JP2001302920A - Aqueous dispersion, its production method and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous dispersion which remarkably excellent in storage stability and, in addition, excellent in the performance balance of adhesivity, alkali resistance, organic chemical resistance, moisture resistance, weatherability, (hot) water resistance, staining recovery properties and the like, and simultaneously can form transparent and high hardness coating films, and is useful as a coating material. SOLUTION: The aqueous dispersion can be obtained by subjecting a mixture containing (A) at least one selected from the group consisting of an organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane and (B) a radically polymerizable vinyl monomer in the emulsified state to hydrolytic condensation reaction and radical polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous dispersion, and more particularly, to storage stability, adhesion, alkali resistance, organic chemical resistance, weather resistance, (hot) water resistance, contamination recovery property, and the like. The present invention relates to an aqueous dispersion capable of forming an excellent, transparent and high hardness coating film.

[0002]

2. Description of the Related Art Conventionally, coating agents have been used in various fields, and the range of application thereof has been steadily expanding. In recent years, there has been a demand for a coating agent capable of forming a coating film having an excellent balance of performances such as adhesion, chemical resistance, moisture resistance, weather resistance, (warm) water resistance, and contamination recovery, and having high hardness. As a coating agent which partially satisfies such a demand, a composition comprising a partial condensate of an organosilane, a dispersion of colloidal silica and a silicone-modified acrylic resin (JP-A-60-1)
No. 35465), or a composition comprising a condensate of an organosilane, a chelate compound of a zirconium alkoxide, and a vinyl resin having a hydrolyzable silyl group (Japanese Patent Application Laid-Open No. 64-1769). However, these coating agents are all of a solvent type, and in recent years, from the viewpoints of low pollution, resource saving, safety and health, etc., there is a strong demand for desolvation, and there is a shift to aqueous coating agents.

Under such circumstances, the development of reactive resin emulsions has been studied extensively as ones which can be expected to improve the performance such as water resistance and chemical resistance, and one of them is a resin emulsion having a hydrolyzable silyl group. Has been proposed. As an example, JP-A-7-26035 discloses a reactive resin emulsion containing a vinyl polymer having a hydrolyzable silyl group and an amine imide group.
JP-91510-A discloses an aqueous coating composition comprising an aqueous dispersion of a vinyl polymer having an alkoxysilyl group and an aqueous dispersion of a tin compound.

However, these hydrolyzable silyl group-containing resin emulsions are inferior in storage stability.
In addition, the coating obtained from the emulsion after long-term storage has a drawback that, unlike the coating obtained from the emulsion immediately after production, stable quality cannot be ensured, and there is a problem in practicality. Alternatively, even when the storage stability is relatively good, adhesion, chemical resistance, moisture resistance, weather resistance,
It is unsatisfactory in terms of the balance of performance, such as resistance to (warm) water and contamination recovery.

Japanese Patent Application Laid-Open No. H11-255846 proposes a silicone resin-containing emulsion composition obtained by emulsion polymerization of a mixed solution containing a silanol group-containing silicone resin and a radically polymerizable vinyl monomer. However, this method cannot be used industrially because a large amount of condensate precipitates during polymerization and the polymerizability is reduced.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has excellent storage stability, and furthermore has excellent adhesion, alkali resistance, organic chemical resistance, and moisture resistance. It is an object of the present invention to provide a water-based dispersion which is excellent in a balance of performances such as weather resistance, (warm) water resistance and stain recovery property, can form a transparent and high hardness coating film, and is particularly useful as a coating agent.

[0007]

The present invention provides (A) at least one kind selected from organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane (hereinafter also referred to as "component (A)"). And a mixture containing (B) a radically polymerizable vinyl monomer (hereinafter also referred to as “(B) component” or “(B) vinyl monomer”) in an emulsified state by hydrolysis / condensation reaction and radical polymerization. , An aqueous dispersion. Here, the aqueous dispersion of the present invention further contains (C) a compound having a polymerizable unsaturated group and a group capable of forming a siloxane bond (hereinafter, also referred to as “(C) silane coupling agent”). May be. Next, the present invention provides a mixture containing (A) at least one selected from an organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane, and (B) a radically polymerizable vinyl monomer, with water and The present invention relates to a method for producing an aqueous dispersion, which comprises emulsifying in the presence of a surfactant and performing hydrolysis / condensation reaction and radical polymerization (hereinafter also referred to as "condensation / polymerization reaction"). Next, the present invention relates to a coated body in which a coating material containing the aqueous dispersion is applied on a substrate. Here, the base material may be provided with an undercoat layer.

[0008] The aqueous dispersion of the present invention has the following advantages which could not be obtained by a conventionally known method. (1) In the emulsion particles, since the (B) vinyl monomer is polymerized in the presence of the (A) component, which is a siloxane component, the siloxane component and the vinyl polymer form an interpenetrating network structure (IPN). As a result, even if a methyl-based silicone resin having poor mutual solubility is used as the siloxane component, a film having excellent transparency is formed, and the shortcomings in the properties of both resins are complemented. In particular, since a large amount of silicone resin rich in hardness, chemical resistance, and weather resistance can be contained, the formed film has excellent film forming properties, and has excellent properties such as scratch resistance, weather resistance, and chemical resistance. Provides a uniform cured film with good flexibility. (2) In the emulsion particles, the polymers are entangled with each other in a solvent-free state, so that the degree of freedom of the condensation-rich silanol groups in the siloxane component is limited. as a result,
Condensation of silanol groups is suppressed, and good storage stability is obtained. (3) When the siloxane component (silicone resin) contains silanol groups of a specific structure in a certain amount or more, the silanol groups in the emulsion particles are restrained in a favorable state,
Its high curing activity is preserved, and excellent curability is secured even at a relatively low temperature. Further, as a hydrolyzable silane compound, by including a large number of silanol groups of a specific structure such as dialkoxysilanes, the linear structure is increased,
Contradictory properties such as flexibility and hardness can be simultaneously imparted to the coating. (4) Since a low-boiling organic solvent having a temperature of less than 100 ° C. or an aromatic organic solvent such as toluene is not substantially contained, a favorable working environment is ensured. (5) If a specific curing catalyst is used in combination, curing at room temperature is possible, and immediate curing is possible even at a relatively low temperature.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in order. (A) Component The organosilane in the component (A) constituting the aqueous dispersion of the present invention is generally represented by the following general formula (1). _{^{(R 1) n Si (OR}} 2) 4-n ····· (1) ( In the formula, R ^1, same or different when there are two pieces, a monovalent organic group having 1 to 8 carbon atoms And R ² is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 0 to 2.)

The hydrolyzate of the organosilane does not need to have all of the OR ² groups in the general formula (1) contained in the organosilane of 2 to 4 hydrolyzed. May be hydrolyzed, two or more may be hydrolyzed, or a mixture thereof. In addition, the condensate of the organosilane is a product in which the silanol groups of the hydrolyzate of the organosilane are condensed to form a Si—O—Si bond, but in the present invention, it is necessary that all the silanol groups are condensed. However, it is a concept that includes a mixture of a small amount of silanol groups condensed and a mixture of those having different degrees of condensation.

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
Examples of the monovalent organic group of 8 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, n-
Alkyl groups such as hexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group; acyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioil group and caproyl group; vinyl group;
In addition to allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, and the like, and substituted derivatives of these groups. it can.

Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) An acryloxy group, a ureido group, an ammonium base and the like can be mentioned. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. When two R ¹ are present in the general formula (1), they may be the same or different from each other.

The alkyl group having 1 to 5 carbon atoms for R ² includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group and t-butyl group. And an acyl group having 1 to 6 carbon atoms, for example, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group, and the like. A plurality of R ² in the general formula (1) may be the same or different from each other.

