JP2002348431A - Aqueous dispersion and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous dispersion excellent in weatherability, stain resistance and particularly adhesiveness to a base material. SOLUTION: The aqueous dispersion comprises (i) an aqueous emulsion of complex polymer particles obtained by mixing (A) an organosilane such as methyltrimethoxysilane or dimethyldimethoxysilane or its partial condensate, (B) a radical polymerizable monomer, (C) an emulsifier, (D) water and (E) a hydrolysis catalyst of the (A) component, progressing hydrolysis of the (A) component to reduce particles in emulsion, and adding (F) a radical polymerization initiator to react to progress a hydrolysis/condensation reaction of the (A) component and a polymerization reaction of the (B) component, (ii) an aqueous emulsion of complex particles of a (meth)acrylic polymer and an organopolysiloxane and/or (iii) an aqueous emulsion of (meth)acrylic polymer particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous dispersion, and more particularly, to a composite polymer particle obtained through a specific condensation / polymerization process of an organosilane and a radical polymerizable monomer, and (meth) Composite particles of acrylic polymer and organopolysiloxane and / or (meth)
The present invention relates to an aqueous dispersion obtained by mixing acrylic polymer particles and useful as a paint and the like, and a coated body coated with a paint containing the aqueous dispersion.

[0002]

2. Description of the Related Art Conventionally, coating materials have been used in various fields, and the range of application thereof has been steadily expanding. Thus, there is a demand for a coating material which has an excellent balance of performances such as adhesion, chemical resistance, moisture resistance, weather resistance, (warm) water resistance, and contamination recovery properties and can form a coating film having high hardness. As a coating material that satisfies a part of such requirements, a composition comprising a partial condensate of an organosilane, a dispersion of colloidal silica, and a silicone-modified acrylic resin (JP-A-60-13)
No. 5465), or a condensate of an organosilane,
A composition comprising a chelate compound of zirconium alkoxide and a hydrolyzable silyl group-containing vinyl resin (Japanese Patent Application Laid-Open No. 64-1769) has been proposed. However, these coating materials are all solvent type, and in recent years, from the viewpoint of low pollution, resource saving, safety and health, etc., there is a strong demand for desolvation, and switching to water-based coating materials has been promoted, Its use is expanding, and accordingly, the required performance of water-based coating materials is becoming increasingly sophisticated.

Under these circumstances, the development of a reactive resin emulsion has been intensively studied as one that can be expected to improve performance such as water resistance and chemical resistance as a water-based coating material. One of them is hydrolyzable silyl. Resin emulsions having groups have been proposed. For example, Japanese Patent Application Laid-Open No. 7-2
JP-A-6035 discloses a reactive resin emulsion containing a vinyl polymer having a hydrolyzable silyl group and an amine imide group. An aqueous coating composition comprising a dispersion and an aqueous dispersion of a tin compound is disclosed. However, these hydrolyzable silyl group-containing resin emulsions are inferior in storage stability.Especially, when this emulsion is stored for a long period of time, gelation occurs, and the performance of a coating film obtained from the emulsion after long-term storage is poor.
Unlike coatings obtained from emulsions immediately after production,
There is a drawback that stable quality cannot be ensured, there is a problem in practicality, and even when storage stability is relatively good, performance balance including adhesion, weather resistance, stain resistance, etc. It is not satisfactory. Also, Japanese Patent Application Laid-Open
JP-A 1-255846 proposes a silicone resin-containing emulsion composition obtained by emulsion polymerization of a solution containing a silanol group-containing silicone resin and a radical polymerizable monomer. Because a large amount of substances precipitate or the polymerizability decreases,
It is difficult to use industrially.

On the other hand, among polymer components conventionally used in coating materials, (meth) acrylic polymers have excellent transparency and film-forming properties, and are widely used as aqueous dispersions in coating materials. In addition, polysiloxane has excellent weather resistance, water repellency, and adhesion to inorganic substrates, and aims at synergistic effect of the excellent performance of these (meth) acrylic polymer and polysiloxane, for example, JP-A-3-45628 and JP-A-4-261454
Japanese Patent Application Laid-Open Publication No. H11-15064 proposes that both polymer components are compounded and used as a coating material or the like. However,
Even though these composites of (meth) acrylic polymer and polysiloxane have good weather resistance, none of them is satisfactory in terms of adhesion to organic substrates and stain resistance to rain streaks and the like. Further, JP-A-4-214747 discloses a polymer latex containing an organopolysiloxane obtained by copolymerizing a carbonyl group-containing monomer and another monomer in the presence of a hydrolyzable silane. And a polyfunctional hydrazine derivative, and a self-crosslinking polymer latex composition has been proposed. However, it was also difficult for this composition to maintain the weather resistance and stain resistance of the coating film for a long period of time.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art.
As a composite material of a vinyl polymer such as a (meth) acrylic polymer and an organopolysiloxane, an aqueous dispersion having excellent weather resistance and stain resistance and particularly excellent adhesion to a substrate is provided. It is in.

[0006]

According to the present invention, (a) the following components (A) to (E) are mixed and emulsified to promote the hydrolysis of the component (A) and to make the emulsion finer. The following component (F) is added and reacted to give (A)
An aqueous emulsion of composite polymer particles obtained by advancing the hydrolysis / condensation reaction of the component and the polymerization reaction of the component (B), and a composite particle of the (b) (meth) acrylic polymer and an organopolysiloxane. An aqueous dispersion comprising an aqueous emulsion and / or (c) an aqueous emulsion of (meth) acrylic polymer particles. (A): at least one selected from the group consisting of an organosilane represented by the following general formula (1), a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate.
Parts by weight,

[0007]

Embedded image (Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and 2
R ¹ may be the same or different from each other, and R ²
Represents a linear or branched alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and two R ²
May be the same or different from each other, and n is an integer of 0 to 2. )

(B): radical polymerizable monomer 99-
1 part by weight [however, (A) + (B) = 100 parts by weight] (C): 0.1 to 5 parts by weight of emulsifier (D): 50 to 2,000 parts by weight of water (E): The above (A) Component hydrolysis catalyst 0.01 to 5
Parts by weight (F): 0.01 to 5 parts by weight of a radical polymerization initiator

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (A) Aqueous Emulsion In the present invention, (A ) an aqueous emulsion of composite polymer particles (hereinafter, simply referred to as "(A) aqueous emulsion").
Is obtained by mixing and emulsifying the components (A) to (E) to promote hydrolysis of the component (A), making the emulsion finer, and then reacting by adding the component (F).
It is obtained by promoting the hydrolysis / condensation reaction of the component (A) and the polymerization reaction of the component (B).

-(A) Component- (A) The component (A) used in the aqueous emulsion is an organosilane represented by the above general formula (1) (hereinafter referred to as "organosilane (1)"), or an organo. It comprises at least one selected from the group consisting of a hydrolyzate of silane (1) and a condensate of the hydrolyzate.

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
Examples of the monovalent organic group of 8 include a phenyl group; a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and n
Linear groups such as -butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, A branched or cyclic alkyl group; an acyl group such as an acetyl group, a propionyl group, a butyryl group, a valeryl group, a benzoyl group, a trioil group, and a caproyl group; an alkenyl group such as a vinyl group and an allyl group;
In addition to the substituted derivatives of these groups, mention may be made of epoxy groups, glycidyl groups, (meth) acryloyloxy groups, ureido groups, amide groups, fluoroacetamide groups, isocyanate groups, and the like.

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,
(Meth) acryloyloxy group, ureido group, ammonium base and the like can be mentioned. However, the total carbon number of R ¹ composed of these substituted derivatives is 8 or less including carbon atoms in the substituent.

The linear or branched 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, t-butyl group, n-pentyl group and the like. Examples of the acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group and a caproyl group. be able to.

Specific examples of the organosilane (1) include:
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, n-propyltrimethoxysilane, n-
Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyl Trimethoxysilane,
n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 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-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2-
(3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) ataacryloyloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Trialkoxysilanes such as propyltriethoxysilane;

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-octyldimethoxy Silane, di-n-octyldiethoxysilane, di-n-
Cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane,
In addition to dialkoxysilanes such as diphenyldiethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropyldiethoxymethylsilane, methyltriacetyloxysilane, dimethyldiacetyloxysilane, and the like can be given. .

Of these organosilanes (1), trialkoxysilanes and dialkoxysilanes are preferred. In addition, trialkoxysilanes are preferably methyltrimethoxysilane and methyltriethoxysilane, and dialkoxysilanes are preferably dimethyldimethoxysilane and dimethyldiethoxysilane. The organosilane (1) can be used alone or in combination of two or more.

Further, the hydrolyzate of the organosilane (1) in the component (A) is obtained by mixing the hydrolyzate of the organosilane (1) with Si.
-OR ² group is hydrolyzed to produce silanol (Si-OH)
In the present invention, it is not necessary that all of the OR ² groups possessed by the organosilane (1) are hydrolyzed. The above may be hydrolyzed or a mixture thereof. In addition, a partial condensate of the hydrolyzate of organosilane (1) in the component (A) (hereinafter, simply referred to as a “partial condensate”) is formed by condensing silanol groups in the hydrolyzate to form siloxane (Si- OS
i) Although a bond is formed, in the present invention, it is not necessary that all of these groups are condensed, and a concept including a mixture of only some of the groups or a mixture of different degrees of condensation is included. It is.

The component (A) in the present invention is preferably used in a state where the organosilane (1) and the partial condensate are mixed. By co-condensing the organosilane (1) and the partial condensate in this manner, a coating film having excellent properties can be formed from the final aqueous dispersion. Further, since the polymerization stability when the radical polymerizable monomer is polymerized by adding the component (F) described later is improved and the polymerization can be easily performed even in a state of a high solid content, it is advantageous in terms of industrialization. There is also.

When the organosilane (1) and the partial condensate are used in combination, it is preferable to use dialkoxysilanes, especially dimethyldimethoxysilane, dimethyldiethoxysilane and the like as the organosilane (1). By using dialkoxysilanes, a linear portion is added to the molecular chain of the organopolysiloxane, and the flexibility of the obtained composite polymer particles is increased. Furthermore, when a coating film is formed using the obtained aqueous dispersion, there is also an effect that a coating film having excellent transparency can be obtained.

Further, when the organosilane (1) and the partial condensate are used in combination, the partial condensate is preferably a trialkoxysilane alone, or 40 to 95 mol% of a trialkoxysilane and a dialkoxysilane. Class 60-5
Those obtained from a combination with mol% are preferred. By using trialkoxysilane and dialkoxysilanes in this ratio, the resulting coating film can be softened and the alkali resistance can be improved.

