has been switched to water-soluble or water-dispersible resins from the viewpoint of pollution control and resource saving. Have been tried. However, the conventional aqueous dispersion type resin is manufactured by an emulsion polymerization method using an ionic or nonionic surfactant, and as a result, a coating film formed by the influence of the surfactant used for polymerization is formed. Had poor defects in weather resistance, water resistance and stain resistance, and inferior luster of the coating film compared to the solvent system due to the difference in film formation mechanism.

Various attempts have been made to improve this drawback, and one of them is to use a water-soluble polymer compound such as maleated polybutadiene, maleated alkyd resin, water-soluble acrylic resin, etc. as a dispersion stabilizer. And a method of performing a polymerization reaction in an aqueous medium, and a functional group capable of reacting with a silyl group in an aqueous solution of a water-soluble synthetic resin having a hydrolyzable silyl group in order to improve water resistance and weather resistance. A method for producing an emulsion polymer characterized by emulsion polymerization of a vinyl monomer having the following (JP-A-2-178301) has been proposed. However, when a trimethoxysilyl group or a triacetoxysilyl group is used as a hydrolyzable silyl group of a water-soluble synthetic resin, it tends to gel during polymerization of an emulsion polymer or during storage, and thus has a drawback in that it cannot be produced stably.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve these problems, and as a result, the general formula
The dispersion polymerization of a silyl group-containing water-soluble resin (A) and a silyl group-containing vinyl copolymer (B) represented by (I) is carried out in the presence of a metal compound (C) and / or an alcohol (D). The silyl group in the water-soluble resin (A) component and the vinyl copolymer (B) component is stabilized, and the dispersion polymerization of the (A) in an aqueous solution can be performed stably. The inventors have found that there is no problem with the storage stability of the obtained emulsion, and have completed the present invention. That is, the present invention provides a compound represented by the general formula (I):

[0005]

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(Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group, an aryl group, and an aralkyl group having 1 to 10 carbon atoms, and X is 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, a is 0, 1 or 2, and when X and R ¹ bonded to Si are two or more, respectively, they are different even if they are the same group. A vinyl group-containing copolymer (B) containing a silyl group represented by the general formula (I) in an aqueous solution of a water-soluble resin (A) having a silyl group represented by the following formula: The obtained aqueous dispersion type resin is mixed with an alkali metal compound, an alkaline earth metal compound, and a transition metal compound (however, the transition metal compound
Products are copper oxide, copper chloride, silver compounds, platinum compounds)
At least one compound (C) or an alkali metal compound, an alkaline earth metal compound, and a transition metal compound
(However, the transition metal compound is copper oxide, copper chloride, silverized
Compound, at least one compound of a platinum compound) (C) and an aqueous dispersion type composition comprising an alcohol (D) and to their preparation.

[0007]

EXAMPLES water-soluble resin having a silyl group used in the present invention [Polymerization of the water-soluble resin having a silyl group (A)] (A)
Are vinyl monomers having a silyl group represented by the general formula (I) (a), vinyl monomers having a water-soluble group or a group capable of forming a water-soluble group (b), and copolymers thereof. other vinyl monomer (c) a metal compound capable (C) or
Other metal compound (C) and copolymerized with A alcohol (D) presence are example by water, if necessary.

[Silyl group-containing vinyl monomer (a)] The silyl group-containing vinyl monomer (a) used for the silyl group-containing water-soluble resin (A) is 1
There is no particular limitation as long as the compound contains a polymerizable carbon-carbon double bond and a group represented by the general formula (I) in the molecule, and specific examples include, for example,

[0009]

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[0010]

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[0011]

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And the like.

These silyl group-containing vinyl monomers include:
One or two or more of them may be used in combination, and preferably 1 to 50 parts by weight, more preferably 2 to 20 parts by weight. If the copolymerization amount is less than 1 part by weight , water resistance and weather resistance are poor, and if it exceeds 50 parts by weight , the stability of the emulsion decreases.

