JPH1025446A - Water-base coating composition and coated article made by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-base two-pack coating composition which gives a coating film excellent in, e.g. stain resistance by combining an aqueous composition containing a specified film-forming component with a composition containing a hydrolyzable silylated compound and a surfactant. SOLUTION: An aqueous composition (A) containing a principal film-forming component comprising an aqueous dispersion of a polymer consisting essentially of units of a fluoroolefin (e.g. tetrafluoroethylene) is combined with a composition (B) containing a hydrolyzable silylated compound and a surfactant to give the water-base two-pack coating composition. A hydroxylated solvent (e.g. methanol) and/or an aqueous binder (e.g. trimethyl orthoacetate) can be incorporated in addition into the composition B. Examples of the hydrolyzable silylated compound used for the component B include methyl silicate and methyltrimethoxysilane. The obtained coating composition is suitable particularly, e.g., for buildings and for the repair of an automobile.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful aqueous coating composition and a coated article using the same. More specifically, the present invention relates to a film-forming component comprising a polymer having a fluorine atom in the main chain, a so-called fluoroolefin polymer, and an additive component comprising a hydrolyzable silyl group-containing compound. The present invention relates to a composition for an aqueous two-pack coating composition and a coated article using the composition.

[0002] The aqueous coating composition according to the present invention is, in use, mixed with each component of the composition at the time of use, and coated. A film can be formed.

[0003]

2. Description of the Related Art As an attempt to extend the life of a coating film, various studies have been made on the components and composition of a coating vehicle (high-molecular polymer), which is a main component of the coating, or on the basis of pigments. Various developments have been pursued through studies on the improvement of weather resistance. As a result of these studies, high durability grades of paint vehicles and pigments were developed,
Products based on such technology have already been introduced in the market.

[0004] However, while the durability of the coating film itself has been increasing, on the other hand, contamination of the coating film has been recognized as a problem. It is getting.

[0005] That is, since the coating film itself has a considerably long-term durability, the appearance deterioration due to the attachment of contaminants has been remarkably observed. In a low-level coating film in which the weather resistance of the coating film itself is not ensured, even if a contaminant adheres, such a problem was not recognized because the coating film itself was lost due to deterioration.

[0006] For example, a solvent-based fluororesin paint, which is a typical example of a highly durable paint, has its own coating film deteriorated by a variety of analytical methods or natural or accelerated exposure methods for a considerably long life. It is acknowledged that there is.
However, dirt due to the attachment of contaminants to the coating film surface is a remarkable difficulty, and a solution is urgently needed.

[0007] As a countermeasure against such a problem, as a measure against a solvent-based paint, by containing an alkyl silicate in the paint composition and forming a condensation layer derived from the alkyl silicate on the surface of the coating film, the adhesion of contaminants is suppressed. A technique was developed to attempt this.

Alternatively, a solvent-based or water-based coating film is formed without mixing such a compound in the coating material, and then an alkyl silicate or a partially hydrolyzed organic solvent solution thereof is applied. A technique for forming a condensation layer derived from an alkyl silicate on the surface of a coating film has also been developed and introduced to the market.

As described above, as a technique for inhibiting the adhesion of contaminants, a technique of using an alkyl silicate or a partial hydrolyzate thereof through an organic solvent-based medium has been generally used.

On the other hand, in the case of aqueous paints, the fact that the alkyl silicate itself is a compound that reacts with water is a bottleneck, and when mixed in an aqueous paint composition, gelation easily occurs. Or if the medium is water, it cannot be easily mixed and eventually cannot be used or if it is forcibly mixed, the dispersed state or solubilized state of the pigment or resin is destroyed. At present, it is impossible to use the paint due to loss of luster or thickening of the paint.

[0011]

Thus, as far as the prior art is concerned, it is inevitable that one of the substances which should inhibit the adhesion of contaminants in handling this kind of aqueous coating composition. So-called alkyl silicate-based compounds, such as alkyl silicates or partial hydrolysates thereof, cannot be used simply or otherwise very difficult.

Accordingly, the problem to be solved by the present invention is to easily use an alkyl silicate-based compound in which various problems as described above have been solved, even for an aqueous paint. It is in. That is, the present invention provides an aqueous paint composition capable of forming a coating film with reduced contaminant adhesion, and also provides a coated article using the aqueous paint composition. Is also to provide.

[0013]

SUMMARY OF THE INVENTION The present inventors have been keen to solve the above-mentioned various problems in the prior art and to meet various demands in the paint industry.
Research has begun.

Therefore, the present inventors have focused on the problems to be solved by the present invention as described above,
As a result of repeated studies, an aqueous composition (B) containing an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit as a main film-forming component and a hydrolyzable silyl group-containing compound (C) )) And a composition (F) comprising a surfactant (D), the various problems in the prior art as described above are brilliantly solved. The inventors have now completed the present invention in finding a solution.

That is, the present invention basically comprises,

(1) an aqueous composition (B) containing an aqueous dispersion (A) of a polymer having a fluoroolefin as an essential constituent unit as a main film-forming component; and (2) a compound containing a hydrolyzable silyl group ( C) and a composition (F) containing a surfactant (D), which is intended to provide a composition for an aqueous two-pack paint,

[0017] Two are (1) an aqueous composition (B) mainly containing an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit, and (2) a hydrolyzable composition. It is composed of a composition (G) containing a silyl group-containing compound (C), a surfactant (D), and a hydroxyl group-containing solvent (E-1) and / or a water binder (E-2). It is an object of the present invention to provide a composition for an aqueous two-pack coating comprising:

[0018]

DETAILED DESCRIPTION OF THE INVENTION As described above, the present patent applications each include,

(1) Aqueous composition (B) mainly comprising an aqueous dispersion (A) of a polymer having a fluoroolefin as an essential constituent unit, and (2) a compound containing a hydrolyzable silyl group ( C) and a composition (F) containing a surfactant (D), which claims a composition for an aqueous two-pack paint,

