JP2003055617A - Stain reducing agent, coating composition containing the same, and painted product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stain reducing agent which can form a coating film that is excellent in resistance to rain foul; a coating composition containing the same; and a product coated with the composition. SOLUTION: The stain reducing agent comprises a polymer containing one or more repeating units each of which has two or more hydroxy groups, wherein the repeating units have a content rate (by mass) of more than 10%. The coating composition comprises the stain reducing agent and a coating resin such as a fluorocarbon resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a low-staining agent, a coating composition containing the low-staining agent, and a coated article.

[0002]

2. Description of the Related Art Conventionally, products made of metals, inorganic materials, plastics, wood, paper, leather, fibers and the like have been surface-coated for the purpose of protecting their surfaces, imparting design and functionality, and Various paints have been developed for the surface coating. In recent years, particularly in urban areas, rain streak contamination of outdoor structures has become a problem, and the development of paints to improve it has been demanded, and various methods have been studied.

(1) JP-A-10-130450 describes an aqueous coating composition comprising an aqueous dispersion containing a coating resin component. In the aqueous coating composition, 4%, 5% or 10% (by weight) of glycerin monomethacrylate having two hydroxy groups.
same as below. ) Is used as a specific example of a coating resin component.

(2) Japanese Patent Laid-Open No. 2001-72928 discloses (a) an emulsion of an organic synthetic resin, (b) a coupling agent, and (c) a hydrophilic group having a group capable of reacting with the coupling agent. A low-staining resin composition for water-based coatings comprising an organic compound is described. As an example of the hydrophilic compound (c), polyvinyl alcohol composed of a repeating unit having one hydroxy group is specifically used.

However, the specific examples of the resin component for paint in (1) above and the polyvinyl alcohol in (2) above are not suitable as a stain-proofing agent for imparting low stain resistance and rain streak stain resistance to the article surface. It is sufficient, and practical performance cannot be realized especially with respect to rain line contamination resistance.

[0006]

An object of the present invention is to impart low stain resistance and rain line stain resistance (hereinafter, these may be collectively referred to as stain resistance) to various article surfaces. To provide a pollutant. Another object of the present invention is to provide a coating composition capable of forming a coating film having excellent stain resistance and a coated article having the coating film having excellent stain resistance.

[0007]

(1) The present invention comprises at least one repeating unit (A) having two or more hydroxy groups, and if necessary, a repeating unit (B) other than the repeating unit (A). ), And the repeating unit (A)
And a content ratio (mass basis) of the polymer is more than 10%. (2) Further, the present invention provides a coating composition comprising a coating resin and the above-mentioned stain-reducing agent.

(3) Furthermore, the present invention provides a coated article having a coating film formed by using the coating composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a repeating unit (A) having two or more hydroxy groups (hereinafter sometimes referred to as a unit (A)) is a polymerizable unit having two or more hydroxy groups. It can be introduced into a polymer by polymerizing a monomer. The unit (A) can also be introduced into the polymer by various modification techniques such as introducing two or more hydroxy groups into the polymer having a reactive site. Hereinafter, the polymerizable monomer that gives the unit (A) will be described as a typical example.

The term (meth) acrylate described in the specific compound names in this specification means acrylate or methacrylate. Similarly, (meta)
Acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylamide means acrylamide or methacrylamide.

Examples of the polymerizable monomer that gives the unit (A) include the following polymerizable monomers. CH ₂ =
CHCOOR ¹ , CH ₂ = C (CH ₃ ) COOR ¹ , C
H ₂ = CHOCOR ¹ , CH ₂ = C (CH ₃ ) OCOR
¹ , CH ₂ = CHOR ¹ , CH ₂ = C (CH ₃ ) O
^{_{R 1, CH 2 = CHCH 2}} OR 1, CH 2 = CHCH 2
OCOR ¹ , CH ₂ = CHCONHR ¹ , CH ₂ = C
(CH ₃ ) CONHR ¹ , CH ₂ = CHCON (R ¹ )
₂ , CH ₂ = C (CH ₃ ) CON (R ¹ ) ₂ , CH ₂ =
CHNHCOR ¹ , CH ₂ = C (CH ₃ ) NHCOR ¹
Etc. However, R ¹ is an organic group having two or more hydroxy groups. From the viewpoint of stain resistance, R ¹ is preferably an organic group having 1 to 100 carbon atoms. More preferably, R ¹ is an organic group having 1 to 20 carbon atoms.
When two or more R ^1's are contained, they may be the same or different. Further, R ¹ may contain a functional group other than a hydroxy group and other atoms such as a nitrogen atom, a chlorine atom and a fluorine atom.

