JPH08337754A - Aqueous coating composition and outdoor article - Google Patents

Abstract

PURPOSE: To obtain the subject composition containing a compound having a specific structure, a water-soluble and/or water-dispersible resin and an aqueous medium each in specific amounts and excellent in resistance to stain attachment, stain-removing property and storage stablity and film-forming property, etc. CONSTITUTION: This coating composition comprises (A) 1-50 pts.wt. compound of the formula [R is a monovalent organic group and/or H; (n) is an integer of 1-100] (preferably a fluorine-containing compound), (B) 100 pts.wt. water-so1 uble and/or water-dispersible resin (preferably a fluororesin) and (C) an aqueous medium and contains preferably (D) 10-200 pts.wt. water soluble and/or self- water-dispersible curing agent and further contains preferably (E) 0.05-5 pts.wt. surfactant. Furthermore, a resin having a group reacting with an isocyanate group is preferably included as the component B and a self-water-dispersible isocyanate-based curing agent is preferably included as the component D. A fluorine-containing surfactant or a modified organosilicone-based surfactant is preferably included as the component E.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous coating composition and an outdoor article.

[0002]

2. Description of the Related Art In recent years, water-soluble or water-dispersible paints have been attracting much attention from the viewpoints of pollution problems and solvent emission regulations. In addition, from the viewpoints of maintaining aesthetics and emphasizing landscapes, various analysis and prevention methods for stains on building exteriors and vehicle exteriors have been studied.Especially for dirt carried by rainwater in urban areas, dirt adheres and accumulates. There is a need for an exterior material that has excellent functions (contamination-preventive adhesion) and that can be easily removed by cleaning even if it adheres and accumulates (contamination removal).
Furthermore, methods such as increasing the crosslink density of the coating film are effective for improving this stain removal property, and the surface of the article is made hydrophilic (lowering the contact angle to water) to improve the stain adhesion property. It is known to be effective.

For example, WO 94/06870, WO
In 95/02645 and WO95 / 02462, an aqueous coating composition containing (organo) silicate and / or a condensate thereof or a surface treatment method using the composition is effective for improving stain adhesion. It is disclosed. However, when hardeners and silicates are added to water-based paints, the problem that the hardeners and silicates are difficult to disperse, and because the hardeners and silicates react rapidly with the water in the paint, storage stability of the paint There was a problem in the properties, pot life, film-forming property, curability, coating workability, antifouling adhesion of coating film, appearance and weather resistance.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an aqueous coating composition which is excellent in antifouling adhesion and decontamination property, storage stability, film-forming property, curability and weather resistance, and the composition. It is to provide an article obtained by painting an article.

[0005]

[Means for Solving the Problems]

 (A) Formula (1):

[0006]

[Chemical 4]

(In the formula, R is the same or different and is a monovalent organic group and / or hydrogen atom, and n is 1 to 100.
1 to 50 parts by weight of a compound represented by
It relates to an aqueous coating composition comprising (B) 100 parts by weight of a water-soluble and / or water-dispersible resin and (C) an aqueous medium.

Further, the present invention provides (A) formula (1):

[0009]

Embedded image

(In the formula, R is the same or different and is a monovalent organic group and / or hydrogen atom, and n is 1 to 100.
1 to 50 parts by weight of a compound represented by
(B) 100 parts by weight of water-soluble and / or water-dispersible resin, (D) water-soluble and / or self-water-dispersible curing agent 1
It relates to an aqueous coating composition comprising 0 to 200 parts by weight and (C) an aqueous medium.

Further, the present invention provides (A) formula (1):

[0012]

[Chemical 6]

(Wherein R is the same or different and is a monovalent organic group and / or hydrogen atom, n is 1 to 100)
1 to 50 parts by weight of a compound represented by
(B) 100 parts by weight of water-soluble and / or water-dispersible resin, (D) water-soluble and / or self-water-dispersible curing agent 1
The present invention relates to an aqueous coating composition composed of 0 to 200 parts by weight, (E) a surfactant of 0.05 to 5 parts by weight, and (C) an aqueous medium.

The present invention further relates to an article obtained by coating any of the above aqueous coating compositions.

[0015]

ACTION AND EXAMPLE In the present invention, antifouling adhesion,
It is not clear why the effect of excellent stain removability is obtained, but for example, silicate causes condensation on the surface of the coating film to increase the crosslink density on the surface of the coating film and generate Si-OH groups. It is conceivable that the surface may be hydrophilized by this, and particularly when the component (A) is a fluorine-containing compound, the compound has a surface concentrating property, so the silicate concentration on the surface increases, It is conceivable that the surface will have a high crosslinking density and a high hydrophilicity efficiently.

Further, in the present invention, by further using a water-soluble and / or self-water-dispersible curing agent, for example, a droplet of the curing agent has a large number of hydrophilic groups on the outside in water and is cured. It is also possible that the functional group involved in the reaction is present in a large amount inside, and further, the component (A) may be present inside the droplets of the curing agent in a large amount. It is considered that the curing agent and the component (A) are stably present in the aqueous coating composition.

Further, in the present invention, by using a surfactant, the surfactant cooperates with a water-soluble and / or self-dispersing curing agent to stabilize the component (A) in an aqueous coating composition. Since it can be present, it is considered to have an excellent effect.

The component (A) is simply dispersed or solubilized in a water-based coating composition using a surfactant, or the component (A) is hydrolyzed with an acid or an alkali to form a water-based coating composition. Even if it is simply dispersed or solubilized in the product,
The effect as in the present invention cannot be obtained.