When the organosilane (1) and the partial condensate are used in combination, the organosilane (1) is previously hydrolyzed and condensed to prepare a partial condensate of the organosilane (1) before use. Is preferred. In preparing the partial condensate, it is preferable to add an appropriate amount of water and, if necessary, an organic solvent to the organosilane (1) to hydrolyze and condense the organosilane (1). In this case, the amount of water used is usually about 1.2 to 3.0 mol, preferably about 1.3 to 2.0 mol, per 1 mol of the organosilane (1).

The organic solvent used as required is not particularly limited as long as it can be uniformly mixed with the obtained partial condensate and the component (B) described later.
For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be mentioned. 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, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene monomethyl ether acetate, diacetone Alcohol and the like can be mentioned.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like, 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, n-propyl acetate, n-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 partial condensate, the condensation
Prior to the polymerization reaction, the organic solvent may be removed.

The weight average molecular weight in terms of polystyrene of the partial condensate (hereinafter referred to as "Mw") is preferably 800 to 800.
100,000, more preferably 1,000 to 50,
000.

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

As the component (A), organosilane (1)
When both the condensate and the partial condensate are used, the mixing ratio of the two is such that the organosilane (1) is 95 to 5% by weight (converted as a complete hydrolysis condensate), preferably 90 to 10% by weight, Is 5 to 95% by weight (converted as a completely hydrolyzed condensate), preferably 10 to 90% by weight [provided that the total of organosilane (1) and its partial condensate is 100% by weight]. When the content of the partial condensate 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 reduced.
If the ratio exceeds the above, the proportion of the organosilane (1) component may decrease, and it may be difficult to emulsify the mixture containing the component (A). The polymerization stability of the component (B) and the stability of the emulsion during polymerization And the film-forming property of the resulting aqueous dispersion may be reduced. Here, the “completely hydrolyzed condensate” refers to the organosilane (1)
It means that 100% of the Si-OR ² group in the inside is hydrolyzed to form a silanol group, which is further completely condensed to form a siloxane bond.

Component (B) The component (B) used in the aqueous emulsion is not particularly limited as long as it is a radical polymerizable monomer having a radically polymerizable unsaturated bond. Examples of the radical polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, and i-butyl (meth). A) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, cyclohexyl (meth)
Acrylate, pt-butylcyclohexyl (meth)
(Meth) acrylates such as acrylate, phenyl (meth) acrylate and benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2
Hydroxyl-containing (meth) acrylates such as -hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate;

2-aminoethyl (meth) acrylate,
2-dimethylaminoethyl (meth) acrylate, 2-
Amino group-containing (meth) acrylic esters such as aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate; glycidyl (meth) ) Acrylate, 2-
Epoxy group-containing (meth) acrylates such as (3,4-epoxycyclohexyl) ethyl (meth) acrylate; fluorine atom-containing such as trifluoroethyl (meth) acrylate and pentadecafluoro-n-octyl (meth) acrylate (Meth) acrylic esters; 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, di Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
Polyfunctional (meth) acrylates such as acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid;
Unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene,
3,4-dimethylstyrene, 4-ethylstyrene, 3,
4-diethylstyrene, 4-t-butylstyrene, 4-
Methoxystyrene, 4-ethoxystyrene, 4-hydroxymethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 2,4-
Aromatic vinyl compounds such as dichlorostyrene, 2,6-dichlorostyrene, 1-vinylnaphthalene and divinylbenzene;

(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth)
Unsaturated amide compounds such as acrylamide, Nn-butoxymethyl (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, maleic amide; unsaturated imides such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide Compounds; vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; 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-phenoxypropyl) amine (meth) acrylimide, and the like Amineimide group-containing vinyl compounds of the following formulas; unsaturated ether compounds such as ethyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-aminoethyl vinyl ether and allyl glycidyl ether; (meth) acrolein, crotonaldehyde, formyl styrene, formyl-α-methyl styrene , (Meth) acrylamide pivalinaldehyde, 3-
(Meth) acrylamidomethyl-anisaldehyde, the following general formula (2)

[0031]

Embedded image (Wherein, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵
Represents an alkyl group having 1 to 3 carbon atoms, and R ⁶ represents 1 to 3 carbon atoms.
4 represents an alkyl group. )

Β- (meth) acryloxy-
Aldo group-containing unsaturated compounds such as α, α-dialkyl propanals; diacetone (meth) acrylamide, vinyl alkyl ketones having 4 to 7 carbon atoms (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl-n-propyl ketone) , Vinyl-i-propyl ketone, vinyl-n-
Butyl ketone, vinyl-i-butyl ketone, vinyl-t
-Butyl ketone), vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone, diacetone (meth) acrylate, acetonitrile (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate-acetyl acetate, 3-hydroxypropyl (meth) acrylate-acetyl acetate, 2-hydroxybutyl (meth) acrylate-acetyl acetate, 3-hydroxybutyl (meth) acrylate-acetyl acetate,
Keto group-containing unsaturated compounds such as 4-hydroxybutyl (meth) acrylate-acetyl acetate, butanediol-1,4- (meth) acrylate-acetyl acetate; dicaprolactone;

UV-absorbing monomers such as p- (meth) acryloyloxyphenyl salicylate and 2-hydroxy-4- (meth) acryloyloxybenzophenone;
2- [2'-hydroxy-5 '-{2 "-(meth) acryloyloxyethyl} phenyl] benzotriazole, 4- (meth) acryloyloxy-2,2,6,6
-Tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine,
-(Meth) acryloyloxy-1,2,2,6,6-
Pentamethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine,
4-cyano-4- (meth) acryloylamino-2,
2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,
2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-
Crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-
Radical scavenging monomers such as tetramethylpiperidine and 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine.

The β- (meth) acryloxy-α, α-
Specific examples of the dialkylpropanals include β- (meth) acryloxy-α, α-dimethylpropanal [that is, β- (meth) acryloxypivalinaldehyde],
β- (meth) acryloxy-α, α-diethylpropanal, β- (meth) acryloxy-α, α-dipropylpropanal, β- (meth) acryloxy-α-methyl-α-butylpropanal, β- (Meth) acryloxy-α, α, β-trimethylpropanal and the like.

Further, in the present invention, a polymerizable unsaturated group copolymerizable with the radical polymerizable vinyl monomer and a group capable of forming a siloxane bond such as an alkoxysilyl group cocondensable with the component (A) are used. Can be used as a radically polymerizable vinyl monomer. By adding the radical polymerizable silane coupling agent to the aqueous dispersion of the present invention, the hybrid property between the organopolysiloxane component and the other polymer components in the aqueous dispersion is improved. There is an advantage that the crack resistance, transparency, weather resistance, and the like of the coating film formed from the dispersion are improved.

Specific examples of the radical polymerizable silane coupling agent include: CH ₂ ＣＨCHSi (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCH
Si (OCH ₃ ) ₃ , CH ₂ ＣＨCHSi (CH ₃ ) Cl ₂ ,
CH ₂ ＣＨCHSiCl ₃ , CH ₂ ＣＨCHCOO (CH ₂ )
₂ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (C
_{H 2) 2 Si (OCH 3} ) 3, CH 2 = CHCOO (CH 2)
₃ Si (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣＨCHCOO (C
_{H 2) 3 Si (OCH 3} ) 3, CH 2 = CHCOO (CH 2)
_{2 Si (CH 3) Cl 2} , CH 2 = CHCOO (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 ) (O
CH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ Si
(OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ S
i (CH ₃ ) (OCH ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ＣC (CH ₃ ) CO
O (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ )
COO (CH ₂ ) ₂ SiCl ₃ , CH ₂ ＣC (CH ₃ ) CO
O (CH ₂ ) ₃ Si (CH ₃ ) Cl ₂ , CH ₂ ＣC (CH ₃ )
COO (CH ₂ ) ₃ SiCl _{3 and the} like can be mentioned.

The radical polymerizable monomer in the present invention is preferably a (meth) acrylic compound, more preferably a (meth) acrylic acid ester, a hydroxyl group-containing (meth) acrylic acid ester, or (meth) acrylic acid. Particularly preferred are methyl methacrylate, n-butyl methacrylate, 2-hydroxyethyl methacrylate and acrylic acid. Hereinafter, these more preferred (meth) acrylic compounds are also referred to as “(meth) acrylic monomers (B-1)”.

As the radical polymerizable monomer in the present invention, it is preferable to use a keto group-containing unsaturated compound and / or an ald group-containing unsaturated compound together with the (meth) acrylic monomer (B-1). Thus, a keto group and / or an ald group can be contained in the obtained composite polymer. In this case, as the unsaturated compound containing a keto group or the unsaturated compound containing an ald group, acrolein, diacetone acrylamide, and vinyl methyl ketone are preferable.

In the present invention, when a mixture of the (meth) acrylic monomer (B-1) and another monomer is used as the radical polymerizable monomer, the (meth) acrylic (B-1) The content is preferably 1 to
It is 99% by weight, more preferably 10 to 90% by weight. Further, when the (meth) acrylic compound (B-1) is used in combination with a keto group-containing unsaturated compound and / or an ald group-containing unsaturated compound, a keto group-containing unsaturated compound and / or an ald group-containing unsaturated compound are used. Is preferably 0.1 to 20% by weight, more preferably 1 to 5% by weight, based on all monomers.

The proportion of the component (A) to the component (B) in the aqueous dispersion of the present invention is such that the component (A) is used in an amount of 1 to 99 parts by weight (converted as a complete hydrolyzed condensate), preferably 10 to 100 parts by weight. To 90 parts by weight, and the component (B) is 99 to 1 part by weight, preferably 90 to 10 parts by weight [provided that (A) +
(B) = 100 parts by weight]. When the use ratio of the component (B) is less than 1 part by weight, the film-forming property and crack resistance deteriorate. On the other hand, when the use ratio exceeds 99 parts by weight, the weather resistance remarkably deteriorates.

-Component (C)-(a) Examples of the emulsifier which is the component (C) used in the aqueous emulsion include alkyl sulfates, alkyl aryl sulfates, alkyl phosphates, and fatty acid salts. Anionic surfactants; Cationic surfactants such as alkylamine salts and alkyl quaternary amine salts; Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, and block type polyethers; carboxylic acids Any type (eg, amino acid type, betainic acid type, etc.) and sulfonic acid type amphoteric surfactants can be used. These surfactants can be used alone or in combination of two or more.