Specific examples of the polymerizable monomer that gives the unit (A) include trifunctional or higher functional polyol compounds, esters of saccharides with (meth) acrylic acid, etc., bifunctional or higher functional polyol compounds having an amino group, or Examples thereof include amides of saccharides having an amino group and (meth) acrylic acid.

As the trifunctional or higher functional polyol compound,
Glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, pentaerythritol, 1,2,6-hexanetriol,
2-hydroxymethyl-2-methyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,3
-Propanediol and the like.

As the saccharides, glucose, mannose,
Examples include monosaccharides such as galactose, gulose, fructose, and D-ribose, glucosides, galactoside or fructosides derived from these monosaccharides, and dimers and trimers thereof.

Examples of the bifunctional or higher functional polyol compound having an amino group include 3-amino-1,2-propanediol and the like. As the saccharide having an amino group, D
-Glucosamine and the like.

The unit (A) may be used alone or in combination of two or more. The larger the content ratio (mass basis) of the unit (A) is, the better the stain resistance is.
% Is used. It is preferably 30% or more.

In the present invention, a repeating unit (B) other than the above-mentioned unit (A) (hereinafter sometimes referred to as a unit (B)) may be contained if necessary. At least one of the units (B) is preferably a repeating unit (b1) having a crosslinkable functional group (hereinafter sometimes referred to as a unit (b1)). Further, as the unit (B), a repeating unit (b) other than the unit (A) and the unit (b1) is used.
2) (hereinafter sometimes referred to as a unit (b2)). As the unit (B), the unit (b1) and the unit (b
You may use together with 2).

Examples of the polymerizable monomer giving the unit (b1) include a monomer having a crosslinkable functional group which is generally used in a crosslinking reaction. For example, as the polymerizable monomer giving the unit (b1), a monomer having an aldehyde carbonyl group, a monomer having a ketone carbonyl group, 1
Monomers having 1 hydroxyl group, monomers having a carboxy group or a salt thereof, monomers having a sulfo group or a salt thereof, monomers having a phosphoric acid residue or a salt thereof, a unit amount having an epoxy group Body, a monomer having an amino group or a salt thereof, a monomer having an oxazoline residue, a monomer having an amide group, a monomer having an alkoxy group, a monomer having a hydrolyzable silyl group, etc. Can be mentioned.

The unit (b1) is at least one monomer selected from the group consisting of a monomer having an aldehyde carbonyl group, a monomer having a ketone carbonyl group and a monomer having an oxazoline residue. Are preferred.

In the present specification, the carbonyl in the aldehyde carbonyl group and the ketone carbonyl group represents a ketone and an aldehyde, and excludes ester, amide and carboxy.

Examples of the monomer having an aldehyde carbonyl group include (meth) acrolein, crotonaldehyde, β-formylstyrene, β-formyl-α-methylstyrene and β- (meth) acryloyloxy-α, α-.
Dialkyl propanals and the like can be mentioned.

Β- (meth) acryloyloxy-α, α
-Specific examples of the dialkylpropanals include β-
(Meth) acryloyloxy-α, α-dimethylpropanal, β- (meth) acryloyloxy-α, α-diethylpropanal, β- (meth) acryloyloxy-α, α-dipropylpropanal, β- ( Examples thereof include (meth) acryloyloxy-α-methyl-α-butylpropanal and β- (meth) acryloyloxy-α, α, β-trimethylpropanal.

The monomer having a ketonic carbonyl group is N- (1,1-dimethyl-3-oxobutyl).
(Meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl propyl ketone, vinyl isopropyl ketone, vinyl butyl ketone, vinyl isobutyl ketone, vinyl tert-butyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone,
(1,1-Dimethyl-3-oxobutyl) (meth) acrylate and the like can be mentioned.

Further, the monomer having a ketonic carbonyl group may be a monomer having an active methylene moiety, and specifically, allyl acetoacetate, 2-
Acetoacetoxyethyl (meth) acrylate, 2-
(Acetoacetoxy) propyl (meth) acrylate,
Examples include 3- (acetoacetoxy) propyl (meth) acrylate, 2- (acetoacetoxy) butyl (meth) acrylate, 3- (acetoacetoxy) butyl (meth) acrylate, and 4- (acetoacetoxy) butyl (meth) acrylate. To be

As the monomer having one hydroxyl group, vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4
-Hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, neopentyl Glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N
-Hydroxymethyl (meth) acrylamide, hydroxymethyl (meth) acrylate, etc. are mentioned.

