JPH1077439A - Water-base coating material composition and article coated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. which gives a coating film formed by the chemical bonding of a fluororesin to a silicone polymer by incorporating a specific water-base compsn. and a compsn. comprising a hydrolyzable silylated compd. and a surfactant into the same. SOLUTION: A water-base fluororesin (A) which is obtd. by polymerizing a monomer essentially having a fluorolefin unit and thus contains fluoroolefin units (pref. a fluoroolefin emulsion polymer), a water-dispersible silica particle dispersion (B) prepd. by using a water-soluble org. solvent as the dispersion medium, a water-base compsn. (C) contg. a thickener (C-1) having a hydroxyl and/or a carboxyl group, a film-forming assistant (C-2), and a pigment (C-3), and a compsn. (F) comprising a hydrolyzable silylated compd. (D) represented by the formula (wherein Ri is a i-10C alkyl, aryl, etc.; X1 is halogen, alkoxy, etc.; and a is 0 or 1) and a noionic surfactant (E) are mutually reacted and bonded, ingredients A and B being the main film-forming ones.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful aqueous coating composition. More specifically, the present invention includes a film-forming component containing a polymer having a fluorine atom in the main chain, a so-called fluoroolefin polymer and a water-dispersible fine particle silica dispersion, and a hydrolyzable silyl group-containing compound. A specific aqueous two-pack coating composition comprising an additive component.

The composition for an aqueous two-pack coating according to the present invention having such a constitution is representative of a fluoropolymer and an inorganic substance by mixing and coating each component at the time of use. It is possible to form a coating film in the form of a composite with a silica-based compound, and it is possible to provide a coating film to which not only contaminants are hardly adhered, but also weather resistance.

[0003]

2. Description of the Related Art Conventionally, as an attempt to extend the life of a coating film, various studies have been made on the composition and composition of a coating vehicle (high-molecular polymer), which is a main component of the coating, or to improve the weather resistance of a pigment. The development has been promoted through the study.

As a result of these studies, high durability grades of paint vehicles and pigments have been developed.
As a result, products based on such technology have been introduced to the market.

[0005] Among them, a fluoropolymer has been proposed as a representative of the high durability grade of the paint vehicle,
A technique of cross-linking the organic solvent solution with a curing agent has been developed, and an aqueous-type technique is also being proposed.

On the other hand, as for the inorganic polymer, in recent years, an almost 100% silicon-based solvent-based paint has been developed and introduced to the market as a baking type.

[0007] The advantages and disadvantages of these various coating agents are as follows: first, the fluoropolymers themselves, among others,
It is excellent in durability and the like, and moreover, has a feature that it is particularly excellent in flexibility because the polymer itself is an organic polymer.

However, in order to provide a coating film having a strong hydrophobicity, there is a problem that a contaminant adheres due to static electricity. On the other hand, in the case of a silicon-based coating agent, the durability of the coating agent itself is also excellent, and the coating film surface is hydrophilic in order to give a coating surface like a glass surface. It has the advantage that adhesion of pollutants derived from static electricity is small.

However, since it is an inorganic polymer, it has a drawback that it is inferior in flexibility, and at the present time, it is an organic solvent solution and requires relatively high-temperature baking. In the water system which is a recent market trend,
In addition, it has characteristics that deviate from market requirements for low-temperature film forming properties.

On the other hand, a technique of forming a composite of a fluoropolymer and a silicon compound has been studied for a long time.

That is, first, US Pat.
No. 0 (1972) introduces a technique comprising a fluororesin dispersion and an alkyl silicate and / or a hydrolyzate thereof.

However, while the present technology also includes aqueous-based compositions, the preferred embodiments are just exemplary of organic solvent-based systems. In addition, there is no description about the functional groups that can react and integrate with each other between the fluororesin dispersion, which is the main component, and the alkyl silicate and / or its hydrolyzate. It can be said that this is a technique of simply mixing and forming a film.

Japanese Patent Application Laid-Open No. 58-53960 discloses a technique relating to an aqueous coating composition comprising an aqueous fluororesin dispersion and colloidal silica. Also, there is no example of introducing a functional group that can react and integrate with each other between the colloidal silica and the aqueous fluorine dispersion, and therefore does not exceed the category of film formation by physical mixing. That is.

Furthermore, Japanese Patent Publication No. 58-53671 discloses a technique comprising an aqueous fluorine dispersion and an aminosilane as a silane coupling agent. Resin and
According to the process shown in the examples, the content of silicon atoms (Si) in the resin component in the final product is generally about 5
%, And therefore it is hard to say that it is a composite of a fluoropolymer and a silicon compound.

[0015]

As described above, as long as the conventional technology is followed, it is absolutely highly practical, in other words, it is excellent in pollution, in other words, it is low pollution. It can be said that it is extremely difficult to provide a novel type of paint that forms a coating film in the form of a composite of a fluorine-based polymer and a silica-based compound that is a representative of inorganic substances.

[0016] However, the present inventors have found that the fluororesin inherently has excellent stainability without deteriorating weather resistance and flexibility, in other words, it has low stainability. In pursuit of a novel type of paint that forms a coating film in the form of a composite of a fluorine-based polymer and a silica-based compound, which is extremely practical,
Research has begun.

Accordingly, an object of the present invention is to provide a water-based coating material, which is capable of chemically bonding to a silicone polymer without impairing the weather resistance and flexibility of a fluororesin. An object of the present invention is to provide the characteristics of the silicon polymer, for example, low contamination by imparting a compound through the compound.

That is, the present invention basically has a very high practicality that a specific coating film in a form in which a fluorine resin and a silicon polymer are chemically bonded can be formed.
An object of the present invention is to provide an aqueous coating composition and a coated article using the same.

[0019]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems in the prior art and to meet various demands in the paint industry. A novel aqueous two-pack coating composition in the form of containing a composition composed of a hydrolyzable silyl group-containing compound and a surfactant in a coating composed of colloidal silica, as described above. The present invention has now been completed by finding that various problems in the conventional technology can be solved brilliantly.

That is, the present invention basically comprises (1) an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit and a dispersion (B) of a water-dispersible fine particle silica. An aqueous composition (C) as a novel film-forming component;

(2) An aqueous two-pack coating composition comprising a hydrolyzable silyl group-containing compound (D) and a composition (F) comprising a surfactant (E). In

[0022] In addition, the composition for aqueous two-pack coating is
Another object of the present invention is to provide a coated article coated on a substrate and then formed at room temperature or under baking conditions.