Specific examples of such organosilanes include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and tetra-n-butoxysilane; methyl Trimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane,
n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,
3-trifluoropropyltrimethoxysilane, 3,
3,3-trifluoropropyltriethoxysilane, 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-
Hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanate Natopropyltriethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acrylyloxypropyltriethoxysilane, 3 Trialkoxysilanes such as ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n -Propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-
Propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n −
Hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n
-Dialkoxysilanes such as -octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane, Acetyloxysilane, dimethyldiacetyloxysilane and the like can be mentioned.

Of these, those preferably used are:
Trialkoxysilanes and dialkoxysilanes, and as the trialkoxysilanes, methyltrimethoxysilane and methyltriethoxysilane are preferable; and further, as the dialkoxysilanes, dimethyldimethoxysilane and dimethyldiethoxysilane Is preferred.

The component (A) is at least one selected from an organosilane, a hydrolyzate of the organosilane, and a condensate of the organosilane. That is, (A)
The components may be only one of these three types, may be a mixture of any two types, or may be a mixture containing all three types. In the present invention, it is preferable that an organosilane and a condensate of an organosilane (hereinafter also referred to as “polyorganosiloxane”) are used as a mixture. In the aqueous dispersion of the present invention, by co-condensing an organosilane and a polyorganosiloxane, a film having excellent properties such as hardness, chemical resistance, weather resistance, film forming property, transparency, and crack resistance is obtained. To form. Further, there is an advantage that the polymerization stability when the vinyl compound is polymerized after emulsification is remarkably improved, and the polymerization can be performed at a high solid content, so that industrialization is easy.

When two types of organosilane and polyorganosiloxane are used, dialkoxysilanes are preferred as the organosilane. When dialkoxysilanes are used, a linear component is added as a molecular chain, and the flexibility of the obtained particles is increased. Furthermore, when a coating film is formed using the obtained aqueous dispersion, there is an effect that a coating film having excellent transparency can be obtained. As the dialkoxysilanes, dimethyldimethoxysilane, dimethyldiethoxysilane, and the like are particularly preferable.

Further, when two kinds of organosilane and polyorganosiloxane are used, the polyorganosiloxane is preferably used alone as a trialkoxysilane, or 40 to 95 mol% of a trialkoxysilane and 60 to 5 mol of a dialkoxysilane. % Is preferably a condensate. By using dialkoxysilane in combination with trialkoxysilane, the resulting coating film can be softened and the alkali resistance can be improved.

The polyorganosiloxane is used as a condensate of an organosilane by previously hydrolyzing and condensing an organosilane. At this time, when preparing the polyorganosiloxane, it is preferable to add an appropriate amount of water to the organosilane and, if necessary, an organic solvent to hydrolyze and condense the organosilane. here,
The amount of water used is usually per mole of organosilane,
It is about 1.2 to 3.0 mol, preferably about 1.3 to 2.0 mol.

In this case, as the organic solvent used as required, polyorganosiloxane or the following (B)
There is no particular limitation as long as the components can be uniformly mixed, and examples thereof include alcohols, aromatic hydrocarbons, ethers, ketones, and esters. Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, and n-hexyl alcohol. -Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone alcohol and the like.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and the like. Specific examples of esters such as methyl isobutyl ketone and diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more. When an organic solvent is contained in the polyorganosiloxane, the organic solvent can be removed from the aqueous dispersion before the condensation / polymerization reaction described later.

The polyorganosiloxane preferably has a weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of 800 to 100,000, more preferably 1,100.
000 to 50,000.

Commercially available polyorganosiloxanes include MKC silicate manufactured by Mitsubishi Chemical Corporation, ethyl silicate manufactured by Colcoat, silicon resin manufactured by Dow Corning Toray, and silicone resin manufactured by Toshiba Silicone Co., Ltd. , Silicone resin manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl group-containing polydimethylsiloxane manufactured by Dow Corning Asia Co., Ltd., and silicon oligomer manufactured by Nippon Yunika Co., Ltd. May be.

When an organosilane and a polyorganosiloxane are used as the component (A), the mixing ratio of the two is 95% in terms of organosilane (complete hydrolytic condensate).
5 to 95% by weight, preferably 90 to 10% by weight, and polyorganosiloxane (complete hydrolyzed condensate) is 5 to 95% by weight, preferably 10 to 90% by weight [organosilane + polyorganosilane = 100% by weight. %].
If the amount of the polyorganosiloxane is less than 5% by weight, the surface of the obtained coating film may be sticky or the curability of the coating film may be unfavorably deteriorated. On the other hand, if it exceeds 95% by weight, the proportion of the organosilane component becomes too small, so that it is difficult to emulsify the mixture containing the component (A), and the polymerization stability of the radically polymerizable vinyl monomer (B) decreases after emulsification. Further, the stability of the emulsion after emulsification is lowered, or the film forming property of the obtained organic-inorganic composite is lowered, which is not preferable. Here, the above-mentioned completely hydrolyzed condensate, R ² O-group of the organosilane becomes 100% hydrolyzed to SiOH groups, more fully condensed refers to became siloxane structure.

(B) The radically polymerizable vinyl monomer (B) is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated double bond. As the component (B), for example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (Meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2
Esters of (meth) acrylic acid such as -ethylhexyl (meth) acrylate, n-octyl (meth) acrylate and cyclohexyl methacrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxy group-containing (meth) acrylates such as hydroxypropyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) Polyfunctional (meth) acrylates such as acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate;
Fluorine atom-containing (meth) acrylic esters such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate; 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl Amino group-containing (meth) acrylic esters such as (meth) acrylates;
(Meth) acrylic compounds such as epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate.

In addition, as the component (B), styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene,
Aromatic vinyl monomers such as 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene and 1-vinylnaphthalene; divinylbenzene Polyfunctional monomers other than the above, such as;

(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth)
Acid amide compounds such as acrylamide, N-butoxymethyl (meth) acrylamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic amide, and maleimide; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; ) Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,
Piperidine monomers such as 2,6,6-tetramethylpiperidine and 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine; and dicaprolactone.

Further, as the component (B) having a functional group, unsaturated carboxylic acids other than those described above, such as crotonic acid, maleic acid, fumaric acid, and itaconic acid; unsaturated carboxylic acids such as maleic anhydride and itaconic anhydride; Acid anhydrides;
Other hydroxyl-containing vinyl monomers such as N-methylol (meth) acrylamide and 2-hydroxyethyl vinyl ether; amino-containing vinyl monomers such as 2-aminoethyl vinyl ether; 1,1,1-trimethylamine ( (Meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-
1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-phenyl-
2'-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-2 '
Examples thereof include vinyl monomers containing an amine imide group such as -phenoxypropyl) amine (meth) acrylimide; and vinyl monomers containing an epoxy group other than the above, such as allyl glycidyl ether.

Among the above components (B), (meth) acrylic compounds are preferable, and among them, (meth) acrylic acid, (meth) acrylic acid ester, and hydroxyl group-containing (meth) acrylic compound are preferable.
Acrylic esters are particularly preferred. More preferred are methyl methacrylate, butyl methacrylate, acrylic acid, and 2-hydroxyethyl methacrylate.

The proportion of the component (A) and the component (B) in the aqueous dispersion of the present invention is such that the total amount of the component (A) (complete hydrolytic condensate) is 1 to 95 parts by weight, preferably 10 to 95 parts by weight.
To 90 parts by weight, the component (B) is 99 to 5 parts by weight, preferably 90 to 10 parts by weight [however, (A) + (B) = 100
Parts by weight]. If the proportion of the component (B) is less than 5 parts by weight, the film-forming properties and crack resistance are undesirably reduced. On the other hand, if it exceeds 99 parts by weight, the deterioration of weather resistance becomes remarkable, which is not preferable.