[0020] Two are (1) an aqueous composition (B) mainly containing an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit, and (2) a hydrolyzable composition. It is composed of a composition (G) containing a silyl group-containing compound (C), a surfactant (D), and a hydroxyl group-containing solvent (E-1) and / or a water binder (E-2). It also claims that the composition for aqueous two-pack coatings,

Further, in the present patent application, each of the above-mentioned aqueous dispersions (A) of a polymer containing a fluoroolefin as an essential constituent unit is particularly useful as a polymer containing the fluoroolefin as an essential constituent unit. It also claims a specific aqueous two-pack coating composition that contains a carboxyl group and / or a tertiary amino group,

The aqueous composition (B) is, in particular, an aqueous dispersion (A) of a polymer containing the above-mentioned fluoroolefin as an essential constituent unit, and a thickener (A) having a hydroxyl group and / or a carboxyl group. -2) and a film-forming auxiliary (A-
3) and a pigment (A-4), which also claims a specific aqueous two-pack coating composition set.

The above-mentioned hydrolyzable silyl group-containing compound (C) is preferably an alkyl silicate and / or a partially hydrolyzed condensate thereof or a compound of the general formula

[0024]

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. And 1 selected from the group consisting of an amino group, a halogen atom, an isopropenyloxy group and an iminooxy group.
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:

The surfactant (D) is preferably a nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester. It is said that it is a surfactant or these same effective substances,
It is also claiming a specific aqueous two-pack coating composition,

[0028] Furthermore, the present patent application relates in part to:
An aqueous composition (B) containing, as a main film-forming component, (1) an aqueous dispersion (A) of a polymer having a fluoroolefin as an essential structural unit, and (2) a hydrolyzable silyl on a substrate to be coated. A composition for two-pack coating composed of a composition (F) containing a group-containing compound (C) and a surfactant (D) is applied and formed at room temperature or under heating conditions. It claims to be about the resulting painted article,

Secondly, an aqueous composition (B) containing, as a main film-forming component, (1) an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit is added to a substrate to be coated.
And (2) a hydrolyzable silyl group-containing compound (C);
Composition (G) containing surfactant (D) and hydroxyl group-containing solvent (E-1) and / or water binder (E-2)
Apply two-part coating composition consisting of and at room temperature,
Alternatively, it claims that a coated article obtained by forming a film under heating conditions is claimed.

Hereinafter, the present invention will be described in detail. First, an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential structural unit, which constitutes the aqueous coating composition according to the present invention. ) Will be explained.

Here, first, such an aqueous composition (A) of a polymer containing a fluoroolefin as an essential constituent unit, that is, an aqueous fluororesin containing a fluoroolefin as a constituent unit, is, for example, a fluoroolefin. A resin obtained by polymerizing a monomer contained as an essential constituent unit, preferably, in an aqueous medium, a fluoroolefin emulsion polymer obtained by performing an emulsion polymerization reaction by a conventional method. The fluoroolefin emulsion polymer of this type is exemplified as a typical example. Examples of such a fluoroolefin-based emulsion polymer include the following.

In the present invention, the above-mentioned fluoroolefin has a polymerizable unsaturated double bond in the molecule,
In addition, it can be defined as a monomer in which at least one fluorine atom is directly bonded to the carbon atom forming the polymerizable double bond. If only typical representative examples of such fluoroolefins are given as examples, the following various compounds are available.

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, chlorotrifluoroethylene is used from the viewpoint of controlling the reaction during polymerization.

In the present invention, the amount of the fluoroolefin to be contained in the fluoroolefin-based emulsion polymer is 10% or more, preferably 15% or more as a fluorine atom per solid content of the polymer. What is necessary is just to use an appropriate amount of fluoroolefin.

If the amount is less than the above range, it becomes difficult to obtain various properties such as the weather resistance specific to the fluororesin. As other constituent components, other monomers that can be copolymerized with the fluoroolefin may be appropriately selected and used.

Here, the following various compounds will be exemplified if only typical examples of the above-mentioned monomers copolymerizable with the fluoroolefin are given.

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

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-t-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 or “biscoat”
8F, 8FM, 3F or 3FM] [trade name of a fluorine-containing (meth) acrylic monomer manufactured by Osaka Organic Chemical Co., Ltd.], or perfluorocyclohexyl (meth) acrylate or Ni-propyl par. Various (meth) acrylates, such as fluorooctanesulfonamidoethyl (meth) acrylate;

8. (Meth) acrylic acid, crotonic acid,
It contains unsaturated groups such as maleic acid, fumaric acid, itaconic acid or citraconic acid or maleic anhydride or itaconic anhydride, and adducts of various acid anhydride group-containing monomers with glycols. Hydroxyalkyl ester monocarboxylic acids; various unsaturated dibasic acids such as maleic acid, fumaric acid or itaconic acid described above;
Half with alkyl alcohol having 1 to 10 carbon atoms
Carboxyl group-containing monomers and dicarboxylic acids represented by esters;

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

10.2 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-hydroxyethyl vinyl ether
Hydroxyl-containing vinyl ethers such as hydroxyhexyl vinyl ether:

12. hydroxyl-containing allyl ethers such as 2-hydroxyethoxy allyl ether or 4-hydroxybutoxy allyl ether;

13. Adducts of monomers having various hydroxyl groups as described above and 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 or N-methylol (meth) acrylamide;

15. p-styrenesulfonamide, N-
Various sulfonic acid amide group-containing monomers represented by methyl-p-styrenesulfonamide or N, N-dimethyl-p-styrenesulfonamide;