[0023]

As described above, the present invention provides,
(1) an aqueous composition (C) containing, as main film-forming components, an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constitutional unit and a dispersion (B) of a water-dispersible fine particle silica;

(2) Claims an aqueous two-pack coating composition comprising a hydrolyzable silyl group-containing compound (D) and a composition (F) comprising a surfactant (E). And

In particular, the present invention also provides a specific aqueous two-pack coating composition wherein the above-mentioned aqueous dispersion (A) contains a carboxyl group and / or a tertiary amino group in a polymer as a constituent unit thereof. That they are doing

In particular, they claim a specific aqueous two-pack coating composition, wherein the water-dispersible fine particle silica dispersion (B) is a medium using a water-soluble organic solvent as a medium. There is

In particular, the above aqueous composition (C) comprises an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential structural unit, a water-dispersible fine particle silica dispersion (B),
A thickener having a hydroxyl group and / or a carboxyl group (C-1), a film-forming auxiliary (C-2), and a pigment (C-3)
And that it also claims a specific aqueous two-pack coating composition,

In particular, the above-mentioned compound (D) containing a hydrolyzable silyl group has the general formula

[0029]

Embedded image

(However, R _{1 in} the formula has 1 to 1 carbon atoms.
X represents a monovalent hydrocarbon group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group, and X ₁ represents a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, an aminooxy group, a phenoxy group, or a thioalkoxy group. , An amino group, a halogen atom, an isopropenyloxy group, an iminooxy group and the like, and a represents an integer of 0, 1 or 2. )

Claims are also directed to a specific aqueous two-pack coating composition which is a compound having a hydrolyzable silyl group represented by the formula:

In particular, the above-mentioned surfactant (E) is preferably a nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester. They claim that they also claim a specific aqueous two-pack coating composition, which is at least one compound selected from the group consisting of surfactants and these same active substances.

In particular, they claim a specific aqueous two-pack coating composition wherein the composition (F) also contains a hydroxyl group-containing solvent and / or a water binder. Yes, and

An aqueous composition comprising (1) a polymer aqueous dispersion (A) containing a fluoroolefin as an essential constituent unit and a water-dispersible fine particle silica dispersion (B) as a main film-forming component is applied to an object to be coated. Object (C),

(2) Each of the aqueous two-pack coating compositions described above, which contains a hydrolyzable silyl group-containing compound (D) and a composition (F) comprising a surfactant (E), is applied. In addition, they claim a coated article formed at room temperature or under heating conditions.

Here, the aqueous dispersion (A) of the polymer comprising the above-mentioned fluoroolefin as an essential constitutional unit, which constitutes the aqueous coating composition according to the present invention.
Will be explained.

That is, the aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit, ie, an aqueous fluororesin containing a fluoroolefin as a constituent unit, contains a fluoroolefin as an essential constituent unit. A resin obtained by polymerizing a monomer, typically, a fluoroolefin emulsion polymer obtained by emulsion polymerization in an aqueous medium by a conventional method is typical.

[0038] Examples of the fluoroolefin emulsion polymer include various types as exemplified below.

Here, the term “fluoroolefin” means a polymerizable unsaturated double bond in one molecule, and at least one fluorine atom is added to a carbon atom forming the polymerizable double bond. , Can be defined as monomers in a directly bonded form. And as such fluoroolefin, the following various compounds can be exemplified.

That is, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene and the like are used. Among them, hexafluoropropylene, chlorotrifluoroethylene and vinylidene fluoride are used. Is desirable. More preferably, the use of chlorotrifluoroethylene is appropriate from the viewpoint of controlling the reaction at the time of polymerization.

In the present invention, the amount of the fluoroolefin to be contained in the fluoroolefin-based emulsion polymer is determined based on the solid content of the polymer.
As the fluorine atom, a fluoroolefin having a content of 10% by weight or more, preferably 15% by weight or more may be used. If it is less than this, it is impossible to obtain a resin having various properties such as weather resistance specific to fluororesin.

Other constituents include other monomers which can be copolymerized with the fluoroolefin, and these copolymerizable monomers are appropriately selected and used. What should I do?

Such other monomers copolymerizable with the fluoroolefin include:

1. Various α-olefins such as ethylene, propylene or butene-1, and various (halogen-substituted, except fluorine) olefins such as vinyl chloride and vinylidene chloride;

2. Vinyl acetate, vinyl propionate,
Vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate (vinyl neononanoate or vinyl neodecanoate), vinyl laurate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl p-tert-butylbenzoate or Vinyl esters of various carboxylic acids, such as "Veova" (trade name of vinyl ester, manufactured by Shell, The Netherlands);

3. Trifluoromethyl vinyl ether, 1,1,1-trifluoroethyl vinyl ether,
2,2-difluoroethyl vinyl ether, tetrafluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorobutyl vinyl ether, perfluorohexyl vinyl ether, perfluorooctyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluoro Various (per) fluoroalkyl vinyl ethers, such as octyl vinyl ether or perfluorocyclohexyl vinyl ether;

4. Methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isoamyl-, n
Various linear or branched alkyl group-containing alkyl vinyl ethers such as -hexyl-, n-octyl- or 2-ethylhexyl-vinyl ether;

5. Various (alkyl-substituted) cyclic alkyl group-containing cycloalkyl vinyl ethers, such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether;

6. Various aralkyl vinyl ethers, such as benzyl vinyl ether or phenethyl vinyl ether;

7. Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-
Butyl (meth) acrylate, iso-butyl (meth)
Acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate, "Biscoat 8F,
8FM, 3F or 3FM "[trade name of fluorine-containing (meth) acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.] or perfluorocyclohexyl (meth) acrylate or Ni-propylperfluorooctane sulfone Various (meth) acrylates, such as amidoethyl (meth) acrylate;

8. (Meth) acrylic acid, crotonic acid,
Contains unsaturated groups such as adducts of various acid anhydride group-containing monomers such as maleic acid, fumaric acid, itaconic acid, citraconic acid, or maleic anhydride or itaconic anhydride with glycols. Hydroxyalkyl ester monocarboxylic acids; or the above-mentioned half esters of various unsaturated dibasic acids such as maleic acid, fumaric acid or itaconic acid, and alkyl alcohols having 1 to 10 carbon atoms, respectively. Carboxyl group-containing monomers and dicarboxylic acids, such as

9. Such as maleic acid or fumaric acid,
Various unsaturated group-containing polyhydroxyalkyl esters, such as di-hydroxyalkyl esters of polycarboxylic acids;

10. Such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate;
Various hydroxyalkyl (meth) acrylates;

11. 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or 6-
Various vinyl ethers having a hydroxyl group, such as hydroxyhexyl vinyl ether;

12. Various allyl ethers having a hydroxyl group, such as 2-hydroxyethoxy allyl ether or 4-hydroxybutoxy allyl ether;

13. Adducts of various hydroxyl-containing monomers as described above with ε-caprolactone;

14. (Meth) acrylamide, N, N
Various carboxylic acid amide group-containing monomers represented by dimethyl (meth) acrylamide, N-alkoxymethylated (meth) acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide and the like;