Production of Aqueous Dispersion The aqueous dispersion of the present invention is obtained by emulsifying a mixture containing the above components (A) and (B) in the presence of water and a surfactant, and subjecting the mixture to a hydrolysis / condensation reaction. And radical polymerization. In this condensation / polymerization reaction, (co) condensation of the component (A) (preferably a mixture of an organosilane and a polyorganosiloxane) in an emulsified state,
(B) The radical polymerization of the radically polymerizable vinyl monomer proceeds simultaneously. The reaction in the case where the component (A) is a mixture of an organosilane and a polyorganosiloxane includes, in addition to the above-mentioned two types of co-condensation, a case where an organosilane or a polyorganosilane undergoes a single condensation reaction. As a result, the siloxane component composed of the component (A) and the vinyl polymer composed of the component (B) form an interpenetrating network structure. In addition, since the polymers are entangled in the emulsion particles without solvent, the degree of freedom of silanol groups having high condensation activity in the siloxane component is limited, the condensation is suppressed, and good storage stability is obtained.

The water used in the production of the aqueous dispersion of the present invention may be water which is present in a previously added aqueous mixture of the component (A), or may be added to the mixture of the component (A). Further, it may be water added together with the surfactant. The amount of water to be used is generally 80 to 1,000 parts by weight, preferably 100 to 100 parts by weight, based on 100 parts by weight of the total amount of the component (A) (in terms of complete hydrolysis condensate) and the component (B).
500 parts by weight. If the amount is less than 80 parts by weight, emulsification is difficult or the stability of the emulsion after emulsification decreases, which is not preferable. On the other hand, if it exceeds 1,000 parts by weight, productivity is undesirably reduced.

Examples of the surfactant used as an emulsifier include anionic surfactants such as alkyl sulfates, alkyl aryl sulfates, alkyl phosphates, and fatty acid salts; alkylamine salts, and alkyl quaternary surfactants. Cationic surfactants such as amine salts; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, block polyethers; carboxylic acid types (eg, amino acid type, betainic acid type, etc.); Any of amphoteric surfactants such as a sulfonic acid type can be used. These surfactants can be used alone or in combination of two or more.

The amount of the surfactant to be used is generally 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the component (A) (in terms of a complete hydrolysis condensate) and the component (B). weight%
It is about. If the amount is less than 0.05% by weight, the emulsification is not sufficient, and the stability during hydrolysis / condensation and radical polymerization decreases, which is not preferable. On the other hand, if it exceeds 10% by weight, foaming becomes a problem, which is not preferable.

In the condensation / polymerization reaction, a radical polymerization initiator is used. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic peroxide, and 2,2. '-Azobis [2
Water-soluble initiators such as benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxy dicarbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, and azobisisobutyro. Oil-soluble initiators such as nitriles; sodium acid sulfite, Rongalit,
Redox initiators and the like in combination with a reducing agent such as ascorbic acid can be used. The amount of the radical polymerization initiator to be used is generally 0.05 to 10% by weight, preferably 0.1 to 10% by weight, based on the (B) radically polymerizable vinyl monomer.
5% by weight.

In the condensation / polymerization reaction of the component (A),
The aqueous system is mini-emulsified using a mechanical means such as a high-pressure homogenizer, ultrasonic waves, and a homomixer. The reaction conditions for the condensation / polymerization reaction at this time are usually 25 to 80 ° C., preferably 40 to 70 ° C., and the reaction time is usually 0.5 to 15 hours, preferably 1 to 8 hours. It is.

In the condensation / polymerization reaction, when the component (A) or the component (B) has an acidic group such as a carboxyl group or a carboxylic anhydride group, after the condensation / polymerization reaction,
Preferably, the pH is adjusted by adding at least one basic compound. On the other hand, when each of the above components has a basic property such as an amino group or an amine imide group, at least one kind of acidic compound is added after the condensation / polymerization reaction to add p.
It is preferred to adjust H. Furthermore, when each of the above components has an acidic group and a basic group, after the condensation / polymerization reaction, at least one basic compound or acidic compound is added depending on the ratio of these groups, and the pH is adjusted. In any case, the hydrophilicity of the resulting aqueous dispersion can be increased to improve the dispersibility.

Examples of the basic compound include amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, and dimethylaminoethanol; and alkali metal hydroxides such as sodium hydroxide and sodium hydroxide. Things.
Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid; formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, citric acid, adipic acid, (meth) acrylic acid, maleic acid, Organic acids such as fumaric acid and itaconic acid are exemplified. The pH value of the aqueous dispersion at the time of the pH adjustment is usually 6 to 10, preferably 7 to 8.

In the aqueous dispersion of the present invention, the organic-inorganic composite is dispersed in an aqueous medium, and the dispersion state may be a particle or an aqueous sol. In this case, the average particle size of the organic-inorganic composite of the present invention is usually 0.01
To 100 μm, preferably 0.05 to 10 μm.
Further, the solid concentration of the aqueous dispersion of the present invention is usually 10%.
-60% by weight, preferably 20-50% by weight. This solid content concentration is usually adjusted by the amount of the water. The aqueous medium in the aqueous dispersion of the present invention is essentially composed of water, but may contain an organic solvent such as alcohol up to about several weight% in some cases. Also,
When the aqueous dispersion of the present invention contains an organic solvent that is used as needed at the time of preparing the component (A), the organic solvent can be removed from the aqueous dispersion. Further, in the aqueous dispersion of the present invention, if necessary,
Various organic solvents as described above used in the preparation of the component (A) can also be added.

(C) Silane Coupling Agent (C) The silane coupling agent includes (B) a polymerizable unsaturated group capable of undergoing radical polymerization with a vinyl monomer, and an alkoxysilyl group capable of co-condensing with the component (A). A compound having a group capable of forming a siloxane bond. When the (C) silane coupling agent is contained in the aqueous dispersion of the present invention, the hybrid property of the organic component and the inorganic component of the aqueous dispersion of the present invention is improved.
Transparency and weather resistance are improved. In order to mix the (C) silane coupling agent, it may be added to the mixture of the above components (A) and (B) before emulsification, or may be added during the above condensation / polymerization. Furthermore, it may be added after preparing the aqueous dispersion of the present invention. Preferably, it is preferably added to a mixture of the above components (A) and (B) before emulsification. Specific examples of the (C) silane coupling agent include: CH ₂ ＣＨCHSi (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHSi (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl ₂ , CH ₂ = CHSiCl ₃
CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ SiCl ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) (OC
_{H 3) 2, CH 2 =} C (CH 3) COO (CH 2) 2 Si (OCH 3) 3
CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (O
_{CH 3) 2, CH 2 =} C (CH 3) COO (CH 2) 3 Si (OCH 3)
₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si (CH ₃ ) Cl _{2
, CH 2 = C (CH 3} ) COO (CH 2) 2 SiCl 3, CH 2 = C (CH 3) COO (CH 2) 3 Si (CH 3) Cl 2
, CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ SiCl _{3 and the} like. (C) The amount of the silane coupling agent is
The amount is usually 20 parts by weight or less, preferably 10 parts by weight, based on 100 parts by weight of the total amount of the component (A) (complete hydrolyzed condensate) and the component (B). In addition, the following (D) hardening accelerators etc. can also be mix | blended with the aqueous dispersion of this invention.

(D) Curing accelerator The component (D) is a catalyst that promotes the hydrolysis / condensation reaction of the component (A). By using the component (D), the curing speed of the obtained coating film is increased, and the molecular weight of the polysiloxane resin produced by the polycondensation reaction of the component (A) is increased, so that the strength and the long-term durability are obtained. Thus, it is possible to obtain an excellent coating film, and the coating film can be easily thickened and painted.