Further, polyoxyalkylene (hereinafter referred to as PO
It is called A. ) A monomer having a chain and a terminal hydroxyl group is also included. For example, CH ₂ = CHOCH ₂ C ₆ H
₁₀ CH ₂ O (C ₂ H ₄ O) _k H (where k is 1 to 1)
00 is an integer, and the same applies hereinafter. ), CH ₂ = CHOC _{4
H 8 O (C 2 H 4} O) k H, CH 2 = CHCOOC 2 H
₄ O (C ₂ H ₄ O) _k H, CH ₂ = C (CH ₃ ) COO
C ₂ H ₄ O (C ₂ H ₄ O) _k H, CH ₂ = CHCOOC
₂ H ₄ O (C ₂ H ₄ O) _m (C ₃ H ₆ O) _n H (where m is 0 or an integer of 1 to 100, and n is 1 to 1).
Is an integer of 00, and m + n is 1 to 100. same as below. ), CH ₂ = C (CH ₃ ) COOC ₂ H ₄ O (C _{2
H 4 O) m (C 3} H 6 O) n H , and the like.

Commercially available products of the above-mentioned monomer having a POA chain and a hydroxyl group at the end are PE-90 and PE-2.
00, PE-350, AE-400, PP-500, P
P-800, PP-1000, AP-400, 50PE
P-300, 70PEP-350B (above, NOF Corporation make) etc. are mentioned.

As the monomer having a carboxy group or a salt thereof, acrylic acid, methacrylic acid, vinyl acetic acid,
Examples thereof include crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid, and salts thereof.

Examples of the monomer having a sulfo group or a salt thereof include vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, 2-hydroxyallyloxy-1-propanesulfonic acid, sulfoethoxyacrylate and sulfoethoxymethacrylate. , 2-acrylamido-2-methylpropanesulfonic acid, or salts thereof.

As the monomer having a phosphoric acid residue or a salt thereof, phosphoric acid 2-acryloyloxyethyl ester, phosphoric acid 2-methacryloyloxyethyl ester,
Alternatively, their salts and the like can be mentioned.

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, and 3,4-epoxy-1-butene.

Examples of the monomer having an amino group or a salt thereof include 2-N-methylaminoethyl (meth) acrylate, 2-N-ethylaminoethyl (meth) acrylate and 3-amino-2-hydroxypropyl (meth). ) Acrylate, allylamine, or salts thereof.

Examples of the monomer having an oxazoline residue include 2-vinyl-2-oxazoline and 2-vinyl-4-.
Methyl-2-oxazoline, 2-vinyl-5-methyl-
2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline may be mentioned.

Examples of the monomer having an amide residue include (meth) acrylamide, N-vinylformamide, N-vinylacetamide and the like.

The monomer having an alkoxy group is 2
-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, N-methoxymethyl (meth) acrylamide, N, N-bis (methoxymethyl)
(Meth) acrylamide, N-ethoxymethyl (meth)
Acrylamide, N, N-bis (ethoxymethyl) (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N, N-bis (propoxymethyl) (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-bis (butoxymethyl) (meth)
Examples thereof include acrylamide and N- (2,2-dimethoxy-1-hydroxyethyl) (meth) acrylamide.

Further, a monomer having a POA chain and having an alkoxy group at the end is also mentioned. For example, CH ₂ =
CHOCH ₂ C ₆ H ₁₀ CH ₂ O (C ₂ H ₄ O) _k CH
₃ (here, k is an integer of 1 to 100, and the same applies hereinafter), CH ₂ = CHOC ₄ H ₈ O (C ₂ H ₄ O) _k C
_{H 3, CH 2 = CHCOOC 2} H 4 O (C 2 H 4 O) k
CH ₃ , CH ₂ = C (CH ₃ ) COOC ₂ H ₄ O (C ₂
H ₄ O) _k CH ₃ , CH ₂ = CHCOOC ₂ H ₄ O (C
₂ H ₄ O) _m (C ₃ H ₆ O) _n CH ₃ (where m is 0
Alternatively, it is an integer of 1 to 100, n is an integer of 1 to 100, and m + n is 1 to 100. same as below. ), C
_{H 2 = C (CH 3)} COOC 2 H 4 O (C 2 H 4 O) m
_{(C 3 H 6 O) n} CH 3 , and the like.

Commercially available products of the above-mentioned monomer having a POA chain and having an alkoxy group at its end are M-20G and M.
-40G, M-90G, M-230G, AM-90G
(Above, manufactured by Shin Nakamura Chemical Co., Ltd.), PME-100, PM
E-200, PME-400 (above, NOF Corporation make) etc. are mentioned.

Examples of the monomer having a hydrolyzable silyl group include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane and 2- (meth) acryloyloxyethyltrimethoxysilane. Silane, 2- (meth) acryloyloxyethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, 3-trimethoxysilylpropyl vinyl ether, 3- Methyldimethoxysilylpropyl vinyl ether and the like can be mentioned.

The units (b1) may be the same or different. The content ratio (mass basis) of the unit (b1) is preferably 0.01% or more and less than 90%. Within this range, the storage stability, the stain resistance and the durability thereof when blended in the paint are better. More preferably, it is 0.1 to 50%.