[Vinyl monomer (b) having a water-soluble group or a group capable of forming a water-soluble group] A water-soluble group or a water-soluble group which is an essential component of the water-soluble resin (A) can be formed. Examples of the vinyl monomer (b) having a group include carboxyl group-containing vinyl monomers, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and croton. Acids having a polymerizable carbon-carbon double bond, such as α, β-ethylenically unsaturated carboxylic acids such as acid, fumaric acid, citraconic acid, styrenesulfonic acid, and vinylsulfonic acid; or
Salts thereof (alkali metal salts, ammonium salts, amine salts, etc.); acid anhydrides such as maleic anhydride or half esters thereof with linear or branched alcohols having 1 to 20 carbon atoms; dimethylaminoethyl (meth) (Meth) acrylates having an amino group such as acrylate, dimethylaminopropyl (meth) acrylate and diethylaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N , N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine, and hydrochloric acid and acetate thereof.

Among them, a method of polymerizing in an acid form and then neutralizing to form a salt is preferred from the viewpoint of stabilizing an alkoxysilyl group and the like. That is, it is preferable to use a carboxyl group-containing vinyl monomer, or an acid anhydride or a half ester. More preferably, a carboxyl group-containing vinyl monomer such as (meth) acrylic acid is used. These monomers may be one or two
More than one kind may be used in combination, preferably from 0.5 to 30 parts by weight, more preferably from 1 to 20 parts by weight. If the amount is less than 0.5 part by weight , it will not be sufficiently water-soluble, and if it exceeds 30 parts by weight , the stability of the emulsion will decrease.

[Copolymerizable Vinyl Monomer (c)] Other copolymerizable vinyl monomers (c) include:
There is no particular limitation, and vinyl monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; Ethyl (meth)
Vinyl compounds containing fluorine such as acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and β- (perfluorooctyl) ethyl (meth) acrylate Monomer; styrene,
Aromatic hydrocarbon vinyl monomers such as α-methylstyrene, chlorostyrene, 4-hydroxystyrene and vinyltoluene; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; and (meth) acrylonitrile Nitrile group-containing vinyl monomer; Epoxy group-containing vinyl monomer such as glycidyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, N -Methylol (meth) acrylamide, hydroxystyrene, Alonix 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), Placel
FA-1, PlacelFA-4, PlacelF
M-1, PlacelFM-4 (all manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-20, HP-10, HP-20
(Nippon Shokubai Chemical Co., Ltd.), Blemmer PP series, Blemmer PE series, Blemmer PEP series, Blemmer AP-400, Blemmer AE-350,
Hydroxyl-containing vinyl monomers such as Blemmer NKH-5050, Blemmer GLM (all manufactured by Nippon Oil & Fats Co., Ltd.), hydroxyl-containing vinyl-modified hydroxyalkyl vinyl monomers; and hydroxyalkyl esters of (meth) acrylic acid. hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids and vinyl compounds containing phosphate groups or vinyl compounds such as (meth) acrylates containing urethane or siloxane bonds; macromonomers manufactured by Toa Gosei Chemical Co., Ltd. AS-6, AN-
6, AA-6, AB-6, and AK-5; other vinyl monomers such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, N-vinylimidazole, and vinyl sulfonic acid And so on.

By copolymerizing a fluorine-containing vinyl monomer and a siloxane-containing vinyl monomer, water repellency is improved, and water resistance and durability are improved. By copolymerizing a hydrophilic monomer such as a hydroxyl group-containing vinyl monomer or polypropylene glycol methacrylate or polyethylene glycol monomethacrylate, the stability of the silyl group-containing water-soluble resin (A) increases, and acrylic acid, dimethyl The amount of the vinyl monomer (b) having a water-soluble group such as aminoethyl (meth) acrylate or a group capable of forming a water-soluble group can be reduced.