As such a component (D), acidic compounds, alkaline compounds, salt compounds, amine compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter referred to as “hydrolysates”)
Organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organometallic compounds or the like”). Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, and phthalic acid, and acetic acid is preferred. Examples of the alkaline compound include sodium hydroxide and potassium hydroxide, and preferably sodium hydroxide. Further, as the salt compound, for example, naphthenic acid, octylic acid,
Examples thereof include alkali metal salts such as nitrous acid, sulfurous acid, aluminate, and carbonic acid.

Examples of the amine compound include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, ethanolamine, triethylamine, and the like. -Aminopropyl-trimethoxysilane, 3-aminopropyl-triethoxysilane, 3- (2-aminoethyl) -aminopropyl-trimethoxysilane, 3- (2-aminoethyl) -aminopropyl-triethoxysilane, 3 -(2-aminoethyl) -aminopropylmethyldimethoxysilane, 3
-Anilinopropyltrimethoxysilane, alkylamine salts, quaternary ammonium salts, and various modified amines used as a curing agent for epoxy resins. Preferred are 3-aminopropyltrimethoxysilane. , 3-aminopropyl-triethoxysilane and 3- (2-aminoethyl) -aminopropyl-trimethoxysilane.

Examples of the organometallic compound and the like include a compound represented by the following general formula (2) (hereinafter referred to as “organometallic compound (2)”), a compound having 1 to 1 carbon atoms bonded to the same tin atom. Examples thereof include organometallic compounds of tetravalent tin having 1 to 2 alkyl groups of 10 (hereinafter referred to as "organotin compounds"), and partially hydrolyzed products of these compounds.

[0045][Wherein M is zirconium, titanium or aluminum
And R^ThreeAnd R^FourAre the same or different and are ethyl
Group, n-propyl group, i-propyl group, n-butyl group,
sec-butyl group, t-butyl group, n-pentyl group, n
-Charcoal such as hexyl, cyclohexyl, phenyl, etc.
A monovalent hydrocarbon group having a prime number of 1 to 6, ^FiveIs R^ThreeAnd
And R^FourAnd other monovalent hydrocarbon groups having 1 to 6 carbon atoms.
Or methoxy, ethoxy, n-propoxy, i-
Propoxy group, n-butoxy group, sec-butoxy group,
t-butoxy group, lauryloxy group, stearyloxy
Represents an alkoxyl group having 1 to 16 carbon atoms such as a group,
And s are integers from 0 to 4, and (r + s) = (valence of M)
It is. ]

Specific examples of the organometallic compound (2) include (a) tetra-n-butoxyzirconium and tri-n-
Butoxy ethyl acetoacetate zirconium, di-
n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, etc. An organic zirconium compound;

(B) Tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium, di-i-propoxybis (acetylacetate) titanium, di-i-propoxybis (acetylacetone) Organic titanium compounds such as titanium; (c) tri-i-propoxyaluminum, di-i-propoxyethyl acetoacetate aluminum,
aluminum i-propoxy acetylacetonate,
i-propoxybis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate)
Organic aluminum compounds such as aluminum, tris (acetylacetonate) aluminum, and monoacetylacetonatobis (ethylacetoacetate) aluminum; and the like.

Of these organometallic compounds (2) and partial hydrolysates thereof, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-i-propoxy・ Ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or
Partial hydrolysates of these compounds are preferred.

Further, specific examples of the organotin compound include:
(C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂
Sn (OCOCH = CHCOOCH ₃ ) ₂ , (C ₄ H ₉ )
₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H
₁₇ ) ₂ Sn (OCOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCO
CH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (O
COCH = CHCOOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(OCOCH = CHCOOC ₁₆ H ₃₃ ) ₂ , (C ₈ H ₁₇ )
₂ Sn (OCOCH = CHCOOC ₁₇ H ₃₅ ) ₂ , (C _{8
H 17) 2 Sn (OCOCH =} CHCOOC 18 H 37) 2,
(C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOOC ₂₀ H ₄₁ )
₂ , (C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ , (C ₄ H ₉ ) S
carboxylic acid type organotin compounds such as n (OCONa) ₃ ;

(C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC)
₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ CH ₂ COOC _{8
H 17) 2, (C 8} H 17) 2 Sn (SCH 2 COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC
₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H
₂₅ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC _{12
H 25) 2, (C 4} H 9) Sn (SCOCH = CHCOO
C ₈ H ₁₇ ) ₃ , (C ₈ H ₁₇ ) Sn (SCOCH = CHC
OOC ₈ H ₁₇ ) ₃ ,

[0051] (C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S, Sulfide type organotin compounds such as;

(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ Sn
Cl ₂ , (C ₈ H ₁₇ ) ₂ SnCl ₂ , (C ₄ H ₉ ) ₂ Sn
Organic tin oxides such as O, (C ₈ H ₁₇ ) ₂ SnO,
Reaction products of these organic tin oxides with ester compounds such as silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate; and the like. The above component (D) can be used alone or as a mixture of two or more kinds, and can also be used as a mixture with a zinc compound or other reaction retarders.

The component (D) may be blended when preparing the aqueous dispersion, or may be blended with the aqueous dispersion at the stage of forming a coating film. And the formation of the coating film.

The amount of component (D) used is usually 100 parts by weight or less based on 100 parts by weight of component (A) (in terms of a completely hydrolyzed condensate) in cases other than organometallic compounds.
Preferably, it is 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight. In the case of an organometallic compound or the like, the above-mentioned component (A) (in terms of complete hydrolysis condensate) is 100
100 parts by weight or less, preferably 0.1 to 80 parts by weight, and more preferably 0.5 to
50 parts by weight. In this case, the amount of the component (D) used is 1
If the amount is more than 00 parts by weight, the storage stability of the aqueous dispersion tends to decrease and the coating film tends to crack.

(E) Other Silicone Resins In the aqueous dispersion of the present invention, other silicone resins other than the component (A) can be blended. Other silicone resins include (E-1) a silyl group-containing polymer and (E-2) an aqueous dispersion obtained by dispersing a hybrid of a polyorganosiloxane and a silyl group-containing polymer in an aqueous medium ( Hereinafter, also referred to as “hybrid aqueous dispersion”). These (E) and other silicone resins can be used alone or in combination of two or more. Hereinafter, (E-1) a silyl group-containing polymer and (E-1) a hybrid aqueous dispersion will be described.

(E-1) a silyl group-containing polymer; The component (E-1) is a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group (hereinafter referred to as “specific silyl group”). It preferably comprises a polymer having terminal and / or side chains of the polymer molecular chain. This (E-
The component (1) is a component that provides excellent coating film performance when the hydrolyzable group and / or hydroxyl group in the silyl group is co-condensed with the component (A) when the coating film is cured. The content of the silicon atom in the component (E-1) is usually 0.001 to 0.001 to the entire component (E-1).
It is 20% by weight, preferably 0.01 to 15% by weight.
Preferred specific silyl groups are groups represented by the following general formula (3).

[0057] (In the formula, X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group or a hydroxyl group, and R ⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or Carbon number 1-10
Wherein i is an integer of 1 to 3. )

The component (E-1) can be produced, for example, by the following method (a) or (b). (A) A hydrosilane compound corresponding to the above general formula (4) (hereinafter referred to as “hydrosilane compound (A)”) is referred to as a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “unsaturated vinyl polymer”). )).

(B) The following general formula (4) Wherein, X, R ^6, i has the same meaning as X, R ^6, i, respectively, in the general formula (4), R ⁷ represents an organic group having a polymerizable double bond. ] (Hereinafter referred to as "unsaturated silane compound (II)") and another vinyl monomer.