15. p-styrenesulfonamide, N
-Methyl-p-styrenesulfonamide or N, N-
Various sulfonic acid amide group-containing monomers represented by dimethyl-p-styrenesulfonamide and the like;

16. Various N, N-dialkylaminoalkyl (meth) acrylates represented by N, N-dimethylaminoethyl (meth) acrylate; N- [2- (meth) acryloyloxyethyl]
Various (meth) such as piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine or N- [2- (meth) acryloyloxyethyl] morpholine
Acrylic acid ester monomers; or 4- (N, N-
Various aromatic monomers such as dimethylamino) styrene, 4- (N, N-diethylamino) styrene or 4-vinylpyridine, and further, 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl Various vinyl ethers such as vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether or 6-dimethylaminohexyl vinyl ether; or various polycarboxylic acid anhydride group-containing monomers such as maleic anhydride. Various tertiary amino group-containing monomers, such as various monomers typified by adducts of a compound having both a reactive active hydrogen group and a tertiary amino group;

17. Various cyano group-containing monomers such as (meth) acrylonitrile;

18. Various phosphate ester group-containing monomers obtained by a condensation reaction between various hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, such as hydroxyalkyl (meth) acrylates, and phosphate esters. Body;

19. Styrene, α-methylstyrene,
various aromatic vinyl compounds represented by styrene or derivatives thereof, such as p-tert-butyl-styrene or p-methylstyrene;

20. Various crotonic esters, such as methyl crotonate, ethyl crotonate or n-butyl crotonate;

21. Various unsaturated dibasic acid dialkyl esters such as dimethyl malate, dimethyl fumarate, dibutyl fumarate or dimethyl itaconate;

22. Various sulfonic acid group-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid;

23. General formulas such as

[0067]

Embedded image CH ₂ ＣＨCHCOO (CH ₂ ) ₃ [Si (CH
₃ ) ₂ O] _n Si (CH ₃ ) ₃ ,

[0068]

Embedded image CH_Two= C (CH_Three) COOC₆H_Four[Si
(CH_Three)_TwoO]_nSi (CH_Three) _Three ,

[0069]

Embedded image CH_Two= C (CH_Three) COO (CH_Two)_Three[S
i (CH_Three)_TwoO]_nSi (CH _Three)_Three ,

[0070]

Embedded image CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ [S
i (CH ₃ ) (C ₆ H ₅ ) O] _n Si (CH ₃ ) ₃

Or

[0072]

Embedded image CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₃ [S
i (C ₆ H ₅ ) ₂ O] _n Si (CH ₃ ) ₃

(Where n in each formula is 0 or 1 to
It is assumed that the integer is 130. )

Various polysiloxane bond-containing monomers represented by the following:

24. Such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, monoalkoxy polyethylene glycol (meth) acrylate or monoalkoxy polypropylene glycol (meth) acrylate
Various polyether chain-containing monomers;

25. Glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate,
Contains various epoxy groups such as 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate or di (β-methyl) glycidyl fumarate Monomers;

26. γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ -(Meth) acryloyloxypropyltriisopropenyloxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane or N-β- (N- Various hydrolyzable silyl group-containing vinyl monomers such as (vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane or its hydrochloride;

27. Ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate,
A radical polymerization reaction is possible in a molecule such as polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, divinylbenzene, hexadiene, octadiene, decadien, tetradecadiene, 2-methyl-octadiene or decatriene. And a class of monomers having two or more polymerizable unsaturated groups.

These monomers are appropriately selected and used in order to adjust the glass transition point or the minimum film-forming temperature of the finally obtained copolymer. Of course, more than one type may be used in combination.

In preparing the fluoroolefin emulsion polymer from the various monomers described above, only non-functional monomers may be used. Further, if necessary, it is desirable to use in combination various monomers having functional groups as described in 8 to 16 and 22 and 25 described above, respectively. More preferably, 8 (carboxyl group-containing monomer) and / or 16 (tertiary amino group-containing monomer)
It is recommended to use in combination with

The effect of introducing the functional group-containing monomers is not only to improve the dispersion of the pigment, but also to obtain a hydrolyzable silyl group-containing compound, which is one of the features of the present invention.
This is to form a chemical bond with the water-dispersible fine particle silica. Furthermore, it can be expected that the fluoroolefin emulsion polymer having a functional group and the water-dispersible fine particle silica and / or pigments are firmly bonded via the hydrolyzable silyl group-containing compound. As a result, in particular, the durability of the coating film formed from the composition of the present invention is further improved.

The fluoroolefin emulsion polymer used in the present invention may be one in which the inside of the particles is not cross-linked or one in which the inside of the particle is cross-linked. In particular, it can be said that water resistance and weather resistance are further improved.

In order to crosslink the inside of the particles of the fluoroolefin-based emulsion polymer, a monomer containing a hydrolyzable silyl group described in 26 is used in combination, or two kinds of monomers each having a mutually reactive functional group are used. Using the above monomers together,
Further, the polyfunctional monomers described in 27 may be used in combination.

In preparing the fluoroolefin-based emulsion polymer, various known and commonly used emulsion polymerization methods can be applied. In other words, various known and commonly used non-reactive emulsifiers such as anionic emulsifiers and nonionic emulsifiers, or various commonly known and commonly used reactive emulsifiers and dispersion stabilizers are used to obtain the following by various known and commonly used methods. A polymerization reaction may be carried out.

If only typical representative examples of anionic emulsifiers are given, sulfates of higher alcohols, alkyl (benzene) sulfonates, alkyl sulfates, polyoxyethylene alkylphenyl sulfonates, alkyls Diphenyl ether sulfonate, polyoxyethylene alkylphenol sulfate, styrene sulfonate, vinyl sulfate, alkyl sulfosuccinate, alkyl naphthalene sulfonate, alkyl phosphate, polyoxyethylene alkyl phosphate, polyacrylic acid ( salt)
And at least one water-soluble oligomer selected from the group consisting of sulfonic acid salts and sulfonates; various compounds such as water-soluble acrylic resins and derivatives thereof;
These may be used alone or in combination of two or more.

As nonionic emulsifiers, only typical ones are exemplified. Polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid In addition to esters, polyoxyethylene-polyoxypropylene block copolymers, polyvinyl alcohols, and the like, various types of cellulose ethers such as hydroxyethylcellulose and the like may be used alone or in combination with two or more. It goes without saying that the above combinations may be used.

