JP2002138251A - Water-based coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-based coating material composition capable of forming coating films which have high surface gloss and excel in stain resistance and its durability. SOLUTION: This water-based coating material composition comprises a synthetic resin (e.g. a fluorine-containing monomer/alkyl vinyl ether copolymer), an alkoxysilane containing a monovalent organic group having a fluorine- containing group and a hydrophilic group and/or its condensate (e.g. a trimethoxy-silane having a perfluroalkyl group and a polyoxyethylene chain), an alkoxy silane having a hydrophilic group and/or its condensate (e.g. a trimethoxysilane having a polyoxyethylene chain) and, if necessary, another alkoxysilane and/or its condenstate (e.g. a partial condensate of tetraethoxy- silane).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for water-based paint, a paint, a coating method and a coated article.

[0002]

2. Description of the Related Art Conventionally, products such as inorganic substances, plastics, wood, paper, leather, and fibers have been subjected to surface coating for the purpose of protecting the surface, imparting design and function, and the like. Paints have been developed.

[0003] In particular, fluororesin paints have been used in various applications as coating materials having excellent weather resistance. Fluororesin paints have significantly better weather resistance than other synthetic resin paints, but do not show much superiority in stain resistance, and improvement is required.

[0004] When a base material such as a building material is coated at a factory, a solvent-based paint or a solvent-based surface treatment agent containing an organic solvent can be used. Use of a water-based paint is required for reasons such as stability and environmental preservation.

[0005] Various techniques have been studied for improving the synthetic resin paint and improving the stain resistance of the coating film surface. WO94 / 0
No. 6870 describes a method of adding tetraalkoxysilane or a condensate thereof to an organic coating composition. In this method, a large amount of addition is required to develop stain resistance to rain streak stains (hereinafter referred to as rain streak stain resistance), and hydrolysis of tetraalkoxysilane or a condensate thereof due to moisture in the paint. In addition, since the condensation reaction proceeds to polymerize, the dispersibility decreases, and the storage stability of the organic coating composition is insufficient. JP-A-8-337754 describes a method of adding a fluorinated alkoxysilane or a condensate thereof to an aqueous coating composition. Although the dispersibility of the fluorine-containing alkoxysilane or its condensate and the stain resistance of the coating film are improved, the pot life of the water-based coating composition is short, and the stain resistance is not sufficiently long.

[0006] Japanese Patent Application Laid-Open No. 10-110078 describes a method of adding a mixed product of a tetraalkoxysilane and an alkyltrialkoxysilane to an aqueous fluororesin paint. However, the dispersion stability is insufficient,
Since a large amount of the mixed product cannot be added, the stain resistance is insufficient. JP-A-2000-44836 describes a method of adding a condensate of an alkoxysilane modified with polyoxyethylene glycol to an aqueous coating of a synthetic resin. In this method, the initial gloss of the coating film is high, but the stain resistance is insufficient.

[0007]

SUMMARY OF THE INVENTION In order to improve the prior art described above, the present invention provides a water-based paint composition, a paint, and a paint capable of forming a coating film having a high surface gloss and having excellent stain resistance and durability. The aim is to provide methods and painted articles.

[0008]

According to the present invention, 0.1 to 50 parts of an alkoxysilane represented by the formula 1 and / or a condensate thereof (B) is added to 100 parts of the synthetic resin (A). 0.1 to 50 parts of the alkoxysilane represented by Formula 2 and / or its condensate (C), and 0 to 50 parts of the alkoxysilane represented by Formula 3 and / or its condensate (D). An aqueous coating composition is provided. (R ¹ ) _a Si (OR ² ) _4-a Formula 1 (R ³ ) _b Si (OR ⁴ ) _4-b Formula 2 (R ⁵ ) _c Si (OR ⁶ ) _4-c Formula 3 , A is an integer of 0 to 3, R ¹ is 1
Valence organic group, R ² represents a monovalent organic group or a hydrogen atom, R ¹
And one or more selected from the group consisting of R ² is a monovalent organic group having a fluorine-containing group and a hydrophilic group. In the formula 2, b is an integer of 0 to 3, R ³ is a monovalent organic group, and R ⁴ is 1
At least one selected from the group consisting of R ³ and R ⁴ represents a valent organic group or a hydrogen atom, and is a monovalent organic group having a hydrophilic group and no fluorinated group. In Formula 3, c represents an integer of 0 to 3, R ⁵ represents a monovalent organic group having no hydrophilic group, and R ⁶ represents a monovalent organic group having no hydrophilic group or a hydrogen atom.

[0009] Further, the present invention is characterized in that the paint contains the composition for aqueous paint, a coating method in which the paint is applied to an object to be coated, and that the paint is applied. Providing painted articles.

[0010] In this specification, "parts" means "parts by mass". In addition, acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid, and the same applies to (meth) acrylate and the like.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As the synthetic resin (A) in the present invention, various known synthetic resins are used without any particular limitation. Specific examples include fluorine resin, acrylic resin, silicon-modified acrylic resin, urethane resin, melamine resin,
Silicone resin, epoxy resin, polyester resin and the like can be mentioned. Synthetic resins may be used alone or in combination of two or more. In particular, it is preferable to use a fluororesin having excellent weather resistance and chemical resistance alone or as a main component.

As the fluororesin, a polymer of a fluorine-containing monomer or a copolymer with another monomer is used. One kind of the fluorinated monomer may be used alone,
Two or more kinds may be used in combination. Other monomers may be used alone or in combination of two or more.

Specific examples of the fluorine-containing monomer include fluoroolefins such as tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, and hexafluoropropylene, (meth) acrylates of a fluorine-containing alkyl alcohol, and fluorine-containing alkylene. Oxides and the like. In particular, fluoroolefins are preferred because of their excellent durability.

Other monomers include hydrocarbon olefins, alkyl vinyl ethers, alkyl isopropenyl ethers, alkyl allyl ethers, vinyl carboxylate, allyl carboxylate, (meth) acrylate and the like. Is mentioned.