Examples of the polymerizable monomer giving the unit (b2) include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, alkyl (meth) acrylic acid esters. And aromatic vinyl compounds, chloroolefins, conjugated dienes, compounds having a polyfunctional polymerizable double bond, and the like. As hydrocarbon-based olefins,
Examples thereof include ethylene, propylene and isobutylene.

The vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, n-.
Chain alkyl vinyl ethers such as pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, n-octyl vinyl ether, 4-methyl-1-pentyl vinyl ether, alicyclic alkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, phenyl vinyl ether,
Examples thereof include aromatic group-containing vinyl ethers such as benzyl vinyl ether.

Examples of isopropenyl ethers include methyl isopropenyl ether, ethyl isopropenyl ether, n-propyl isopropenyl ether and n-butyl isopropenyl ether.

Examples of allyl ethers include ethyl allyl ether and cyclohexyl allyl ether. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl octanoate, vinyl versatate, vinyl octadecanoate, and the like.

As allyl esters, allyl acetate,
Examples include allyl propionate and the like.

As the (meth) acrylic acid esters,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-
Methyl butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (meth)
Acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be mentioned.

As the aromatic vinyl compound, styrene,
α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene,
4-tert-butylstyrene, 3,4-dimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene,
2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 4-chloro-3-methylstyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylpyridine , 4-vinylpyridine and the like.

Examples of chloroolefins include vinyl chloride, vinylidene chloride, isopropenyl chloride and allyl chloride. Examples of the conjugated dienes include 1,3-butadiene, isoprene, chloroprene, and 2,3-dimethyl-1,3-butadiene.

As the compound having a polyfunctional polymerizable double bond, divinylbenzene, divinyl ether, allyl (meth) acrylate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol (meth) diacrylate, 1,6-hexanediol di (meth) acrylate, glycerin Examples thereof include tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

The units (b2) may be the same or different. The content ratio (mass basis) of the unit (b2) is preferably 89.99 in consideration of stain resistance.
It is less than%. It is more preferably 0 to 30%.

The polymer constituting the antifouling agent in the present invention contains two or more units (A), and the number average molecular weight thereof is preferably 160 to 1,000,000, more preferably 320 to 100,000. When the number average molecular weight is in this range, the stain resistance becomes better.

The antifouling agent in the present invention can be synthesized by the following method. For example, it is a method in which the monomer that gives the unit (A) is dissolved in a solvent and heated together with the monomer that gives the unit (B) if necessary, and a polymerization initiator is added to react. As the solvent in the synthesis method, water or a water-soluble solvent is preferable. For example, water, methanol, ethanol, 1-propanol, 2-propanol, n-butyl alcohol, 2-methyl-1-propanol, ethylene glycol, propylene glycol, 1,3-butanediol, glycerol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2- (2-
Methoxyethoxy) ethanol, methyl acetate, ethyl acetate, 2,2'-dichlorodiethyl ether, chloropropanol, acetone, methyl ethyl ketone, 1,4-dioxane, dimethylformamide, formamide, acetonitrile and the like. These may be used alone or in combination of two or more. From the viewpoint of polymerization stability and ease of solvent substitution, methanol and acetone are preferable.

Examples of the polymerization initiator include known organic peroxides, inorganic peroxides, azo compounds and the like. The organic peroxide and the inorganic peroxide can be used as a redox catalyst in combination with a reducing agent. These may be used alone or in combination of two or more.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, tert-butyl hydroperoxide, ter.
Examples thereof include t-butyl-α-cumyl peroxide.
Examples of the inorganic peroxide include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, percarbonate and the like.

Examples of the azo compound are 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1'-carbonitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile). ), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 2,2 '
-Azobis (2-amidinopropane) dihydrochloride and the like.

Further, in order to adjust the molecular weight, known chain transfer agents such as mercaptans and alkyl halides can be used. These may be used alone or in combination of two or more. Examples of mercaptans include n-butyl mercaptan, n-dodecyl mercaptan, t-butyl mercaptan, ethyl thioglycolate, and 2-ethylhexyl thioglycolate. Examples of the halogenated alkyls include chloroform, carbon tetrachloride, carbon tetrabromide and the like.

The octane desorption work calculated from the contact angle of octane in water of the coating film formed from the low-polluting agent obtained as described above is 3.0 × 10 ^−2.
It is preferably less than J / m ² . The work of desorbing octane is obtained by measuring the contact angle of octane with respect to the coating film in water.