16. Various N, N-dimethylaminoethyl (meth) acrylates
N-dialkylaminoalkyl (meth) acrylates; N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine or N- [2- (meth) acryloyloxyethyl ] Various (meth) acrylate monomers such as morpholine; various such as 4- (N, N-dimethylamino) styrene, 4- (N, N-diethylamino) styrene or 4-vinylpyridine And aromatic vinyl monomers such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 4-dimethylaminobutyl vinyl ether, 4-diethylaminobutyl vinyl ether and 6-dimethylaminohexyl vinyl ether. Kinds; Anhydrous Such as in acid, the active hydrogen group and a third reactive with various polycarboxylic acid anhydride group-containing monomers
Various tertiary amino group-containing monomers such as monomers represented by adducts with compounds having a tertiary amino group;

17. Cyano group-containing monomers represented by (meth) acrylonitrile;

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

19. Styrene, α-methylstyrene, p
Various aromatic vinyl compounds such as styrene or derivatives thereof, such as -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. Respectively,

[0060]

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

[0061]

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

[0062]

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

[0063]

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

[0065]

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 general formula:

24. Various polyethers 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 Chain-containing monomers;

25. Glycidyl (meth) acrylate,
(Β-methyl) glycidyl (meth) acrylate, 3,
Various epoxy group-containing monomers such as 4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate or di (β-methyl) glycidyl fumarate Body;

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,
Radical reactive in the molecule, such as polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, divinylbenzene, hexadiene, octadiene, decadiene, tetradecadiene, 2-methyl-octadiene or decatriene, etc. And various monomers having two or more polymerizable unsaturated groups.

These monomers are appropriately selected and used in order to adjust the glass transition point, the minimum film forming temperature, etc. of the finally obtained copolymer.
These may be used alone or in combination of two or more.

In preparing the fluoroolefin-based emulsion polymer from the various monomers described above, only non-functional monomers may be used. As a main component, and if necessary, so-called functional group-containing monomers as listed in item numbers 8 to 16 and item numbers 22 and 25 are preferably used in combination. Even more preferably, the combined use of a carboxyl group-containing monomer represented by item number 8 and / or a tertiary amino group-containing monomer represented by item number 16 can be recommended.

The effect of introducing these functional group-containing monomers is, inter alia, that the dispersibility of the pigment is improved, and at the same time, the chemical bonding with the hydrolyzable silyl group-containing compound, which is a feature of the present invention. Is formed.
Furthermore, it can be expected that the fluoroolefin emulsion polymer having a functional group and the pigments are firmly bonded via the hydrolyzable silyl group-containing compound. As a result, the durability of the coating film formed from the composition of the present invention, in particular, the durability is further improved.

The fluoroolefin emulsion polymer used in the present invention may be one in which the polymer particles are not crosslinked or one in which the inside thereof is crosslinked. In particular, water resistance, weather resistance, and the like can be further improved.

In order to crosslink the inside of the particles of the fluoroolefin-based emulsion polymer, the hydrolyzable silyl group-containing monomers described above (ie, those of item No. 26) are used.
Or a combination of two or more monomers each having a functional group capable of reacting with each other, or a combination of polyfunctional monomers (that is, those having item number 27). And so on.

In preparing the fluoroolefin-based emulsion polymer, various known and commonly used emulsion polymerization methods can be applied. That is, various known non-reactive emulsifiers such as anionic emulsifiers or nonionic emulsifiers; or various known and commonly used reactive emulsifiers and dispersion stabilizers are used in various known and commonly used methods. Thus, the polymerization reaction may be performed.

Here, only typical representative examples of the above-mentioned anionic emulsifier are given below.
Higher alcohol sulfates, alkyl (benzene) sulfonates, alkyl sulfates, polyoxyethylene alkylphenyl sulfonates, alkyl diphenyl ether sulfonates, polyoxyethylene alkylphenol sulfates, styrene sulfonates or vinyl sulfates, Various water-soluble oligomers selected from the group consisting of alkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyethylene alkyl phosphates, polyacrylic acids (salts), and sulfonates; And various compounds such as derivatives thereof, and these may be used alone or in combination of two or more.

Further, only typical examples of the nonionic emulsifiers mentioned above are polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene alkyl ester. Oxyethylene sorbitan fatty acid ester, polyoxyethylene
Various types of cellulose ethers, such as polyoxypropylene block copolymers, polyvinyl alcohol, and hydroxyethyl cellulose, may be used alone or in combination of two or more.

Further, only particularly representative examples of the above-mentioned cationic emulsifiers are exemplified, and quaternary ammonium salts such as alkylamine salts and alkyltrialkylammonium chlorides, alkyl betaines,
Various cationic functional group-containing compounds, such as amine oxides, may be used alone or in combination of two or more.

In addition, various fluoroalkyl carboxylate salts represented by perfluorooctanoate and the like, and various fluorine atom-containing emulsifiers represented by fluoroalkyl sulfate and the like can be used in combination.

Further, if only typical representative examples of the reactive emulsifier described above are given as examples, the above-mentioned simple emulsifiers having various salt structures such as a sulfonic acid group, a sulfate group or a phosphate group can be used. Such as dimers,
These classes of compounds can be used.

The use amount of these emulsifiers and dispersants is appropriately in the range of about 0.5 to about 10% by weight based on the total amount of the monomers, including the anionic emulsifier and the nonionic emulsifier. is there.

Further, a method in which the amount of these emulsifiers and dispersants used is extremely small to carry out the polymerization reaction, or a method in which the polymerization reaction is carried out without using it at all, that is, a so-called soap-free polymerization method can also be applied.

At that time, as the polymerization initiator, if it is a class generally used in emulsion polymerization,
Although it is not particularly limited, if only a typical one of them is exemplified,

Various water-soluble inorganic peroxides, such as hydrogen peroxide, ammonium persulfate, potassium persulfate or sodium persulfate;

Various organic peroxides, such as cumene hydroperoxide, benzoyl peroxide or t-butyl hydroperoxide;

Or various azo initiators such as azobisisobutyronitrile or azobiscyanovaleric acid, which may be used alone or in combination of two or more.