Examples of the cationic emulsifiers which are particularly typical are: alkylamine salts; various quaternary ammonium salts represented by alkyltrialkylammonium chlorides; alkylbetaines; and amines. Various cationic functional group-containing compounds represented by oxides and the like may be used alone or in combination of two or more.

In addition, various fluoroalkyl carboxylate salts such as perfluorooctanoates and various fluorine atom-containing emulsifiers such as fluoroalkyl sulfates can be used in combination. .

Further, as the reactive emulsifier, monomers having various salt structures such as sulfonate, sulfate or phosphate as described above can be used.

The amount of the emulsifier used is suitably in the range of about 0.5 to about 10% by weight based on the total amount of the monomers.

Further, a method in which polymerization is carried out with the use amount of the emulsifier extremely small or polymerization is carried out without using the emulsifier at all, that is, a so-called soap-free polymerization method can also be applied.

The polymerization initiator is not particularly limited as long as it is one generally used in emulsion polymerization, but if only typical representatives thereof are exemplified, excessive polymerization initiators may be used. Various water-soluble inorganic peroxides, such as hydrogen oxide, ammonium persulfate, potassium persulfate or sodium persulfate;

Various organic peroxides, such as cumene hydroperoxide, benzoyl peroxide or tert-butyl hydroperoxide; or various azo initiators, such as azobisisobutyronitrile or azobiscyanovaleric acid And of course, these may be used alone or in combination of two or more. An appropriate amount of such a polymerization initiator is in the range of about 0.1 to about 2% by weight based on the total amount of monomers.

It is a matter of course that a so-called redox polymerization method using these polymerization initiators in combination with a metal ion and a reducing agent may be used.

As typical examples of such reducing agents, only typical ones may be mentioned, such as sodium bisulfite,
Sodium metabisulfite, sodium bithiosulfate, sodium hydrosulfate, sodium formaldehyde sulfoxylate or reducing sugar. Further, if only particularly typical examples of the above-mentioned metal ions are exemplified, copper sulfate, ferric chloride,
Ferric sulfate or silver nitrate. Further, it goes without saying that various chain transfer agents can be used.

In preparing the fluoroolefin-based emulsion polymer used in the present invention, the monomers are separately prepared as they are in an aqueous medium, preferably in the presence of ion-exchanged water and an emulsifier. , Or in an emulsified state, dropped in a lump, dividedly or continuously into a reaction vessel, and in the presence of the above-mentioned polymerization initiator, a gauge pressure of about 1 kg / cm ² to about 100 k.
The polymerization reaction may be carried out at a reaction temperature of about 50 ° C. to about 150 ° C. within a range of g / cm ² . In some cases, the polymerization reaction may be carried out under a higher pressure condition or a lower temperature condition.

The ratio of the total monomers to water is within the range of about 1 to about 60% by weight of the final solid content, preferably about 15 to about 60% by weight.
It should be set so as to be within the range of 55% by weight.

In carrying out the emulsion polymerization reaction,
In order to grow or control the particle size,
It is a matter of course that a so-called seed polymerization method in which the emulsion reaction is carried out in the presence of the emulsion particles in the aqueous phase may be employed.

As the water in the aqueous medium used herein, basically, ion-exchanged water is used, and the amount thereof is suitably within the range of about 70% by weight or more in the aqueous medium. is there. Here, the remaining less than about 30% by weight may be used in combination with an organic solvent.

The pH during the reaction can be adjusted to a value such as disodium phosphate, borax, sodium bicarbonate or ammonia.
The adjustment may be made by using various pH buffers.

In particular, when a vinyl ether-based monomer is used in a copolymerization reaction, it may be used in a low pH range or a high
In this case, a side reaction may be caused in the region. In this case, the reaction should be performed under the condition of pH 4 to 10.

As the state of the system after the completion of the reaction, unreacted gaseous monomers remain in the emulsion particles, although only partially. Most of these remaining monomers are unreacted fluoroolefins,
By removing the gaseous monomer according to a conventional method so as not to destroy the obtained emulsion, the desired product can be obtained.

The number average molecular weight of the fluoroolefin emulsion polymer thus prepared is generally at least 10,000, preferably at least 50,000, and most preferably at least 100,000. .

The minimum film forming temperature is about -10 ° C. to +6
It is general to design within the range of 0 ° C.

The particle size of the fluoroolefin-based emulsion polymer is not particularly limited, but the number average particle size of about 30 to about 1,000 nanometers (nm) indicates that the emulsion film is formed. It is also desirable from the viewpoint of film properties. Thus, the aqueous dispersion (A) used in the present invention is obtained.

Next, the water-dispersible fine particle silica dispersion (B) is a colloidal solution in which ultra-fine silica particles are dispersed in water or a hydrophilic organic solvent. As the particle size of B),
Generally, it is in the range of 10 nm to 100 nm. The surface of the particle generally contains silanol groups, but a part thereof may be stabilized by partially neutralizing it with a basic compound.

Of these, it is desirable that the particle surface is not neutralized or partially neutralized with a volatile base compound. More preferably, from the viewpoint that the aqueous dispersion of the component (A) shows alkalinity, a silanol group on the particle surface is partially neutralized with a volatile basic compound.

If only typical examples of such volatile basic compounds are given, examples thereof include ammonia, and volatile organic basic compounds such as triethylamine.

Further, only particularly representative examples of the hydrophilic organic solvent are exemplified, and examples thereof include methanol, isopropanol, ethylene glycol, ethylene glycol mono-n-propyl ether, dimethylacetamide and dimethylacetamide. Silica dispersions in the form of being dispersed in these various hydrophilic organic solvents are commercially available.

Here, the mixing ratio of the component (A) and the component (B) is generally expressed by a solid content ratio,
(A) / (B) = about 90/10 to about 50/50,
This is a desirable range for use.

When the amount of the component (B) is less than about 10 parts, it is difficult to say that it is an inorganic / organic composite which is one of the objects or the main purpose of the present invention, and it is difficult to exhibit its effect. If the amount of the component (B) is too large exceeding about 50 parts, the solid content of the commercially available component (B) is relatively low as compared with the component (A), so that the final This is also undesirable from the viewpoint that the solid content of the obtained paint is high and difficult to set.

The aqueous composition (C) containing a polymer aqueous dispersion (A) containing a fluoroolefin as an essential constituent unit and a water-dispersible fine particle silica dispersion (B) as a main film-forming component is defined as The composition itself can be used as a coating composition. Here, in addition to the aqueous dispersion (A) and the water-dispersible fine particle silica dispersion (B), the aqueous composition (C) may optionally contain a thickener (C-1) and a film forming agent. It may contain the auxiliary agent (C-2) and the pigments (C-3).