Each component that can be used in the aqueous coating composition of the present invention will be described below.

In the formula (1) of the component (A), the carbon number of R is 1 to 15 from the viewpoint of excellent balance among stability, hydrolyzability and condensability, and 2-1.
It is preferably 0.

Further, n is an integer of 1 to 100, and an integer of 2 to 10 from the viewpoint of excellent storage stability of the paint, workability, and resistance to scattering during coating. More preferable.

Further, R is an alkyl group, a monovalent organic group in which some or all of hydrogen atoms are substituted with fluorine atoms from the viewpoint of excellent balance of stability, hydrolyzability and condensability. Of these, an alkyl group in which some or all of hydrogen atoms are substituted with fluorine atoms is particularly preferable from the viewpoint of stability and surface concentrating property.

As such R, for example, H (CH
₂ ) _n , (CH ₃ ) ₂ CH, H (CH ₂ ) _n C = O, F (CF
₂ ) _n (CH ₂ ) _m , (CF ₃ ) ₂ CH, H (CF ₂ ) _n (CH
₂ ) _m , F (CF ₂ ) _n (CH ₂ ) _m C = O, H (CF ₂ )
_{n (CH 2) m C =} O, (H (CH 2) n) 2 C = N, ((C
H ₃ ) ₂ CH) ₂ C = N, H (CH ₂ ) _n C = ONZ, (F
_{(CF 2) n (CH 2} ) m) 2 C = N, ((CF 3) 2 CH) 2
C = N, (H (CF 2) n (CH 2) m) 2 C = N, F (C
F ₂ ) _n (CH ₂ ) _m C = ONZ, H (CF ₂ ) _n (CH ₂ ) _m
C = ONZ (In the formula, n is an integer of 1 to 10, m is 0 or an integer of 1 to 6, Z is an alkyl group having 1 to 10 carbon atoms, and some of the fluorine atoms are substituted with chlorine atoms. R may be linear or branched) and the like.

Of these R's, H (CH ₂ ) _n and F (CF ₂ ) are excellent in terms of balance between stability, hydrolyzability and condensability, dispersibility, and easy availability. _n (C
H ₂ ) _m is preferred. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group and CF ₃ C.
Examples thereof include F ₂ CH ₂ , F (CF ₂ ) ₄ CH ₂ CH _{2 and the} like, with a methyl group, an ethyl group and a propyl group being particularly preferable.

Commercially available products of the compound represented by the above formula (1) are, for example, Methyl silicate 39, Methyl silicate 51, Ethyl silicate 28, manufactured by Colcoat Co., Ltd.,
Examples thereof include ethyl silicate 40. When R is a hydrogen atom, HAS manufactured by Colcoat Co., Ltd. is commercially available.
-1 and the like.

Examples of the water-soluble and / or water-dispersible resin as the component (B) include acrylic emulsion,
Water-soluble acrylic resin, acrylic silicone emulsion,
Examples thereof include fluororesin emulsions, water-soluble fluororesins, and crosslinkable type of these.

Commercial products or prototypes of the acrylic emulsion and water-soluble acrylic resin are, for example, Bihydrol TPLS-2940 manufactured by Sumitomo Bayer Urethane,
Examples thereof include TPLS-2052.

Examples of the fluororesin emulsion include fluoroolefin copolymers described in JP-A-7-53911. Furthermore, Japanese Patent Application No. 5-
A water-dispersible vinylidene fluoride copolymer aqueous composition described in No. 236493 and an aqueous composition obtained by post-polymerizing a monomer having a functional group such as a hydroxyl group using the vinylidene fluoride copolymer aqueous dispersion as a seed. And more preferable.

As the water-soluble fluororesin, for example, a hydroxyl group and // as described in JP-A-62-143915.
Further, a fluoroethylene copolymer containing a carboxyl group and the like can be mentioned, and more preferable.

Examples of the water-soluble and / or self-water-dispersible curing agent for the component (D) include (block) isocyanates, aminoplasts, oxazolines, siloxanes, aziridines, epoxies, hydrazides, carbodiimides. And ketimines.

The self-water dispersibility is, for example, the above (D).
Among the hardeners of the components, it is possible to introduce a hydrophilic group (polyethylene oxide, ionic group, etc.) into a water-insoluble one to disperse it in water.

Examples of the (blocked) isocyanates include 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate,
Lysine methyl ester diisocyanate, methyl cyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate,
Examples thereof include n-pentane-1,4-diisocyanate and trimers thereof, adducts, burettes, polymers of these polymers having two or more isocyanate groups, and blocked isocyanates.

Of these, isocyanates containing no aromatic group are preferred from the viewpoints of weather resistance and yellowing resistance. Further, those modified with polyethylene oxide or a carboxyl group to be (self) water-soluble or (self) water-dispersible can be mentioned.

Examples of the water-soluble or self-water-dispersible isocyanate include those described in JP-A-5-179191. Furthermore, JP-A-5-221
50, JP-A-5-27177, EP-54866.
Two-component type modified at room temperature with polyethylene oxide or carboxyl group as described in JP-A-9
And the isocyanates are preferred. Examples of commercially available products or prototypes thereof include Bayhydur TPLS-2032 and SB manufactured by Sumitomo Bayer Urethane Co., Ltd.
U-isocyanate L801 and the like can be mentioned.