The amount of the polymerization initiator used is suitably in the range of about 0.1 to about 2% by weight based on the total amount of the monomers.

It is a matter of course that the 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.

In addition, only typical examples of the above-mentioned metal ions include copper sulfate, ferric chloride, ferric sulfate and silver nitrate.

Further, it is needless to say that various chain transfer agents can be used.

In preparing the fluoroolefin-based emulsion polymer used in the present invention, the monomers are separately used as they are in an aqueous medium, preferably in the presence of ion-exchanged water and an emulsifier. , Or in an emulsified state, in a lump, in a divided manner, or continuously, into a reaction vessel, and in the presence of a polymerization initiator as described above, a gauge pressure of about 1 kg / cm ² to
100 kg / cm ² , from about 50 ° C to about 15
The polymerization reaction may be performed at a reaction temperature of 0 ° C. 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 such that the final solid content of the fluoroolefin emulsion polymer is about 1%.
It should be set to be in the range of ~ 60% by weight, preferably in the range of 15-55% by weight.

In conducting the emulsion polymerization, a so-called seed polymerization method may be used in which emulsion particles are preliminarily polymerized in an aqueous phase in order to grow or control the particle diameter. Of course.

The water in the aqueous medium used here is basically ion-exchanged water, and its amount is suitably in the range of about 70% by weight or more in the aqueous medium.
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.
What is necessary is just to make it adjust using various pH buffers.

In particular, when a vinyl ether-based monomer is used in a copolymerization reaction, a side reaction may be caused in a low pH region or a high pH region. The reaction should be carried out at a pH of about 4 to about 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 the remaining monomers are unreacted fluoroolefins, but the purpose is to remove the gaseous monomers according to a conventional method so as not to destroy the emulsion. Thus, the target emulsion is obtained.

The number average molecular weight of the fluoroolefin emulsion polymer thus prepared is generally 10,000 or more, preferably 50,000.
A value of at least 0, most preferably at least 100,000 is suitable.

In general, the minimum film forming temperature is designed to fall within a range of about -10 ° C. to + 60 ° C.

The particle size of the fluoroolefin emulsion polymer is not particularly limited, but the number average particle size is preferably from about 30 to about 1,000 nm in view of the film forming property of the emulsion film. Is also desirable. Thus,
An aqueous dispersion (A), which is one essential component of the composition for an aqueous paint according to the present invention, is obtained.

Next, the aqueous composition (B) containing, as a main film-forming component, an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constitutional unit can be used as a coating composition by itself. Things, and
The aqueous composition (B) is mainly composed of a thickener (A-2), a film-forming auxiliary (A-3) or a pigment (A-4) in addition to the aqueous dispersion (A) described above. ) Is also contained.

The thickener (A-2) generally includes various water-soluble cellulosic derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose and the like, as well as water-soluble urethane derivatives; Pyrrolidone derivatives; alkali thickening type polycarboxylic acid derivatives and the like are typical, and these are used in an arbitrary mixture thereof. Among them, it is desirable to use those having a hydroxyl group and / or a carboxyl group in the molecule.

In addition, if only typical examples of the above-mentioned film-forming auxiliary (A-3) are given as examples, 2-propoxyethanol, 2-n-butoxyethanol,
Ethylene glycol derivatives such as -n-butoxyethyl acetate;

2-n-propoxypropanol, 3-n
Propylene glycol derivatives such as -propoxypropanol, 2-n-butoxypropanol, 3-n-butoxypropanol;

Diethylene glycol derivatives such as diethylene glycol monobutyl ether and diethylene glycol dibutyl ether; or N-methylpyrrolidone and its derivatives;

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

Alternatively, polybasic acid esters such as dibutyl phthalate or butyl benzyl ester phthalate and the like, and alcohol-based organic solvents typified by 2-ethylhexanol, etc. Aliphatic organic solvents, aromatic organic solvents,
A ketone-based organic solvent or an ester-based organic solvent may be used alone or in combination of two or more, and may be appropriately selected and used.

Further, only typical examples of the above-mentioned pigment (A-4) include carbon black, titanium oxide, calcium carbonate, clay, iron oxide and iron hydroxide. Including various inorganic pigments,

Various organic pigments such as phthalocyanine, quinacridone, and azo are used. These various pigments are appropriately selected and used according to the final use. What should I do?
Among these, the use of inorganic pigments is desirable in order not to impair high weather resistance, which is one of the features of the fluoroolefin emulsion polymer.

This is because, in comparison with inorganic pigments, in the case of organic pigments, deterioration is more likely to be caused by light or heat at the time of exposure and further by the combined action with water. However, among the inorganic pigments, it is known that, in the presence of water, ultraviolet rays generate active radicals on the surface of the titanium oxide in the presence of water, thereby deteriorating the resin layer existing in the vicinity of the titanium oxide particles. Have been. Therefore, when this titanium oxide is selected, it is desirable to use a grade that has been treated to suppress the above reaction of titanium oxide.

The aqueous composition (B) may contain the following curing catalyst. Various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide or sodium methylate may be mentioned only as typical examples of such curing catalysts;

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-butyltin dioctoate, di-n-butyltin dilaurate or di-n-
Various metal-containing compounds such as butyltin maleate or tris (ethylacetoacetate) aluminum, monoacetylacetonate bis (ethylacetoacetate) aluminum or tris (acetylacetonate);

Or p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid,
Mono- or dialkyl phosphites,
Various acidic compounds and the like.

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

Among them, particularly typical ones are exemplified, and fillers other than the above-mentioned pigments;
Pigment dispersants; pH adjusters; leveling agents; water repellents; defoamers; plasticizers; antioxidants; ultraviolet absorbers; cissing inhibitors; anti-skinning agents;
Various known and commonly used additives can be appropriately added and used.

The aqueous composition (B) used in the present invention can be prepared from the various raw material components listed above.

Next, the hydrolyzable silyl group-containing compound (C) refers to a compound having a hydrolyzable silyl group as shown below.