[Metal compound (C)] Alkali metal compound, alkaline earth metal compound and transition metal compound (provided that the transition metal compound is copper oxide,
The compound (C) selected from copper chloride, a silver compound and a platinum compound ) is represented by the general formula (I) contained in (A) by being present during the polymerization of the water-soluble resin (A). Stabilizes silyl groups. Specific examples of such metal compounds include lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride,
Examples include calcium acetate, calcium chloride, copper oxide, copper chloride, silver compounds, platinum compounds, and the like. Non-metallic compounds include borates such as triethyl borate.
Among them, potassium acetate is particularly effective.

The metal compound (C) is used in an amount of 1 × 10 4 based on a total of 100 parts by weight of the silyl group-containing water-soluble resin or monomer.
^It is desirable to add ^{-5 to} 0.5 part by weight, preferably 1 × 10 ^{-4 to} 0.1 part by weight. If the amount is less than 1 × 10 ⁻⁵ parts by weight, the stabilizing effect is not sufficient. If the amount is more than 0.5 parts by weight, the stability of the emulsion is reduced and aggregation occurs.

[Alcohol (D)] Alcohol (D)
Stabilizes the silyl group by an equilibrium reaction. Specific examples of alcohol include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-
Alcohols having 1 to 4 carbon atoms such as butanol are preferred, and methanol is particularly preferred.

The alcohol (D) is used in an amount of 1 part by weight or more, preferably 2 parts by weight or more, based on 100 parts by weight of the total of the silyl group-containing water-soluble resin or monomer. If it is less than 1 part by weight, the stabilizing effect is insufficient. Alcohol (D)
May be added at an early stage of the polymerization of the component (A), may be continuously added by mixing into a monomer mixture, or may be used as a polymerization solvent.

The polymerization of the silyl group-containing water-soluble resin (A) comprises
Usually carried out polymerization methods, that is, emulsion polymerization method, suspension polymerization method, solution polymerization method, etc., can be carried out by any method, but from the simplicity of operation, preferably the solution polymerization method is used .

In carrying out the solution polymerization, the solvent to be used is not particularly limited as long as it can dissolve the copolymerization reaction product, but the polymer is dissolved in an aqueous medium to be used as a dispersion stabilizer for polymerization. In such a case, it is preferable to use a water-soluble organic solvent because the operation is simpler without the need to collect the solvent. Alternatively, the solvent may be recovered, and polymerization may be performed using the isolated copolymer as a dispersion stabilizer.

As the solvent to be used, an alcoholic solvent having a straight and / or branched chain having 1 to 10 carbon atoms, HO
— (CH ₂ CH ₂ —O) _n R ² (poly) ethylene glycol monoalkyl ether (R ² has 1 carbon atom)
An alkyl group having up to 10 linear and / or branched, n
Is an integer of 1 to 5), R ³ CO—O— (CH ₂ CH ₂ —
O) represented by _n R ² (poly) ethylene glycol ether esters (R ^2, R ³ is straight-chain and (or 1 to 10 carbon atoms) alkyl groups having a branched alkyl group at both terminals is a same may be, may be different .n is an integer of from 1 to _{5), HO- (CH 2 CH 2} CH 2 -O) n
Represented by R ² (poly) propylene glycol monoalkyl ether (linear R ³ is from 1 to 10 carbon atoms and (or) an alkyl group having a branch, n represents an integer of 1 to 5), R ³
CO-O- represented by _{(CH 2 CH 2 CH 2 -O} ) n R 2 ( poly) propylene glycol ether ester (R
² and R ³ may be a straight-chain and / or branched alkyl group having 1 to 10 carbon atoms, and the alkyl groups at both terminals may be the same or different. n is an integer of 1 to 5) and the like. Specifically, for example, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, hexyl alcohol, octyl alcohol; cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monoethyl ether, diethylene glycol monoethylene Butyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether Ethers such as tripropylene glycol monoisobutyl ether; and glycol ether esters such as butyl cellosolve acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monobutyl ether acetate, and tripropylene glycol monoisobutyl ether acetate. .