Examples of the hydrocarbon olefins include ethylene, propylene, isobutylene and the like. Alkyl vinyl ethers include methyl vinyl ether,
Ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like can be mentioned. Examples of the alkyl isopropenyl ethers include methyl isopropenyl ether, ethyl isopropenyl ether, propyl isopropenyl ether, and butyl isopropenyl ether. As alkyl allyl ethers,
Examples include ethyl allyl ether and cyclohexyl allyl ether.

Examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl octanoate, vinyl versatate, and vinyl octadecanoate. Examples of the allyl carboxylate include allyl acetate and allyl propionate. Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and fluorine-containing alkyl (meth) acrylate. The other monomer may include a monomer having a functional group.

Examples of the monomer having a functional group include monomers having a hydroxyl group, monomers having a carboxy group or a salt thereof, monomers having a polyoxyalkylene chain, monomers having an epoxy group, and monomers having a hydrolyzable silyl group. And monomers.

Examples of monomers having a hydroxyl group include 2-
Examples include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1-vinyloxymethyl-4-hydroxymethylcyclohexane, 4-hydroxybutyl allyl ether, and 2-hydroxyethyl acrylate. Examples of monomers having a carboxy group or a salt thereof include (meth) acrylic acid, crotonic acid, and salts thereof. Examples of monomers having a polyoxyalkylene chain include monomers obtained by adding an average of 10 molecules of ethylene oxide to 4-hydroxybutyl vinyl ether. Examples of monomers having an epoxy group include glycidyl vinyl ether, glycidyl allyl ether, and glycidyl methacrylate. Examples of monomers having a hydrolyzable silyl group include vinyltrimethoxysilane, 3-vinyloxypropyltrimethoxysilane, and the like.

In a copolymer of a fluorinated monomer and another monomer, if the copolymerization ratio of the fluorinated monomer is too small, the durability is reduced. Therefore, the copolymerization ratio of the fluorinated monomer is from 30 to 90 mol%, especially 40-80 mol% is preferred. When the monomer having a functional group is not copolymerized, the copolymerization ratio of other monomers (excluding the monomer having a functional group) is preferably from 10 to 70 mol%, particularly preferably from 20 to 60 mol%. When a monomer having a functional group is copolymerized, the copolymerization ratio of other monomers (excluding the monomer having a functional group) is preferably 9 to 69 mol%, particularly preferably 18 to 58 mol%, The copolymerization ratio of the monomer having a functional group is 1 to 2
0 mol%, especially 2 to 15 mol%, is preferred.

The copolymerization of other monomers is preferred because the dispersion stability of the aqueous coating composition, the transparency of the coating film, the adhesion to the substrate and the like are improved. Further, copolymerization of a monomer having a functional group is preferable because the mechanical strength, hardness, adhesion, durability, and the like of the coating film are further improved.

(B) in the present invention is an alkoxysilane represented by the formula 1 and / or a condensate thereof. In Formula 1, a represents an integer of 0 to 3. a is preferably 0 or 1. R ¹ represents a monovalent organic group, R ² represents a monovalent organic group or a hydrogen atom, and at least one selected from the group consisting of R ¹ and R ² is a monovalent having a fluorine-containing group and a hydrophilic group. Organic group. When at least ^one of R ¹ is a monovalent organic group having a fluorine-containing group and a hydrophilic group, the durability of stain resistance is further improved. When (B) is a condensate of an alkoxysilane, it is preferably a partial condensate.

The monovalent organic group having a fluorine-containing group and a hydrophilic group is more preferably a monovalent organic group represented by the formula (3). ^Rf -XYZ-Formula 4 Here, ^Rf represents a monovalent fluorine-containing group, Y represents a divalent hydrophilic group, and X and Z represent a bonding group or a single bond.

In Formula 4, R ^f is preferably a monovalent organic group having a polyfluoroalkyl group, and Y is preferably a divalent organic group having a nonionic group, a cationic group, or an anionic group. preferable. The carbon number of R ^f is preferably 1 to 20 in order to improve the stain resistance.

Specific examples of R ^f include CF ₃ —, H (CF
_{2) 2 -, CF 3 CF} 2 -, CF 3 (CF 2) 2 -, H (C
_{F 2) 4 -, (CF} 3) 2 CF-, CF 3 (CF 2) 3 -, H
_{(CF 2) 6 -, CF} 3 (CF 2) 4 -, CF 3 (CF 2)
_{6 -, CF 3 (CF 2} ) 2 OCF (CF 3) CF 2 -, CF 3
_{(CF 2) 5 -, H} (CF 2) 8 -, CF 3 (CF 2) 7 -,
_{CF 3 (CF 2) 8 -} , (CF 3) 2 CF (CF 2) 6 -, C
F ₃ (CF ₂ ) ₉ −, CF ₃ (CF ₂ ) ₁₁ −, CF ₃ (C
F ₂ ) _13- , CF ₃ (CF ₂ ) _15- and the like.

As the divalent organic group having a nonionic group, a divalent organic group having a polyoxyalkylene (hereinafter referred to as POA) chain is preferable. In order to improve dispersibility in an aqueous medium, polyoxyethylene (hereinafter referred to as P
OE. ) Chains, polyoxypropylene chains, polyoxybutylene chains are preferred, and POE chains are most preferred. When the POA chain is composed of two or more alkylene oxide copolymer chains such as an ethylene oxide / propylene oxide copolymer chain, it may be a random copolymer chain or a block copolymer chain.

The degree of polymerization of the oxyalkylene unit in the POA chain is preferably from 1 to 100. In the case of a POE chain, if the degree of polymerization is low, the hydrophilicity is insufficient, and if the degree of polymerization is high, the coating film is softened and stains are easily attached. The degree of polymerization of the POA chain is more preferably from 2 to 30.

The divalent organic group having a cationic group is preferably a divalent organic group having a base neutralized with an acid.
Specific examples include a divalent organic group having a primary amino group, a divalent organic group having a secondary amino group, and a divalent organic group having a tertiary amino group neutralized with an acid. A group consisting of a neutralized tertiary amino group is more preferred. Examples of the acid used for neutralizing the base include carboxylic acids, organic sulfonic acids, and inorganic acids, and inorganic acids are more preferable. The divalent organic group having a cationic group has 2 to 2 carbon atoms.
It is preferably 0.