As the aminoplasts, Japanese Patent Laid-Open No.
Examples thereof include those described in Japanese Patent No. 179191. Further, for example, methylol melamines, methylol guanamines, methylol ureas and the like can be mentioned. Examples of the methylolmelamines include those etherified with a lower alcohol such as butylated methylolmelamine and methylated methylolmelamine, and epoxy-modified methylolmelamine.

Examples of the methylolureas include alkylated methylolureas such as methylated methylolurea and ethylated methylolurea. Also,
Examples thereof include water-soluble or water-dispersible aminoplasts modified with polyethylene oxide or a carboxyl group. When using the above aminoplasts, an acidic catalyst or a blocked acidic catalyst can be used.

Examples of the surfactant as the component (E) include anionic surfactants, nonionic surfactants,
Alternatively, a combination thereof and an amphoteric surfactant can be given.

Examples of the anionic surfactants include higher alkyl sulfates such as sodium alkyl sulfonate, sodium alkyl benzene sulfonate, sodium succinate dialkyl ester sulfonate and sodium alkyl diphenyl ether disulfonate.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, glycerin esters, and their derivatives. can give.

Examples of the amphoteric surfactant include lauryl betaines.

Fluorine-containing anionic surfactants can also be used. For example, F (CF ₂ ) _q (CH ₂ ) _P CO
₂ H, H (CF ₂ ) _q (CH ₂ ) _p CO ₂ H (In the formula, p is 0 or an integer of 1 to 6, q is an integer of 1 to 10, and some of the fluorine atoms are replaced with chlorine atoms. The fluorine-containing alkyl group may be a straight chain as well as a branched chain) and the like metal (Li, Na, K, Ca, Mg, Zn, etc.) salts and amines (NH ₃ , methylamine) , Ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, etc.) salts and the like.

Further, a fluorine-containing nonionic surfactant can be used, for example, Rf- (CH ₂ CH ₂ O) x-.
_{(CH 2 CHCH 3 O) y} -Rf or Rf- (CH ₂ C
_{H 2 O) x- (CH 2} CHCH 3 O) y-Ra [ wherein, x
Is 0 or an integer of 1 to 100, y is 0 or 1 to 100
And these compounds represent block or random copolymers, Rf is F (CF ₂ ) q (CH ₂ ) p,
(CF ₃ ) ₂ CH, H (CF ₂ ) q (CH ₂ ) p, F (CF
_{2) q (CH 2) pCO} 2, H (CF 2) q (CH 2) pC
O ₂ (In the formula, p is 0 or an integer of 1 to 6, and q is 1 to 10)
, A part of the fluorine atom may be substituted with a chlorine atom, and the fluorine-containing alkyl group may be a straight chain as well as a branched chain), and Ra is a hydrogen atom, or methyl, ethyl, butyl, lauryl. Such as an alkyl group, a phenyl group, or an alkylphenyl group].

As the organosilicon type surfactant,
For example, polyether (for example, polyoxyethylene,
Examples include modified silicones such as polypropylene oxide. Furthermore, those having a functional group such as a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group, an epoxy group or the like on the side chain or terminal of these modified silicones can be mentioned, and preferred.

Examples of the aqueous medium of the component (C) include water, ethylene glycol monomethyl ether acetate,
Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol acetate, ester solvents such as diethylene glycol acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ether, ethylene glycol monobutyl ether,
Ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ether solvents such as diethylene glycol dimethyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, N ，
N-dimethylacetamide, N-methylacetamide,
Acetamide, N, N-dimethylformamide, N, N
-Amide type solvents such as diethylformamide and N-methylformamide, methanol, ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (degree of polymerization 3-10
0), CF ₃ CH ₂ OH, F (CF ₂ ) ₂ CH ₂ OH, (C
F ₃ ) ₂ CHOH, F (CF ₂ ) ₃ CH ₂ OH, F (CF ₂ )
₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ CH ₂ OH, H (CF ₂ ) ₃ C
Examples thereof include alcohol solvents such as H ₂ OH and H (CF ₂ ) ₄ CH ₂ OH.

Among these solvents, water, N, N-dimethylacetamide and N, N-dimethylformamide are preferable from the viewpoint of interaction with the silanol groups formed.

The mixing ratio of each of the above components for obtaining the aqueous coating composition of the present invention is 1 to 50 parts of the (A) component to 100 parts of the (B) component (parts by weight, hereinafter the same).
Parts, preferably 10 to 30 parts, by mixing the component (A) within this range, the stability of the aqueous coating composition,
The workability, the appearance of the coating film, the antifouling adhesion property, the stain removal property, and the flexibility are excellent.

The component (C) can be mixed with 100 parts of the component (B) in the following ratio, for example.

The mixing ratio of the component (C) is 10 to 1
000 parts, preferably 50 to 300 parts. By mixing within this range, coating workability, pot life,
The effect is that the appearance of the coating film is excellent.

The mixing ratio of each of the above components for obtaining another aqueous coating composition of the present invention is as follows: Component (B) 1
To 100 parts (parts by weight, the same applies hereinafter), the above component (A) 1
To 50 parts, preferably 10 to 30 parts, and (B)
The components (C) and (D) can be further mixed with 100 parts of the components in the following ratios, for example.

The mixing ratio of the component (D) is 10 to 2
The amount is 00 parts, preferably 50 to 150 parts. By mixing within this range, the effects of excellent curability, flexibility of the coating film, solvent resistance, and appearance can be obtained.

The mixing ratio of the component (C) is 10 to 1
000 parts, preferably 50 to 300 parts. By mixing within this range, coating workability, pot life,
The effect is that the appearance of the coating film is excellent.