The polymerization initiator is not particularly limited as long as it is a commonly used initiator, and a redox initiator, an azo initiator, or a peroxide may be used. Among these initiators, azo-based initiators are preferable, and specific examples include, for example, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobismethylbutyronitrile, azobis Azo nitriles such as bisdimethylmethoxyvaleronitrile;
V-50, VA-041, VA-044, VA-061
VA-080, such as azoamidines such as those manufactured by Wako Pure Chemical Industries, Ltd.)
, VA-086, VA-088 (Wako Pure Chemical Industries, Ltd.)
Azoamides such as azodi-tert-octane and azodi-tert-butane; cyanopropylazoformamide, azobiscyanovaleroyl acid, dimethylazobismethylpropionate, azobishydroxymethylpropionitrile Is raised. If necessary, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, (CH ₃ O) ₃ Si-SS-Si-
_{(OCH 3) 3, (CH} 3 O) 3 Si- (CH 2) 3 -
SS— (CH ₂ ) ₃ —Si— (OCH ₃ ) ₃ , (CH
_The molecular weight may be adjusted by using a chain transfer agent such as ₃ O) ₃ Si—S ₈ —Si (OCH ₃ ).

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

[Solubilization of Silyl Group-Containing Water-Soluble Resin (A)] The water-solubilization is preferably carried out 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, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monomethanolamine, dimethanolamine, trimethanolamine, Examples thereof include monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, and diethylethanolamine.

When the compound has a basic group, hydrochloric acid,
Neutralize with an acidic compound such as acetic acid and perform quaternization.

The amount of the basic compound or the acidic compound used for neutralization may be less than or equal to the equivalent of the carboxyl group, or may be used in a small excess, but it is preferable to use an equivalent or a small excess. From the viewpoint of the stability of the hydrolyzable silyl functional group, pH 5 to 10 by neutralization,
Preferably, the pH is adjusted to 6 to 8.

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

[Polymerization of Silyl Group-Containing Vinyl Copolymer (B)] Using the water-soluble resin (A) thus obtained as a dispersion stabilizer, a polymerization reaction is carried out in an aqueous medium to obtain an intended aqueous dispersion composition. (B) can be obtained.

As for the polymerization operation, a usual emulsion polymerization polymerization operation can be employed.

The silyl group (I) of the silyl group-containing vinyl copolymer (B) may be the same as the silyl group-containing vinyl resin described in the description of the polymerization of the silyl group-containing water-soluble resin (A). The monomer (a) can be introduced by copolymerization with another vinyl monomer, and the specific examples of (a) can be used as they are, or one or more of them may be used in combination. The vinyl monomer having a silyl group is 1 to 50 parts by weight, preferably 2 to 20 parts by weight based on 100 parts by weight of the vinyl monomer mixture.
Parts by weight. If the amount is less than 1 part by weight , the water resistance and weather resistance are inferior, and if it exceeds 50 parts by weight , the stability of the emulsion decreases.

The other vinyl monomer copolymerizable with the vinyl monomer having a silyl group is not particularly limited, and specific examples thereof include a portion described in the polymerization of silyl group-containing water-soluble resin (A). The vinyl-based monomer (b) having a water-soluble group or a group capable of forming a water-soluble group and the other copolymerizable vinyl-based monomer (c) can be used.

In addition, a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate and the like is used to crosslink the polymer produced. It is also possible to have a structure.

One or more of these monomers can be appropriately selected according to the quality of the final product.

The amount of the water-soluble resin used in the dispersion stabilizer is from 1/20 to 1/0 by weight relative to the monomer to be polymerized.
The ratio is preferably 1/10 to 1/1.

As the aqueous medium in which the dispersion stabilizer is dissolved, water is usually used. However, when the dispersant resin is used in a state of being dissolved in an organic solvent, the amount of the organic solvent corresponding to the amount of the dispersant resin is consequently increased. A solvent will be included in the system. In addition, for the purpose of increasing the solubility of the dispersant resin, it is also possible to add a water-soluble organic solvent in 1/2 or less with respect to water.