The amount of the emulsifier used is a total of 1 component (A) (however, converted as a complete hydrolysis condensate) and 1 component (B).
The amount is 0.1 to 5 parts by weight, preferably 1.0 to 3 parts by weight based on 00 parts by weight. When the use amount of the emulsifier is less than 0.1 part by weight, it becomes difficult to sufficiently emulsify the reaction components, and the stability of the emulsion at the time of hydrolysis / condensation and at the time of radical polymerization is reduced. ,
Foaming becomes intense, which is not preferable.

-Component (D)-(A) The amount of water used as the component (D) in the aqueous emulsion is as follows: water added to the component (A) in advance;
As the total amount of water added when mixing the components (A) to (C) and (E), the sum of the component (A) (provided as a complete hydrolysis condensate) and the component (B) 50 to 2,000 parts by weight, preferably 100 to 100 parts by weight,
It is 1,000 parts by weight. If the amount of water used is less than 50 parts by weight, emulsification becomes difficult or the stability of the emulsion after emulsification decreases, while if it exceeds 2,000 parts by weight, productivity decreases, which is not preferable.

-(E) Component- (A) The component (E) used in the aqueous emulsion includes:
The component (A) is a hydrolysis catalyst (hereinafter simply referred to as “hydrolysis catalyst”). By using the hydrolysis catalyst, the molecular weight of the organopolysiloxane produced by the condensation reaction of the component (A) used is increased, and a coating film having excellent strength, long-term durability, etc. can be obtained from the final aqueous dispersion. It can be formed, and the coating film can be made thicker and the coating operation can be facilitated.

Examples of the hydrolysis catalyst include an acidic compound, an alkaline compound, a salt compound, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter referred to as “hydrolysis product”).
Organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organometallic compounds and the like”. ) And the like. Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyltitanic acid, p-toluenesulfonic acid, phthalic acid, and (meth) acrylic acid which is also the component (B). Of these acidic compounds, acetic acid and (meth) acrylic acid are preferred. Also,
Examples of the alkaline compound include sodium hydroxide and potassium hydroxide. Of these alkaline compounds, sodium hydroxide is preferred. Examples of the salt compound include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.

Examples of the amine compound include ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, m-phenylenediamine, p-phenylenediamine, and ethanolamine. , Triethylamine,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl)
-Aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropyltriethoxysilane, 3-
In addition to (2-aminoethyl) -aminopropylmethyldimethoxysilane, 3-anilinopropyltrimethoxysilane, alkylamine salts, quaternary ammonium salts, and various modified amines used as a curing agent for epoxy resins. it can. Among these amine compounds, 3-aminopropyl trimethoxysilane, 3-aminopropyl
Aminopropyltriethoxysilane and 3- (2-aminoethyl) -aminopropyltrimethoxysilane are preferred.

Examples of the organometallic compound include, for example, tetra-n-butoxyzirconium, 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. Organic zirconium compounds: tetra-i-propoxytitanium, di-i-propoxybis (ethylacetoacetate) titanium,
Organic titanium compounds such as di-i-propoxy bis (acetylacetate) titanium and di-i-propoxy bis (acetylacetone) titanium; tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di- Aluminum i-propoxy acetylacetonate, aluminum i-propoxybis (ethylacetoacetate), aluminum i-propoxybis (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), mono In addition to organoaluminum compounds such as acetylacetonate bis (ethylacetoacetate) aluminum, and partial hydrolysates of these organometallic compounds,

(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 (O
COCH = CHCOOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (O
COCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn
(OCOCH = CHCOOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ S
n (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,

[0049]

Embedded image

(C ₄ H ₉ ) Sn (OCOC ₁₁ H ₂₃ ) ₃ ,
₄ H ₉₎ Sn (OCONa) carboxylic acid type organic tin compounds such as _{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 = CHCOOC ₈ H ₁₇ ) ₃ , (C ₈ H ₁₇ ) S
n (SCOCH = CHCOOC ₈ H ₁₇ ) ₃ ,

[0051]

Embedded image

(C ₄ H ₉ ) ₂ Sn = S, (C ₈ H ₁₇ ) ₂ Sn = S, and the like.

[0053]

Embedded image

(C ₄ H ₉ ) SnCl ₃ , (C ₄ H ₉ ) ₂ SnCl ₂ , (C
₈ H ₁₇ ) ₂ SnCl ₂ ,

[0055]

Embedded image

(C ₄ H)
₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO and other organic tin oxides, and reaction products of these organic tin oxides with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate and dioctyl phthalate. Can be mentioned.

Of these organometallic compounds, etc.
n-butoxyethylacetoacetate zirconium,
Di-i-propoxybis (acetylacetonato) titanium, di-i-propoxyethylacetoacetate aluminum, tris (ethylacetoacetate) aluminum, or partial hydrolysates of these compounds are preferred. The hydrolysis catalyst can be used alone or as a mixture of two or more thereof, and can also be used as a mixture with a zinc compound or another reaction retarder.

The amount of the hydrolysis catalyst to be used is 0.01 to 5 parts by weight based on 100 parts by weight of component (A) (converted as a complete hydrolysis condensate) in cases other than organometallic compounds.
Parts by weight, preferably 0.1 to 4 parts by weight, and in the case of an organometallic compound or the like, 100 parts by weight of the component (A) (however,
0.1 to 5
Parts by weight, preferably 0.1 to 4 parts by weight. If the amount of the hydrolysis catalyst used is less than the above range, the hydrolysis / condensation reaction of the component (A) may be delayed, and a desired high-molecular-weight organopolysiloxane may not be obtained. (A) The storage stability of the aqueous emulsion is lowered, and cracks tend to occur in the coating film formed from the final aqueous dispersion, which is not preferable.

-(F) Component- (A) The component (F) used in the aqueous emulsion is:
It comprises a radical polymerization initiator for initiating the polymerization of the component (B). As the radical polymerization initiator, for example, potassium persulfate, sodium persulfate, persulfates such as ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butylperoxymaleic acid, succinic peroxide, Water-soluble initiators such as 2,2'-azobis [2-N-benzylamidino] propane hydrochloride; benzoyl peroxide, cumene hydroperoxide, diisopropyl peroxy dicarbonate, cumyl peroxy neodecanoate, cumyl peroxy Octoate,
Oil-soluble initiators such as azobisisobutyronitrile; and redox initiators using a reducing agent such as sodium acid sulfite, Rongalit, or ascorbic acid in combination.

The amount of the radical polymerization initiator used is 0.01 to 5 parts by weight based on 100 parts by weight of the total of the component (A) (however, converted as a complete hydrolysis condensate) and the component (B). Preferably it is 0.1 to 3 parts by weight. If the amount of the radical polymerization initiator is less than 0.01 part by weight, the rate of initiation of the polymerization of the radically polymerizable monomer (B) will be low, while if it exceeds 5 parts by weight, the rate of initiation will be too high, and Is not preferred because the stability of the polymer decreases and aggregates are easily generated.

(A) Preparation of Aqueous Emulsion (A) The aqueous emulsion is obtained by mixing and emulsifying the components (A) to (E) to promote hydrolysis of the component (A) and to refine the emulsion. Next, the component (F) is added and reacted to carry out the hydrolysis and condensation reaction of the component (A) and the polymerization of the component (B) (hereinafter, hydrolysis and condensation of these components).
Condensation reaction and polymerization reaction
Also called. ) Is prepared. In the step of mixing and emulsifying to promote the hydrolysis of the component (A), the condensation reaction of the hydrolyzate may also proceed. The component (E) is preferably added after mixing and emulsifying the components (A) to (D), and thereafter adjusting the average particle size of the emulsion.

(A) The polymerization of the component (B) after the emulsion is made fine when preparing an aqueous emulsion can be said to be one type of miniemulsion polymerization. In the miniemulsion polymerization, the component (B) is usually added to an aqueous medium,
This is emulsion polymerization in which the emulsion is finely emulsified and dispersed so as to have an average particle size of 0.5 μm or less, preferably 0.3 μm or less, particularly preferably 0.03 to 0.2 μm, and the dispersion is maintained while maintaining the dispersion state. (A) When preparing an aqueous emulsion, the process for making the emulsion finer is as follows:
The hydrolysis may be performed simultaneously with the progress of the hydrolysis of the component (A), or may be performed after the hydrolysis of the component (A) has progressed to some extent.

(A) The mixing and emulsification of each component at the time of preparing the aqueous emulsion can be carried out using ordinary stirring means. It can be carried out using a mixer, an ultrasonic disperser or the like. In addition, the conditions of the condensation / polymerization reaction are such that the reaction temperature is usually 25 to 80.
C., preferably 40 to 70 ° C., and the reaction time is usually 0.
It is 5 to 15 hours, preferably 1 to 8 hours.

In this condensation / polymerization reaction, the emulsified state
The hydrolysis / condensation reaction of the organosilane (1) in the component (A) and the polymerization reaction of the component (B) proceed simultaneously. In the case where the component (A) contains the organosilane (1) and the partial condensate, the reaction may be carried out by a hydrolysis reaction of the organosilane (1) or a condensation reaction of the partial condensate alone, or by the organosilane (1). The co-condensation reaction between the hydrolyzate and the partial condensate may proceed simultaneously. According to such a condensation / polymerization reaction, a network structure in which an organopolysiloxane component derived from the component (A) and a vinyl polymer component derived from the component (B) penetrate into each other in the obtained composite polymer particles. (IPN). When the component (B) contains a radical polymerizable silane coupling agent, the organopolysiloxane component and the vinyl polymer component are chemically bonded, and further, the chain transfer of the reactive radical during the polymerization of the component (B). May occur, and the vinyl-based polymer component is grafted to the organopolysiloxane chain and chemically bonded. Further, in the condensation / polymerization reaction, 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, so that a favorable working environment is ensured.

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,
It is preferable to adjust the pH by adding a basic compound, and when each of these components has a basic group such as an amino group or an amine imide group, after the condensation / polymerization reaction, an acidic compound is added. It is preferred to adjust the pH. Furthermore, when each of these components has both an acidic group and a basic group, and when the ratio of either one of the groups is large, after the condensation / polymerization reaction, according to the ratio of these groups,
It is preferable to adjust the pH by adding a basic compound or an acidic compound. Thereby, the hydrophilicity of the obtained composite polymer particles can be increased, and the dispersibility can be improved.