Examples of the hydrosilane compound (a) used in the method (a) include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldimethoxysilane, methyldiethoxysilane Alkoxysilanes such as phenyldimethoxysilane, trimethoxysilane, and triethoxysilane; acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane, and triacetoxysilane; methyldiaminooxysilane, triaminoxysilane, and dimethyl. Examples thereof include aminoxysilanes such as aminoxysilane. These hydrosilane compounds (a) can be used alone or in combination of two or more.

The unsaturated vinyl polymer used in the method (A) is not particularly limited as long as it is other than a polymer having a hydroxyl group. For example, the following (A-1) and (A)
It can be produced by the method 2) or a combination thereof. (A-1) After (co) polymerizing a vinyl monomer having a functional group (hereinafter referred to as "functional group (α)"), the functional group (α) in the (co) polymer is replaced with the functional group (α). By reacting a functional group capable of reacting with the group (α) (hereinafter referred to as “functional group (β)”) with an unsaturated compound having a carbon-carbon double bond, carbon- A method for producing an unsaturated vinyl polymer having a carbon double bond.

(A-2) A radical polymerization initiator having a functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid or the like) is used, or a radical polymerization initiator and a chain transfer agent are used. A vinyl monomer is (co) polymerized using a compound having a functional group (α) on both sides (eg, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid) to obtain a polymer. After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at one or both ends of the molecular chain, the functional group (α) in the (co) polymer is synthesized. Is reacted with an unsaturated compound having a functional group (β) and a carbon-carbon double bond to obtain an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain. A method of manufacturing coalescence.

Examples of the reaction between the functional group (α) and the functional group (β) in the methods (a-1) and (a-2) include:
Esterification reaction between carboxyl group and hydroxyl group, ring-opening esterification reaction between carboxylic anhydride group and hydroxyl group, ring-opening esterification reaction between carboxyl group and epoxy group, amidation reaction between carboxyl group and amino group, carboxyl group Examples include a ring-opening amidation reaction between an acid anhydride group and an amino group, a ring-opening addition reaction between an epoxy group and an amino group, a urethanation reaction between a hydroxyl group and an isocyanate group, and a combination of these reactions.

Examples of the vinyl monomer having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid; maleic anhydride, itaconic anhydride Unsaturated carboxylic anhydrides such as acids; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Hydroxyl-containing vinyl monomers such as 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, and 2-hydroxyethyl vinyl ether; 2
Amino-containing vinyl monomers such as -aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 2-aminoethyl vinyl ether; 1,1,1-trimethylamine ( (Meth) acrylimide, 1-methyl-1-
Ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine ( (Meth) acrylimide, 1,1-dimethyl-1- (2'-hydroxy-
Examples thereof include vinyl monomers containing an amine imide such as 2'-phenoxypropyl) amine (meth) acrylimide; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether. These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.

Examples of other vinyl monomers copolymerizable with the vinyl monomer having a functional group (α) include (a) styrene, α-methylstyrene, 4-methylstyrene, and 2-methylstyrene. Styrene, 3-methylstyrene, 4-
Methoxystyrene, 2-hydroxymethylstyrene, 4
-Ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 3,4-diethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-t-butylstyrene, Aromatic vinyl monomers such as 2,4-dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene;

(B) methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, amyl (meth) acrylate,
(meth) acrylate compounds such as i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, and cyclohexyl methacrylate;

(C) divinylbenzene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) Polyfunctional monomers such as acrylates and pentaerythritol tetra (meth) acrylate;

(D) (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N, N'-methylenebisacrylamide, diacetone acrylamide, maleic amide,
Acid amide compounds such as maleimide; (e) vinyl compounds such as vinyl chloride, vinylidene chloride and fatty acid vinyl ester; (f) 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1 , 3-butadiene, 2-
Neopentyl-1,3-butadiene, 2-chloro-1,
Substituted linear conjugated pentadienes substituted with substituents such as 3-butadiene, 2-cyano-1,3-butadiene, isoprene, an alkyl group, a halogen atom, and a cyano group; linear and side-chain conjugated hexadienes; An aliphatic conjugated diene;

(G) vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; fluorine atom-containing monomers such as (thi) trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate; (Meth) acryloyloxy-2,2,6
6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine,
4- (meth) acryloyloxy-1,2,2,6,6
Piperidine monomers such as pentamethylpiperidine; and dicaprolactone. These can be used alone or in combination of two or more.

Examples of the unsaturated compound having a functional group (β) and a carbon-carbon double bond include, for example, a vinyl monomer similar to the vinyl monomer having a functional group (α) and the above-mentioned hydroxyl group. An isocyanate group-containing unsaturated compound obtained by reacting a vinyl monomer containing a diisocyanate compound with a diisocyanate compound in an equimolar amount.

In addition, the unsaturation used in the above method (b)
Specific examples of the sum silane compound (II) include CH_Two= CH
Si (CH_Three) (OCH_Three)_Two, CH_Two= CHSi (OCH_Three)
_Three, CH_Three= CHSi (CH_Three) Cl_Two, CH_Two= CHSi
Cl_Three , CH_Two= CHCOO (CH_Two)_TwoSi (CH_Three)
(OCH_Three)_Two, CH_Two= CHCOO (CH_Two)_TwoSi (OC
H_Three)_Three, CH_Two= CHCOO (CH_Two)_ThreeSi (CH_Three) (O
CH_Three)_Two , CH_Two= CHCOO (CH_Two)_ThreeSi (OC
H_Three)_Three, CH_Two= CHCOO (CH_Two)_TwoSi (CH_Three) C
l_Two, CH_Two= CHCOO (CH_Two)_TwoSiCl_Three , CH_Two
= CHCOO (CH_Two)_ThreeSi (CH_Three) Cl_Two , CH_Two=
CHCOO (CH_Two)_ThreeSiCl_Three , CH_Two= C (CH_Three)
COO (CH_Two)_TwoSi (CH_Three) (OCH_Three)_Two , CH_Two=
C (CH_Three) COO (CH_Two)_TwoSi (OCH_Three)_Three , CH_Two
= C (CH_Three) COO (CH_Two)_ThreeSi (CH_Three) (OC
H_Three)_Two , CH_Two= C (CH_Three) COO (CH_Two)_ThreeSi (O
CH_Three)_Three , CH_Two= C (CH_Three) COO (CH_Two)_TwoSi
(CH_Three) Cl_Two , CH_Two= C (CH_Three) COO (CH_Two)_Two
SiCl_Three , CH_Two= C (CH_Three) COO (CH_Two)_ThreeS
i (CH _Three) Cl_Two , CH_Two= C (CH_Three) COO (CH
_Two)_ThreeSiCl_Three ,

[0072]

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The following can be mentioned. These can be used alone or in combination of two or more. Examples of other vinyl monomers to be copolymerized with the unsaturated silane compound (b) include, for example, vinyl monomers having the functional group (α) exemplified in the method (a-1) and other vinyl monomers. At least one vinyl monomer.

As another example of the component (E-1),
Specific silyl group-containing epoxy resins, specific silyl group-containing polyester resins, and the like can be given. The specific silyl group-containing epoxy resin is, for example, an epoxy group in an epoxy resin such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol A epoxy resin, an aliphatic polyglycidyl ether, or an aliphatic polyglycidyl ester. And aminosilanes, vinylsilanes, carboxysilanes, glycidylsilanes and the like having a specific silyl group. The specific silyl group-containing polyester resin is, for example, produced by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with an aminosilane having a specific silyl group, a carboxysilane, a glycidylsilane, or the like. Can be.

The Mw of the component (E-1) is preferably 2,
000 to 100,000, more preferably 4,000
~ 50,000. The amount of the component (E-1) used is the same as that of the component (A) (in terms of complete hydrolysis condensate) and the component (B).
It is usually at most 95 parts by weight, preferably at most 50 parts by weight, per 100 parts by weight of the total amount of the components.