Further, in order to stabilize the silyl group of the vinyl copolymer containing a silyl group, an alkali metal compound, an alkaline earth metal compound and a transition metal compound (such as
However, the transition metal compound includes copper oxide, copper chloride, and silver compound.
Things, a compound selected from a platinum compound) (C) or an alkali metal compound, an alkaline earth metal compound and a transition metal compound (provided that the transition metal compound, oxide
A compound (C) selected from copper, copper chloride, a silver compound and a platinum compound ) and an alcohol (D) can be added during and / or after the polymerization.

Specific examples of the metal compound (C) and the alcohol (D) are the same as those listed for the polymerization of the water-soluble resin (A).

The metal compound (C) is added in an amount of about 1 × 10 ^{−5 to} 0.5 parts by weight based on 100 parts by weight of the total amount of the silyl group-containing vinyl copolymer (B) or the monomer. Among them, 1 × 10 ^{−4 to} 0.1 part by weight is preferred. If the amount is less than 1 × 10 ⁻⁵ parts by weight, the stabilizing effect is not sufficient. If the amount is more than 0.5 parts by weight, the stability of the emulsion becomes poor, and aggregation of the emulsion particles occurs.

When the alcohol (D) is used , the amount added is at least 1 part by weight, preferably at least 2 parts by weight, based on 100 parts by weight of the total amount of the polymer (B) or monomer. If the amount is less than 1 part by weight, the stabilizing effect is insufficient.

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

The initiator is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight, based on the weight of the monomer (100 parts by weight).
-5 parts by weight.

Further, the ionicity usually used for emulsion polymerization,
Although it is possible to use a nonionic surfactant in combination, it is preferable to use only a small amount in view of water resistance, weather resistance and the like. Specific examples of ionic and nonionic surfactants include, for example, potassium n-dodecylsulfonate, sodium isooctylbenzenesulfonate, sodium laurate, polyethylene glycol nonylphenyl ether, and the like.

The polymerization can be carried out at a polymerization temperature of 30 to 90 ° C., preferably 40 to 80 ° C.

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

If the solid concentration exceeds 70% by weight, the viscosity of the system will be remarkably increased, and it will be difficult to remove the heat generated by the polymerization reaction, and it will take a long time to take out from the polymerization machine. Occurs. When the solid content concentration is 20% by weight or less, there is no problem in terms of polymerization operation, but the amount of resin generated by one polymerization operation is small. I see
Also, if the concentration is less than 20% by weight, the film thickness of the coating film becomes thinner from the demands of the application, resulting in deterioration of performance and disadvantage in workability of coating.

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

For the purpose of assisting film formation, a solvent can be added. The amount of the solvent to be added is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the aqueous dispersion composition. 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, and dipropylene glycol monoethyl ether. , Dipropylene glycol monobutyl ether, dipropylene glycol isobutyl ether, tripropylene glycol monoethyl ether,
Ethers such as tripropylene glycol monobutyl ether and tripropylene glycol monoisobutyl ether; glycol ethers such as butyl cellosolve acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monobutyl ether acetate and tripropylene glycol monoisobutyl ether acetate; Esters and the like.

These solvents may be added at the time of polymerization of the aqueous dispersion type resin, or may be added after completion of the polymerization.

The aqueous dispersion type composition thus obtained includes:
A curing catalyst may or may not be used, but a catalyst can be used to promote the curability and bring out the required physical properties. Specific examples of such curing catalysts include, for example, organic tin compounds such as dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate, dioctyltin malate, and tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate Phosphoric acid or phosphoric acid esters such as monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, 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, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, manufactured by Yuka Shell Epoxy Co., Ltd. Cardura (E), Epikote 828
An addition reaction product of an epoxy compound such as Epicoat 1001 with phosphoric acid and / or an acid monophosphate;
Organic titanate compounds; organic aluminum compounds; organic zirconium compounds; maleic acid, adipic acid, azelaic acid, sebacic acid, itaconic acid, citric acid, succinic acid, trimellitic acid, pyromellitic acid, their acid anhydrides, paratoluene sulfone Acidic compounds such as acids; amines such as hexylamine, di (2-ethylhexyl) amine, N, N-dimethyldodecylamine and dodecylamine; mixtures or reactants of these amines with acidic phosphate esters; sodium hydroxide And alkaline compounds such as potassium hydroxide.