Examples of the basic compound used for adjusting the pH include amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine and dimethylaminoethanol;
Examples thereof include alkali metal hydroxides such as caustic potash and caustic soda. 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, Examples thereof include citric acid, adipic acid, (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. The pH of the aqueous emulsion (a) after the pH adjustment is usually 6 to 10, preferably 7 to 8.

(A) The average particle size of the composite polymer particles in the aqueous emulsion is preferably 0.01 to 50 μm, more preferably 0.1 to 5 μm. The solid content concentration of the aqueous emulsion (a) is usually 10 to 60% by weight, preferably 20 to 50% by weight. This solid content concentration is usually adjusted by the amount of the component (D). (A) The medium in the water-based emulsion consists essentially of water, but may contain an organic solvent such as alcohol up to about several weight% in some cases. When (a) the aqueous emulsion contains the organic solvent used in the preparation of the component (A), the final aqueous dispersion can be prepared after removing the organic solvent. Further, an organic solvent, for example, an organic solvent used at the time of preparing the component (A) can be added to the aqueous emulsion (a) if necessary.

(B) Aqueous Emulsion Aqueous emulsion of composite particles of (b) (meth) acrylic polymer and organopolysiloxane in the present invention (hereinafter, simply referred to as “(b) aqueous emulsion”).
Is, for example, in the presence of (meth) acrylic polymer particles (hereinafter, referred to as “(meth) acrylic polymer particles (i)”) having a functional group capable of condensing with an organosilane that forms an organopolysiloxane. To produce an organopolysiloxane by condensing the organosilane. In this case, the (meth) acrylic polymer particles react in advance with a condensable functional group in the (meth) acrylic polymer to form a group capable of forming the linking group (hereinafter referred to as a “linking functional group”). ) Having a silane compound capable of co-condensing with the organosilane (hereinafter referred to as “reactive silane compound”), and then condensing the remainder of the organosilane.

The (meth) acrylic polymer particles (i)
Preferably, a (meth) acrylate ester having no functional group (hereinafter referred to as “(meth) acrylate ester (i-
a) ". ) As a main component and another radical polymerizable monomer having a (meth) acrylic acid ester (ia) and a condensable functional group (hereinafter referred to as “radical polymerizable monomer (i
-B) ". ), If necessary, in combination with another radical polymerizable monomer having no condensable functional group (hereinafter, referred to as “radical polymerizable monomer (ic)”). Is done.

As the (meth) acrylate (ia), for example, the same compounds as the (meth) acrylates exemplified for the component (B) used in the aqueous emulsion (a) can be mentioned. it can. Among these (meth) acrylates, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate are particularly preferable. The (meth) acrylic esters can be used alone or in combination of two or more.

Further, a radical polymerizable monomer (ib)
Examples of the condensable functional group (for example, carboxyl group, carboxylic anhydride group, hydroxyl group, amino group, epoxy group, etc.) among the compounds exemplified for the component (B) used in the aqueous emulsion (a) A compound having the following formula: Among these radically polymerizable monomers (ib), 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid are particularly preferred. .
The radical polymerizable monomers (ib) can be used alone or in combination of two or more.

Further, a radical polymerizable monomer (ic)
Examples of the compound include, among the compounds exemplified for the component (B) used in the aqueous emulsion (a), compounds having no condensable functional group. Among these radically polymerizable monomers (ic),
Acrolein, diacetone acrylamide, and vinyl methyl ketone, which are unsaturated compounds containing a keto group or ald groups, are preferred. The radical polymerizable monomers (ic) can be used alone or in combination of two or more.

The proportion of each monomer used in producing the composite particles [I] is (meth) acrylate (ia)
The weight ratio of the monomer and the radical polymerizable monomer (ib) is preferably 70:30 to 99.9: 0.1, and more preferably 80:20 to 99.5: 0.5. Further, the weight ratio of the (meth) acrylate (ia) to the radical polymerizable monomer (ic) is preferably 100: 0.
80:20, more preferably 99: 1 to 95: 5. Further, the total of the keto group-containing unsaturated compound and the ald group-containing unsaturated compound when the (meth) acrylate (ia) is used in combination with the keto group-containing unsaturated compound and / or the ald group-containing unsaturated compound. The content is preferably from 0.1 to 20% by weight, more preferably from 1 to 5% by weight, based on all monomers.

The (meth) acrylic polymer particles (i)
For example, it can be prepared by an emulsion polymerization method in which the radical polymerizable monomer is emulsion-polymerized in an aqueous medium, an emulsion method in which the radical polymerizable monomer is solution-polymerized, and then the polymer solution is emulsified in an aqueous medium. The emulsion polymerization method is carried out using a radical polymerization initiator and in a soap-free system or in the presence of an emulsifier.

Examples of the radical polymerization initiator include an oxidizing agent comprising an organic hydroperoxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, and a sugar-containing iron pyrophosphate formulation; A redox-based initiator comprising a combination with a reducing agent such as a rate formulation, a sugar-containing iron pyrophosphate / sulfoxylate mixed formulation;
Persulfates such as potassium persulfate and ammonium persulfate; azo compounds such as azobisisobutyronitrile, dimethyl-2,2'-azobisisobutyrate, 2-carbamoylazaisobutyronitrile; benzoyl peroxide;
Lauroyl peroxide, t-butyl peroxy-2
Organic peroxides such as -ethylhexanoate. Among these radical polymerization initiators, a redox initiator and a persulfate are preferred. The radical polymerization initiators can be used alone or in combination of two or more. The amount of the radical polymerization initiator used is usually based on 100 parts by weight of the radical polymerizable monomer in total.
It is about 0.05 to 5 parts by weight, preferably about 0.1 to 2 parts by weight.

As the emulsifier, an anionic emulsifier,
Examples thereof include a nonionic emulsifier, a cationic emulsifier, and an amphoteric emulsifier, and a reactive emulsifier having a polymerizable ethylenically unsaturated bond in a molecule is particularly preferable. Examples of the anionic emulsifier include an alkali metal salt of a higher alcohol sulfate, an alkali metal salt of an alkylbenzene sulfonic acid, an alkali metal salt of a dialkyl succinate sulfonic acid, an alkali metal salt of an alkyl diphenyl ether disulfonic acid, and polyoxyethylene. In addition to sulfates of alkyl ethers, sulfates of polyoxyethylene alkyl phenyl ethers, etc., trade name Latemul S-180A (Kao Corporation)
Eleminol JS-2 (manufactured by Sanyo Chemical Co., Ltd.), Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap SE-10N (manufactured by Asahi Denka Kogyo Co., Ltd.), An
Reactive emulsifiers such as tox MS-60 (Nippon Emulsifier Co., Ltd.) can be mentioned. Examples of the nonionic emulsifier include, in addition to polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and the like, Aqualon RS-20 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecalia Soap Reactive emulsifiers such as NE-20 (manufactured by Asahi Denka Kogyo KK) can be used.
Examples of the cationic surfactant include, for example, alkylpyridinyl chloride and alkylammonium chloride.Examples of the amphoteric emulsifier include:
Lauryl betaine is suitable. The emulsifiers can be used alone or as a mixture of two or more. The amount of the emulsifier used is usually 5 parts by weight or less based on 100 parts by weight of the total of the radical polymerizable monomers used.

In the emulsion polymerization method, in addition to a radical polymerization initiator and an emulsifier, if necessary, a chain transfer agent, an electrolyte, a pH adjuster and the like are used in combination, and water is usually added per 100 parts by weight of the radically polymerizable monomer. 100 to 500 parts by weight, a radical polymerization initiator and an emulsifier are used in amounts within the above range, and the polymerization temperature is usually 5 to 100 ° C, preferably 50 to 90 ° C.
The polymerization is usually carried out under the conditions of a temperature of 0.1 ° C and a polymerization time of 0.1 to 10 hours. As the polymerization method at that time, a batch method, a method of dividing or continuously adding a radical polymerizable monomer, a method of dividing or continuously adding a pre-emulsion of a radical polymerizable monomer, or a stepwise method of these methods Combination methods can be used, but especially when the proportion of low water-soluble monomer used is high, use a high-pressure homogenizer or ultrasonic disperser to forcibly emulsify the radical polymerizable monomer, water and emulsifier in advance It is preferable to prepare a pre-emulsion and then polymerize it by a batch method, a divided or continuous addition method, or the like. The polymerization conversion in the emulsion polymerization method is 99.5.
It is preferred that the content be not less than% by weight.

Further, the aqueous emulsion of the (meth) acrylic polymer particles (i) uses a part of the radically polymerizable monomer, and uses the polymer particles obtained by the emulsion polymerization method as seeds to prepare the remaining emulsion. It can also be prepared by emulsion polymerization of a radical polymerizable monomer. In this case, the radical polymerization initiator, components such as an emulsifier and a chain transfer agent added as needed, and the polymerization conditions are the same as those in the emulsion polymerization method.

The thus obtained (meth) acrylic polymer particles (i) preferably have an average particle diameter of 0.0
It is 1 to 1 μm, more preferably 0.03 to 0.5 μm. The solid concentration of the aqueous emulsion of the (meth) acrylic polymer particles (i) is preferably 10 to 60.
%, More preferably 20 to 50% by weight.

The glass transition temperature of the (meth) acrylic polymer forming the (meth) acrylic polymer particles (i) is preferably 0 to 50 ° C, more preferably 10 to 40 ° C. By setting the glass transition temperature of the (meth) acrylic polymer within this range, a coating film having an excellent balance between stain resistance and weather resistance can be obtained.

(B) The aqueous emulsion is prepared by mixing the above (meth)
In an aqueous emulsion of acrylic polymer particles (i),
It can be prepared by polycondensing an organosilane. (B) As the organosilane used in the aqueous emulsion, for example, the organosilane (1)
The same can be mentioned. Of these organosilanes, methyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferred. These organosilanes can be used alone or in combination of two or more.

(B) In preparing the aqueous emulsion, it is preferable to react the (meth) acrylic polymer particles (i) with a reactive silane compound in advance and then to polycondense the organosilane.

Examples of the reactive silane compound include a compound represented by the following general formula (3).

[0084]

Embedded image Wherein, R ¹ and R ² have the same meanings as R ¹ and R ^2, respectively, in the general formula (1), X represents a monovalent group having a linking functional group, i is an integer of 0 to 3, j is an integer of 1 to 3, and (i + j) is an integer of 0 to 3. ]

Examples of the reactive silane compound include compounds having a connecting functional group such as an amino group and an epoxy group among the compounds exemplified for the organosilane (1). Among these reactive silane compounds, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3
-Glycidoxypropyldimethoxymethylsilane, 3-
Glycidoxypropyldiethoxymethylsilane is preferred.