The mixing ratio of each of the above components to obtain still another aqueous coating composition of the present invention is 100 parts by weight of the component (B) (parts by weight; The amount is 50 parts, preferably 10 to 30 parts, and the respective components (C) to (E) can be mixed with 100 parts of the component (B) in the following ratios, for example.

The mixing ratio of the component (D) is 10 to 2
The amount is 00 parts, preferably 50 to 150 parts. By mixing within this range, the effects of excellent curability, flexibility of the coating film, solvent resistance, and appearance can be obtained.

The mixing ratio of the component (E) is 0.05.
It is -5 parts, preferably 0.5-2 parts. By mixing within this range, the effect of excellent dispersion stability can be obtained.

The mixing ratio of the component (C) is 10 to 1
000 parts, preferably 50 to 300 parts. By mixing within this range, coating workability, pot life,
The effect is that the appearance of the coating film is excellent.

The coating composition of the present invention includes, for example, pigments, pigment dispersants, thickeners, leveling agents, defoamers, film-forming aids, ultraviolet absorbers, HALS, matting agents, fillers,
Additives for coatings such as colloidal silica, antifungal agents, and silane coupling agents can also be added.

Examples of the silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane. Those containing an amino group or an isocyanate group such as methoxysilane, 3-trimethoxysilylpropyl isocyanate, and 3-triethoxysilylpropyl isocyanate are preferable.

The mixing ratio of these coating additives may be 0.1 to 50 parts with respect to 100 parts of the component (B), and the mixing method may be an ordinary method.

As a method for mixing the respective components to obtain each of the aqueous coating compositions of the present invention, for example, the component (A) is put in a container equipped with a stirrer and then stirred at a speed of 100 to 5000 rpm while stirring ( The component (D) may be mixed with the component (C) or the component (E), and the component (B) may be mixed with the component (C) or other additives.

Each of the aqueous coating compositions thus obtained is applied to an outdoor article. Examples of the outdoor article in the present invention include an outdoor article coated with a paint, a metal panel, a plastic board, a tile, Examples include glass and film.

As a method for coating each of the aqueous coating compositions on the outdoor article, for example, the aqueous coating composition is spray coated on the surface of the outdoor article and dried and cured at 0 to 200 ° C. for 1 minute to 10 days, A coating film having a film thickness of 0.1 to 100 μm may be formed.

In each of the water-based coating compositions of the present invention, the following are preferred. In the following, the formula means the formula (1), and Rf represents a fluoroalkyl group.

(1) Compound in which R is Rf in the formula (A1) 1 to 50 parts (B) Water-soluble and / or water-dispersible resin 100 parts (C) Aqueous medium In this composition, the compound (A1) is It is advantageous in that it is highly hydrophobic, has low compatibility with an aqueous medium, and has low reactivity.

More preferably, the compound (A1) in which R is Rf is 1 to 50 parts (B1) Water-soluble and / or water-dispersible fluororesin 100 parts (C1) Water. This composition is excellent in that the compound (A1) is highly hydrophobic, has low compatibility with an aqueous medium, and has low reactivity, weather resistance of a coating film, antifouling adhesion, and stain removability.

(2) Compound in which R is Rf in the formula (A1) 1 to 50 parts (B) Water-soluble and / or water-dispersible resin 100 parts (D) Water-soluble and / or self-water-dispersible curing agent 10 ~ 200 parts (C) Aqueous medium This composition has a high hydrophobicity of the compound (A1), low compatibility with the aqueous medium, and low reactivity. It is advantageous in terms of strength, solvent resistance, water resistance, antifouling adhesion, and stain removal.

More preferably, the compound (A1) in which R is Rf is 1 to 50 parts (B1) Water-soluble and / or water-dispersible fluorine-containing resin 100 parts (D1) Self-water-dispersible curing agent 10 200 parts (C1) water In this composition, the compound (A1) is highly hydrophobic, has low compatibility with an aqueous medium, and has low reactivity.
1) In terms of high water dispersion, and because the fluorine-containing resin is chemically cross-linked, physical properties of the coating film, weather resistance, solvent resistance, water resistance, antifouling adhesion, and stain removability Are better.

Further, 1 to 50 parts of the compound (A1) in which R is Rf (B2) 100 parts of a water-soluble and / or water-dispersible fluorine-containing resin having a group that reacts with an isocyanate group (D2) self-water Dispersible isocyanate-based curing agent 10 to 200 parts (C1) water In this composition, the compound (A1) is highly hydrophobic, has low compatibility with an aqueous medium, and has low reactivity.
2) Highly dispersed in water, isocyanate can be cured at room temperature because of high reactivity, urethane group generated from isocyanate has good compatibility with silicate (silanol group), fluororesin is chemically crosslinked Therefore, the coating film is excellent in physical strength, weather resistance, solvent resistance, water resistance, stain-proof adhesion, and stain-removal property.

Further, the (D2) self-emulsifying isocyanate-based curing agent is preferably one containing no aromatic group from the viewpoint of weather resistance and yellowing resistance.

(3) Compound in which R is Rf in the formula (A1) 1 to 50 parts (B) Water-soluble and / or water-dispersible resin 100 parts (D) Water-soluble and / or self-water-dispersible curing agent 10 ˜200 parts (E) Surfactant 0.01 to 20 parts (C) Aqueous medium In this composition, the compound (A1) is highly hydrophobic, has low compatibility with an aqueous medium, and has low reactivity. A1) is (E)
Is easily dispersed in water, and since the resin is chemically crosslinked, it is advantageous in terms of physical strength of the coating film, solvent resistance, water resistance, antifouling adhesion, and stain removability.