As the polymerization method for producing the above-mentioned component (E-1), for example, a method in which a monomer is added at a time and polymerization is performed, a part of the monomer is polymerized, and then the remainder is A method in which the monomer is added continuously or intermittently, a method in which the monomer is continuously added from the beginning of the polymerization, and the like can be mentioned. Further, a polymerization method in which these polymerization methods are combined may be employed. Preferred polymerization methods include solution polymerization. As the solvent used for the solution polymerization, a usual solvent can be used, and among them, ketones and alcohols are preferable. In this polymerization, known polymerization initiators, molecular weight regulators, chelating agents and inorganic electrolytes can be used.

In the present invention, the component (E-1) can be used alone or as a mixture of two or more kinds obtained as described above.

(E-2) Hybrid type aqueous dispersion; The component (E-2) is composed of a polyorganosiloxane and the above-mentioned (E)
-1) A specific polymer comprising a silyl group-containing polymer is dispersed in an aqueous medium. This specific polymer is
For example, it is dispersed in the form of particles or an aqueous sol, and the average particle diameter of the particles is usually 0.001 to 100 μm.
m, preferably 0.001 to 1 μm. The aqueous medium in the aqueous dispersion is essentially composed of water, but may contain an organic solvent such as alcohol up to about several weight% in some cases.

The component (E-2) is preferably obtained by hydrolyzing and / or condensing an organosilane and the component (E-1) in an organic solvent in the presence of the above-mentioned organometallic compound and water. The obtained reaction solution is dispersed in an aqueous medium, and then manufactured by a method of removing an organic solvent. In the above method, water present at the time of hydrolysis and / or condensation is usually 0.1 to 1 mol of organosilane.
It is about 5 to 3.0 mol, preferably about 0.5 to 2.0 mol.

When the reaction product is dispersed in the aqueous medium in the above method, a surfactant or the like can be used. As the above-mentioned surfactant, the same surfactant as used as an emulsifier in the production of the aqueous dispersion of the present invention is used.

As the organic solvent used in the above method, alcohols, aromatics, ethers, ketones, esters, and the like, which may be used in the production of the polyorganosiloxane, are suitable. These organic solvents can be removed before dispersing the reaction solution in an aqueous medium. The reaction conditions at the time of hydrolysis and / or condensation in the above method are usually 40 to 70 ° C.
And the reaction time is usually 1 to 8 hours. In the above method, a pH adjuster can be used, and examples of the pH adjuster include the same pH adjusters that may be used in the production of the aqueous dispersion of the present invention. Also, the pH value at the time of pH adjustment at this time is usually
6-10, preferably 7-8. The amount of the component (E-2) used is the above component (A) (in terms of a completely hydrolyzed condensate).
And 100 parts by weight of the total amount of component (B),
It is 1,000 parts by weight or less, preferably 200 parts by weight or less.

Component (F) The component (F) comprises a powder and / or a sol or a colloid of an inorganic compound, and is blended according to the desired properties of the coating film. When the component (F) is in the form of a sol or a colloid, the average particle size is usually 0.001 to 100 μm.
It is about.

Specific examples of the compound constituting the component (F)
Is TiO_Two , TiO_Three , SrTiO_Three, FeTi
O_Three, WO_Three, SnO_Two, Bi_TwoO_Three, In_TwoO_Three , Zn
O, Fe_TwoO_Three, RuO_Two, CdO, CdS, CdSe,
GaP, GaAs, CdFeO_Three, MoS_Two, LaRhO
_Three, GaN, CdP, ZnS, ZnSe, ZnTe, N
b_TwoO_Five, ZrO_Two, InP, GaAsP, InGaAl
P, AlGaAs, PbS, InAs, PbSe, In
In addition to semiconductors having photocatalytic activity such as Sb, SiO_Two,
Al_TwoO_Three, AlGa, As, Al (OH)_Three, Sb
_TwoO_Five, Si_ThreeN_Four, Sn-In_TwoO _Three, Sb-In_TwoO_Three ,
MgF, CeF_Three, CeO_Two , 3Al_TwoO_Three・ 2Si
O_Two, BeO, SiC, AlN, Fe, Co, Co-F
eOx, CrO_Two, Fe_FourN, BaTiO_Three, BaO-A
l_TwoO_Three-SiO_Two, Ba ferrite, SmCO_Five, YCO
_Five, CeCO_Five PrCO_Five, Sm_TwoCO₁₇, Nd_TwoFe₁₄
B, Al_FourO_Three, Α-Si, SiN_Four, CoO, Sb-S
nO_Two, Sb_TwoO_Five, MnO_Two, MnB, Co_ThreeO_Four, Co_Three
B, LiTaO_Three, MgO, MgAl_TwoO_Four, BeAl_TwoO
4, ZrSiO_Four, ZnSb, PbTe, GeSi, F
eSi_Two, CrSi_Two, CoSi_Two, MnSi_{1.7 Three}, Mg_Two
Si, β-B, BaC, BP, TiB_Two, ZrB_Two, Hf
B_Two, Ru_TwoSi _Three, TiO_Two(Rutile type), TiO_Three, P
bTiO_Three, Al_TwoTiO_Five, Zn_TwoSiO_Four, Zr_TwoSiO
_Four, 2MgO_Two-Al_TwoO_Three-5SiO_Two, Nb_TwoO_Five, Li_Two
O-Al_TwoO_Three-4SiO_Two, Mg ferrite, Ni ferrite
Light, Ni-Zn ferrite, Li ferrite, Sr
Ferrite and the like can be mentioned. These (F)
Can be used alone or in combination of two or more.
it can.

The component (F) may be in the form of a powder, an aqueous sol or colloid dispersed in water, a polar solvent such as isopropyl alcohol, or a solvent sol or colloid dispersed in a nonpolar solvent such as toluene. There is. In the case of a solvent-based sol or colloid, depending on the dispersibility of the semiconductor, it may be used after being diluted with water or a solvent, or may be used after surface treatment to improve the dispersibility.
When the component (F) is an aqueous sol or colloid, or a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less.

As a method of blending the component (F) into the aqueous dispersion, the component (F) may be added after the preparation of the aqueous dispersion, or may be added during the preparation of the aqueous dispersion, and the component (F) is added.
It may be co-hydrolyzed / condensed with the component (A) or the like.

Component (F) is used in an amount of solids, usually 500 parts by weight or less, based on 100 parts by weight of the total of component (A) (in terms of complete hydrolysis condensate) and component (B). Preferably, it is 0.1 to 400 parts by weight.

Other Additives Further , the aqueous dispersion of the present invention may contain
A filler may be separately added and dispersed for thickening the film. As such a filler, for example, water-insoluble organic pigments and inorganic pigments, other than pigments, particulate, fibrous or flaky ceramics, metals or alloys,
And oxides, hydroxides, carbides, nitrides, and sulfides of these metals.

Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigment, aluminum oxide, chromium oxide, manganese oxide, and manganese oxide. Iron, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide,
Silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica,
Zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shale green, green earth, manganese green, pigment green, ultramarine blue, navy blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, copper borate, Molybdenum blue, copper sulfide, cobalt purple, mars purple, manganese purple, pigment violet, lead oxide, calcium plumbate, zinc yellow, lead sulfide, chrome yellow, loess, cadmium yellow, strontium yellow, titanium yellow, litharge,
Pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate,
Zircon oxide, tungsten white, lead, zinc white, bunchesone white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, etc. Can be mentioned. These fillers can be used alone or in combination of two or more. The amount of the filler used is based on 100 parts by weight of the total amount of the component (A) (in terms of complete hydrolysis condensate) and the component (B).
Usually, it is 300 parts by weight or less.