In the condensation reaction of the organosilane for preparing the aqueous emulsion (b), the compound wherein n is 3 in the general formula (1) or (i +
The compound in which j) is 3 may be added in a small amount, preferably 0.5 mol or less per 1 mol of organosilane.

The reaction between the (meth) acrylic polymer particles (i) and the reactive silane compound is performed by adjusting the pH of the aqueous emulsion of the (meth) acrylic polymer particles (i) to 2 to 10, ) The reactive silane compound is added to 100 parts by weight of the acrylic polymer particles (i).
To 20 parts by weight, more preferably 0.5 to 10 parts by weight, and is usually performed by stirring at a temperature of 20 to 90 ° C., preferably 40 to 80 ° C., usually for 0.1 to 6 hours. Can be.

(B) The condensation reaction of the organosilane at the time of preparing the aqueous emulsion is carried out by adjusting the pH of the aqueous emulsion of the (meth) acrylic polymer particles (i) to preferably 4
To 10, more preferably 5 to 9.5, particularly preferably 6 to 9, and after addition of organosilane, usually 3 to
0 ° C or higher, preferably 50 to 90 ° C, particularly preferably 6 ° C
It is usually carried out by stirring at a temperature of 0 to 80 ° C. for 0.1 to 10 hours.

The amount of the organosilane used in this case is
It is preferably 0.5 to 100 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer particles (i). By setting the amount of the organosilane in this range, the coating film formed from the final aqueous dispersion becomes excellent in weather resistance, stain resistance and the like.

In the present invention, a part of the organopolysiloxane is (meth) acrylic polymer particles (i).
It is preferably present on the surface and / or near the surface.

Further, (b) in the condensation reaction of the organosilane at the time of preparing the aqueous emulsion, a metal alkoxide which can be co-condensed with the organosilane, for example, tetramethoxytitanium, tetraethoxytitanium, tetra-titanium,
n-propoxytitanium, tetra-n-butoxytitanium,
One or more organic titanium compounds such as methyltrimethoxytitanium and methyltriethoxytitanium; and organic aluminum compounds such as triethoxyaluminum and tri-n-propoxyaluminum may be added for cocondensation.

(B) The average particle size of the composite particles in the aqueous emulsion is preferably 0.01 to 1 μm, more preferably 0.03 to 0.5 μm. The solid content of the aqueous emulsion (b) is preferably 10 to 60% by weight, more preferably 20 to 50% by weight.

The medium in the aqueous emulsion (b) consists essentially of water, but may contain an organic solvent such as an alcohol up to about several weight% in some cases. Further, an organic solvent, for example, one used at the time of preparing the component (A) in the aqueous emulsion (a) can be added to the aqueous emulsion (b) as needed.

(C) Aqueous Emulsion In the present invention, (c) an aqueous emulsion of (meth) acrylic polymer particles (hereinafter simply referred to as “(c) aqueous emulsion”) is a mixture of (meth) acrylic polymer particles. ,
It consists of an emulsion dispersed in an aqueous medium. (C) The (meth) acrylic polymer in the aqueous emulsion is
Preferably, a (meth) acrylate ester having no condensable functional group (hereinafter referred to as “(meth) acrylate ester (ii
-A) ". ) Is replaced with another radical polymerizable monomer (hereinafter referred to as “radical polymerizable monomer (ii-
b) ". ) And by polymerization.

As the (meth) acrylate (ii-a), for example, the same compounds as the (meth) acrylates exemplified for the component (B) used in the aqueous emulsion (a) can be mentioned. it can. Among these (meth) acrylates, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate are particularly preferable. The (meth) acrylic esters can be used alone or in combination of two or more.

The radical polymerizable monomer (ii-b)
Examples of the compound include compounds other than the (meth) acrylates among the compounds exemplified for the component (B) used in the aqueous emulsion (a). Among these radically polymerizable monomers (ii-b), in particular, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, and acrolein, di- as unsaturated compounds containing a keto group or unsaturated compounds containing an ald group Acetone acrylamide and vinyl methyl ketone are preferred. The radical polymerizable monomer (ii-b) is
They can be used alone or in combination of two or more.

(C) (meth) acrylic acid ester (ii-a) and radical polymerizable monomer (ii-
The weight ratio with b) is preferably from 100: 0 to 80: 2
0, more preferably 99: 1 to 95: 5. Further, the total of the keto group-containing unsaturated compound and the ald group-containing unsaturated compound when the (meth) acrylate (ii-a) and the keto group-containing unsaturated compound and / or the ald group-containing unsaturated compound are used in combination. The content is preferably from 0.1 to 20% by weight, more preferably from 1 to 5% by weight, based on all monomers.

(C) The aqueous emulsion is, for example, an emulsion polymerization method in which the above-mentioned radically polymerizable monomer is emulsion-polymerized in an aqueous medium, or an emulsion in which the above-mentioned radically polymerizable monomer is solution-polymerized and then a polymer solution is emulsified in an aqueous medium. It can be prepared by a method or the like. (C) The emulsion polymerization method for preparing an aqueous emulsion uses a radical polymerization initiator,
It is carried out in a soap-free system or in the presence of an emulsifier.
Examples of the radical polymerization initiator and the emulsifier include those similar to those exemplified for the emulsion polymerization method for preparing the (meth) acrylic polymer particles (i) in the (b) water-based emulsion. it can.
The amount of the radical polymerization initiator to be used is generally about 0.05 to 5 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the total of the radically polymerizable monomers. Is a total of 100 radical polymerizable monomers.
It is usually 5 parts by weight or less based on parts by weight.

(C) The emulsion polymerization method for preparing the aqueous emulsion is carried out in the same manner as the emulsion polymerization method for preparing the (meth) acrylic polymer particles (i) in the aqueous emulsion (ii). be able to.

(C) The average particle size of the (meth) acrylic polymer particles in the aqueous emulsion is preferably from 0.01 to
It is 1 μm, more preferably 0.03 to 0.5 μm. The solid concentration of the aqueous emulsion is preferably 10 to 60% by weight, more preferably 20 to 5% by weight.
0% by weight.

(C) (meth) in an aqueous emulsion
The glass transition temperature of the (meth) acrylic polymer forming the acrylic polymer particles is preferably 0 to 50C, more preferably 10 to 40C. By setting the glass transition temperature of the (meth) acrylic polymer within this range, a coating film having an excellent balance between stain resistance and weather resistance can be obtained.

The medium in the water-based emulsion (c) consists essentially of water, but may contain an organic solvent such as an alcohol up to about several weight% in some cases. Further, (c) an aqueous solvent, if necessary, for example, an organic solvent used in the preparation of the component (A) in the (a) aqueous emulsion can be added to the aqueous emulsion.

Aqueous Dispersion The aqueous dispersion of the present invention is obtained by mixing (a) the aqueous emulsion and (b) the aqueous emulsion and / or (c) the aqueous emulsion prepared as described above. . In the aqueous dispersion of the present invention, the mixing ratio of (a) the aqueous emulsion and [(b) the total amount of the aqueous emulsion and (c) the aqueous emulsion] is preferably 5 /.
95-50 / 50, more preferably 10 / 90-40
/ 60, particularly preferably 20/80 to 30/70. If the mixing ratio is less than 5/95, the weather resistance and stain resistance of the coating film tend to decrease, while if it exceeds 50/50, the adhesion to various substrates tends to decrease.

Other Additives— Crosslinking Agent— The aqueous dispersion of the present invention contains (a) a composite polymer in an aqueous emulsion or (b) a (meth) acrylic polymer and / or (c) in an aqueous emulsion. ) The (meth) acrylic polymer in the aqueous emulsion contains keto groups and / or
Alternatively, when it has an ald group, a crosslinking agent for crosslinking these (meth) acrylic polymers can be blended. Examples of such a cross-linking agent include a compound having two or more hydrazide groups in a molecule (hereinafter, referred to as a “hydrazide-based cross-linking agent”) and a compound having one or more oxazoline groups in a molecule (hereinafter, “oxazoline”). Referred to as “system cross-linking agent”).

Examples of the hydrazide crosslinking agent include oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, phthalic dihydrazide, isophthalic dihydrazide, and terephthalic dihydrazide. Total carbon number of 2-1 such as dihydrazide, fumaric dihydrazide, itaconic dihydrazide, etc.
0, especially dicarboxylic acid dihydrazides having a total of 4 to 6 carbon atoms; citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide,
Trihydric or higher functional hydrazides such as ethylenediaminetetraacetic acid tetrahydrazide Among these hydrazide-based crosslinking agents,
Preferred are adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide. The hydrazide-based crosslinking agent may be used in a state of being dissolved in water and / or an organic solvent, or may be used in a state of being dispersed in a particulate or aqueous sol. The average particle diameter in the case of particles is usually
It is about 0.01 to 0.5 μm.

Examples of the oxazoline crosslinking agent include, for example, a compound having one or more, preferably two or more oxazoline groups in one molecule, and a radical polymerizable monomer having one or more oxazoline groups in one molecule. And copolymers having repeating units derived from.
The latter copolymer is usually synthesized by polymerizing a radically polymerizable oxazoline derivative such as 2-isopropenyl-2-oxazoline and another copolymerizable monomer by an emulsion polymerization method, a suspension polymerization method or the like. . Commercially available oxazoline-based crosslinking agents include Epocross K-1000, K-1020E, and K-1030 manufactured by Nippon Shokubai Chemical Industry Co., Ltd.
E, K-2010E, K-2020E, K-2030
E, WS-500 and the like. Among these oxazoline-based crosslinking agents, K-2020E, WS-5
00 and the like are preferable. The oxazoline-based crosslinking agent may be used in a state of being dissolved in water and / or an organic solvent, or may be used in a state of being dispersed in a particulate or aqueous sol. The average particle diameter in the case of particles is usually 0.01 to 0.5.
It is about μm. In the present invention, the crosslinking agents can be used alone or in combination of two or more.