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

These curing catalysts may be used alone or in combination of two or more. The amount of the curing catalyst used is not particularly limited, but is usually 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the solid content of the curable composition for aqueous dispersion type paint. If the amount used exceeds 20 parts by weight, the appearance of the coating film tends to decrease.

The obtained aqueous dispersion-type composition is added, if necessary, to pigments usually used in coatings (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, and kaolin, and colored pigments such as carbon, red iron, and cyanine blue). It is also possible to mix and use additives such as plasticizers, solvents, dispersants, thickeners, defoamers, preservatives, and ultraviolet absorbers, which are used as ordinary components for coatings.

It is also possible to blend with commercially available water-based paints, for example, acrylic paints,
Thermosetting acrylic paint, such as acrylic melamine paint,
Alkyd paints and epoxy paints can be mentioned, and the weather resistance, acid resistance and solvent resistance of these paints can be improved.

It is also possible to add a melamine resin and an isocyanate compound as a cross-linking agent to achieve quick curing.

Next, the preparation method and the production method of the composition of the present invention will be described based on examples.

Production Examples 1 to 5 (Polymerization of water-soluble resin) Isopropyl alcohol 60 was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe and a dropping funnel.
Parts (parts by weight, hereinafter the same) were charged, and the temperature was raised to 75 ° C. while introducing nitrogen gas. Thereafter, a mixture having the composition shown in Table 1 was dropped at a constant speed over a period of 5 hours using a dropping funnel. After dripping of the mixture was completed, the mixture was aged at 75 ° C. for 2 hours.
For Example 3, 8.5 parts of ammonia were added, followed by cooling. For Production Examples 4 and 5, 2 parts of glacial acetic acid were added, followed by cooling to obtain a water-soluble resin having a number average molecular weight of 5,500.
Further, isopropyl alcohol was added to the resin solution so that the solid content concentration became 60% (% by weight, the same applies hereinafter) .

[0060]

[Table 1]

Examples 1 to 7 and Comparative Examples 1 and 2 93 parts of deionized water were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet and a dropping funnel.
1 part of ascorbic acid and 0.1 part of ferrous sulfate were added, and the resin solutions (A-1) to (A-5) synthesized in Production Examples 1 to 5 were added.
After adding 18.5 parts and dissolving with sufficient stirring, the temperature was raised to 70 ° C. while introducing nitrogen gas.
The mixture of 1) to (B-3) was dropped at a constant speed over 5 hours by a dropping funnel. After completion of the dropwise addition of the mixture, the mixture was aged at 70 ° C. for 2 hours, cooled, and deionized water was added to the aqueous dispersion to prepare a solid content concentration of 50%. Tables 3 and 4 show the results of a storage stability test of the obtained water-dispersed composition.

The tests and evaluations of stability in Tables 3 and 4 are as follows.

Polymerization stability: After the polymerization was completed, the emulsion was visually evaluated whether it was stably present as an emulsion when cooled to room temperature and the state of the particles. ：: No agglomerated particles existed, and no gelation occurred.

Emulsion stability: After storage at room temperature for one month, the presence of the resin that had settled was visually evaluated. ：: Presence of precipitated resin was not recognized.

Stability of silyl group: The presence of a hydrolyzable silyl group was confirmed by FT-IR. : The existing amount of the hydrolyzable silyl group hardly changed. △ to △: the amount of hydrolyzable silyl groups is slightly reduced. Δ: The amount of hydrolyzable silyl groups was significantly reduced.

Storage stability: Initially and after storage for one month at 50 ° C., measured using a B-type viscometer in a constant temperature and humidity room at 23 ° C.