The aqueous dispersion of the present invention may further contain, if desired, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, a polyoxyethylene fatty acid ester, a polycarboxylic acid type polymer surfactant, and a polycarboxylate. , Polyphosphates, polyacrylates, polyamide ester salts, dispersants such as polyethylene glycol; celluloses such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, castor oil derivatives, and ferrosilicates. Thickeners: inorganic blowing agents such as ammonium carbonate, ammonium bicarbonate, ammonium nitrite, sodium borohydride, calcium azide, and azo compounds such as azobisisobutyronitrile , 3,3'
In addition to organic blowing agents such as hydrazine compounds such as disulfohydrazine, semicarbazide compounds, triazole compounds, N-nitroso compounds, and other additives such as surfactants, silane coupling agents, titanium coupling agents, and dyes. You can also. In particular, when the aqueous dispersion of the present invention is used in an undercoating composition, an ultraviolet absorber, an ultraviolet stabilizer, and the like may be blended for the purpose of improving weather resistance and durable adhesion. As an ultraviolet absorber, ZnO,
Examples include inorganic semiconductors such as TiO ₂ (which does not exhibit a photocatalytic function) and CeO ₂ ; and organic ultraviolet absorbers such as salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and triazine. Examples of the ultraviolet stabilizer include piperidine.

Further, a leveling agent can be blended to further improve the coating property of the aqueous dispersion of the present invention. Among such leveling agents, as a fluorine-based leveling agent (trade name; the same applies hereinafter), for example,
BM100 from BM-CHEMIE
0, BM1100; Efka 77 of Efka Chemicals
2, Fuka 777; Floren series manufactured by Kyoeisha Chemical Co., Ltd .; FC series manufactured by Sumitomo 3M Limited; Fluonal TF series manufactured by Toho Chemical Co., Ltd .; BYK series of Big Chemie; Sshmego series of Shmegmann; Examples of the ether-based or ester-based leveling agent include Carfinol manufactured by Nissin Chemical Industry Co., Ltd .; and Emulgen and Homogenol manufactured by Kao Corporation.

By incorporating such a leveling agent, the finished appearance of the coating film is improved, and the coating film can be uniformly applied. The amount of leveling agent used is
It is preferably at most 5% by weight, more preferably at most 3% by weight, based on the aqueous dispersion (in terms of solid content).

As a method of blending the leveling agent, it may be blended when preparing the aqueous dispersion of the present invention, or may be blended with the aqueous dispersion at the stage of forming a coating film. You may mix | blend at both the stage of preparation of a dispersion, and formation of a coating film.

The aqueous dispersion of the present invention may be blended with another resin. Other resins include acryl-urethane resin, epoxy resin, polyester, acrylic resin, fluorine resin, acrylic resin emulsion, epoxy resin emulsion, polyurethane emulsion, polyester emulsion and the like.

The total solid content of the aqueous dispersion of the present invention containing other components prepared as described above is usually
The content is 10 to 55% by weight, preferably 15 to 50% by weight, and is appropriately adjusted according to the purpose of use. If the total solid content exceeds 45% by weight, storage stability tends to decrease.

Coated Body The aqueous dispersion of the present invention can be used as a paint as it is or by blending the above-mentioned additives after the component (D). These aqueous dispersions of the present invention can be used as an undercoating coating composition in addition to an overcoating coating composition. Examples of the configuration of the coated body of the present invention include all configurations in which a coating material containing the aqueous dispersion of the present invention is applied on a base material, and examples include the following configurations. Base material / (E-1) silyl group-containing polymer / aqueous dispersion of the present invention [aqueous dispersion alone, blend of aqueous dispersion and (E-1) silyl group-containing polymer, aqueous dispersion and (E -2)
Blend with Hybrid Aqueous Dispersion] Base Material / Aqueous Dispersion of the Present Invention [Aqueous Dispersion Alone, Blend of Aqueous Dispersion and (E-1) Silyl Group-Containing Polymer, Aqueous Dispersion and (E-2 ) Blend with hybrid aqueous dispersion] Base material / primer / aqueous dispersion of the present invention [aqueous dispersion alone, blend of aqueous dispersion and (E-1) silyl group-containing polymer, aqueous dispersion and E-2) Blend with Hybrid Aqueous Dispersion] Base Material / Primer / (E-1) Silyl Group-Containing Polymer /
Aqueous dispersion of the present invention [aqueous dispersion alone, blend of aqueous dispersion and (E-1) silyl group-containing polymer, blend of aqueous dispersion and (E-2) hybrid type aqueous dispersion] Become.

When a coating containing the aqueous dispersion of the present invention is applied to a substrate, any of the aqueous dispersions may be coated with a brush, a roll coater, a flow coater, a centrifugal coater, or the like.
An ultrasonic coater, a (micro) gravure coater, or the like may be used, or dip coating, flow coating, spraying, a screen process, electrodeposition, vapor deposition, or the like may be used.

The aqueous dispersion of the present invention has a dry film thickness
A coating film having a thickness of about 0.05 to 200 μm can be formed. Then dry at room temperature, or 30 ~
By heating and drying at a temperature of about 200 ° C. for about 1 to 60 minutes, a coating film can be formed.

When an undercoat is previously made using the aqueous dispersion of the present invention or another paint, the dry film thickness is about 0.05 to 20 μm in a single coat.
In the recoating, a coating film having a thickness of about 0.1 to 40 μm can be formed. Thereafter, the coating film can be formed on various substrates by drying at normal temperature or by heating at a temperature of about 30 to 200 ° C., usually for about 1 to 60 minutes and drying. In addition, the total film thickness of the undercoat and the overcoat is a dry film thickness, and is usually about 0.1 to 400 μm, preferably about 0.2 to 300 μm.

Substrates The substrates to which the paint containing the aqueous dispersion of the present invention can be applied include polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene-terephthalate.
Polyesters such as 2,6-naphthalate (PEN);
Polyamides such as nylon 6, nylon 6,6; polyolefins such as polyethylene (PE) and polypropylene (PP); polyacryls such as polycarbonate (PC) and polymethyl methacrylate (PMMA); ABS resins, AES resins, and polychlorinated biphenyls In addition to plastic molded products and films such as fluororesins such as polyvinyl alcohol, polyurethane, polyimide, polytetrafluoroethylene (PTFE) and ethylenetetrafluoroethylene (ETFE), and organic base materials such as wood and paper; iron , Aluminum, stainless steel and other metal substrates; cement, concrete, ALC, flexible board, mortar, slate, gypsum, ceramics,
Examples thereof include inorganic ceramic base materials such as bricks.

These substrates may be subjected to a surface treatment in advance for the purpose of adjusting the base, improving the adhesion, filling the porous substrate, smoothing, and patterning. For example, blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and the like can be mentioned.

The coating specifications include the type and condition of the substrate,
It depends on the application method. For example, in the case of a metal base material,
If rust prevention is required, an undercoat layer such as a primer or sealer may be provided. In the case of inorganic ceramic base materials, the opacity of the coating film may vary depending on the characteristics of the base material (surface roughness, impregnation, alkalinity, etc.) Usually, a primer or a sealer is used. In the case of an organic resin-based substrate, a primer or a sealer is usually used. In the case of repainting of a deteriorated coating film, if the old coating film is significantly deteriorated, use a primer or a sealer. In the case of other substrates, for example, metals, tiles, and glass that do not require rust prevention, an undercoat layer may or may not be provided depending on the application.