The amount of the hydrazide-based cross-linking agent or oxazoline-based cross-linking agent used in the present invention may be (a) a composite polymer in an aqueous emulsion, (b) a (meth) acrylic polymer in an aqueous emulsion, and (c) an aqueous polymer. The equivalent ratio of the total amount of keto groups and ald groups in the (meth) acrylic polymer in the emulsion to the total amount of hydrazide groups and oxazoline groups is usually 1: 0.1 to 5, preferably 1: 0. 0.5-1.5, more preferably 1: 0.7-
The amount is in the range of 1.2. If the amount of the cross-linking agent is less than this range, the water resistance of the coating film, damage resistance, etc. may decrease, while if it exceeds this range, the water resistance of the coating film, transparency, etc. may decrease. .

In the drying process after the application of the aqueous dispersion of the present invention, the crosslinking agent reacts with the hydrazide group or oxazoline group with the keto group or ald group in each polymer to form a network structure. Has an action of crosslinking. By containing such a cross-linking agent, the aqueous dispersion of the present invention allows the cross-linking reaction to proceed rapidly at a low temperature of 100 ° C. or lower, and also allows the cross-linking at room temperature. In addition, the crosslinking reaction has a feature that the initial hardness of the coating film is greatly improved.

-Β-Keto Compound- In the aqueous dispersion of the present invention, when an organometallic compound or the like is used as the hydrolysis catalyst (E), for example, a β-diketone is used to further improve the storage stability. Kind and / or
Alternatively, β-keto esters (hereinafter, these compounds are collectively referred to as “β-keto compounds”) can be blended. Such β-keto compounds include, for example,
Acetyl acetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, acetoacetate-sec-
Butyl, t-butyl acetoacetate, hexane-2,4-
Dione, heptane-2,4-dione, heptane-3,5
-Dione, octane-2,4-dione, nonane-2,4
-Dione, 5-methylhexane-2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,
Examples thereof include 2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, and salicylaldehyde. Of these, acetylacetone and ethyl acetoacetate are preferred. The β-keto compounds can be used alone or in combination of two or more. The amount of the β-keto compound to be used is generally 2 mol or more, preferably 3 to 20 mol, per 1 mol of the organometallic compound in the organometallic compound or the like. If the amount of the β-keto compound used is less than 2 mol, the effect of improving the storage stability of the resulting aqueous dispersion tends to decrease.

-Resinous Additives-The aqueous dispersion of the present invention includes a water-soluble polyester resin, a water-soluble or water-dispersible epoxy resin, and a water-soluble or water-dispersible acrylic resin which are generally used in aqueous paints. And a resinous additive such as a carboxyl group-containing aromatic vinyl resin such as a styrene-maleic acid copolymer and a urethane resin. These resinous additives are
They can be used alone or in combination of two or more. The compounding amount of the resinous additive is 1% of the total solid content of the aqueous dispersion.
The amount is usually 50 parts by weight or less, preferably 30 parts by weight or less based on 00 parts by weight.

—Ultraviolet Absorber— The aqueous dispersion of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
-Hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′
-Dihydroxy-4-methoxybenzophenone, 2,
2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5
Benzophenone ultraviolet absorbers such as -benzoylphenyl) methane;

2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole,
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3',
5′-di-t-amylphenyl) benzotriazole,
2- (2'-hydroxy-4'-octoxyphenyl)
Benzotriazole, 2- [2'-hydroxy-3'-
(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-
Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], i-octyl-3- [3
-(2H-benzotriazol-2-yl) -5-t-
Butylphenyl] propionate, methyl-3- [3-
(2H-benzotriazol-2-yl) -5-t-butylphenyl] propionate and a condensate of polyethylene glycol and the like, a benzotriazole ultraviolet absorber;

2-ethylhexyl-2-cyano-3,
3'-diphenyl acrylate, ethyl-2-cyano-
Cyanoacrylate-based ultraviolet absorbers such as 3,3′-diphenylacrylate; CeO ₂ , ZnO, TiO ₂ , B
Examples thereof include metal oxides having an ultraviolet absorbing ability such as aO ₂ . These ultraviolet absorbers can be used alone or in combination of two or more. The amount of the ultraviolet absorber to be used is generally 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the total solid content of the aqueous dispersion.

-Light Stabilizer- The aqueous dispersion of the present invention may contain a light stabilizer. As the light stabilizer, for example, organic nickel-based, hindered amine-based, etc., any of the light stabilizers conventionally used in paints, synthetic rubbers, synthetic resins, synthetic fibers and the like can be used. And preferably bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-)
4-piperidyl) sebacate, 4-benzoyloxy-
2,2,6,6-tetramethylpiperidine, tetraxy (2,2,6,6-tetramethyl-4-piperidyl)-
It is a hindered amine light stabilizer such as 1,2,3,4-butanetetracarboxylate. These light stabilizers can be used alone or in combination of two or more. The amount of the light stabilizer to be used is generally 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the total solid content of the aqueous dispersion.

—Inorganic Compound— The aqueous dispersion of the present invention may contain an inorganic compound. As the inorganic compound, for example, SiO ₂ ,
Al ₂ O ₃ , Al (OH) ₃ , Sb ₂ O ₅ , Si ₃ N
_{4, Sn-In 2 O 3} , Sb-In 2 O 3, MgF, C
_{eF 3, CeO 2, SiO 2} , Al 2 O 3, 3Al 2 O
_{3 · 2SiO 2, BeO, SiC} , AlN, Al 2 O
_{3, Fe, Fe 2 O 3} , Co, Co-FeO X, CrO
₂ , Fe ₄ N, Ba ferrite, SmCO ₅ , YC
O ₅ , CeCO ₅ , PrCO ₅ , Sm ₂ CO ₁₇ , Nd ₂
Fe ₁₄ B, ZrO ₂ , Al ₄ O ₃ , AlN, SiC, α
—Si, SiN ₄ , CoO, Sb—SnO ₂ , Sb ₂ O
₅ , MnO ₂ , MnB, Co ₃ O ₄ , Co ₃ B, LiT
aO ₃ , MgO, MgAl ₂ O ₄ , BeAl ₂ O ₄ , Z
rSiO ₄ , ZnSb, PbTe, GeSi, FeSi
₂ , CrSi ₂ , CoSi ₂ , MnSi _1.73 , Mg ₂ S
i, β-B, BaC, BP, TiB ₂ , ZrB ₂ , Hf
B ₂ , Ru ₂ Si ₃ , BaTiO ₃ , PbTiO ₃ , B
_{aO-Al 2 O 3 -SiO 2} , Al 2 TiO 5, Zn 2
_{SiO 4, Zr 2 SiO 4,} 2MgO 2 -Al 2 O 3 -
_{5SiO 2, Li 2 O-Al} 2 O 3 -4SiO 2, Mg
Ferrite, Ni ferrite, Ni-Zn ferrite,
Li ferrite, Sr ferrite, and the like can be given.

The inorganic compound 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 dispersed in a non-polar solvent such as toluene. There are colloids. In the case of a solvent-based sol or colloid, the sol or colloid may be used after being diluted with water or a solvent, or may be used after surface treatment to improve dispersibility. When the inorganic compound is an aqueous sol or colloid and a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less. The inorganic compounds may be used alone or in combination of two or more. The amount (solid content) of the inorganic compound is usually 500 parts by weight or less, preferably 4 parts by weight, based on 100 parts by weight of all the polymer components in the aqueous dispersion.
Not more than 00 parts by weight.

-Filler-A filler can be separately added to the aqueous dispersion of the present invention in order to color and thicken the obtained coating film. As the 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 of these metals , Nitrides, sulfides and the like. Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigments, aluminum oxide, chromium oxide, manganese oxide, iron oxide, and oxide. Zirconium, 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. be able to. These fillers can be used alone or in combination of two or more. The amount of the filler is usually 300 parts by weight or less based on 100 parts by weight of the total solid content of the aqueous dispersion.

-Leveling Agent- A leveling agent can be added to the aqueous dispersion of the present invention in order to further improve the applicability of the aqueous dispersion.
Among such leveling agents, fluorine leveling agents include, for example, BM-Chem (BM-C
HEMIE) BM1000, BM1100; Efka Chemicals, Inc .; Efka 772, Efka 777; Kyoeisha Chemical Co., Ltd. Floren series; Sumitomo 3M
FC series manufactured by Toho Chemical Co., Ltd.
F series and the like. Silicone leveling agents are trade names such as BYK series manufactured by Big Chemie; Sshmego series manufactured by Sshmegmann;
0, Efka 31, Efka 34, Efka 35, Efka 3
6, Efka 39, Efka 83, Efka 86, Efka 88
Examples of the ether-based or ester-based leveling agent include trade names such as Carfinol manufactured by Nissin Chemical Industry Co., Ltd .; and Emulgen and Homogenol manufactured by Kao Corporation. . These leveling agents can be used alone or in combination of two or more. The amount of the leveling agent is usually 5% by weight or less, preferably 3% by weight, based on the total aqueous dispersion.
It is as follows.

-Additives Other than the Above- Further, the aqueous dispersion of the present invention may optionally contain a dehydrating agent such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane; polyoxyethylene alkyl ether and polyoxyethylene alkyl. Dispersants such as phenyl ether, polyoxyethylene fatty acid ester, polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt, polyethylene glycol, etc .; methyl cellulose, ethyl cellulose, hydroxy Cellulose such as ethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose, and thickeners such as castor oil derivative and ferrosilicate; ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrite, sodium borohydride Inorganic blowing agents such as sodium and calcium azides; azo compounds such as azobisisobutyronitrile; hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine; semicarbazide compounds; triazole compounds; N-nitroso compounds; In addition to the organic foaming agent, a surfactant, a silane coupling agent, a titanium coupling agent, a dye, and the like can be added.

Coated Body The coated body of the present invention is obtained by applying a coating containing the aqueous dispersion of the present invention to a substrate. When applying the aqueous dispersion of the present invention to a substrate, a brush, a roll coater, a flow coater, a centrifugal coater, an ultrasonic coater, or the like may be used, or a dip may be used. By a coating method such as coating, flowing coating, spraying, a screen process, electrodeposition, and vapor deposition, the thickness is about 1 to 40 μm in a single coating, and 2 to 80 in a 2-3 coating.
A coating film of about μm can be formed. Then, dry at room temperature, or at a temperature of about 30 to 200 ° C for 1 hour.
By heating and drying for about 0 to 60 minutes, a coating film can be formed on various substrates.

The base to which the aqueous dispersion of the present invention can be applied includes, for example, metals such as iron, aluminum and stainless steel; cement, concrete, ALC, flexible boards, mortar, slates, gypsum, and the like. Inorganic ceramic materials such as ceramics and bricks; phenol resin, epoxy resin, polyester such as polyethylene terephthalate (PET), polycarbonate, polyethylene, polypropylene, ABS resin (acrylonitrile-butadiene-styrene resin), polymethyl Methacrylate (PMMA)
Plastic molded products such as polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, PE
Examples thereof include plastic films such as T, polyurethane, and polyimide, wood, paper, and glass. Further, the aqueous dispersion of the present invention is also useful for repainting a deteriorated coating film.