The divalent organic group having an anionic group is preferably a divalent organic group having an acidic group neutralized with a base. Specific examples include a divalent organic group having a carboxy group, a divalent organic group having a phosphate group, a divalent organic group having an acidic phosphate group, and a divalent group having a phosphite group neutralized with a base. Examples thereof include an organic group, a divalent organic group having a sulfo group, and a divalent organic group having a sulfi group. A divalent organic group having a carboxy group neutralized with a base is more preferable. Bases used for neutralization of acidic groups include organic amines,
Ammonia, quaternary ammonium hydroxide, inorganic bases and the like are mentioned, and organic amines and ammonia are more preferable. The divalent organic group having an anionic group has 2 to 2 carbon atoms.
It is preferably 20.

X is a single bond, 2-20 carbon atoms.
Valent organic group, and a hetero atom., -CH ₂ -, - C
_{H 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH (CH 3) C
H ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) C
_{H 2 CH 2 -, - CH} 2 (CH 2) 3 CH 2 -, - CH 2 CH
(CH ₃ ) CH ₂ CH ₂ —, —COO—, —SO ₂ N
(R ⁵⁾ - (provided that, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and so forth..), - CON (R
_{^{5) -, - CH 2 COO}} -, - CH 2 OCOO -, - CH 2
_{OCONH (CH 2) 6 NHCOO -} , - CH 2 CH 2 S i
(CH ₃ ) ₂ O—, —O— and the like are exemplified. Particularly, a divalent organic group having 1 to 20 carbon atoms is preferable.

As Z, a divalent organic group having 1 to 20 carbon atoms is preferable, and —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH
_{2 CH 2 -, - CH (} CH 3) CH 2 -, - CH 2 CH 2 CH
₂ CH ₂ —, —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ (C
_{H 2) 3 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 -,
_{-CONHCH 2 CH 2 CH 2 -,} - COCH 2 CH 2 CH 2
—, —COOCH ₂ CH ₂ CH ₂ — and the like.

In particular, the monovalent fluorinated group is preferably a monovalent polyfluoroalkyl group, and the divalent hydrophilic group is preferably a polyoxyalkylene chain. Specific examples of the monovalent organic group having a group include the following. However, C ₄ F ₉ , C ₆
F ₁₃ , C ₈ F ₁₇ , C ₁₀ F ₂₁ , C ₂ H ₄ , C ₄ H ₈ represent a linear structure, C ₃ H ₆ represents a CH ₂ CH (CH ₃ ) branched chain structure, and so on. is there.

C_FourF₉(CH_Two)_TwoO (C_TwoH_FourO)₈CON
H (CH_Two)_Three-, C₆F₁₃(CH_Two)_TwoO (C_TwoH_FourO)_Ten
CONH (CH_Two)_Three-, C₆F₁₃(CH_Two)_TwoO (C_ThreeH₆
O)_Five(CH_Two)_Three-, CF_Three(CF_Two)_TwoOCF (CF_Three)
CF_TwoCH_TwoO (C_TwoH_FourO)_TenCONH (CH _Two)_Three-, C
₇F_FifteenCH_TwoO (C_TwoH_FourO)_TenCONH (CH_Two)_Three-, C
₈F₁₇(CH_Two)_TwoO (C_TwoH_FourO)₁₃CONH (CH_Two)_Three
-, C₈F₁₇(CH_Two)_TwoO (C_TwoH_FourO)₁₃(CH_Two)
_Three-, C₈F₁₇(CH_Two)_TwoO (C_TwoH_FourO)₁₃CO (C
H_Two)_Two-, C₈F₁₇(CH_Two)_TwoO (C_TwoH_FourO)₂₀CON
H (CH_Two)_Three-, C₈F₁₇(CH_Two)_TwoO (C_TwoH_FourO)_{twenty five}
(CH_Two)_Three-, C₈F₁₇(CH_Two)_TwoO (C_TwoH_FourO)₈(C
_ThreeH₆O)_FourCONH (CH_Two)_Three-, C₈F₁₇(CH_Two)_TwoO
(C_TwoH_FourO)_Ten(C_FourH₈O)_Three(CH_Two)_Three-, C₈F
₁₇(CH_Two)_ThreeO (C_ThreeH₆O)_TenCONH (CH_Two)_Three−,
C₈F₁₇(CH_Two)_ThreeO (C_TwoH_FourO)₈(C_ThreeH₆O)_FourCO
NH (CH_Two)_Three-, C₈F₁₇(CH_Two)_ThreeO (C_TwoH_FourO)
₁₃CONH (CH_Two)_Three-, C₈F₁₇(CH_Two)_FourO (C_ThreeH
₆O)_TenCONH (CH_Two)_Three-, C₈F₁₇(CH_Two)_FourO
(C_TwoH_FourO)₁₃CONH (CH_Two)_Three-, C₈F₁₇(C
H_Two)_FourO (C_TwoH_FourO)_Ten(C_ThreeH₆O)_ThreeCONH (C
H_Two)_Three-, C₈F₁₇CON (CH_Three) (C_TwoH_FourO)₁₃CO
NH (CH_Two)_Three-, C₈F₁₇SO_TwoN (CH_Three) (C_TwoH_Four
O)₁₃CONH (CH_Two)_Three-, C₈F₁₇(CH_Two)_TwoOC
ONH (CH_Two)₆NHCOO (C_TwoH_FourO)₂₀(CH_Two) _Three
-, C₈F₁₇(CH_Two)_ThreeOCONH (CH_Two)₆NHCO
O (C_TwoH_FourO)₂₀(CH_Two) _Three-, C_TenF_{twenty one}(CH_Two)_TwoO
(C_TwoH_FourO)₂₀CONH (CH_Two)_Three-, C_TenF_{twenty one}(CH
_Two)_TwoO (C_TwoH_FourO)_Fifteen(C_ThreeH₆O)_FiveCONH (CH_Two)
_Three-.

R ¹ having a fluorine-containing group and a hydrophilic group
When it is not a valent organic group, R ¹ is preferably a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of improving the compatibility with the synthetic resin (A) and the stain resistance, a monovalent organic group having 10 or less carbon atoms is more preferable, and an oxygen atom, a sulfur atom, a nitrogen atom, and a chlorine atom are contained in the monovalent organic group. May be included. However, 1
A valent organic group is directly bonded to a silicon atom via a carbon atom. When two or more R ¹ are contained in the molecule,
R ¹ may be the same or different.