Here, such a hydrolyzable silyl group is, for example, a group represented by the following general formula (I):
It refers to a silyl group in which a hydrolyzable group is bonded, that is, a hydroxyl group bonded to a silicon atom is generated by hydrolysis.

[0123]

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. And 1 selected from the group consisting of an amino group, a halogen atom, an isopropenyloxy group and an iminooxy group.
And a represents an integer of 0, 1 or 2. )

The hydrolyzable silyl group-containing compound (C)
Examples thereof include alkyl silicates and / or partially hydrolyzed condensates thereof if only typical ones are exemplified.

Of these, only typical ones are mentioned, and various alkyl silicate compounds such as methyl silicate, ethyl silicate, isopropyl silicate or n-butyl silicate, etc. And alkyl silicate oligomers containing no free silanol groups in the form obtained by partially hydrolyzing and condensing various silicate compounds described above.

In addition to these, the above-mentioned alkyl silicate and / or its partially hydrolyzed condensate was modified using a compound having a hydrolyzable silyl group and / or silanol group as shown below. It may be in the form of a compound, and if only a particularly typical example of such a compound is given,

Various trifunctional silane compounds such as methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane or isobutyltrimethoxysilane;

Various bifunctional silane compounds such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane or diphenyldimethoxysilane;

Various halosilanes such as methyltrichlorosilane, phenyltrichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane or diphenyldichlorosilane;

Various bifunctional or trifunctional compounds as described above.
A so-called low molecular weight silanol compound in a form such that it is obtained by almost completely hydrolyzing a functional silane compound;

Linear or cyclic polysiloxanes having silanol groups, obtained by subjecting these silanol compounds to dehydration condensation.

As described above, at least one compound selected from the group consisting of various bifunctional silane compounds, trifunctional silane compounds and silicate compounds is partially hydrolyzed and condensed. And a linear or cyclic polysiloxane compound having an alkoxysilyl group.

As the silicate compound modified in this manner, a silicate compound having a structure substantially free of a free silanol group is preferably used.

Next, the above-mentioned surfactant (D) is
The aforementioned hydrolyzable silyl group-containing compound (C) is used for stably dispersing or solubilizing it in water. The aforementioned anionic emulsifier, nonionic emulsifier and / or cationic emulsifier And the like. Further, in the composition of the present invention, these emulsifiers are preferably used in an anhydrous state.

Each of these anionic emulsifiers,
Needless to say, the nonionic emulsifier or the cationic emulsifier may be used alone or in combination of two or more.

Among them, emulsifiers which can be particularly preferably used are substantially anhydrous emulsifiers, and more preferably nonionic emulsifiers containing no ionic group.

Next, the composition (F) was prepared by adding the surfactant (D) to the hydrolyzable silyl group-containing compound (C) in an amount of about 0.05% to about 50% by weight. , Preferably within a range of 0.1% by weight to 30% by weight.

The component (F) desirably contains a hydroxyl group-containing solvent (E-1) and / or a water binder (E-2). Hereinafter, the composition containing the hydroxyl group-containing solvent (E-1) and / or the water binder (E-2), respectively, is also referred to as a composition (G).

At that time, the above-mentioned hydroxyl group-containing solvent (E-
1) can be appropriately selected and used from solvents containing an alcoholic hydroxyl group among the above-mentioned solvents. In addition, it may be appropriately selected from the following solvents and used.

That is, a linear, branched or cyclic alcohol having an alkyl group such as methanol, ethanol, isopropanol or butanol; or ethylene glycol, propylene glycol or diethylene glycol or an alkyl-substituted aliphatic polyhydric alcohol; And the like.

On the other hand, only typical examples of the above-mentioned water binder (E-2) include various trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate and tributyl orthoformate. ;

Or trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate;

Alternatively, various types of trialkyl orthoborate, such as trimethyl orthoborate, triethyl orthoborate, and tributyl orthoborate, may be used when the alcohol is not present in the system.
As -2), various isocyanates can be used.

As typical examples of such isocyanates, benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, 2,4-toluene diisocyanate, and meta-xylylene diisocyanate can be mentioned. Or hexamethylene diisocyanate, preferably benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, phenyl isocyanate, p-
It is desirable to use various monoisocyanates such as chlorophenyl isocyanate.

In the composition (F) or the composition (G),
In addition to the various components as described above, a coupling agent can also be blended, but among those coupling agents, if only representative examples are given,

Γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane Silane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyl (tris-β-methoxyethoxy) silane, vinyltriacetoxysilane,
A hydrolyzable silyl group-containing vinyl monomer such as vinyltrichlorosilane or N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, or 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; various aminosilane compounds such as γ-aminopropyltrimethoxysilane is there.

The aqueous coating composition of the present invention thus obtained may be used as follows.

That is, first, if necessary, a primer, an undercoat or an intermediate coat is applied to the substrate to be coated, and the composition of the present invention thus obtained is applied as an overcoat. do it. In this case, the coating system for the base of the coating film formed from the composition of the present invention is not limited at all, and may be of an aqueous type or a solvent type. It does not matter. Alternatively, it may be an existing coating film (old coating film) or a newly applied coating film. Further, the base may be coated with the composition of the present invention on a completely cured coating film, or on a coating film that has not been cured or is insufficiently dried.

The composition of the present invention is obtained by mixing the aqueous composition (B) and the composition (F) or (G) at the time of construction.
The mixture may be sufficiently agitated, and if necessary, diluted with water and painted.

In this case, a preferred embodiment is such that the hydrolyzable silyl group-containing compound present in the composition (F) is added to the solid content of the fluoroolefin emulsion polymer present in the aqueous composition (B). , About 3 to about 20% by weight
May be used by being blended so as to be contained within the range.