Examples of the thickener (C-1) include water-soluble cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose and carboxymethylcellulose, as well as water-soluble urethane derivatives and water-soluble polypyrrolidone. The system derivatives and the alkali thickening type polycarboxylic acid system derivatives are particularly typical, but any of these mixed systems can be used. Among them, those having a hydroxyl group and / or a carboxyl group are particularly desirable.

Next, only typical representative examples of the film-forming auxiliary (C-2) will be given below, for example, 2-propoxyethanol, 2-n-butoxyethanol, 2-n-butanol.
Ethylene glycol derivatives such as butoxyethyl acetate;

2-n-propoxypropanol, 3-n
Propylene glycol derivatives such as propoxypropanol, 2-n-butoxypropanol and 3-n-butoxypropanol; diethylene glycol derivatives such as diethylene glycol monobutyl ether and diethylene glycol dibutyl ether; N-methylpyrrolidone and its derivatives;

2,2,4-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol monobutyrate, 2,2,4-trimethyl-
Alkyl-substituted aliphatic polyhydric alcohol derivatives such as 1,3-pentanediol dibutyrate;

Polybasic acid esters such as dibutyl phthalate or butyl benzyl phthalate, alcohol-based organic solvents such as 2-ethylhexanol, various aliphatic organic solvents and aromatic solvents Group-based organic solvents, ketone-based organic solvents, ester-based organic solvents, and the like. Of course, these may be used alone or in combination of two or more.

As pigments (C-3), only typical ones are exemplified. Inorganic pigments represented by carbon black, titanium oxide, calcium carbonate, clay, iron oxide, iron hydroxide, etc. ;

Organic pigments such as phthalocyanine-based, quinacridone-based and azo-based pigments, etc., which are appropriately selected and used according to the final use. In particular, inorganic pigments are desirably used because they do not impair the high weather resistance, which is a characteristic of the fluoroolefin emulsion polymer.

Compared with inorganic pigments, organic pigments are liable to be degraded by the action of light during exposure, by the action of heat, and further by the combined action with water. is there. However, among the inorganic pigments, in the presence of water, in the presence of water, ultraviolet rays generate active radicals on the surface of the titanium oxide due to ultraviolet rays, thereby deteriorating the resin layer near the titanium oxide particles. Are known.

For this reason, when selecting titanium oxide, it is desirable to use a grade which has been subjected to a treatment for suppressing the above-mentioned reactive deterioration in titanium oxide. In the aqueous composition (C), the following class of curing catalysts can be blended.

Examples of such curing catalysts are only typical ones, and various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide or sodium methylate; tetraisopropyl titanate; , Tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate,

Di-n-butyltin diacetate, di-n-
Such as butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate, aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate) or aluminum tris (acetylacetonate);
Various metal-containing compounds; or various acidic compounds such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid or dialkylphosphorous acid, or these compounds in an aqueous medium. And those solubilized.

The aqueous composition (C) used in the present invention may contain, in addition to the various components described above, various known and commonly used additives as exemplified below. .

[0125] Of these, particularly typical ones are only examples. Fillers other than the above-mentioned pigments, pigment dispersants, pH adjusters, leveling agents, water repellents, defoamers, etc. Various known and commonly used additives such as agents, plasticizers, antioxidants, ultraviolet absorbers, anti-cissing agents, anti-skinning agents, and antifreezing agents can be appropriately added and used.

The aqueous composition (C) used in the present invention can be prepared from the various raw materials described above.

Next, the hydrolyzable silyl group-containing compound (D) is a compound having a hydrolyzable silyl group in the molecule as shown below.

Here, the term “hydrolyzable silyl group” means that a hydroxyl group bonded to a silicon atom is generated by hydrolysis, for example, as shown in the following general formula (I).
It refers to a silyl group in which a group that is easily hydrolyzed is bonded.

[0129]

Embedded image

(However, R1 in the formula has 1 to 1 carbon atoms.
X represents a halogen atom, an alkoxy group, a substituted alkoxy group, an acyloxy group, an aminooxy group, an aminooxy group, a phenoxy group, a thioalkoxy group, or a monovalent hydrocarbon group selected from the group consisting of an alkyl group, an aryl group, and an aralkyl group. A represents a monovalent group selected from the group consisting of an amino group, a halogen atom, an isopropenyloxy group, an iminooxy group and the like, and a represents 0, 1 or 2
Be an integer. )

The hydrolyzable silyl group-containing compound (D)
If we only exemplify especially typical ones,
Examples thereof include an alkyl silicate and / or a partially hydrolyzed condensate thereof, or a silane coupling agent. These can be used alone or in combination.

As the alkyl silicate and / or its partial hydrolyzed condensate, various alkyl silicates such as methyl silicate, ethyl silicate, isopropyl silicate and n-butyl silicate may be mentioned, if only typical ones are mentioned. Compounds; and alkyl silicate oligomers containing no free silanol groups obtained by subjecting various silicate compounds described above to partial hydrolysis and condensation.

If only typical representative silane coupling agents are mentioned, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth)
Acryloyloxypropyltriethoxysilane, γ-
(Meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane,

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane or N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane,
Or a hydrolyzable silyl group-containing vinyl monomer such as a hydrochloride thereof;

Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane or γ-
Various epoxysilane compounds (epoxy group-containing silane coupling agents) such as glycidoxypropyltriisopropenyloxysilane;

Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriethoxysilane
Mercaptopropylmethyldimethoxysilane or γ-
A compound having both a mercapto group and a hydrolyzable silyl group, such as mercaptopropyltriisopropenyloxysilane;

Various isocyanate silane compounds such as γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxysilane; or various aminosilane compounds such as γ-aminopropyltrimethoxysilane It is typical.

In addition to the above, alkyl silicate and / or its partial hydrolyzate as described above is prepared by using a compound having a hydrolyzable silyl group and / or silanol group in the molecule as shown below. Condensate or
The modified silane coupling agent may be used.

To illustrate only such compounds, various trifunctional silane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane or isobutyltrimethoxysilane; Various bifunctional silane compounds, such as dimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane or diphenyldimethoxysilane;

Various halosilanes such as methyltrichlorosilane, phenyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane or diphenyldichlorosilane; various difunctional or trifunctional silane compounds as described above can be used. So-called low molecular weight silanol compounds in such a form as to be obtained completely by hydrolysis;

The above silanol compounds are
Further, a linear or cyclic polysiloxane having a silanol group obtained by dehydration condensation; selected from the group consisting of various bifunctional silane compounds, trifunctional silane compounds and silicate compounds as described above. And a linear or cyclic polysiloxane compound having an alkoxysilyl group obtained by partially hydrolyzing and condensing at least one compound.

Here, as the modified silicate compound, it is preferable to use a compound having a structure having substantially no free silanol group.