[0034] 1 in which R ² and a fluorine-containing group and a hydrophilic group
When it is not a valent organic group, R ² is preferably a monovalent organic group having 1 to 10 carbon atoms. As R ² , an alkyl group or an alkoxyalkyl group is preferable, and in particular, a group having 1 carbon atom such as methyl group, ethyl group, propyl group,
A monovalent alkyl group having 1 to 6 carbon atoms and an alkoxyalkyl group having 1 to 6 carbon atoms such as a 2-methoxyethyl group are more preferable.
Further, when two or more R ² are contained in the molecule, R ² may be the same or different.

The compounding amount of (B) is 100 parts of synthetic resin (A).
0.1 to 50 parts per part. If the amount is too small, the gloss decreases, and if it is too large, the stain resistance decreases. Preferably 0.2 to 20 parts, more preferably 0.5 to 10
Department.

(C) in the present invention is an alkoxysilane represented by Formula 2 and / or a condensate thereof. In Formula 2, b represents an integer of 0 to 3. b is preferably 0 or 1. R ³ represents a monovalent organic group, R ⁴ represents a monovalent organic group or a hydrogen atom, and at least one selected from the group consisting of R ³ and R ⁴ has a hydrophilic group and has a fluorine-containing group. There are no monovalent organic groups. Further, when two or more R ³ are contained in the molecule, R ³ may be the same or different. (C)
Is a condensate of alkoxysilane, it is preferably a partial condensate. Examples of the hydrophilic group include a nonionic, cationic or anionic hydrophilic group.

As the nonionic hydrophilic group, a POA chain is preferable. In order to improve dispersibility in an aqueous medium, a POE chain, a polyoxypropylene chain, and a polyoxybutylene chain are preferred, and a POE chain is most preferred. Also,
When the POA chain is composed of a copolymer chain of two or more oxide monomers such as an ethylene oxide / propylene oxide copolymer chain, it may be a random copolymer chain or a block copolymer chain. The degree of polymerization of the oxyalkylene unit of the POA chain is preferably from 1 to 100. In the case of a POE chain, if the degree of polymerization is low, the hydrophilicity is insufficient, and if the degree of polymerization is high, the coating film is softened and stains are easily attached. The degree of polymerization of the POA chain is more preferably from 2 to 30.

As the cationic hydrophilic group, an organic group having a base neutralized with an acid is preferable. As a specific example,
An organic group having a primary amino group, an organic group having a secondary amino group, an organic group having a tertiary amino group, or the like, which is neutralized with an acid, includes a group consisting of a tertiary amino group neutralized with an acid. Most preferred. Examples of the acid used for neutralizing the base include carboxylic acids, organic sulfonic acids, and inorganic acids.
Inorganic acids are more preferred. The number of carbon atoms of the cationic hydrophilic group is preferably 2 to 20.

As the anionic hydrophilic group, an organic group having an acidic group neutralized with a base is preferable. Specific examples include an organic group having a carboxy group, an organic group having a phosphate group, an organic group having an acidic phosphate group, an organic group having a phosphite group, and an organic group having a sulfo group neutralized with a base. An organic group having a carboxy group neutralized with a base is more preferable.

As the base used for neutralization of the acidic group,
Examples thereof include organic amines, ammonia, quaternary ammonium hydroxide, and inorganic bases. Organic amines and ammonia are more preferable. The number of carbon atoms of the anionic hydrophilic group is preferably 2 to 20.

Particularly preferred hydrophilic groups are groups having a POA chain, and specific examples thereof include the following. _{HO (C 2 H 4 O)} 6 CONH (CH 2) 3 -, CH 3 O (C
_{2 H 4 O) 8 (CH} 2) 3 -, CH 3 O (C 2 H 4 O) 8 CON
_{H (CH 2) 3 -,} HO (C 2 H 4 O) 10 (CH 2) 3 -, C
_{H 3 COO (C 2 H 4} O) 10 (CH 2) 3 -, CH 3 (C
_{H 2) 3 O (C 2} H 4 O) 10 (CH 2) 3 -, CH 3 O (C 2 H
_{4 O) 10 (CH 2)} 3 -, HO (C 2 H 4 O) 12 CONH
_{(CH 2) 3 -, CH} 3 O (C 2 H 4 O) 15 (CH 2) 3 -,
_{CH 3 O (C 2 H 4} O) 8 (C 3 H 6 O) 7 (CH 2) 3 -, H
O (C ₂ H ₄ O) ₈ (C ₃ H ₆ O) ₇ (CH ₂ ) ₃ —, CH ₃ O
_{(C 2 H 4 O) 15} CO (CH 2) 2 -, CH 3 O (C 2 H
_{4 O) 10 (C 4 H} 8 O) 10 (CH 2) 3 -.

When R ³ does not have a hydrophilic group, it is preferably a monovalent organic group having 1 to 20 carbon atoms. In view of improving the compatibility with the synthetic resin (A) and the stain resistance, it has 1 carbon atom.
A monovalent organic group of 0 or less is more preferable, and the monovalent organic group may contain an oxygen atom, a sulfur atom, a nitrogen atom, and a chlorine atom. However, a monovalent organic group is directly bonded to a silicon atom via a carbon atom. Further, when two or more R ³ are contained in the molecule, R ³ may be the same or different.

When R ⁴ does not have a hydrophilic group, it is preferably a monovalent organic group or a hydrogen atom. As the monovalent organic group, an alkyl group or an alkoxyalkyl group is preferable, and a monovalent alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group is more preferable. When two or more R ⁴ are contained in a molecule, R ⁴ may be the same or different.

The compounding amount of (C) is 100 parts of synthetic resin (A).
0.1 to 50 parts per part. If the amount is too small, the gloss decreases, and if it is too large, the stain resistance decreases. Preferably 0.2 to 20 parts, more preferably 0.5 to 10
Department.