The composition of the present invention, after its coating, undergoes volatile escape of water and / or an organic solvent in the system,
A condensed layer derived from a hydrolyzable silyl group-containing compound is formed on the surface of the coating film, and the formation of the condensed layer results in particularly excellent stain resistance and the like.

[0156] In this case, the coating method is as follows.
The coating can be performed by making use of various known and commonly used coating methods such as brush coating, spray coating, roll coater or flow coater, and thus the coated article according to the present invention is obtained.

In obtaining the coated article according to the present invention, a coating film is formed by drying at normal temperature or by drying at an arbitrary temperature from about 50 ° C. to about 220 ° C. for an arbitrary time. do it. In some cases, even if the top coat is applied while the undercoat remains undried, it does not matter.

The aqueous coating composition according to the present invention is preferably
For building, building materials, or repair of old coatings on buildings; for tiles; for glass; or for various plastics products; for woodworking; for automotive repair; aluminum, stainless steel, chrome plating, tin It can be widely used for various substrates to be coated, such as for a metal plate or a tin plate.

[0159]

Next, the present invention will be described more specifically with reference examples, examples and comparative examples. However, the present invention is in no way limited to only these illustrative examples. is not. In the following, 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. And dissolved. Next, 415 parts of vinyl neodecanoate, 15 parts of crotonic acid, and 500 parts of chlorotrifluoroethylene collected by liquefaction were charged.

Next, ethylene gas was supplied at 15 kg / cm ²
And press the autoclave to 80 ° C.
The temperature was raised to ° C. At this time, ethylene gas was adjusted so that the pressure in the system during the reaction was approximately 30 kg / cm ² . Then, at the same temperature, 5 parts of potassium persulfate
A catalyst aqueous solution dissolved in 200 parts of ion-exchanged water was pressed into the reaction vessel over 3 hours. After the addition of the catalyst aqueous solution, the polymerization reaction was allowed to proceed at the same temperature for 10 hours.

The pH during the reaction proceeded at 3.5. During the reaction, the pressure in the system decreased with the consumption of the monomer. In each case, the pressure of the reaction system was 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 thereto at a pH of about 7.
5 and add “Nopco 8034L”
1.0 part of a 5% aqueous dispersion of [trade name of silicon-based defoamer manufactured by San Nopco Co., Ltd.] was added thereto, and the mixture was stirred well.

Next, unreacted gas was gradually taken out of the system, and the pressure in the system was returned to normal pressure. Thereafter, unreacted gas dissolved in the dispersion was distilled off under reduced pressure. The dispersion of the target polymer thus obtained has a nonvolatile content of 48.5%, a pH of 7.2, a minimum film-forming temperature of 30 ° C., and an average particle size of 0.08 μm. (Μm). Hereinafter, this is abbreviated as (A-1-1).

This aqueous dispersion (A-1-1) was analyzed by elemental analysis, ion chromatography, infrared absorption spectrum and compositional analysis by pyrolysis gas chromatography to find that it contained 7.4% ethylene and Olefin is 4
At 7.3%, the vinyl carboxylate monomer was 43.3%.
The content was 7% and the content of the acid group-containing monomer was 1.6%.

Reference Example 2 (same as above) In a reaction vessel similar to that of Reference Example 1, 800
, 20 parts of sodium dodecylbenzenesulfonate, 20 parts of polyoxyethylene nonylphenyl ether and 10 parts of borax as a pH buffer were dissolved therein. Next, 400 parts of vinyl neodecanoate, 15 parts of crotonic acid, 15 parts of dimethylaminoethyl methacrylate, and 500 parts of chlorotrifluoroethylene collected by liquefaction were charged. After that, 1 ethylene gas
It was press-fitted to 5 kg / cm ² .

Further, potassium persulfate and a reducing agent are used as a catalyst, the reaction temperature is set to 65 ° C., and 2 parts of a 0.05% ferric chloride aqueous solution is added at the initial charging stage. A potassium persulfate as an aqueous catalyst solution was prepared by dissolving 5 parts of potassium persulfate in 100 parts of ion-exchanged water in the same manner as in Example 1 except for the above change. The reducing agent as the aqueous catalyst solution was 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-1-2).

This aqueous dispersion (A-1-2) was subjected to elemental analysis, ion chromatography analysis, infrared absorption spectrum, and composition analysis by pyrolysis gas chromatography,
7.2% ethylene and 48.5 fluoroolefins
%, The carboxylic acid vinyl ester monomer was 41.2%
The content of the acid group-containing monomer was 1.5%, and the content of the tertiary amino group-containing monomer was 1.6%.

Reference Example 3 (same as above) The reaction was carried out in the same manner as in Reference Example 2 except that the same amount of dimethylaminoethyl methacrylate was introduced instead of crotonic acid to obtain the desired emulsion weight. A coalescence was obtained.

This dispersion, which is an emulsion polymer thus obtained, has a nonvolatile content of 48.5% and a pH of 7.
7 was a white aqueous dispersion having a minimum film-forming temperature of 35 ° C. and an average particle size of 0.08 μm. Less than,
This is abbreviated as (A-1-3).

The aqueous dispersion (A-1-3) was subjected to elemental analysis, ion chromatography analysis, infrared absorption spectrum, and composition analysis by pyrolysis gas chromatography,
7.4% ethylene and 48.4 fluoroolefins
%, The carboxylic acid vinyl ester monomer is 41.0%
And the tertiary amino group-containing monomer was 3.2%.

Reference Example 4 [Preparation example of composition (G) comprising hydrolyzable silyl group-containing compound, surfactant and water binder]

5 parts of polyoxyethylene nonylphenyl ether (HLB = 13) and 3 parts of polyoxyethylene alkyl ether (HLB = 17) were mixed well, and “ethyl silicate 40” which was a partial hydrolysis condensate of ethyl silicate was mixed. , And simultaneously adding 1.0 part of methyl orthoformate for the purpose of simultaneously removing a small amount of water in the system, and mixing well to prepare an intended composition. . Hereinafter, this product is abbreviated as (G-1).