More preferably, (A1) a compound in which R is Rf 1 to 50 parts (B1) water-soluble and / or water-dispersible fluorine-containing resin 100 parts (D1) self-water-dispersible curing agent 10 200 parts (E1) Fluorine-containing surfactant or modified organosilicon-based surfactant 0.01 to 20 parts (C1) Water In this composition, the compound (A1) is highly hydrophobic, has low compatibility with an aqueous medium, and has low compatibility. In terms of reactivity, the compound (A1) is (D
1) and (E1) for high water dispersion, good compatibility between the compounds (A1) and (E1), the resin being chemically cross-linked, the physical strength and weather resistance of the coating film, Excellent in solvent resistance, water resistance, antifouling adhesion, and stain removal.

Further, 1 to 50 parts of the compound (A1) in which R is Rf (B2) 100 parts of a water-soluble and / or water-dispersible fluorine-containing resin having a group reactive with an isocyanate group (D2) self-water Dispersible isocyanate curing agent 10 to 200 parts (E1) Fluorine-containing surfactant or modified organosilicon surfactant 0.01 to 20 parts (C1) Water In this composition, the compound (A1) is highly hydrophobic. The compound (A1) is (D) low in compatibility with an aqueous medium and low in reactivity.
2) and (E1) for high water dispersion, good compatibility between the compounds (A1) and (E1), room temperature curing due to high reactivity of isocyanate, urethane group formed from isocyanate Has good compatibility with silicates (silanol groups), and because the resin is chemically cross-linked, the physical strength of the coating film, weather resistance, solvent resistance, water resistance, stain-proofing adhesion, and stain-removing properties Are better.

The (D2) self-water-dispersible isocyanate curing agent is more preferably one containing no aromatic group from the viewpoint of weather resistance and yellowing resistance. (E1) F (CF ₂ ) _n COOQ (n is 1 to 9, Q is an ammonium group, a sodium atom or a potassium atom) as the fluorine-containing surfactant
Is particularly preferred.

(4) Compound (A2) wherein R has an alkyl group and / or hydrogen atom 1 to 50 parts (B) Water-soluble and / or water-dispersible resin 100 parts (D1) Self-water dispersion Hardening agent 10 to 200 parts (C) Aqueous medium In this composition, the compound (A2) is highly water-dispersed by the self-water-dispersible hardening agent, and the compound (A2) is industrially produced in large quantities. Since it is inexpensive, it contains almost no impurities, and because the resin is chemically crosslinked, it is advantageous in terms of physical strength, solvent resistance, water resistance, antifouling adhesion, and decontamination of the coating film. Is.

More preferably, (A2) a compound in which R is an alkyl group and / or a hydrogen atom in the formula 1 to 50 parts (B1) a water-soluble and / or water-dispersible fluorine-containing resin 100 parts (D1) self-water Dispersible curing agent 10 to 200 parts (C1) Water This composition has a point that the compound (A2) is highly water-dispersed by (D1), and the compound (A2) is industrially produced in large quantities. It is inexpensive, contains almost no impurities, and because the fluororesin is chemically cross-linked, the physical strength of the coating film, weather resistance, solvent resistance, water resistance, stain-proofing adhesion,
Excellent in removing stains.

Further, 1 to 50 parts of the compound (A2) in which R is an alkyl group and / or a hydrogen atom (B2) A water-soluble and / or water-dispersible fluorine-containing resin having a group reactive with an isocyanate group 100 Parts (D2) Self-water dispersible isocyanate-based curing agent 10 to 200 parts (C1) Water In this composition, the compound (A2) is highly water-dispersed by (D2), and the compound (A2) is industrial. It is inexpensive because it is produced in large quantities, and it contains almost no impurities. It can be cured at room temperature because isocyanate is highly reactive, and the urethane group generated from isocyanate is compatible with silicate (silanol group). Good point: Fluorine resin is chemically crosslinked, so it is excellent in physical strength of coating film, weather resistance, solvent resistance, water resistance, stain-proof adhesion, and stain-removal property. .

The (D2) self-water-dispersible isocyanate-based curing agent preferably contains no aromatic group from the viewpoint of weather resistance and yellowing resistance.

(5) Compound (A2) wherein R is an alkyl group and / or hydrogen atom 1 to 50 parts (B) Water-soluble and / or water-dispersible resin 100 parts (D1) Self-water-dispersible curing agent 10 to 200 parts (E) Surfactant 0.01 to 20 parts (C) Aqueous medium In this composition, compound (A2) is highly dispersed by (D1) and (E), compound (A2). Is inexpensive because it is industrially produced in large quantities, and it contains almost no impurities. The resin is chemically crosslinked, so the physical strength of the coating film, solvent resistance, water resistance, and stain-proof adhesion. It is advantageous from the standpoint of property and stain removability.

More preferably, (A2) a compound in which R is an alkyl group and / or a hydrogen atom in the formula 1 to 50 parts (B1) a water-soluble and / or water-dispersible fluorine-containing resin 100 parts (D1) self-water Dispersible curing agent 10-200 parts (E1) Fluorine-containing surfactant or modified organosilicon-based surfactant 0.01-20 parts (C1) Water In this composition, (A2) is (D1) and (E1). Is inexpensive because the compound (A2) is industrially produced in large quantities, and contains almost no impurities, and (E1) remaining in the coating film is water resistant. It is excellent in physical strength, weather resistance, solvent resistance, water resistance, stain-proofing adhesion and stain-removing property because the fluororesin is chemically crosslinked because it has no adverse effect.