(D) in the present invention is an alkoxysilane represented by Formula 3 and / or a condensate thereof. In Formula 3, c represents an integer of 0 to 3. c is preferably 0 or 1, and most preferably 0. R ⁵ has no hydrophilic group 1
It is a valent organic group. R ⁵ is preferably a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of improving the compatibility with the synthetic resin (A) and the stain resistance, a monovalent organic group having 10 or less carbon atoms is more preferable, and an oxygen atom, a sulfur atom, a nitrogen atom, and a chlorine atom are contained in the monovalent organic group. May be included. However, 1
A valent organic group is directly bonded to a silicon atom via a carbon atom. Further, it may be a fluorine-containing alkyl group having 10 or less carbon atoms. When two or more R ⁵ are contained in the molecule,
R ⁵ may be the same or different. When (D) is a condensate of an alkoxysilane, it is preferably a partial condensate.

R in Equation 3⁶Is 1 without a hydrophilic group
Represents a valent organic group or a hydrogen atom. Monovalent organic groups include
Alkyl group, alkoxyalkyl group or fluorinated alkyl
Groups are preferred, methyl, ethyl, propyl,
A monovalent alkyl group having 1 to 6 carbon atoms such as
An alkoxyalkyl group having 1 to 6 carbon atoms, such as _Three
CH_Two-, CF_ThreeCH_TwoCH_Two−, H (CF_Two)_TwoCH_Two−,
CF_ThreeCF_TwoCH_Two-, CF_ThreeCF_TwoCH_TwoCH_Two-Carbon etc.
Fluorine-containing alkyl groups of formulas 1 to 6 are more preferred. R⁶
Is more than one in the molecule, R⁶May be the same
And may be different.

Specific examples of (D) include tetraethoxysilane, tetramethoxysilane in which a part of a methyl group is substituted by an ethyl group, and tetramethoxysilane in which a part of a methyl group is substituted by a propyl group and / or a butyl group. Tetramethoxysilane, tetraethoxysilane in which a part of the ethyl group is substituted with a propyl group and / or a butyl group, tetrakis (2,2,2-trifluoroethoxy) silane, tetrakis (2,2,3,3 , 3-pentafluoropropoxy) silane, tetrakis (4,4,5,5,5-pentafluoropentyloxy) silane, methyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 2-perfluorooctyl Ethyltrimethoxysilane, vinyltrimethoxysilane, (3-methacryloyloxypropyl) to Silane, 3-chloropropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, and condensates thereof.

The compounding amount of (D) is 100 parts of synthetic resin (A).
0 to 50 parts per part. (D) is an optional component, and may or may not be contained, but if the amount is small, the stain resistance may not be sufficient. If the amount is too large, the gloss and stain resistance deteriorate. Preferably 0.1 to 30
Parts, more preferably 1 to 20 parts.

In the present invention, when (B), (C) and (D) are condensates, the number average molecular weight thereof is preferably in the range of 200 to 100,000,
The range of 200 to 20,000 is more preferable. If the number average molecular weight is too large, it is difficult to transfer (B), (C) and (D) to the surface of the coating film, and the stain resistance to rain streak decreases.

The water-based coating composition of the present invention contains (D) as required together with (B) and (C), and is composed of (B), (C) and (D). It is also preferable that two or more kinds selected from are mixed in advance. The mixing treatment refers to stirring and mixing different alkoxysilanes and / or compositions thereof. It is also preferable to produce the aqueous coating composition of the present invention by mixing and then mixing with the synthetic resin (A). It is also preferable to add the below-described alkoxysilane condensation catalyst during the mixing treatment and mix by stirring. When the alkoxysilane condensation catalyst is added and stirred and mixed, it is presumed that a co-condensate is also formed between different alkoxysilanes and / or compositions thereof.

Therefore, the water-based paint composition of the present invention can be used in addition to (B), (C) and (D), as well as a co-condensate of (B) and (C), and (B) and (D). Co-condensate, (C)
And (D) or a co-condensate of (B), (C) and (D) can also be considered as one of the preferred embodiments. In the case where the co-condensate is contained, if the content of the co-condensate is too small, it is difficult to exhibit the rain stain resistance. If the amount is too large, the water resistance and weather resistance of the coating film are not sufficient, and the stain resistance to rain streaks is hardly exhibited. In addition, the number average molecular weight of the co-condensate is preferably in the range of 200 to 100,000 in which migration to the coating film surface is favorable, and 200 to 100,000.
20,000 is more preferred.

Table 1 shows examples of more preferable combinations of the respective components in the present invention. ○ is a preferred combination, ◎
Represents a more preferable combination.

[0053]

[Table 1]

Here, A1 to A4 represent the following copolymers, respectively, and B1 to B3, C1, D1, and D2 represent the following alkoxysilanes, respectively. A1: a copolymer of tetrafluoroethylene, alkyl vinyl ether, and a monomer having a POA chain, A2: a copolymer of chlorotrifluoroethylene, an alkyl vinyl ether, a monomer having a POA chain, and a monomer having a hydroxyl group, A3: tetrafluoro A4: a copolymer of ethylene and a hydrocarbon olefin, A4: a blend of a copolymer of tetrafluoroethylene and a hydrocarbon olefin and a (meth) acrylate copolymer.

B1: In the formula 1, a is 1 and R ¹
Is a monovalent organic group containing nC ₈ F ₁₇ — and a POE chain, and R ² is an alkoxysilane having a methyl group and / or an ethyl group. B2: In the formula 1, a is 1, R ¹ Is CF ₃ (CF
₂ ) an alkoxysilane in which a monovalent organic group containing ₂ OCF (CF ₃ ) CF ₂ — and a POE chain, and R ² is a methyl group or an ethyl group; B3: In the formula 1, a is 0; One of R ² is n-
An alkoxysilane in which a monovalent organic group containing C ₈ F ₁₇ — and a POE chain and the other R ² is a methyl group or an ethyl group; B4: in the formula 1, a is 1 and R ¹ is methyl One of R ² is a group comprising n—C ₈ F ₁₇ — and a POE chain.
An alkoxysilane having a valence organic group and another R ² being a methyl group or an ethyl group;

C1: In the formula 2, b is 1 and R ³
Is a monovalent organic group having a POE chain, and alkoxysilane wherein R ⁴ is a methyl group and / or an ethyl group. D1: In the formula 3, c is 0, and R ⁶ is a methyl group and / or an ethyl group. A certain alkoxysilane, D2: in the formula 3, c is 0, R ⁶ is a methyl group,
An alkoxysilane that is a group selected from the group consisting of an ethyl group and a 2-perfluoroalkylethyl group.