The surfactant (E) is used to stably disperse or solubilize the hydrolyzable silyl group-containing compound (D) in water, as described above. And an anionic emulsifier, a nonionic emulsifier and a cationic emulsifier, respectively.
Further, in the composition of the present invention, these emulsifiers
The use of the anhydrous state is preferred.

These anionic emulsifiers, nonionic emulsifiers and cationic emulsifiers may be used alone or in combination of two or more. Among them, as an emulsifier that can be particularly preferably used, an emulsifier substantially in an anhydrous state is preferably used, and a nonionic emulsifier containing no ionic group is more preferably used.

The composition (F) is prepared by adding the above-mentioned surfactant (E) to the above-mentioned hydrolyzable silyl group-containing compound (D) in an amount of about 0.05% by weight to about 50% by weight. Therefore, it is preferable that the content is preferably in the range of 0.1% by weight to 30% by weight.

It is desirable to include a hydroxyl group-containing solvent and / or a water binder in the component (F).

The hydroxyl group-containing solvent can be appropriately selected from the compounds having an alcoholic hydroxyl group among the solvents described above and used. In addition, among the compounds exemplified below,
What is necessary is just to select and use it.

Alcohols having various linear, branched or cyclic alkyl groups such as methanol, ethanol, isopropanol or butanol; or ethylene glycol, propylene glycol, diethylene glycol, alkyl-substituted aliphatic polyhydric alcohols, etc. Furthermore, these various derivatives are mentioned.

On the other hand, particularly typical water binders include various trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate and tributyl orthoformate; trimethyl orthoacetate, triethyl orthoacetate. Various trialkyl orthoacetates, such as tributyl orthoacetate;

Various types of trialkyl orthoborate, such as trimethyl orthoborate, triethyl orthoborate, and tributyl orthoborate, and when no alcohol is present in the system, the water binder includes various isocyanates. Can be used.

Specific examples of such isocyanates include benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, 2,4-toluene diisocyanate, meta-xylylene diisocyanate, hexamethylene diisocyanate and the like. However, preferably, monoisocyanates such as benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, phenyl isocyanate, and p-chlorophenyl isocyanate are suitable.

The aqueous coating composition according to the present invention may be used as follows.

First, if necessary, a primer, an undercoat, or an intermediate paint is applied to the base material, and the aqueous coating composition according to the present invention is applied as a topcoat. Good.

In this case, the coating system for the base of the coating film formed from the composition of the present invention is not limited and may be of an aqueous type or a solvent type. That is, it may be. Alternatively, the coating film may be an old coating film or an existing coating film, or a newly applied coating film. Furthermore, the undercoating may be completely cured, uncured, or may be coated on a poorly dried coating film with the composition of the present invention.

The composition for water-based paint according to the present invention is prepared by mixing the water-based composition (C) and the composition (F) at the time of construction, stirring them sufficiently, and, if necessary, diluting with water. What is necessary is just to paint. In a preferred embodiment, the hydrolyzable silyl group-containing compound present in the composition (F) is present in an amount of about 3 to about 2 with respect to the solid content of the fluoroolefin emulsion polymer present in the aqueous composition (C).
What is necessary is just to mix and use so that it may contain 0 weight%.

As a coating method, it can be said that the coating is carried out by using various coating methods such as brush coating, spray coating, roll coater or flow coater according to a conventional method.

Further, by drying at room temperature, or
The coating may be formed by drying at an arbitrary temperature of 0 ° C. to approximately 220 ° C. for an arbitrary time. In some cases, the overcoat may be applied while the undercoat is still undried.

According to the present invention, the polymer having a carboxyl group and / or a tertiary amino group in the polymer containing a fluoroolefin which is a solid component (A) as an essential constitutional unit has the following meaning: The silanol group in the finely divided silica, which is the solid component B), and the hydrolyzable silyl group in the component (D), and in some cases, react with each other due to the effect of the curing catalyst in the system, and the fluorine resin and the silicon The components form a chemical bond and provide a cured coating in a complexed form.

At the same time, the aqueous coating composition according to the present invention comprises:
After the coating, a condensed layer derived from a hydrolyzable silyl group-containing compound is formed on the surface of the coating film through volatilization of water and / or an organic solvent in the system, and the condensed layer provides, in particular, stain resistance. It gives excellent coatings. As described above, the cured coating film obtained from the composition of the present invention has a property combining the properties of a fluororesin and the properties of a silicon compound as an inorganic material.

The aqueous coating composition according to the present invention is preferably
For repair of old paint film (existing paint film) for building or building materials or building, for tile, for glass or for various plastics products, woodworking, for car repair, aluminum, stainless steel, chrome For various coated objects such as plating, galvanized sheet, tin plate, etc.
Can be used extensively.

[0161]

EXAMPLES Next, the present invention will be described in more detail by reference examples, examples and comparative examples, but the present invention is in no way limited to these examples. Not something. Hereinafter, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Fluoroolefin Emulsion Polymer (A)] A 2-liter stainless steel pressure-resistant reaction vessel (autoclave) equipped with a stirrer, a nitrogen inlet tube, a thermometer and a temperature controller was charged with nitrogen. The system was sufficiently replaced with gas, and 800 parts of ion-exchanged water, 20 parts of sodium dodecylbenzenesulfonate and 20 parts of polyoxyethylene nonylphenyl ether, and 10 parts of borax as a pH buffer were used. Add and dissolve.

Next, 415 parts of vinyl neodecanoate, 15 parts of crotonic acid, and 500 parts of liquefied and collected chlorotrifluoroethylene are charged. Thereafter, ethylene gas is injected until the pressure becomes 15 kg / cm ² . The internal temperature of the autoclave is raised to 80 ° C.

At this time, the pressure in the system during the reaction was almost 30
Adjust ethylene gas to be kg / cm ² .

Subsequently, at the same temperature, an aqueous catalyst solution obtained by dissolving 5 parts of potassium persulfate in 200 parts of ion-exchanged water is pressed into the reaction vessel over 3 hours. After addition of the catalyst aqueous solution, the polymerization reaction is continued by maintaining the same temperature for 10 hours. The pH during the reaction proceeded at 3.5.

During the reaction, as the monomer is consumed, the pressure in the system decreases. In each case, the pressure in the reaction system is maintained at 30 kg / cm ² by introducing ethylene. After the completion of the reaction, the reaction mixture was cooled to room temperature, and 14% aqueous ammonia was added until the pH became approximately 7.5.
1.0 part of a 5% aqueous dispersion of "Nopco 8034L" (trade name of a silicon-based antifoaming agent manufactured by San Nopco Co., Ltd.) is added, and the mixture is stirred well.

Next, the pressure inside the system is returned to normal pressure by gradually removing unreacted gas from the system.
Subsequently, unreacted gas dissolved in the dispersion is distilled off under reduced pressure.