[0057] elimination work of octane _(W A ') can be represented by the following formula. W _A ′ = γ _SW + γ _WO −γ
_SO (However, γ _SW is the interfacial tension between the film surface and water (J
/ M ² ), γ _WO is the interfacial tension between water and octane (J / m 2
² ) and γ _SO are the interfacial tension between the coating surface and octane (J /
m ² ) is represented. ) Young's equation [γ _SW = γ _SO + γ _WO
= Cos θ (where θ is the contact angle that octane makes with the coating film in water)], and the expanded Fo
Using the wkes formula, noting that the dispersive components of the surface tension of water and octane are equal, the following formula can be derived.

W_A′ = C (1 + cos θ) (where C
Is a polar component of the surface tension of water, and C = 0.051 (J
/ M^Two). ) Since θ can change from 0 to 180 °, W_A'Is 0 to 1
0.2 x 10^-2(J / m^Two) Changes in the range.
W_AThe smaller the ′, the more octane in water
Means less energy to separate from
It On the other hand, there are many oily substances among the substances that cause dirt.
Oily substances such as octane easily in water
The surface of the film to be separated easily becomes oily due to rain, etc.
The surface of the coating to be washed away, and the contamination resistance is good.
It is presumed to be the membrane surface. To demonstrate stain resistance
Is octane desorption work in water is 3.0 × 10
^-2J / m ^TwoIt is preferably less than. Furthermore, 2.
0x10^-2J / m^TwoIt is preferably less than.

As the paint resin, various known synthetic resins can be used without particular limitation. Specific examples include fluorine-containing resins, acrylic resins, silicone-modified acrylic resins, urethane resins, melamine resins, silicone resins, epoxy resins, polyester resins and the like. The synthetic resins may be used alone or in combination of two or more. In particular,
It is preferable to use a fluorine-containing resin having excellent weather resistance and chemical resistance alone or as a main component. As the form of the synthetic resin as the paint resin, any form of solvent type, water type and powder can be used.

Examples of the fluorine-containing resin include a polymer of a fluorine-containing monomer and a copolymer of the fluorine-containing monomer and a monomer other than the fluorine-containing monomer. Examples of the fluorine-containing monomer include fluoroolefins and monomers having a polyfluoroalkyl group. The fluorinated monomers may be used alone or in combination of two or more.

Examples of fluoroolefins include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene and hexafluoropropylene.

Examples of the monomer having a polyfluoroalkyl group include CH ₂ = CR ² COOR ³ R ^f and CH ₂ = CR.
² COO (CH ₂ ) _n NR ⁴ SO ₂ R ^f , CH ₂ = CR
² COO (CH ₂ ) _n NR ⁴ COR ^f , CH ₂ = CR ²
_{COOCH 2 CH (OH) (CH} 2) n R f , and the like. However, n is an integer of 1 to 10 and R ^f is a carbon number 1
~ 18 polyfluoroalkyl group, R ² is a hydrogen atom or a methyl group, R ³ is a divalent organic group having 1 to 6 carbon atoms,
R ⁴ represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.

R^fMay be linear or branched, and
It may contain a telluric oxygen atom. R^fAs a concrete example of
Is CF_Three, CF_ThreeCF_Two, H (CF_Two)_Two, CF
_Three(CF _Two)_Two, CF_Three(CF_Two)_Three, H (C
F_Two)_Four, CF_Three(CF_Two)_Four, CF_Three(CF_Two)₅,
CF_Three(CF_Two)_TwoOCF (CF_Three), H (C
F_Two)₆, CF_Three(CF_Two)₆, CF_Three(CF_Two)₇,
H (CF_Two)₈, CF_Three(CF_Two)₈, CF _Three(C
F_Two)₉, CF_ThreeCF (CF_Three) (CF_Two)₆, CF_Three
(CF_Two)₁₀, H (CF_Two)₁₀, CF_Three(CF_Two)
₁₁, H (CF_Two)₁₄, CF_Three(CF_Two)₁₅, CF
_Three(CF_Two)₁₇Etc.

R^ThreeAs a concrete example of_Two, CH_TwoC
H_Two, CH (CH_Three), CH_TwoCH _TwoCH_Two, C (CH
_Three)_Two, CH (CH_TwoCH_Three), CH_TwoCH_TwoCH_TwoC
H_Two, CH (CH_TwoCH_TwoCH_Three), CH_Two(CH_Two)
_ThreeCH_Two, CH (CH_TwoCH (CH_Three)_Two) Etc.
Be done.

R^FourAs specific examples of, a hydrogen atom, or
CH_Three, CH_ThreeCH_Two, CH_ThreeCH _TwoCH_Two, CH_ThreeC
H_TwoCH_TwoCH_TwoEtc. Especially fluoro oleph
The tins are preferable because they have excellent durability.