The undercoat layer may be a primer containing no filler and used for the purpose of ensuring adhesion to a substrate or a coating composition, preventing rust, preventing effluent, preventing moisture penetration, and the like. And a sealer containing a filler, which is used for imparting a design property of the appearance of the coating film. The types of the primer and the sealer are not particularly limited, and can be selected according to the type of the base material, the purpose of use, and the like. Examples of the type of polymer used in the undercoat layer include, for example, alkyd resins, amino alkyd resins,
Epoxy resin, polyester, acrylic resin, urethane resin, fluorine resin, acrylic silicone resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, acrylic urethane emulsion, acrylic silicone emulsion, polysiloxane, other silicone-containing emulsions, etc. Can be. These polymers are preferably used by blending two or more kinds, and the above-mentioned aqueous dispersion may be used as a component to be blended. Preferred combinations of primers include acrylic emulsion / water-based dispersion, acrylic emulsion / epoxy emulsion, silicon-containing emulsion / epoxy emulsion, epoxy emulsion / acrylic urethane emulsion, acrylic silicone emulsion / epoxy emulsion / acrylic emulsion, and the like. In addition, these polymers can be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required. Such functional groups include
For example, hydroxyl group, carboxyl group, carbonyl group, amide group, amine group, glycidyl group, alkoxysilyl group,
Examples thereof include an alkylsilyl group, an ether bond, and an ester bond. Further, a curing accelerator may be added to the resin used for the undercoat layer. For the acrylic resin, urethane resin and the like, the compounds exemplified as the (D) curing accelerator used as an optional component of the aqueous dispersion described above may be used. Specifically, amines, imidazole derivatives, acid anhydrides, polyamide resins and the like are used.

Further, on the surface of the coating film formed from the aqueous dispersion of the present invention, for example, US Pat. No. 3,986,99
No. 7, US Pat. No. 4,027,073, etc., it is also possible to form a clear layer composed of a siloxane resin-based coating such as a stable dispersion of colloidal silica and a siloxane resin. .

[0104]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods.

(1) Adhesion A cross-cut test according to JIS K5400 (Masumi 100
), The tape peel test was performed three times, and the average was used. (2) Hardness Based on pencil hardness according to JIS K5400. (3) Alkali Resistance After the test piece was immersed in a saturated calcium hydroxide aqueous solution for 60 days, the state of the coating film was visually observed. Those that did not change were regarded as “good”.

(4) Resistance to Organic Chemicals 2 cc of isopropyl alcohol was dropped on the coating film, and after 5 minutes, wiped off with a cloth. The state of the coating film was visually observed. Those that did not change were regarded as “good”. (5) Moisture Resistance After the test piece was kept under an environment of a temperature of 50 ° C. and a humidity of 95% for 1,000 hours, the test piece was taken out and the state of the coating film was visually observed. Those that did not change were regarded as “good”. (6) Weather Resistance According to JIS K5400, an irradiation test was carried out with a sunshine weather meter for 3,000 hours, and the appearance (crack, peeling, etc.) of the coating film was visually observed. Those that did not change were regarded as “good”.

(7) Water Resistance After the test piece was immersed in tap water at normal temperature for 60 days, the state of the coating film was visually observed. Those that did not change were regarded as “good”. (8) Stain resistance Carbon black / kerosene = 1/2 (weight ratio) on the coating film
Was left at room temperature for 24 hours, washed with water using a sponge, the state of contamination of the coating film was observed, and evaluated according to the following criteria. ○: No contamination △: Slightly contaminated ×: Severe contamination

Examples 1 to 6 and Comparative Examples 1 to 2 A homogeneous solution obtained by mixing the component (A), the component (B) and the component (C) shown in Table 1 was cooled on ice, and then dodecylbenzene sulfone was used as an emulsifier. Sodium acid mixed, added to product hopper and stirred with agitator 4k
The mixture was emulsified with a high-pressure homogenizer (Microfluidizer M-110Y; manufactured by Mizuho Industry Co., Ltd.) while driving air of gf / cm ² was applied. This emulsion was charged into a separable flask, and a predetermined amount of an initiator: potassium persulfate aqueous solution shown in Table 1 was added with stirring. After nitrogen replacement 65
C. and polymerized for 4 hours. Table 1 shows the polymerization results.
Shown in

[0109]

[Table 1]

Examples 7 to 12 and Comparative Examples 3 to 4 The aqueous dispersions obtained in Examples 1 to 6 and Comparative Examples 1 to 2 and 2% of aqueous dibutyltin dilaurate as a curing accelerator
(Solid content) and oxazoline-based aqueous emulsion K2
020 (manufactured by Nippon Shokubai Co., Ltd.) 5% (solid content)
By mixing, a coating agent (clear) was prepared. 50 g / m2 of a primer, as required, on a dry weight basis
^{2 After} applying and drying, each obtained coating agent,
A test piece was prepared by applying 50 g / m ² by dry weight and heating at 120 ° C. for 10 minutes. About the obtained test piece,
Various evaluations were made. Table 2 shows the evaluation results.

[0111]

[Table 2]

* 1: JIS A5043F * 2: thickness 12 mm

Examples 13 to 18 Using the aqueous dispersions A to F obtained in Examples 1 to 6,
Was mixed by a sand mill, and aqueous dibutyltin dilaurate was added as a hardening accelerator in 2 parts.
% (Solid content) and oxazoline-based aqueous emulsion K
2020 (manufactured by Nippon Shokubai) was added at 5% (solid content) and mixed to prepare a coating agent (enamel). To each substrate, a primer (enamel) was added at a dry weight of 50 g / m ^2.
After application and drying, each of the obtained coating agents was applied at a dry weight of 50 g / m ² and heated at 120 ° C. for 10 minutes to prepare a test piece. Various evaluations were performed on the obtained test pieces. Table 3 shows the evaluation results. As the primer, 55 parts of titanium oxide (white) and 28.7% of calcium carbonate were used for 100 parts of the resin or emulsion described in Table 4 (described in Table 3 as “primer”).
Part, clay 7 parts, bengara 7 parts, HEC thickener 27.
A mixture obtained by adding 7 parts and mixing with a sand mill was used.

[0114]

[Table 3]

The primers in Tables 2 and 3 are as follows. : Acrylic silicone emulsion: Acrylic emulsion / water-based dispersion A (100/2)
0): acrylic emulsion / epoxy emulsion (5
0/50): Acrylic urethane emulsion: Acrylic emulsion: Epoxy emulsion / silicon-containing emulsion (100/20): Epoxy emulsion / polyamideamine (curing agent) (100/50): Epoxy emulsion / triethylamine (curing agent) (100/20) 5)

[0116]

According to the aqueous dispersion of the present invention, storage stability is extremely excellent, and adhesion, alkali resistance,
It is capable of forming a transparent and high hardness coating film having an excellent balance of performances such as resistance to organic chemicals, moisture resistance, weather resistance, (warm) water resistance and contamination recovery, and is particularly useful as a coating agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 5/02 C09D 5/02 157/00 157/00 157/06 157/06 183/00 183/00 / / C08F 2/24 C08F 2/24 Z 2/44 2/44 B

Claims (5)

[Claims] 1. A mixture comprising (A) at least one selected from an organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane and (B) a radically polymerizable vinyl monomer in an emulsified state, An aqueous dispersion obtained by hydrolysis / condensation reaction and radical polymerization. 2. The aqueous dispersion according to claim 1, further comprising (C) a compound having a polymerizable unsaturated group and a group capable of forming a siloxane bond. 3. A mixture containing at least one selected from the group consisting of (A) an organosilane, a hydrolyzate of the organosilane and a condensate of the organosilane, and (B) a radical polymerizable vinyl monomer, is mixed with water and a surfactant. The method for producing an aqueous dispersion according to claim 1, wherein the emulsion is emulsified in the presence of an agent, and a hydrolysis / condensation reaction and radical polymerization are performed. 4. A coated body in which a coating material containing the aqueous dispersion according to claim 1 is coated on a base material. 5. The coated body according to claim 4, wherein the base material is provided with an undercoat layer.