The dispersion thus obtained has a nonvolatile content of 4%.
8.5%, pH 7.2, minimum film forming temperature 30 ° C
And a white aqueous dispersion having an average particle size of 0.08 μm (μm). Hereinafter, this is referred to as (A-
Abbreviated as 1).

This aqueous dispersion (A-1) was subjected to elemental analysis,
According to the composition analysis by ion chromatography analysis, infrared absorption spectrum analysis and pyrolysis gas chromatography analysis, ethylene was 7.4%, fluoroolefin was 47.3%, and carboxylic acid vinyl ester monomer was 43%. 0.7% and 1.6% of the acid group-containing monomer.

Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 800 parts of ion-exchanged water, 20 parts of sodium dodecylbenzenesulfonate and 20 parts of polyoxyethylene nonylphenyl ether were added.
And 10 parts of Borax as a pH buffer are added and dissolved.

Then, 400 parts of vinyl neodecanoate,
15 parts of crotonic acid and 15 parts of dimethylaminoethyl methacrylate, and 500 parts of liquefied and collected chlorotrifluoroethylene are charged. Subsequently, ethylene gas is injected until the pressure becomes 15 kg / cm ² .

Further, as a catalyst, potassium persulfate;
Same as Example 1 except that a reducing agent was used, the reaction temperature was changed to 65 ° C., and in the initial preparation stage, 2 parts of a 0.05% ferric chloride aqueous solution was added. To carry out a polymerization reaction.

As the catalyst at this time, the above-mentioned potassium persulfate was prepared by dissolving 5 parts of potassium persulfate in 100 parts of ion-exchanged water. One is prepared by dissolving 5 parts of sodium formaldehyde sulfoxylate in 100 parts of ion-exchanged water.

The dispersion thus obtained has a nonvolatile content of 4%.
8.0%, pH 7.3, minimum film forming temperature 32 ° C
And a white aqueous dispersion having an average particle size of 0.08 μm. Hereinafter, this is abbreviated as (A-2).

This (A-2) was analyzed by elemental analysis, ion chromatography analysis, infrared absorption spectrum analysis and composition analysis by pyrolysis gas chromatography analysis to find that 7.2% of ethylene and 4% of fluoroolefin were present.
At 8.5%, the carboxylic acid vinyl ester monomer was 41.
It is known that 2%, 1.5% of the acid group-containing monomer and 1.6% of the tertiary amino group-containing monomer.

Reference Example 3 [Preparation Example of Composition (F)] Polyoxyethylene nonylphenyl ether (HLB =
13) and 3 parts of polyoxyethylene alkyl ether (HLB = 17) are mixed well, and 50 parts of "ethyl silicate 40" which is a partial hydrolysis condensate of ethyl silicate and γ-glycidoxy At the same time as adding 20 parts of propyltrimethoxysilane, 3 mol of methyl orthoformate was added for the purpose of removing trace water in the system.
Parts and 20 parts of isopropanol were also added and mixed well to prepare the desired composition. Hereinafter, this is abbreviated as F-1.

Reference Example 4 (same as above) Polyoxyethylene nonylphenyl ether (HLB =
4.2 parts of 13) and 3 parts of polyoxyethylene alkyl ether (HLB = 17) were mixed well,
At the same time as adding 80 parts of “ethyl silicate 40” and 10 parts of γ-glycidoxypropyltrimethoxysilane, 3 parts of methyl orthoformate and 20 parts of isopropanol were used for the purpose of removing a trace amount of water in the system. Was added and mixed well to prepare the desired composition. Hereinafter, this is abbreviated as F-2.

Reference Example 5 [Method for Preparing Pigment Paste (C-3)] "Taipec CR-97" [trade name of rutile-type titanium oxide surface-treated with zirconium, manufactured by Ishihara Sangyo Co., Ltd.] 8 parts, 5.6 parts of "Orotan SG-1" (trade name of pigment dispersant, manufactured by Rohm and Haas Company, USA), 3.9 parts of a 10% aqueous solution of sodium tripolyphosphate, "Neugen" EA-120 "[trade name of polyoxyethylene nonylphenyl ether-based emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 14.5 parts of ethylene glycol and" Best Side FX "[Dainippon Ink 0.8 parts of a trade name of a preservative manufactured by Chemical Industry Co., Ltd., 0.6 parts of "SN Deformer 121" [a trade name of an antifoaming agent manufactured by San Nopco Co., Ltd.], and 59 parts of water .1 and 2 % And 0.4 parts of aqueous ammonia allowed mixing, at room temperature, using a disper, the mixture was sufficiently stirred. The paste thus obtained is hereinafter abbreviated as pigment paste (Paste, C-3).

Examples 1 and 2 and Comparative Examples 1 to 3 The fluoroolefin emulsion polymer (A-1) or (A-
2) and an aqueous dispersion of water-dispersible fine particle silica in which a part of the silanol groups on the particle surface is neutralized with ammonia water [Nonvolatile content = 20% and average particle diameter = 10 nanometers (nm) This is hereinafter abbreviated as (B-1). ) And an ethylene glycol dispersion of the same water-dispersible fine particle silica as in (B-1) [Nonvolatile content = 20%,
And an average particle diameter of 10 nm; hereinafter, (B-
Abbreviated as 2). Is mixed at the mixing ratio as described in Table 1,

In addition, "Primal TT-935" (trade name of an alkali thickening type carboxylic acid group-containing emulsion manufactured by Rohm and Haas Co.) is used as the thickener (C-1). To increase the viscosity up to the coating viscosity, and diethylene glycol dibutyl ether was added as a film-forming auxiliary (C-2) to (A-1) or (A-
2) In addition to 5 parts,
Aqueous compositions (C1) and (C2) were obtained.

Next, the aqueous composition (C1) or (C2) was mixed with (F-1) obtained in Reference Example 3 at the mixing ratio as shown in Table 1. Thus, the composition of the present invention was obtained.

Thereafter, these were applied by brush coating twice on a slate which is a flexible plate manufactured by Nozawa Corporation. The coating amount at that time is 250 to 280 g /
m ² .

On the other hand, as comparative examples, first, in the case of comparative examples 2 and 3, use of the composition (F-1) was described.
Absent form [above, (C1) or (C
This corresponds to 2). Then, in the case of Comparative Example 1, the use of the aqueous dispersion (B-1) of the water-dispersible fine particle silica was completely absent [hereinafter referred to as the aqueous composition (C
Abbreviated as 3). Was prepared in the same manner as described above, and thereafter, the slate was painted with a brush.