As the monomer other than the fluorine-containing monomer, a monomer copolymerizable with the fluorine-containing monomer is used. Specific examples include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, alkyl (meth)
Examples thereof include acrylic acid esters, aromatic vinyl compounds, chloroolefins, conjugated dienes and the like. Moreover, the compound which has a polyfunctional polymerizable double bond, and the monomer which has a functional group are also mentioned. These may be used alone or 2
You may use together 1 or more types.

Examples of the hydrocarbon olefins include ethylene, propylene and isobutylene. Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and te.
Chain alkyl vinyl ethers such as rt-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, n-octyl vinyl ether, 4-methyl-1-pentyl vinyl ether, and cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether. And aromatic group-containing vinyl ethers such as phenyl vinyl ether and benzyl vinyl ether.

Examples of isopropenyl ethers include methyl isopropenyl ether, ethyl isopropenyl ether, n-propyl isopropenyl ether and n-butyl isopropenyl ether. Examples of allyl ethers include ethyl allyl ether and cyclohexyl allyl ether.

Vinyl esters include vinyl acetate,
Examples thereof include vinyl propionate, vinyl pivalate, vinyl octoate, vinyl versatate, vinyl octadecanoate and the like. Examples of the allyl ester include allyl acetate and allyl propionate.

As the (meth) acrylic acid esters,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert- Butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-
Methyl butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (meth)
Acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be mentioned.

As the aromatic vinyl compound, styrene,
α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene,
4-tert-butylstyrene, 3,4-dimethylstyrene, 4-methoxystyrene, 4-ethoxystyrene,
2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 2,6-dichlorostyrene, 4-chloro-3-methylstyrene, divinylbenzene, 1-vinylnaphthalene, 2-vinylpyridine , 4-vinylpyridine and the like.

Examples of chloroolefins include vinyl chloride, vinylidene chloride, isopropenyl chloride and allyl chloride. Examples of the conjugated dienes include 1,3-butadiene, isoprene, chloroprene, and 2,3-dimethyl-1,3-butadiene.

As the compound having a polyfunctional polymerizable double bond, divinylbenzene, divinyl ether, allyl (meth) acrylate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol (meth) diacrylate, 1,6-hexanediol di (meth) acrylate, glycerin Examples thereof include tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

As the monomer having a functional group, a monomer having a hydroxymethyl group, a monomer having an aldehyde carbonyl group, a monomer having a ketone carbonyl group, a monomer having a carboxy group or Salts, monomers having epoxy groups, monomers having amino groups or salts thereof, monomers having oxazoline residues, monomers having amide groups, monomers having alkoxy groups, hydrolyzable A monomer having a silyl group, a monomer having a polyoxyalkylene chain (hereinafter referred to as a monomer having a POA chain), a monomer having a hydroxyl group, a monomer having a sulfo group or a salt thereof, Examples thereof include a monomer having a phosphoric acid residue or a salt thereof, a monomer having a zwitterion, and a monomer having a cyano group.

Examples of the monomer having a hydroxymethyl group include N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N, N-bis (hydroxymethyl) acrylamide, N, N-bis (hydroxymethyl) methacrylamide, Hydroxymethyl acrylate, hydroxymethyl methacrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and the like can be mentioned.

Examples of the monomer having an aldehyde carbonyl group include (meth) acrolein, crotonaldehyde, β-formylstyrene, β-formyl-α-methylstyrene and β- (meth) acryloyloxy-α, α-.
Dialkyl propanals and the like can be mentioned. Specific examples of β- (meth) acryloyloxy-α, α-dialkylpropanals include β- (meth) acryloyloxy-α, α-dimethylpropanal and β- (meth) acryloyloxy-α, α- Diethylpropanal, β
-(Meth) acryloyloxy-α, α-dipropylpropanal, β- (meth) acryloyloxy-α-methyl-α-butylpropanal, β- (meth) acryloyloxy-α, α, β-trimethylpropanal Examples include Panhard.

The monomer having a ketonic carbonyl group is N- (1,1-dimethyl-3-oxobutyl).
(Meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl propyl ketone, vinyl isopropyl ketone, vinyl butyl ketone, vinyl isobutyl ketone, vinyl tert-butyl ketone, vinyl phenyl ketone, vinyl benzyl ketone, divinyl ketone,
(1,1-Dimethyl-3-oxobutyl) (meth) acrylate and the like can be mentioned.

Further, the monomer having a ketonic carbonyl group may be a monomer having an active methylene moiety, and specifically, allyl acetoacetate, 2-
Acetoacetoxyethyl (meth) acrylate, 2-
(Acetoacetoxy) propyl (meth) acrylate,
Examples include 3- (acetoacetoxy) propyl (meth) acrylate, 2- (acetoacetoxy) butyl (meth) acrylate, 3- (acetoacetoxy) butyl (meth) acrylate, and 4- (acetoacetoxy) butyl (meth) acrylate. To be

Examples of the monomer having a carboxy group or a salt thereof include acrylic acid, methacrylic acid, vinyl acetic acid,
Examples thereof include crotonic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid, and salts thereof. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether,
3,4-epoxy-1-butene and the like can be mentioned.