Further, (A2) a compound in which R is an alkyl group and / or a hydrogen atom in the formula 1 to 50 parts (B2) a water-soluble and / or water-dispersible fluorine-containing resin having a group reactive with an isocyanate group 100 Parts (D2) Self-water-dispersible isocyanate-based curing agent 10 to 200 parts (E1) Fluorine-containing surfactant or modified organosilicon-based surfactant 0.01 to 20 parts (C1) Water This composition comprises a compound ( A2) is (D2) and (E
1) that it is highly water-dispersed, that isocyanate is highly reactive, and that it can be cured at room temperature, that urethane groups formed from isocyanate have good compatibility with silicates (silanol groups), and they remain in the coating film ( E1) has no adverse effect on water resistance and is excellent in physical strength of coating film, weather resistance, solvent resistance, water resistance, antifouling adhesion, and stain removability because the resin is chemically crosslinked. There is.

The (D2) self-water-dispersible isocyanate-based curing agent is more preferably one that does not contain an aromatic group in terms of weather resistance and yellowing resistance. (E1) F (CF ₂ ) _n COOQ (n is 1 to 9, Q is an ammonium group, a sodium atom or a potassium atom) as the fluorine-containing surfactant
Is particularly preferable.

(6) Compound (A2) wherein R is an alkyl group and / or hydrogen atom 1 to 50 parts (B) Water-soluble and / or water-dispersible resin 100 parts (D1) Self-water-dispersible curing agent 10 to 200 parts (C2) Water and amide group-containing compound In this composition, the compound (A2) is highly water-dispersed by the self-water dispersible curing agent, and the compound (A2) contains the amide group of (C2). Point compound (A
2) is inexpensive because it is industrially produced in large quantities, and it contains almost no impurities. The resin is chemically crosslinked, so the physical strength of the coating film, solvent resistance, water resistance,
It is advantageous in terms of antifouling adhesion and decontamination.

More preferably, (A2) a compound in which R is an alkyl group and / or a hydrogen atom in the formula 1 to 50 parts (B1) a water-soluble and / or water-dispersible fluorine-containing resin 100 parts (D1) self-water Dispersible curing agent 10 to 200 parts (C2) Water and amide group-containing compound In this composition, the compound (A2) is highly dispersed by (D1), and the compound (A2) is an amide group of (C2). Stabilized by the contained compound, inexpensive because the compound (A2) is industrially produced in large quantities, and contains almost no impurities, and the fluororesin is chemically crosslinked, so that the coating film It has excellent physical strength, weather resistance, solvent resistance, water resistance, stain-proof adhesion, and stain-removal properties.

Compound (A2) in which R is an alkyl group and / or hydrogen atom 1 to 50 parts (B2) Water-soluble and / or water-dispersible fluorine-containing resin having a group reactive with an isocyanate group 100 Parts (D2) Self-water-dispersible isocyanate-based curing agent 10 to 200 parts (C2) Water and amide group-containing compound This composition has a point that the compound (A2) is highly water-dispersed by (D2). A2) is stabilized by the amide group-containing compound of (C2), is inexpensive because the compound (A2) is industrially produced in large quantities, and contains almost no impurities. Isocyanate is highly reactive. Since it is water-soluble, it can be cured at room temperature, the urethane group generated from isocyanate has good compatibility with silicate (silanol group), and the fluororesin is chemically crosslinked. Physical strength because the coating film, weather resistance, solvent resistance, water resistance, stain-proofing property,
Excellent in removing stains.

The (D2) self-water-dispersible isocyanate curing agent preferably contains no aromatic group from the viewpoints of weather resistance and yellowing resistance.

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these.

Synthesis Example 1 Acetone 1.6 k in a 6 L stainless steel autoclave
g, isopropyl alcohol 500 g, tetrafluoroethylene 680 g (6.8 mol) were added, and the atmosphere was replaced with nitrogen.
Raise the temperature to 67.5 ° C. While stirring, 60 g of octanoyl peroxide solution (solid content 30%) was added, and ethyl vinyl ether 178 g (2.5 mol), hydroxybutyl vinyl ether 287 g (2.5 mol), 3-
A mixture of 250 g (1.2 mol) of (2-allyloxyethoxycarbonyl) propionic acid [a reaction product of ethylene glycol monoallyl ether and succinic anhydride] was added over 2 hours. An additional 60 g of the same peroxide solution was added 2 hours after the addition of the monomers was completed. After continuing stirring for further 2 hours, the temperature was raised to 80 ° C. and stirring was continued for 3 hours. The reaction mixture was cooled to room temperature, unreacted monomers were purged, and then the atmosphere was replaced with nitrogen to obtain 3.4 kg of the product.
(Solid content 36.9%) was obtained. The obtained polymer had a composition of tetrafluoroethylene 50 mol%, ethyl vinyl ether 20 mol%, hydroxybutyl vinyl ether 20 mol%, 3- (2-allyloxyethoxycarbonyl) propionic acid 10 mol%, and a number average molecular weight Mn500.
0, hydroxyl value 104 (mg / KOH), acid value 52 (mg
/ KOH). Ammonia water is added to this solution,
The carboxyl groups were neutralized. While gradually removing the organic solvent under reduced pressure, 2.8 kg of water was gradually added to the aqueous solution (solid content: 3
0%). This is W-1.