The aqueous coating composition of the present invention may contain an alkoxysilane condensation catalyst. The content of the alkoxysilane condensation catalyst is preferably 100% of the sum of (B), (C) and (D) in order to prevent the coloring of the coating film and the decrease in gloss.
10 parts by weight or less is preferable.

Examples of the condensation catalyst include metal compound catalysts such as metal chelates, metal esters and metal alkoxides, phosphates, amines, acid anhydrides, organic sulfonic acids and the like. The condensation catalyst may be used alone or in combination of two or more.

As the metal compound catalyst, aluminum,
Examples include compounds of metals such as titanium, zirconium, tin, and zinc. Specifically, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetonate), tetrabutyl titanate, tetraisopropyl titanate, tetrakis (2-aminoethyl) titanate , Diisopropoxytitanium bis (ethylacetoacetate), zirconium tetrakis (acetylacetonate), dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltindi (maleic acid monoester), dibutyltin diacetate, etc. No.

Although the mechanism of the stain resistance and high gloss exhibited by the water-based coating composition of the present invention is not necessarily clear,
It is considered as follows. (B) has a fluorine-containing group and exhibits stain resistance. In addition, since the surface energy of the fluorine-containing group is low, (B) easily migrates to the surface of the coating film, and it is considered that the stain resistance of the coating film can be exhibited by containing a small amount of (B). Further, (B) has a hydrophilic group and thus improves the dispersibility of the alkoxysilane compound. As a result, the alkoxysilane is considered to be finely dispersed in the coating film and to exhibit high gloss.

Further, (C) also has a hydrophilic group and improves the dispersibility of the alkoxysilane compound.
By including (C), the gloss of the coating film can be further increased. (D) imparts hydrophilicity to the coating film by hydrolysis,
Along with (B) and (C), it is considered to show an effect of removing attached dirt. Therefore, the water-based coating composition of the present invention has a surface stain resistance due to such a synergistic effect,
In particular, it is considered that a coating film having excellent rain streak stain resistance can be formed.

The aqueous coating composition of the present invention may contain, if necessary, a curing agent, a coloring agent, a film-forming aid, a thickener, a plasticizer, an antifoaming agent, an ultraviolet absorber, a leveling agent, and an anti-cissing agent. Additives used in ordinary aqueous paints, such as anti-skinning agents and pigment dispersants, may be mixed.

As the curing agent, polyisocyanates,
Aminoplast, polybasic anhydride, hydrazide derivative,
Carbodiimide derivatives, aziridine derivatives, oxazoline derivatives, and the like.

Examples of the polyisocyanates include polyisocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate; silyl isocyanate compounds such as methylsilyl triisocyanate; and / or condensates and polymers thereof; And the like. Particularly, a non-yellowing type is preferable.

As aminoplast, melamine resin,
Examples thereof include a guanamine resin and a urea resin. In particular, methylol melamine which is at least partially etherified with one or more lower alcohols such as methanol, ethanol, propanol and butanol is preferable. Examples of the polybasic acid anhydride include aromatic polycarboxylic anhydrides such as phthalic anhydride and pyromellitic anhydride, and aliphatic polycarboxylic anhydrides such as maleic anhydride and succinic anhydride.

Examples of the coloring agent include dyes, organic pigments, inorganic pigments, metallic pigments such as aluminum paste and the like. The use of inorganic pigments is preferred because of excellent weather resistance. Organic solvents that do not impair the stability of the dispersion can be used as the film-forming auxiliary. Dipropylene glycol mono n-
Organic acid esters of polyhydric alcohol monoalkyl ethers such as butyl ether, tripropylene glycol mono n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, etc. And 3-ethoxypropionates. Examples of the plasticizer include plasticizers such as dioctyl phthalate, and high molecular weight plasticizers such as a vinyl polymer plasticizer and a polyester plasticizer.

As the coating method, any commonly used coating method such as coating with a brush and a roller brush, air spray coating, airless spray coating, coating with a curtain flow coater, and coating with a roll coater can be used without any particular limitation.

The drying of the coating film may be carried out at room temperature,
It may be carried out at a higher temperature.

The paint containing the obtained aqueous paint composition is as follows:
The coating may be applied to a newly-installed base material / article before installation, or may be applied after the base material / article is installed. In addition, it is also suitable for repair painting for painting on already painted substrates and articles. In particular, it is suitable for coating of substrates and articles used outdoors.

As the substrate to be coated, concrete,
Examples thereof include inorganic materials such as natural stone and glass, metals such as iron, stainless steel, aluminum, copper, brass, and titanium, and composite materials such as fiber-reinforced plastics, resin-reinforced concrete, and fiber-reinforced concrete.

Examples of articles to be coated include vehicles such as automobiles and trains, aircraft, building members such as exterior panels, doors, windows, and gates, road medians, road members such as guardrails, bridge members, and steel towers. , Tanks, pipes, communication equipment, electrical and electronic components, and the like.

[0072]

EXAMPLES The present invention will be described below with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. The number average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance.

[Preparation of Base Paint] Base white paint 1: a polymerization unit based on a monomer obtained by adding an average of 10 molecules of ethylene oxide to chlorotrifluoroethylene / ethyl vinyl ether / cyclohexyl vinyl ether / 4-hydroxybutyl vinyl ether / 4-hydroxybutyl vinyl ether , 50/15/33 / 1.5 / 1.5
(Mol%) of an aqueous dispersion of the fluororesin 1 was prepared. The solid content concentration was 50% by mass, and the average particle size of the dispersed fine particles was 140 nm.

The aqueous dispersion of the fluorine-containing resin 1
Parts, 3.6 parts of a film-forming assistant (Cs-12, manufactured by Chisso Corporation)
0.3 of thickener (Leobis CR, manufactured by Hoechst Gosei)
Part, titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.)
4 parts, 0.8 part of a pigment dispersant (Nopcosperse 44-C, manufactured by San Nopco), an antifoaming agent (FS Antifoam 9)
0, manufactured by Dow Corning Co., Ltd.) and 10.3 parts of ion-exchanged water to obtain Base White Paint 1. The concentration of the fluororesin 1 in the base white paint 1 is 34.8% by mass.
Met.