Examples of the monomer having an amino group or a salt thereof include 2-N-methylaminoethyl (meth) acrylate, 2-N-ethylaminoethyl (meth) acrylate and 3-amino-2-hydroxypropyl (meth). ) Acrylate, allylamine, or salts thereof.

Examples of the monomer having an oxazoline residue include 2-vinyl-2-oxazoline and 2-vinyl-4-.
Methyl-2-oxazoline, 2-vinyl-5-methyl-
2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline may be mentioned. Examples of the monomer having an amide residue include (meth) acrylamide, N-vinylformamide, N-vinylacetamide and the like.

As the monomer having an alkoxy group, 2
-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, N-methoxymethyl (meth) acrylamide, N, N-bis (methoxymethyl)
(Meth) acrylamide, N-ethoxymethyl (meth)
Acrylamide, N, N-bis (ethoxymethyl) (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N, N-bis (propoxymethyl) (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-bis (butoxymethyl) (meth)
Examples thereof include acrylamide and N- (2,2-dimethoxy-1-hydroxyethyl) (meth) acrylamide.

Examples of the monomer having a hydrolyzable silyl group include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane and 2- (meth) acryloyloxyethyltrimethoxysilane. Silane, 2- (meth) acryloyloxyethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, 3-trimethoxysilylpropyl vinyl ether, 3- Methyldimethoxysilylpropyl vinyl ether and the like can be mentioned.

Commercially available products of the monomer having a POA chain are M-20G, M-40G, M-90G and M-230.
G (above, Shin-Nakamura Chemical Co., Ltd.), PE-90, PE-
200, PE-350, AE-400, PP-500,
PP-800, PP-1000, AP-400, 50P
EP-300, 70PEP-350B, PME-10
0, PME-200, PME-400 (above, NOF Corporation make) etc. are mentioned.

Examples of the monomer having a hydroxyl group include vinylphenol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 3
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) ) Acrylate, glycerin mono (meth) acrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl (meth) acrylate, N-hydroxymethyl (meth) acrylamide, N, N-bis (hydroxymethyl) (meth) Examples thereof include acrylamide and hydroxymethyl (meth) acrylate.

As the monomer having a sulfo group or a salt thereof, vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, 2-hydroxyallyloxy-1-propanesulfonic acid, sulfoethoxyacrylate, sulfoethoxymethacrylate. , 2-acrylamido-2-methylpropanesulfonic acid, or salts thereof.

Examples of the monomer having a phosphoric acid residue or a salt thereof include phosphoric acid 2-acryloyloxyethyl ester, phosphoric acid 2-methacryloyloxyethyl ester,
Alternatively, their salts and the like can be mentioned. Examples of the zwitterionic monomer include phosphorylcholine group-containing (meth) acrylate.

Examples of the monomer having a cyano group include (meth) acrylonitrile, crotonnitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate and cinnamic acid. Examples include nitrile and the like.

By copolymerizing a monomer other than the fluorine-containing monomer, the dispersibility of the pigment is improved, the film-forming property of the coating film and the adhesion to the base are improved, the hardness is improved, and the strength is improved. Effects such as improvement of elongation and improvement of gloss value may be obtained. In a copolymer of a fluorine-containing monomer and a monomer other than the fluorine-containing monomer, the copolymerization ratio of the fluorine-containing monomer is preferably 30 to 90 mol% in consideration of durability and the like. More preferably, it is 40 to 80 mol%.

The copolymerization ratio of the monomers other than the fluorine-containing monomer is preferably 10 to 70 mol%, more preferably 20.
Is about 60 mol%. When a monomer having a functional group is copolymerized, the copolymerization ratio of the monomer having a functional group is
It is preferably 1 to 20 mol%, more preferably 2 to 15 mol%.

In the present invention, a mixture of a fluorine-containing resin and another resin may be used as the coating resin. In this case, as the other resin, an acrylic resin is preferable because it is excellent in the durability of the rain line contamination resistance. Fluorine-containing resin / acrylic resin mixing ratio (mass basis) is preferably 100/0
~ 20/80, more preferably 100/0 to 50/50
Is.

The content of the low-staining agent in the coating composition of the present invention is 0.1 to 100 parts by mass of the coating resin.
100 parts by mass is preferred. Within this range, the stain resistance and weather resistance are good. The amount is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass.