Synthesis Example 2 In a 300 ml three-necked flask equipped with a thermometer, a reflux tube and a dropping funnel, 50.0 g of methyl silicate 51 (0.106 mol as a tetramer) and 0.1 of triethylamine were added.
1 g and 239 g (1.59 mol) of 2,2,3,3,3-pentafluoropropanol (5FP) were added to 85-
The mixture was heated at 120 ° C. and distilled components were removed during 4 hours. The product (yield 97 g) remaining in the flask was subjected to NMR and elemental analysis, and it was found to be a compound having a fluorine content of 46%.
This is 5F-1.

Synthesis Example 3 Instead of 5FP in Synthesis Example 2, F (CF ₂ ) ₄ C ₂ H ₄ OH was used.
The product obtained in the same manner except that 74.0 g of (9FOH) was used and triethylamine was not used (yield 1
The fluorine content of 10 g) was 42%. 9F-
Set to 1.

Example 1 50 g of Bihydrol TPL in a 100 ml poly cup
Add S-2940 and add 0.55g of Primal Q
R708, 0.33 g of Byk023 and 5.13 g of ion-exchanged water were added, and 1000 r was added using a homodisper.
Stirred at pm for 20 minutes and left overnight. 14.5g to this
Baihydur TPLS-2032, methoxypropyl acetate 4.83g and 7.5g (acrylic resin 10
0 parts by weight to 50 parts by weight of ethyl silicate 40
23.41 g of ion-exchanged water was gradually added while stirring at 2000 rpm, and the mixture was stirred for about 5 minutes. This mixture was filtered through a mesh, coated with a solvent-soluble crosslinkable fluorine coating (white) in advance and sanded on an aluminum plate to coat with an applicator to obtain a coated plate. This is left at room temperature for 1 week to make a test piece,
In Osaka Prefecture, the following test was carried out after outdoor exposure for 3 months and 6 months under the condition that the south surface was inclined at 30 °.

The stain adhesion was evaluated as follows by measuring the difference (-ΔL *) between the initial brightness of the coated plate and the brightness after exposure.

A when the value of -ΔL * is 0 to less than 2; 2 to 5
When it was less than B, it was evaluated as B, when it was less than 5 to 8, it was evaluated as C, and when it was 8 or more, it was evaluated as D.

Regarding the appearance, when there was no abnormality, A was given, when there was some dullness, B was given, and when there was abnormality, C was given.

Further, the following test was conducted on a coated plate which had been similarly coated and which had been cured at room temperature for 3 hours and then heated and dried at 80 ° C. for 3 hours.

Gloss: 6 according to JIS K-5400
The specular gloss of 0 degree was measured.

Pencil hardness: Measured according to JIS K-5400. The results are shown in Table 1.

Examples 2 to 5 50 g of the above W-1 was placed in a 100 ml poly cup,
0.5g Primal QR708, 0.25g Byk
023, 5.0 g of ion-exchanged water was added, the mixture was stirred with a homodisper at 1000 rpm for 20 minutes, and left overnight. 14.5g of Baihydur TPLS-2032,
Methoxypropyl acetate 3.5g and fluororesin 10
A mixed solution of each silicate in an amount shown in Table 1 was added to 0 part by weight, and ion-exchanged water 2 was added while stirring at 2000 rpm.
0 g was gradually added and stirred for about 5 minutes. This mixture was filtered through a mesh, coated with a solvent-soluble cross-linking fluorine coating (white) in advance and sanded on an aluminum plate to be coated using an applicator, and the coated plate and the test piece according to Example 1 Was prepared and the same test as in Example 1 was performed. The results are shown in Table 1.

Comparative Example 1 A coated plate and a test piece were prepared in the same manner as in Example 2 except that silicate was not used.
The same test as in Example 2 was performed. The results are shown in Table 1.

Example 6 50 g of W-1 was put in a 100 ml polycup, and 0.5 g of Primal QR708 and 0.25 g of Byk were added.
023 and 5.0 g of ion-exchanged water were stirred with a homodisper at 1000 rpm for 20 minutes, and left overnight.
14.5g of Baihydur TPLS-203
2, methoxypropyl acetate 3.5g and 7.5g
A mixed solution of ethyl silicate 40 (50 parts by weight with respect to 100 parts by weight of fluororesin) and 0.05 g of ammonium salt of perfluorooctanoic acid were added to obtain 2000 r
20 g of ion-exchanged water and 3.0 g of dimethylformamide were gradually added with stirring at pm, and the mixture was stirred for about 5 minutes. This mixture was filtered through a mesh, coated with a solvent-type cross-linking fluorine coating (white) and sanded in advance on an aluminum plate using an applicator, and coating and test pieces were prepared according to Example 1. The same test as in Example 1 was performed. The results are shown in Table 1.

Example 7 50 g of W-1 was placed in a 100 ml polycup, and 0.5 g of Primal QR708 and 0.25 g of Byk were added.
023 and 5.0 g of ion-exchanged water were stirred with a homodisper at 1000 rpm for 20 minutes, and left overnight.
14.5g of Baihydur TPLS-203
2, methoxypropyl acetate 3.5g and 4.5g
5F (30 parts by weight for 100 parts by weight of fluororesin)
1. The mixed solution of -1 and 0.05 g of ammonium salt of perfluorooctanoic acid were added, and 20 g of ion-exchanged water and dimethylformamide were added while stirring at 2000 rpm.
0 g was gradually added and stirred for about 5 minutes. This mixture was filtered through a mesh, coated with a solvent-type cross-linking fluorine coating (white) and sanded in advance on an aluminum plate using an applicator to prepare a coated plate and a test piece according to Example 1. The same test as in Example 1 was performed.
The results are shown in Table 1.