Reference Example 5 (same as above) Polyoxyethylene nonylphenyl ether (HLB =
8) and 2 parts of polyoxyethylene alkyl ether (HLB = 16) and polyoxyethylene-polyoxypropylene block copolymer (HLB = 16)
The two parts are mixed well under heating,
For the purpose of adding 500 parts of "methyl silicate 56" which is a partial hydrolysis condensate of methyl silicate, 80 parts of isopropyl alcohol and 20 parts of diethylene glycol monobutyl ether, and at the same time, removing a small amount of water in the system. And 10 parts of methyl orthoformate were added and mixed well to prepare the desired composition. Hereinafter, this product is abbreviated as (G-2).

Reference Example 6 (same as above) 3 parts of diisopropanol salt of dodecylbenzenesulfonic acid and 2 parts of polyoxyethylene nonylphenyl ether (HLB = 17) were mixed well.
125 parts of ethyl silicate 40, which is a partially hydrolyzed condensate of ethyl silicate, and 75 parts of isopropyl alcohol, and simultaneously 2 parts of methyl orthoformate for the purpose of removing a trace amount of water in the system. in addition,
By mixing well, the desired composition was prepared. Hereinafter, this product is abbreviated as (G-3).

Reference Example 7 (Example of preparing pigment paste) 200.8 parts of "Taipec CR-97" (trade name of rutile-type titanium oxide surface-treated with zirconium, manufactured by Ishihara Sangyo Co., Ltd.), "Orotan 5.6 parts of "SG-1" (trade name of a pigment dispersant manufactured by Rohm and Haas Company, USA), 3.9 parts of a 10% aqueous solution of sodium tripolyphosphate, "Neugen EA-120" [ Brand name of polyoxyethylene nonylphenyl ether emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], 14.5 parts of ethylene glycol and "Best Side FX" [Dainippon Ink and Chemicals, Inc.] Brand name of the preservative]
And 0.6 parts of "SN Deformer 121" [trade name of defoamer manufactured by San Nopco Co., Ltd.] and 5 parts of water
9.1 parts and 0.4 part of 28% aqueous ammonia were mixed and sufficiently stirred at room temperature using a disper.
The paste thus obtained is hereinafter referred to as a pigment paste (P
aster).

Reference Example 8 [Preparation example of composition (F) comprising a hydrolyzable silyl group-containing compound and a surfactant]

Except that the use of trimethyl orthoformate as a water binder was changed to be completely absent,
In the same manner as in Reference Example 4, the desired composition (F) was obtained. Hereinafter, this product is abbreviated as (F-1).

Examples 1 to 5 and Comparative Examples 1 to 4 Using the fluoroolefin emulsion polymers (A-1-1) to (A-1-3) obtained in Reference Examples 1 to 3, Reference Example 7 By mixing Paste (A-4) obtained in the above, the pigment volume concentration (PVC) is 15%
(See Table 1).

[0180] In preparing such a coating, "Primal TT-9" as a thickener (A-2) is used in accordance with a conventional method.
35 "(trade name of an alkali-thickened carboxylic acid group-containing emulsion manufactured by Rohm and Haas Co.), and" Texanol "(US) as a film-forming aid (A-3). , Eastman Chemical Co., Ltd.).
° C water-based paints (P-1) to (P-3).

The water-based paint (P-3) described above used as a thickener (A-2) was “Primal TT-935” / hydroxyethyl cellulose = 90, respectively.
/ 10 (solid parts by weight ratio)
Parts are used in parts.

The compositions (G-1) to (G-3) obtained in Reference Examples 4 to 6 were separately added to each of these water-based paints, whereby various compositions according to the present invention were obtained. An aqueous coating composition was prepared. Next, these compositions of the present invention were treated with a slate [flexible plate manufactured by Nozawa Corporation].
The top was brush-painted twice. The coating amount at this time was set to be 250 to 280 g / m ² .

As a comparative example, each of the compositions was prepared by mixing one of the compositions (G-1) to (G-3) with the coating composition without mixing them. "Ethyl silicate 40" or methyl silicate was directly mixed with water-based paints (P-1) to (P-3) to form a paint composition. In three, 10 parts of ethyl silicate were used. A specific alkyl silicate (R-1) diluted with 90 parts of isopropyl alcohol was directly mixed with the water-based coatings (P-1) to (P-3) to form a coating composition. What is described in Examples 1 to
In the same manner as in No. 5, the slate was painted with a brush.

Each of the test pieces thus obtained was allowed to dry at room temperature for one week, and then dried in Sakai City, Osaka Prefecture for three months, six months and 12 months, respectively. The color difference ΔE of the coating film (expressed as a color difference with respect to the state before the exposure, the smaller the value, the more the sample is not contaminated) was measured. The results are summarized in Table 2.

[0185]

[Table 1]

<< Footnote to Table 1 >>
Each number in the table represents parts by weight.

[0187]

[Table 2]

<< Footnote of Table 2 >>
Each number in the table represents parts by weight.

[0189] In Comparative Example 2, "Methyl silicate 5
The amount of "6" was the same as that in Example 2.

In Comparative Example 3, “ethyl silicate 4
The amount of “0” was the same as that in Example 3.

The amount of “ethyl silicate 40” in Comparative Example 4 was the same as that in Examples 1 and 5.

[0192]

[Table 3]

<< Footnotes in Table 2 >> State after blending

The evaluation criteria are as follows.

◎: A case where a stable compound is given without any increase in viscosity or aggregation at the time of compounding

△: The case in which the solvent thickens due to the solvent at the time of compounding, making it impossible to prepare a stable coating. As a result,
When a coating film having poor gloss is given (for example, as in Comparative Example 4)

X: The case where the paint thickens during the compounding, making it impossible to prepare a stable paint. In addition, at the time of coating, repelling occurs in the coating film, and especially, In the case where the paint film is inferior in gloss and the like (for example, in the case of Comparative Example 3) XX: At the time of compounding, the viscosity increases immediately, Can not be prepared

Initial gloss

Each paint was applied on a glass plate with a 3 mil applicator and allowed to dry at room temperature for one week, and the gloss value (mirror reflectivity at 60 °) was determined by Murakami. It is indicated by the value measured by a gloss meter.