Base white paint 2: In a stainless steel autoclave having a stirrer of 2.5 L in internal volume, 1100 g of ion-exchanged water and a fluorine-based anionic emulsifier (FC-14)
3: 4.75 g of Sumitomo 3M, 2.2 parts of a nonionic emulsifier (N-1110; manufactured by Nippon Emulsifier) and 47 g of tert-butyl alcohol were charged, degassed by a vacuum pump, and nitrogen gas was used. Pressing was repeated.
Next, 72 g of tetrafluoroethylene, 1.1 g of propylene, and 1.4 g of ethylene were charged.

When the temperature inside the autoclave reached 70 ° C., the pressure showed 1.34 MPa. 2 mL of a 25% by mass aqueous solution of ammonium persulfate was added to initiate polymerization. As the pressure decreases, tetrafluoroethylene /
A propylene / ethylene 50/25/25 (mol%) mixed gas was charged and the pressure was maintained. Further, 30 mL of a 25% by mass aqueous solution of ammonium persulfate was continuously added. After 8 hours, the supply of the mixed gas was stopped, and the autoclave was cooled to room temperature with water, and then the unreacted monomer was purged.
An aqueous dispersion of fluorinated resin 2 was obtained. The post-charge amount of the mixed gas was 861.5 g in total. The solid concentration of the aqueous dispersion was 43.1% by mass.

A part of the aqueous dispersion of the fluorine-containing resin 2 was settled by a centrifugal separator, filtered through a glass filter, and water was removed under reduced pressure for 5 hours. A powder of fluorinated resin 2 was obtained. As a result of composition analysis by ¹³ C-NMR spectrum, fluorinated resin 2 contained polymerized units based on tetrafluoroethylene / propylene / ethylene at a ratio of 52/28/20 (mol%). The melting point was 96.2 ° C.

In a glass flask having an internal volume of 200 mL,
104 g of the aqueous dispersion of the fluororesin 2 was charged,
Warmed until the temperature reached 70 ° C. 1.2 g of methyl methacrylate, te
6.2 g of rt-butyl, 0.6 g of methacrylic acid ester of alcohol having POE chain (Blenmer PE200, manufactured by NOF Corporation), 0.04 g of N-1110, 0.02 g of sodium lauryl sulfate, and ion exchange A pre-emulsion emulsified by stirring 10 g of water was added dropwise over 1 hour. After further stirring for 1 hour, 1 mL of a 0.5% by mass aqueous solution of ammonium persulfate was added to initiate polymerization. After 4.5 hours, an aqueous dispersion containing the fluororesin 2 and the methacrylate copolymer 1 in a mass ratio of 85:15 was obtained. The solid concentration of the aqueous dispersion was 42.9% by mass.

[0079] 71 parts of the obtained aqueous dispersion, Cs-12
3.6 parts of Reobis CR, 0.3 part of CR-97
5.4 parts, 0.8 parts of Nopcosperse 44-C, 0.6 parts of FS Antifoam 90, and 1 part of ion-exchanged water
The base white paint 2 was obtained by mixing 0.3 parts. The concentration of the resin component in the base white paint 2 was 29.9% by mass.

[Synthesis of Alkoxysilanes] Synthesis Example 1 (Alkoxysilane B-1): 300 m in internal volume
In the glass flask of L, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃
183 of O (CH ₂ CH ₂ O) _n H (average molecular weight 955)
g, 0.18 g of dibutyltin dilaurate. At 50 ° C., isocyanate group-containing silane OCNCH ₂
48 g of CH ₂ CH ₂ Si (OCH ₃ ) ₃ (KBE9007, manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over 3 hours. 50 ℃
For 4 hours to obtain alkoxysilane B-1 having a fluorine-containing group and a POE chain. Alkoxysilane B
The number average molecular weight of -1 was 1200.

Synthesis Example 2 (Mixed product 1): Thermometer, stirring
Glass flask with a capacity of 300 mL
Add a condensate of tetraethoxysilane (average degree of condensation approx.
5. Silica content 40% by mass (trade name: ethyl silicate 40)
(Hereinafter, referred to as ES40)), manufactured by Colcoat Co., Ltd.)
43.6 g, 57.9 g of alkoxysilane B-1, P
OE chain-containing alkoxysilane CH_ThreeO (CH_TwoCH_TwoO)_m
Si (OCH_TwoCH_Three) _Three(M is about 10, A-1230;
32.6 g of dibutyltin dilau
Rate 0.10 g and ion exchange water 4.3 g
And reacted at 80 ° C. for 4 hours to obtain a mixture 1
Was. The number average molecular weight of the mixed product 1 was 4,700.

Synthesis Example 3 (Mixed product 2): Internal volume 300
143.6 g of ES40 and 0.11 g of triethylamine were charged into a 3-mL three-necked flask. Then 100 ° C
And the above-mentioned CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ O (CH ₂
92.2 g of CH ₂ O) _n H (average molecular weight 955)
The product obtained by removing the volatile components over 5 hours at 100 ° C. was transferred to a glass flask having an internal volume of 300 mL, and 32.6 g of A-1230, 0.10 g of dibutyltin dilaurate, And 3.8 of ion exchanged water
g, and reacted at 80 ° C. for 4 hours to obtain a mixed product 2. The number average molecular weight of the mixed product 2 was 4,500.

Synthesis Example 4 (Mixed product 3): Internal volume 300
160 ml of ES40, A-
36.3 g of 1230, 0.13 g of dibutyltin dilaurate, and 3.9 g of ion-exchanged water were charged.
The mixture was reacted at 0 ° C. for 4 hours to obtain a mixed product 3. The number average molecular weight of the mixed product 3 was 3,800.