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. Examples of the surface treatment for the metal-based substrate include polishing, degreasing, plating, chromate treatment, flame treatment, and coupling treatment. Examples of the surface treatment for the plastic-based substrate include blasting. Treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment,
UV irradiation treatment, plasma treatment, ion treatment and the like can be mentioned. Examples of the surface treatment for the inorganic ceramic substrate include polishing, filling, patterning, and the like, and surface treatment for the wood substrate. The, for example, polishing, filling, insect repellent treatment and the like can be mentioned, as the surface treatment for the paper base material, for example, filling, insect repellent treatment and the like, and further as the surface treatment for the deteriorated coating film And, for example, kerosene.

The coating operation using the aqueous dispersion of the present invention varies depending on the type and state of the substrate and the coating method. For example, in the case of a metal-based substrate, a primer is used if rust prevention is necessary. Are different from each other, a primer is usually used. In the case of repainting a deteriorated coating film, a primer is used when the old coating film is significantly deteriorated. Other substrates, such as plastic, wood,
In the case of paper, glass or the like, a primer may or may not be used depending on the application. The type of primer is not particularly limited as long as it has an effect of improving the adhesion between the substrate and the coating composition. Select as appropriate. The primers can be used alone or as a mixture of two or more, and may be an enamel containing a coloring component such as a pigment or a clear containing the coloring component.

The types of primers include, for example, alkyd resin, aminoalkyd resin, epoxy resin, polyester, acrylic resin, urethane resin, fluorine resin, acrylic silicone resin, acrylic emulsion, epoxy emulsion, polyurethane emulsion, polyester emulsion, Examples of the present invention include (a) an aqueous emulsion, (b) an aqueous emulsion, (c) an aqueous emulsion, and a mixture of (b) an aqueous emulsion and (c) an aqueous emulsion. In addition, these primers 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, a hydroxyl group,
Carboxyl group, carbonyl group, amide group, amine group,
Examples include a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond. Further, on the surface of the coating film formed from the aqueous dispersion of the present invention, for the purpose of further increasing the abrasion resistance and gloss of the coating film, for example, US Pat. No. 3,986,997, US Pat. 4th, 0th
A clear layer composed of a siloxane resin-based coating material such as a stable dispersion of colloidal silica and a siloxane resin described in Japanese Patent No. 27,073 can also be formed.

The following are examples of the form of the coated body in which the aqueous dispersion of the present invention is applied to a substrate. (A) substrate / water-based dispersion (clear, enamel) (b) substrate / water-based dispersion (enamel) / coating composition (clear) (c) substrate / water-based dispersion (clear, enamel) ) / Other organic paint / water-based dispersion (clear) In the cases of the above (a) to (c), a primer layer can be provided in advance on the base material as necessary, as described above.

[0126]

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 the examples and comparative examples,
It carried out by the following method. Weather Resistance In accordance with JIS K5400, an irradiation test was carried out for 3,000 hours using a sunshine weather meter, and then the gloss retention was measured and evaluated according to the following criteria. ：: Gloss retention of 80% or more Δ: Gloss retention of 50% or more and less than 80% ×: Gloss retention of less than 50% Stain resistance: Carbon black / kerosene = 1/2 on coating film
(Weight ratio) A paste consisting of the mixture was applied, left at room temperature for 24 hours, washed with water using a sponge, and the state of contamination of the coating film was observed and evaluated according to the following criteria. ：: No contamination △: Slightly contaminated X: Severely contaminated Adhesion: Immediately after preparing test pieces (initial stage) by JIS K5400 grid test (100 squares), temperature 50 ° C, humidity 95% After leaving for 30 days in the atmosphere of (3) (moisture resistance of 30 days), a tape peeling test was performed three times, and the average was evaluated.

Synthesis Example 1 [(a) Preparation of Aqueous Emulsion] The components (A) to (D) and the component (G) shown in Table 1 were mixed and emulsified by stirring at room temperature for 10 minutes. The component (E) was added, and the hydrolysis reaction was allowed to proceed at room temperature for 2 hours while stirring was continued. Thereafter, the emulsion was treated with a high-pressure homogenizer [Microfluidizer M110Y manufactured by Mizuho Industry Co., Ltd.] at a pressure of 70 MPa to reduce the average particle diameter of the emulsion to 0.2 μm. Thereafter, this emulsion was charged into a separable flask and replaced with nitrogen gas while stirring. Then, the component (F) shown in Table 1 was added, and the condensation / polymerization reaction was allowed to proceed at 75 ° C. for 4 hours. Thereafter, an aqueous ammonia solution was added to adjust the pH of the reaction system to 7.0 to obtain (a) an aqueous emulsion. The average particle size of the composite polymer particles in this (a) aqueous emulsion (measured with a Nanosizer manufactured by Coulter Inc .; the same applies hereinafter) was 0.2 μm. This (a) water-based emulsion is referred to as a water-based emulsion (a-1).

Synthesis Example 2 [(a) Preparation of Aqueous Emulsion] (A) Aqueous emulsion was obtained in the same manner as in Synthesis Example 1 except that the components (A) to (G) shown in Table 1 were used. The average particle size of the composite polymer particles in this (a) aqueous emulsion was 0.2 μm. This (a) water-based emulsion is referred to as a water-based emulsion (a-2).

Among the components (A) in Table 1, SX101 and X40-9220
And X40-9225 are as follows. SX101: Partial condensate of 2 mol of dimethyldimethoxysilane and 2 mol of methyltrimethoxysilane (manufactured by Dow Corning Toray Silicone Co., Ltd.) X40-9220: Partial condensate of 10 to 15 mol of methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. )

[0130]

[Table 1]

Synthesis Example 3 [(b) Preparation of Water-based Emulsion] A 2-liter separable flask equipped with a stirrer, a thermometer, a heater, a monomer addition pump, and a nitrogen gas introducing device was charged with 70 parts of ion-exchanged water. Adekaria Soap SE-10N (0.2 part), which is a reactive emulsifier, and potassium persulfate (0.3 part) were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 15 parts of n-butyl acrylate, 15 parts of 2-ethylhexyl acrylate
, 25 parts of methyl methacrylate, 40 parts of cyclohexyl acrylate, 2 parts of 2-hydroxyethyl methacrylate and 3 parts of acrylic acid were mixed and stirred to prepare a pre-emulsion. Next, this pre-emulsion was continuously dropped into the separable flask over 3 hours.
During the dropwise addition, nitrogen gas was introduced to keep the temperature of the reaction system at 80 ° C. After completion of the dropwise addition, the mixture was aged at 85 to 95 ° C. for 2 hours to complete the polymerization reaction, and then cooled to 25 ° C., adjusted to pH 7 with aqueous ammonia, and treated with (meth) acrylic polymer particles (i). Emulsion was obtained. Thereafter, 1 part of γ-glycidoxypropyldimethoxymethylsilane and 2 parts of γ-glycidoxypropyltriethoxysilane were added to the separable flask, and the mixture was vigorously stirred for about 1 hour. Then, 6 parts of methyltriethoxysilane was added. Two parts of tetraethoxysilane was added, the temperature was raised to 70 ° C., and a condensation reaction was performed for 3 hours with stirring. Thereafter, the mixture was cooled and filtered through a wire mesh of 120 mesh (JIS) to obtain (b) an aqueous emulsion. The solids concentration of this emulsion is 45.1%,
The average particle size of the composite particles was 0.13 μm, and the (meth) acrylic polymer had a glass transition temperature of 30 ° C. This (b) water-based emulsion is referred to as a water-based emulsion (b-1).

Synthesis Example 4 [(b) Preparation of Aqueous Emulsion] A 2-liter separable flask equipped with a stirrer, thermometer, heater, monomer addition pump, and nitrogen gas introducing device was charged with 70 parts of ion-exchanged water. Adekaria Soap SE-10N (0.2 part), which is a reactive emulsifier, and potassium persulfate (0.3 part) were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 25 parts of n-butyl acrylate, 20 parts of 2-ethylhexyl acrylate
, 25 parts of methyl methacrylate, 22 parts of cyclohexyl acrylate, 2 parts of 2-hydroxyethyl methacrylate, 3 parts of acrylic acid, and 3 parts of diacetone acrylamide were mixed and stirred to prepare a pre-emulsion. Next, this pre-emulsion was continuously dropped into the separable flask over 3 hours. During the dropwise addition, nitrogen gas was introduced to keep the temperature of the reaction system at 80 ° C. After completion of the dropwise addition, the mixture was aged at 85 to 95 ° C. for another 2 hours to complete the polymerization reaction.
The emulsion was adjusted to 7 to obtain an emulsion of (meth) acrylic polymer particles (i). Then, 1 part of γ-glycidoxypropyldimethoxymethylsilane and 2 parts of γ-glycidoxypropyltriethoxysilane were placed in the separable flask.
After stirring vigorously for about 1 hour, 6 parts of methyltriethoxysilane and 2 parts of tetraethoxysilane were added, the temperature was raised to 70 ° C., and a condensation reaction was performed for 3 hours with stirring. Thereafter, the mixture was cooled and filtered through a wire mesh of 120 mesh (JIS) to obtain (b) an aqueous emulsion. The solid content concentration of this emulsion was 45.1%, the average particle size of the composite particles was 0.13 μm, and the (meth) acrylic polymer had a glass transition temperature of 5 ° C. This (b) water-based emulsion is referred to as a water-based emulsion (b-2).