Comparative Example 2 50 g of W-1 was placed in a 100 ml polycup, and 0.5 g of Primal QR708 and 0.25 g of Byk were added.
Add 023 and use homodisper at 1000 rpm for 20
Stir for minutes and let stand overnight. 16g of Coronate H
X (hexamethylene diisocyanate trimer), a mixed solution of 3.5 g of methoxypropyl acetate and 7.5 g (50 parts by weight with respect to 100 parts by weight of fluororesin) of ethyl silicate 40, and ammonium salt of perfluorooctanoic acid. 0.3 g was added, ion-exchanged water 20 g and dimethylformamide 3.0 while stirring at 2000 rpm.
g was gradually added and stirred for about 10 minutes. This mixture was filtered through a mesh, coated with a solvent-type cross-linking fluorine coating (white) and sanded in advance on an aluminum plate using an applicator to prepare a coated plate and a test piece according to Example 1. The same test as in Example 1 was performed.
The results are shown in Table 1.

The abbreviations used in Examples and Comparative Examples are as follows.

Et40: pentamer of ethyl silicate manufactured by Colcoat Co., Ltd. Bu: tetrabutyl silicate (monomer) Primal QR708: additive by Rohm and Haas Japan Co., Ltd. Byk023: manufactured by Big Chemie Japan Co., Ltd. Additives Bihydrol TPLS-2940: Water-soluble acrylic polyol manufactured by Sumitomo Bayer Urethane Co., Ltd. Bayhidur TPLS-2032: Self-water-dispersible isocyanate manufactured by Sumitomo Bayer Urethane Co. Coronate HX: Isocyanate manufactured by Nippon Polyurethane Co., Ltd.

[0103]

[Table 1]

As is clear from the results shown in Table 1, the aqueous coating composition of the present invention is excellent in room temperature curability, antifouling adhesion of coating film, appearance and hardness.

[0105]

EFFECT OF THE INVENTION The aqueous coating composition of the present invention is excellent in room temperature curing property, stability, workability, antifouling adhesion property of coating film, and stain removability.

Further, the outdoor article of the present invention has anti-fouling adhesion,
It has excellent stain removability and appearance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Chida 1-1 No. 1 Nishiichitsuya, Settsu City, Osaka Prefecture Daikin Industries, Ltd. Yodogawa Works (72) Inventor Nagato Dai No. 1 Nishiichitsuya, Settsu City, Osaka Prefecture Daikin Industries Yodogawa Manufacturing Co., Ltd. (72) Inventor Keiko Kunimasa 1-1 Nishiichitsuya, Settsu City, Osaka Daikin Industries Yodogawa Manufacturing Co., Ltd.

Claims (12)

[Claims] (A) Formula (1): (Wherein R is the same or different, both are monovalent organic groups and / or hydrogen atoms, n is an integer of 1 to 100), 1 to 50 parts by weight of a compound, (B) water-soluble and / or Or 100 parts by weight of water-dispersible resin and (C)
An aqueous coating composition comprising an aqueous medium. 2. Formula (A) (1): (Wherein R is the same or different, both are monovalent organic groups and / or hydrogen atoms, and n is an integer of 1 to 100), and 1 to 50 parts by weight of a compound represented by the formula (B) water-soluble and / or Alternatively, an aqueous coating composition comprising 100 parts by weight of a water-dispersible resin, (D) 10 to 200 parts by weight of a water-soluble and / or self-water-dispersible curing agent, and (C) an aqueous medium. 3. (A) Formula (1): (Wherein R is the same or different, both are monovalent organic groups and / or hydrogen atoms, and n is an integer of 1 to 100), and 1 to 50 parts by weight of a compound represented by the formula (B) water-soluble and / or Or 100 parts by weight of a water-dispersible resin, (D) a water-soluble and / or self-water-dispersible curing agent of 10 to 200 parts by weight, (E) a surfactant of 0.05 to 5 parts by weight, and (C) an aqueous medium. Aqueous coating composition. 4. The (A) is a fluorine-containing compound.
The water-based coating composition according to any one of 1 to 3. 5. The method according to claim 1, wherein (B) is a fluororesin.
The water-based coating composition according to any one of 4 above. 6. The aqueous coating composition according to claim 1, which contains (B) a resin having a group that reacts with an isocyanate group and (D) contains a self-water-dispersible isocyanate curing agent. 7. The method according to claim 1, wherein (E) contains a fluorinated surfactant or a modified organosilicon surfactant.
7. The water-based coating composition according to any of 6. 8. In the formula (1) of (A), R is a carbon number of 2 to 1.
The aqueous coating composition according to any one of claims 1 to 7, which has a monovalent organic group of 0. 9. The aqueous coating composition according to claim 1, which contains, as (D), a polyethylene oxide monoalkyl ether-modified isocyanate-based curing agent. 10. The water-based coating composition according to claim 1, wherein the water-based coating is a room temperature cross-linking curable water-based coating. 11. The aqueous coating composition according to claim 1, wherein (C) is water and / or a compound having an amide group. 12. An outdoor article obtained by coating the water-based coating composition according to any one of claims 1 to 11.