Synthesis Example 5 (Mixed product 4): Internal volume 300
A 50 mL three-necked flask was charged with 50 g of ES40 and 0.11 g of triethylamine. Next, the mixture was heated to 100 ° C, 220 g of 4,4,5,5,5-pentafluoropentyl alcohol (manufactured by Asahi Glass Co., Ltd.) was added dropwise over 10 minutes, and volatile components were removed at 100 ° C over 5 hours. A mixed product 4 was obtained. The number average molecular weight of the mixed product 4 is 1000
Met.

[Examples 1 to 11] Mixtures 1 to 4 and ES40 obtained in Synthesis Examples 2 to 5 were added to base white paints 1 and 2 at mixing ratios shown in Tables 2 and 3 to obtain paints. 200x
The paint was applied to an aluminum plate having a size of 95 × 8 mm using an applicator so that a dry film thickness became 20 μm, and dried at 20 ° C. and 65% RH for 1 week to obtain a coated plate. . Tables 2 and 3 show the evaluation results of the paint and the coated plate. Examples 1 to 5 are Examples, and Examples 6 to 11 are Comparative Examples. Table 4 shows the composition ratios of (B), (C) and (D) in the mixed products 1 to 4 used.

Compatibility: After mixing the base white paint and the mixed product, the mixture was allowed to stand at 20 ° C. and 65% RH for 1 hour, and the presence or absence of liquid separation was visually checked. The sample without liquid separation was indicated by "O", and the sample with liquid separation was indicated by "X". Stability of paint: After mixing the base white paint with the mixed product, 5
It was stored at 0 ° C. for one week, and the stability was visually evaluated. A sample having no abnormality was indicated by ○, and a gelled one was indicated by ×. Gloss: A specular gloss of 60 degrees was measured according to JIS Z8741.

Accelerated stain resistance: 50 ° C., 95% R
After curing for 1 day under H, a 5% by weight aqueous dispersion of hydrophobic carbon black was applied to the coated surface and dried at 60 ° C. for 1 hour. Then, it was washed with gauze. The lightness (L ^* value) before and after the test was measured, and the difference (ΔL ^* ) was calculated.
It is described as an absolute value. The L ^* value was measured using SQ2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS Z8730. Slope resistance: Painted board (size: 200 x 95 x 8m)
m) at a position of 100 mm (that is, the center in the longitudinal direction)
And the exposed surface was exposed outside in summer in Kawasaki City, Kanagawa Prefecture, with the painted surface outside so that the upper portion was at an angle of 30 degrees from the horizontal plane and the lower portion was vertical. The L ^* value of the 30-degree slope was measured three months after the exposure of the coated plate. The difference ΔL ^* between the L ^* values before and after the test was calculated and described as an absolute value.

Rain streak stain resistance: The condition of rain streak stain on the vertical surface of the outdoor exposure plate evaluated for slope stain was evaluated. When the stain on the rain streak was not conspicuous, the result was indicated by ○, when the test was slightly conspicuous, and when notable, the test was indicated by x. Accelerated weathering resistance: The gloss retention after the carbon arc lamp accelerated weathering test described in JIS K5400 9.8.1 was performed for 4000 hours was measured. 80% gloss retention
The above was described as ○, and the gloss retention of less than 80% was described as ×.

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

[Table 4]

[0092]

As described above, the aqueous coating composition of the present invention can form a highly glossy coating film on a painted surface. In addition, it is excellent in stain resistance, rain streak stain resistance, dirt washability, dirt detachment effect, etc., and
A coating film having excellent weather resistance can be formed.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CB021 CB091 CB131 CD091 CD111 CD121 CE051 CF021 CF091 CG141 DA161 DB001 DD001 DG031 DL022 DL031 DL032 DL072 DL082 DL092 DL152 GA02 GA03 GA06 GA07 GA12 GA15 KA04 MA08 MA10 MA18 PB07 PB09 PC02 PC03 PC04 PC08

Claims (8)

[Claims] 1. An alkoxysilane represented by the formula 1 and / or a condensate thereof (B) based on 100 parts of the synthetic resin (A).
0.1 to 50 parts of the alkoxysilane represented by Formula 2 and / or its condensate (C) 0.1 to 50 parts, and Formula 3
The composition for water-based paints, comprising 0 to 50 parts of an alkoxysilane represented by the formula (1) and / or a condensate (D) thereof. (R ¹ ) _a Si (OR ² ) _4-a Formula 1 (R ³ ) _b Si (OR ⁴ ) _4-b Formula 2 (R ⁵ ) _c Si (OR ⁶ ) _4-c Formula 3 , A is an integer of 0 to 3, R ¹ is 1
Valence organic group, R ² represents a monovalent organic group or a hydrogen atom, R ¹
And one or more selected from the group consisting of R ² is a monovalent organic group having a fluorine-containing group and a hydrophilic group. In the formula 2, b is an integer of 0 to 3, R ³ is a monovalent organic group, and R ⁴ is 1
At least one selected from the group consisting of R ³ and R ⁴ represents a valent organic group or a hydrogen atom, and is a monovalent organic group having a hydrophilic group and no fluorinated group. In Formula 3, c represents an integer of 0 to 3, R ⁵ represents a monovalent organic group having no hydrophilic group, and R ⁶ represents a monovalent organic group having no hydrophilic group or a hydrogen atom. 2. The aqueous coating composition according to claim 1, wherein two or more kinds selected from the group consisting of (B), (C) and (D) are mixed and treated in advance. 3. The water-based coating composition according to claim 1, wherein the monovalent organic group having a fluorine-containing group and a hydrophilic group in (B) is a monovalent organic group represented by the formula (4). Composition. R ^f -XYZ- Formula 4 wherein R ^f represents a monovalent fluorine-containing group, Y represents a divalent hydrophilic group, and X and Z represent a bonding group or a single bond. 4. The monovalent fluorinated group in (B) is a monovalent organic group having a polyfluoroalkyl group, and the divalent hydrophilic group is a divalent organic group having a polyoxyalkylene chain. 4. The composition for an aqueous coating composition according to item 3. 5. The aqueous coating composition according to claim 1, wherein the hydrophilic group in (C) is a polyoxyalkylene chain. 6. A paint comprising the water-based paint composition according to any one of claims 1 to 5. 7. A coating method comprising applying the paint according to claim 6 to an object to be coated. 8. A coated article having a coating film formed from the coating composition according to claim 6.