Color difference ΔE

The color difference ΔE with respect to the state before the exposure was shown. The smaller the value, the less contaminated.

[0202]

[Table 4]

[0203]

[Table 5]

Example 6 The composition (F-1) obtained in Reference Example 8 was prepared in the same manner as in Examples 1 to 5 and Comparative Examples 1 to 4, and particularly in the same manner as in Example 1. The coating composition was used, and the state after blending, the gloss, and the ΔE value after exposure showed the same tendency as in Example 1.

That is, 20 parts of each of the composition (F-1) and the composition (G-1) were precisely weighed in a 100 milliliter container, and the temperature was 25 ° C.
% Relative humidity for 10 minutes,
Next, the container was sealed, and the storage stability at 50 ° C. was evaluated.

As a result, in the system using the composition (G-1) in which the water binder was present, no change was still observed even after one month, and the system was extremely stable. However, in the system using the composition (F-1) in which the water binder was not present, the composition solution after one month had already been slightly turbid. Was confirmed.

Therefore, from the viewpoint of long-term storage, it can be said that a system containing a water binder is more desirable. However, with respect to these two compositions, the composition (F-1) and the composition (G-1), in the same manner as in Example 1, other properties were evaluated and evaluated. No particular difference could be observed between these two compositions.

[0208]

The water-based coating composition according to the present invention obtained as described above is extremely practicable in that it can form a film excellent in stainability and the like.

Thus, the aqueous coating composition of the present invention
Especially for construction, building materials, repair of old paint film of building, tile, glass or various plastics products, woodworking, car repair, aluminum, stainless steel, chrome plating It can be widely used for various substrates to be coated, such as for a metal such as a galvanized sheet and a tin plate, and therefore, the composition of the present invention can be applied to such a coated substrate. The coated article according to the present invention, which is obtained by using the material substrate, is also extremely practical.

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[Procedure amendment]

[Submission date] August 20, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

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;

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction contents]

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 various monomers having two or more polymerizable unsaturated groups.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0111

[Correction method] Change

[Correction contents]

Alternatively, it is a polybasic acid ester such as dibutyl phthalate or butyl benzyl phthalate, or an alcoholic organic solvent represented by 2-ethylhexanol.
Other examples include various aliphatic organic solvents, aromatic organic solvents, ketone organic solvents, and ester organic solvents. These may be used alone or in combination of two or more, and may be appropriately selected and used.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

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-butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate, tris (ethylacetoacetate) aluminum, monoacetylacetonatebis (ethylacetoacetate) aluminum or Various metal-containing compounds, such as aluminum tris (acetylacetonate);

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0154

[Correction method] Change

[Correction contents]

In a preferred embodiment in this case, the solid content of the fluoroolefin emulsion polymer present in the aqueous composition (B) is compared with the hydrolysis present in the composition (F) or (G). Reactive silyl group-containing compound,
What is necessary is just to mix and use so that it may be contained in the range of about 3 to about 20% by weight.

Claims (8)

[Claims] 1. An aqueous composition (B) containing, as a main film-forming component, an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit, and (2) containing a hydrolyzable silyl group. An aqueous two-pack coating composition comprising: a composition (F) containing a compound (C) and a surfactant (D). 2. An aqueous composition (B) containing, as a main film-forming component, an aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constituent unit, and (2) containing a hydrolyzable silyl group. Compound (C), surfactant (D), hydroxyl group-containing solvent (E-1) and / or water binder (E-
(2) A composition for aqueous two-pack coatings, comprising: 3. The aqueous dispersion (A) of a polymer containing a fluoroolefin as an essential constitutional unit as a polymer containing the fluoroolefin as an essential constitutional unit as a carboxyl group and / or a tertiary amino group The composition according to claim 1, which comprises: 4. The aqueous composition (B) comprises an aqueous dispersion (A) of a polymer containing the fluoroolefin as an essential constituent unit and a thickener (A) having a hydroxyl group and / or a carboxyl group. -2) and a film-forming auxiliary (A-3)
And a pigment (A-4).
Or the composition according to 2. 5. The method according to claim 1, wherein the hydrolyzable silyl group-containing compound (C) is an alkyl silicate and / or a partially hydrolyzed condensate thereof or a compound represented by 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. A monovalent group selected from the group consisting of a group, an acyloxy group, an aminooxy group, a phenoxy group, a thioalkoxy group and an amino group, a halogen atom, an isopropenyloxy group and an iminooxy group; The composition according to claim 1, which is a compound having a hydrolyzable silyl group represented by the following formula: 6. The surfactant (D) is a nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene higher fatty acid ester, sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester. The composition according to claim 1 or 2, which is a surfactant or an equivalent thereof. 7. An aqueous dispersion (A) of a polymer containing (1) a fluoroolefin as an essential constituent unit on a substrate to be coated.
An aqueous composition (B) containing, as a main film-forming component,
(2) An aqueous two-pack coating composition comprising a hydrolyzable silyl group-containing compound (C) and a composition (F) containing a surfactant (D) is applied, and at room temperature or A coated article obtained by forming a film under heating conditions. 8. An aqueous dispersion (A) of a polymer containing (1) a fluoroolefin as an essential constituent unit on a substrate to be coated.
An aqueous composition (B) containing, as a main film-forming component,
(2) A composition (G) containing a hydrolyzable silyl group-containing compound (C), a surfactant (D), and a hydroxyl group-containing solvent (E-1) and / or a water binder (E-2). ) Is applied at room temperature,
Alternatively, a coated article obtained by forming a film under heating conditions.