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

From Tables 3 and 4, it can be seen that the composition of the present invention has excellent stability at the time of polymerization, and also has good emulsion stability and silyl group stability. It shows that storage stability is good.

[0071]

The composition of the present invention can be used for dispersing and polymerizing a silyl group-containing vinyl copolymer in an aqueous solution of a silyl group-containing water-soluble resin. By performing the polymerization of the copolymer in the presence of the metal compound and the alcohol, the dispersion polymerization can be stably performed, the stability of the emulsion is good, the stability of the silyl group is good, and the storage stability is excellent. It is a composition, and when used for paints, its performance is greatly improved as compared with conventional water-based paints.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-16712 (JP, A) JP-A-5-331408 (JP, A) JP-A-6-16735 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 43/04 C08F 2 / 44,30 / 08

Claims (6)

(57) [Claims] [Claim 1] General formula (I): (Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, and X is a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminooxy group, a phenoxy group. , A thioalkoxy group, a group selected from amino groups, a is 0, 1 or 2, S
and when X and R ¹ bonded to i are two or more, respectively, they may be the same or different groups.) The aqueous liquid of the water-soluble resin (A) having a silyl group represented by Wherein an aqueous dispersion type resin obtained by polymerizing a silyl group-containing vinyl copolymer (B) represented by the general formula (I), an alkali metal compound, an alkaline earth metal compound, and a transition metal compound (However, the transition metal compound is an acid
At least one compound (C) or an alkali metal compound, an alkaline earth metal compound, or a transition metal compound ( copper chloride, copper chloride, a silver compound, a platinum compound).
And the transition metal compound is copper oxide, copper chloride, a silver compound,
Aqueous compound comprising at least one compound (C) which is a platinum compound ) and an alcohol (D). 2. An alkali metal compound, an alkaline earth metal compound, a transition metal compound (provided that the transition metal compound
Is a copper oxide, a copper chloride, a silver compound, a platinum compound), an alkali metal compound, an alkaline earth metal compound, a transition metal compound
(However, the transition metal compound is copper oxide, copper chloride, silverized
Compound (C) and a platinum compound ), the water-soluble resin (A) and / or a vinyl-based copolymer (B) containing a silyl group. The aqueous dispersion composition according to claim 1, which is added during and / or after the polymerization. 3. The aqueous dispersion composition according to claim 1, wherein the alcohol (D) is methanol. 4. The method according to claim 1, wherein the alkali metal compound is potassium acetate,
At least one compound of sodium acetate, potassium chloride and sodium chloride, wherein the alkaline earth metal compound is calcium chloride, and the transition metal compound (only
And the transition metal compound is copper oxide, copper chloride, a silver compound,
3. The aqueous dispersion composition according to claim 1, wherein the platinum compound is at least one compound selected from copper oxide and copper chloride. 5. The water-soluble resin (A) having a silyl group,
The aqueous dispersion composition according to claim 1, which is a water-soluble resin having a carboxyl group neutralized with ammonia or an organic amine compound. 6. A compound of the general formula (I): (Wherein, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, and X is a halogen atom, an alkoxy group, a hydroxy group, an acyloxy group, an aminooxy group, a phenoxy group. , A thioalkoxy group, a group selected from amino groups, a is 0, 1 or 2, S
when X and R ¹ bonded to i are two or more, respectively, they may be the same or different groups), and have a silyl group represented by the following formula (A):
And an alkali metal compound, an alkaline earth metal compound, a transition metal compound (provided that the transition metal compound is copper oxide,
At least one compound (C) or an alkali metal compound, an alkaline earth metal compound, or a transition metal compound ( copper chloride, silver compound or platinum compound)
Metal transfer compounds include copper oxide, copper chloride, silver compounds, platinum compounds
At least one compound (C) and an aqueous solution of an alcohol (D), vinyl copolymer containing a silyl group represented by the general formula (I) and (B) polymerization of at which) ones A method for producing an aqueous dispersion composition.