Synthesis Example 5 [(b) Preparation of Water-based Emulsion] A 2-liter separable flask equipped with a stirrer, a thermometer, a heater, a monomer addition pump, and a nitrogen gas introducing device was charged with 70 parts of ion-exchanged water. Adekaria Soap SE-10N (0.2 part), which is a reactive emulsifier, and potassium persulfate (0.3 part) were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 35 parts of n-butyl acrylate, 20 parts of 2-ethylhexyl acrylate
Parts, 15 parts of methyl methacrylate, 22 parts of cyclohexyl acrylate, 2 parts of 2-hydroxyethyl methacrylate, 3 parts of acrylic acid, and 3 parts of diacetone acrylamide were mixed and stirred to prepare a pre-emulsion. Next, this pre-emulsion was continuously dropped into the separable flask over 3 hours. During the dropwise addition, nitrogen gas was introduced to keep the temperature of the reaction system at 80 ° C. After completion of the dropwise addition, the mixture was aged at 85 to 95 ° C. for another 2 hours to complete the polymerization reaction.
The emulsion was adjusted to 7 to obtain an emulsion of (meth) acrylic polymer particles (i). Then, 1 part of γ-glycidoxypropyldimethoxymethylsilane and 2 parts of γ-glycidoxypropyltriethoxysilane were placed in the separable flask.
After stirring vigorously for about 1 hour, 6 parts of methyltriethoxysilane and 2 parts of tetraethoxysilane were added, the temperature was raised to 70 ° C., and a condensation reaction was performed for 3 hours with stirring. Thereafter, the mixture was cooled and filtered through a wire mesh of 120 mesh (JIS) to obtain (b) an aqueous emulsion. The solid content concentration of this emulsion was 45.1%, the average particle size of the composite particles was 0.13 μm, and the (meth) acrylic polymer had a glass transition temperature of −10 ° C. This (b)
The aqueous emulsion is referred to as an aqueous emulsion (b-3).

Synthesis Example 6 [(c) Preparation of aqueous emulsion] 70 parts of ion-exchanged water was placed in a 2-liter separable flask equipped with a stirrer, thermometer, heater, monomer addition pump, and nitrogen gas introducing device. Adekaria Soap SE-10N (0.2 part), which is a reactive emulsifier, and potassium persulfate (0.3 part) were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 15 parts of n-butyl acrylate, 15 parts of 2-ethylhexyl acrylate
, 25 parts of methyl methacrylate, 37 parts of cyclohexyl acrylate, 2 parts of 2-hydroxyethyl methacrylate, 3 parts of acrylic acid, and 3 parts of diacetone acrylamide were mixed and stirred to prepare a pre-emulsion. Next, this pre-emulsion was continuously dropped into the separable flask over 3 hours. During the dropwise addition, nitrogen gas was introduced to keep the temperature of the reaction system at 80 ° C. After completion of the dropwise addition, the mixture was aged at 85 to 95 ° C. for another 2 hours to complete the polymerization reaction.
7, to obtain (c) an aqueous emulsion. The solid content of this emulsion was 44.1%, the average particle size of the composite particles was 0.13 μm, and the (meth) acrylic polymer had a glass transition temperature of 20 ° C. This (c)
The aqueous emulsion is referred to as an aqueous emulsion (C-1).

Synthesis Example 7 [(c) Preparation of water-based emulsion] 70 parts of ion-exchanged water was placed in a 2-liter separable flask equipped with a stirrer, thermometer, heater, monomer addition pump, and nitrogen gas introducing device. Adekaria Soap SE-10N (0.2 part), which is a reactive emulsifier, and potassium persulfate (0.3 part) were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. In a separate container, 30 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 5 parts of n-butyl acrylate, 5 parts of 2-ethylhexyl acrylate, 35 parts of methyl methacrylate, 47 parts of cyclohexyl acrylate, 2 parts of 2-hydroxyethyl methacrylate ,
A pre-emulsion was prepared by mixing and stirring 3 parts of acrylic acid and 3 parts of diacetone acrylamide. Next, this pre-emulsion was continuously dropped into the separable flask over 3 hours. During dropping, introduce nitrogen gas,
The temperature of the reaction system was kept at 80 ° C. After dropping, 85-
After aging at 95 ° C. for 2 hours to complete the polymerization reaction, the mixture was cooled to 25 ° C. and adjusted to pH 7 with aqueous ammonia to obtain (c) an aqueous emulsion. The solid content of this emulsion was 44.1%, the average particle size of the composite particles was 0.13 μm, and the glass transition temperature of the (meth) acrylic polymer was 50 ° C. This (c) water-based emulsion is referred to as a water-based emulsion (c-2).

Example 1 30 parts of the aqueous emulsion (a-1) and 70 parts of the aqueous emulsion (b-1) were stirred and mixed, and then 5 parts of a 10% aqueous solution of adipic dihydrazide was added as a crosslinking agent and mixed. Thus, an aqueous dispersion was prepared. The obtained aqueous dispersion was applied to a degreased hard aluminum plate at a dry weight of 25 g / m ^2, and then heated at 80 ° C. for 6 minutes to prepare a test piece. The obtained test piece was evaluated for weather resistance and stain resistance. Further, test pieces were prepared in the same manner as described above using the same aqueous dispersion and various base materials, and the adhesion was evaluated. Table 2 shows the evaluation results.

Examples 2 to 8 (b) Types of aqueous emulsion or (c) aqueous emulsion, mixing ratio of aqueous emulsion (a-1) to (b) aqueous emulsion or (c) aqueous emulsion, type of crosslinking agent A water-based dispersion was obtained in the same manner as in Example 1 except that the amount was changed, and each test piece was prepared. Each of the obtained test pieces was evaluated for weather resistance and stain resistance. Further, each test piece was prepared in the same manner as in Example 1 using the same aqueous dispersion and various base materials, and the adhesion was evaluated. Table 2 shows the evaluation results.

Comparative Example 1 An aqueous emulsion (a-1) was used in place of 30 parts of the aqueous emulsion (a-1) and 70 parts of the aqueous emulsion (ii-1).
1) An aqueous dispersion was obtained and a test piece was prepared in the same manner as in Example 1 except that 100 parts was used. The obtained test piece was evaluated for weather resistance and stain resistance. In addition, test pieces were prepared in the same manner as in Example 1 using the same aqueous dispersion and various base materials, and the adhesion was evaluated. Table 3 shows the evaluation results.

Comparative Examples 2 to 5 Except that the type of the aqueous emulsion used, the mixing ratio between the aqueous emulsion (a-1) and the aqueous emulsion (b) or (c) the aqueous emulsion, and the type and amount of the crosslinking agent were changed. In the same manner as in Example 1, an aqueous dispersion was obtained, and each test piece was prepared. Each of the obtained test pieces was evaluated for weather resistance and stain resistance. Further, each test piece was prepared in the same manner as in Example 1 using the same aqueous dispersion and various base materials, and the adhesion was evaluated. Table 3 shows the evaluation results.
Shown in

[0140]

[Table 2] (* 1) Epocross WS500 (trade name) manufactured by Nippon Shokubai Co., Ltd. (* 2) Specified in JIS A5043F (* 3) Specified in JIS A6901

[0141]

[Table 3] (* 1) Epocross WS500 (trade name) manufactured by Nippon Shokubai Co., Ltd. (* 2) Specified in JIS A5043F (* 3) Specified in JIS A6901

[0142]

The aqueous dispersion according to the present invention is a composite material of a vinyl polymer such as a (meth) acrylic polymer and a polysiloxane polymer, which is inherent in chemical resistance, moisture resistance and (temperature) water resistance. In addition to maintaining excellent properties, weather resistance and stain resistance are excellent, and especially, initial adhesion and long-term adhesion to various substrates including inorganic and organic substrates are excellent.
Therefore, the aqueous dispersion of the present invention can be used for interior and exterior of buildings, for building materials, for steel structures, for concrete structures, for precast materials, for interior and exterior of automobiles, airplanes, passenger cars, ships, etc., for aluminum coating, and for sealants. It is extremely useful as a paint or a paint component in a wide range of fields, such as for use in floor polishing and floor polishing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 133/10 C09D 133/10 151/08 151/08 151/10 151/10 157/00 157/00 183 / 02 183/02 183/10 183/10 F term (reference) 4J002 BG05Y BN23W CP17X ER016 EU216 FD146 GH01 HA06 4J038 CC021 CC022 CE051 CE052 CF101 CF102 CG021 CG022 CG061 CG062 CG141 CH1 CH1 CH2 CH2 CH1 CH2 CH2 CH1 CH2 CH1 CH2 CH2 CH1 CH2 CH2 CH1 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH1 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH1 CH2 CH2 CH081 CH082 CH121 CH122 CH171 CH172 CH201 CH202 CP091 CP092 DL021 DL022 DL031 DL032 DL051 DL052 DL071 DL072 DL081 DL082 DL111 DL112 DL121 DL122 GA02 JA34 JB17 JB38 KA03 KA04 LA02 MA13 MA14 NA03 NA04 NA05 NA12 NA27 PB05 P

Claims (6)

[Claims] 1. (A) The following components (A) to (E) are mixed and emulsified to promote hydrolysis of the component (A),
The emulsion is refined, and then the following component (F) is added and reacted to promote the hydrolysis / condensation reaction of the component (A) and the polymerization reaction of the component (B). An emulsion containing (ii) an aqueous emulsion of composite particles of a (meth) acrylic polymer and an organopolysiloxane and / or (c) an aqueous emulsion of (meth) acrylic polymer particles. Aqueous dispersion. (A): at least one selected from the group consisting of an organosilane represented by the following general formula (1), a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate.
Parts by weight, (Wherein, R ¹ represents a monovalent organic group having 1 to 8 carbon atoms, and 2
R ¹ may be the same or different from each other, and R ²
Represents a linear or branched alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and two R ²
May be the same or different from each other, and n is an integer of 0 to 2. (B): 99 to 1 part by weight of a radical polymerizable monomer (however, (A) + (B) = 100 parts by weight) (C): 0.1 to 5 parts by weight of an emulsifier (D): 50 to 2 parts of water 000 parts by weight (E): hydrolysis catalyst of component (A) 0.01 to 5
Parts by weight (F): 0.01 to 5 parts by weight of a radical polymerization initiator 2. The glass transition temperature of the (meth) acrylic polymer in the component (b) and the (meth) acrylic polymer in the component (c) are each 0 ° C. to 50 ° C. The aqueous dispersion according to claim 1. 3. The composite polymer in the component (A) or the (meth) acrylic polymer in the component (B) and / or the (meth) acrylic polymer in the component (C) contains a keto group and / or 3. The aqueous dispersion according to claim 1, which has an ald group. 4. The method according to claim 3, further comprising a crosslinking agent having at least two hydrazide groups in the molecule and / or a crosslinking agent having an oxazoline group in the molecule.
2. The aqueous dispersion according to item 1. 5. The component (a) / [(b) component and (c)
The aqueous dispersion according to any one of claims 1 to 4, wherein the mixing ratio of the total of the components is 5/95 to 50/50. 6. A coated body obtained by applying a coating containing the aqueous dispersion according to claim 1 to a substrate.