Each of the test pieces thus obtained was dried at room temperature for one week and then subjected to various tests such as weather resistance, hardness, gel fraction, and contamination. The contamination test was carried out in Sakai City, Osaka Prefecture, for 3 months, 6 months, and 12 months, respectively, and the color difference ΔE of the coating film (that is, the color difference of the coating film before and after exposure was represented by the color difference ΔE). So, the smaller this value,
It means that it is not contaminated. ) Was measured and evaluated. The results are summarized in Table 1.

[0185]

[Table 1]

<< Footnotes in Table 1 >> Hardness: Evaluated by scratching pencil hardness.

Gel fraction: The dried free film was treated at room temperature with
It was expressed as a fraction of the residual film relative to the initial weight when immersed in acetone for 24 hours.

Stainability: The stain test was carried out in Sakai City, Osaka for 3 months, 6 months and 12 months, and evaluated by measuring the color difference ΔE of the coating film.

Weather resistance: Expressed using a Sunshine Weatherometer (SWOM) as a gloss retention after exposure for 4,000 hours.

[0190]

[Table 2]

Examples 3 and 4 and Comparative Examples 4 and 5 The fluoroolefin emulsion polymers (A-1) or (A-2) obtained in Reference Examples 1-2 and (B-1)
And Paste (C-3) obtained in Reference Example 5 are blended at a ratio as shown in Table 2 so that the pigment volume concentration as a concentration with respect to the fluoroolefin emulsion polymer becomes 15%. Made with white paint.

In preparing such a coating, “Primal TT-” as a thickener having a carboxyl group (C-1) is used.
935 ”to increase the viscosity.
By blending “Texanol” (a product of Eastman Chemical Co., USA) as a film-forming auxiliary (C-2), a paint (C) having a minimum film-forming temperature of 5 ° C.
4) or (C5).

In addition, the thickener (C5)
As (-1), (C-1 ′) having a composition of “primal TT-935” / hydroxyethylcellulose = 90/10 (weight ratio of solid content) was used.

On the other hand, as a comparative example, the use of an aqueous dispersion of water-dispersible fine-particle silica was prepared in the same manner as in the case of an absent form. Abbreviated as C6).

That is, the aqueous composition further comprises:
Compositions (F-1) to (F-) obtained in Reference Example 3 or 4
By mixing 2), a water-based coating composition according to the present invention was prepared. Next, the composition of the present invention thus obtained was applied by brush application twice on a slate which is a flexible board manufactured by Nozawa Corporation. The coating amount at this time was set to be 250 to 280 g / m ² .

On the other hand, as a comparative example, the use of the water-dispersible fine particle silica dispersion (B) and the use of the composition without the composition (F-1) or (F-2) were described. All of the missing forms were prepared and similarly brush painted on the slate.

Each of the test pieces thus obtained was dried at a room temperature for one week, and then subjected to various evaluation judgment tests. The results are summarized in Table 2.

[0198]

[Table 3]

Example 5 and Comparative Examples 6 to 9 The blends shown in Table 3 were evaluated for storage stability and the like of the blends. For comparison, the case where the F component was variously changed was evaluated.

[0200]

[Table 4]

<< Footnotes in Table 1 >> Nonionic emulsifier: The same amount was used by using the same kind contained in 20 parts of F-1.

Silicate compound: The same amount was used by using the same kind contained in 20 parts of F-1.

Silane coupling agent: The same amount was used by using the same kind contained in 20 parts of F-1.

Water binder: The water binder and the solvent contained in 20 parts of F-1 were used in the same amount.

Stability of the formulation: Evaluation was made according to the following criteria.

◎: When thickening and agglomeration are not observed at the time of blending with the C component, and a stable blend is given. ×: At the time of blending with the C component, the paint thickens and a stable paint is obtained. It is the case that it could not be prepared, or the case where so-called cissing occurred on the coating film at the time of painting, resulting in a coating film with poor gloss

Storage stability of component F: Evaluation was made on the stability of component (F) alone when stored at 50 ° C. for 2 months.

◎: When thickening or aggregation was not observed and stable, ×: When thickening or aggregation occurred and stability was poor.

[0209]

[Table 5]

[0210]

As described above, the water-based coating composition and the coated article according to the present invention obtained as described above can form a highly practical film, particularly excellent in stainability and the like. .

Thus, the water-based paint composition according to the present invention is particularly useful for building, for building materials, for repairing old paint films on buildings, etc., for tiles, for glass, for various plastics products, and for woodworking. It can be widely used for various objects to be coated such as for automobile repair, aluminum, stainless steel, chrome plating, metal plate and tin plate.

Claims (8)

[Claims] (1) An aqueous composition (C) comprising a polymer aqueous dispersion (A) containing a fluoroolefin as an essential constituent unit and a water-dispersible fine particle silica dispersion (B) as a main film-forming component. And (2) a composition (F) comprising a hydrolyzable silyl group-containing compound (D) and a surfactant (E). 2. The aqueous dispersion (A) contains a carboxyl group and / or 3
The aqueous two-part coating composition according to claim 1, which comprises a secondary amino group. 3. The aqueous two-part coating composition according to claim 1, wherein the water-dispersible fine particle silica dispersion (B) is a medium containing a water-soluble organic solvent as a medium. 4. An aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit, a water-dispersible fine particle silica dispersion (B), a hydroxyl group and / or Or a thickener having a carboxyl group (C-
The aqueous two-pack coating composition according to any one of claims 1 to 3, which comprises 1), a film-forming auxiliary (C-2), and a pigment (C-3). 5. The compound (D) containing a hydrolyzable silyl group according to the general formula: (However, R ₁ in the formula is a monovalent hydrocarbon group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group and an aralkyl group, and X ₁ is a halogen atom, an alkoxy group, a substituted alkoxy group. Group, acyloxy group, aminooxy group, phenoxy group, thioalkoxy group, amino group,
It represents a monovalent group selected from the group consisting of a halogen atom, an isopropenyloxy group, an iminooxy group and the like, and a is an integer of 0, 1 or 2. 5) The composition for an aqueous two-pack paint according to any one of claims 1 to 4, which is a compound having a hydrolyzable silyl group represented by the formula: 6. The nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Selected from the group consisting of surfactants and these same active substances,
The aqueous two-pack coating composition according to any one of claims 1 to 5, which is at least one compound. 7. The composition for an aqueous two-pack paint according to claim 1, wherein the composition (F) also contains a hydroxyl group-containing solvent and / or a water binder. 8. A coating material comprising (1) an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential structural unit and a dispersion (B) of a water-dispersible fine particle silica as main film-forming components. 8. The composition according to claim 1, comprising an aqueous composition (C) and (2) a composition (F) comprising a hydrolyzable silyl group-containing compound (D) and a surfactant (E). 9. A coated article formed by applying the composition for aqueous two-pack coating of the above, and forming the film at room temperature or under heating conditions.