As the curing agent capable of reacting with the crosslinkable functional group of the unit (b1), various known curing agents can be used. For example, amino resins, polyisocyanate compounds, compounds having two or more hydrazino groups, polycarbodiimide compounds, compounds having two or more epoxy groups, compounds having two or more oxazoline residues, and two or more aziridine residues. Group-containing compounds, polyvalent metals, 2
Examples thereof include compounds having two or more amino groups, polyketimines, compounds having two or more carboxy groups, acid anhydrides, compounds having two or more mercapto groups, and the like. These may be used alone or in combination of two or more.

As the amino resin, melamine compounds,
A compound obtained by hydroxymethylating a part or all of amino groups of a guanamine compound, a urea compound, or the like, or methanol, ethanol, n-butyl alcohol, 2-methyl of a part or all of hydroxyl groups of the hydroxymethylated compound. Examples include compounds etherified with -1-propanol and the like, such as hexamethoxymethylmelamine.

Examples of the polyisocyanate compound include polyisocyanate compounds such as hexamethylene diisocyanate and isophorone diisocyanate, isocyanate silane compounds such as methyltriisocyanate silane and / or condensates and multimers thereof, and these. And water-dispersible type, blocked polyisocyanate compounds in which the isocyanate group is blocked with a blocking agent such as phenol. A non-yellowing type is particularly preferable.

Examples of the compound having two or more hydrazino groups include dihydrazide, polyfunctional hydrazide, polyfunctional semicarbazide and the like. Examples of dihydrazides include carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, heptane diacid dihydrazide, octane dihydrazide, nonanedioic acid dihydrazide, dodecanedioic acid, dodecane dihydric acid, dodecane dihydric acid, dodecane dihydric acid Dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 2,6-naphthoic acid dihydrazide,
4,4'-bisbenzenedihydrazide, 2,6-pyridinedihydrazide, 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, itaconic acid dihydrazide and the like can be mentioned.

As the polyfunctional hydrazide, ethylenediaminetetraacetic acid tetrahydrazide, citric acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide,
Trimellitic acid trihydrazide, pyromellitic acid trihydrazide, pyromellitic acid tetrahydrazide, 1,4
5,8-naphthoic acid tetrahydrazide, alkyl (me)
A reaction product of hydrazine with an oligomer containing an alkyloxycarbonyl group such as an acrylate oligomer is also included.

Examples of the polyfunctional semicarbazide include reaction products of polyisocyanate and hydrazine. The polycarbodiimide compound is obtained by a known carbon dioxide decarbonization condensation reaction. At this time, a phosphoric acid compound such as trimethyl phosphate or triethyl phosphate can be used as a known catalyst. Further, a nonionic hydrophilic polycarbodiimide compound can be obtained by using a mixture of organic diisocyanate and hydroxyl group-containing polyethylene glycol. Water dispersibility,
From the viewpoint of stability, nonionic hydrophilic polycarbodiimide compounds are preferred.

Examples of the compound having two or more epoxy groups include glycerol polyglycidyl ether compound and the like. As the compound having two or more oxazoline residues, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-
Methyl-2-oxazoline, 2-isopropenyl-2-
Oxazoline, 2-isopropenyl-4-methyl-2-
Examples thereof include copolymers of polymerizable monomers such as oxazoline.

As the compound having two or more aziridine residues, 2,2-bishydroxymethylbutanol-
Tris [3- (1-aziridinyl) propionate],
2,2,2-trishydroxymethylethanol-tris [3- (1-aziridinyl) propionate] and the like can be mentioned.

Examples of polyvalent metals are zinc chloride, zinc ammonium chloride, zinc nitrate, zinc carbonate, zinc sulfate, chromic acid and its salts, dichromic acid and its salts, diisopropoxytitanium bisacetylacetone, aluminum sulfate, trisulfate. Acetyl aluminum, zirconyl nitrate, zirconyl acetate, zirconyl ammonium carbonate, potassium zirconium fluoride, ammonium zirconium fluoride and the like can be mentioned. Examples of the compound having two or more amino groups include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and heterocyclic polyamines.

As the aliphatic polyamines, ethylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, Examples include dicyandiamine and the like.

As the alicyclic polyamines, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, N-3-aminopropylcyclohexylamine,
1,4-diaminocyclohexane, bis (aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 1,4-bis (ethylamino) cyclohexane and the like can be mentioned.

Examples of the aromatic polyamines include m-xylylenediamine, p-xylylenediamine, 4- (1-aminoethyl) aniline, metaphenylenediamine and diaminodiphenylmethane.

Examples of the heterocyclic polyamines include N-aminoethylpiperazine and 1,4-bis (3-aminopropyl) piperazine. Examples of the compound having two or more carboxy groups include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic carboxylic acids and trifunctional or higher functional polycarboxylic acids.

Examples of the aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, tartaric acid, malic acid and iminodiacetic acid. Examples of the alicyclic dicarboxylic acids include maleic acid, fumaric acid, itaconic acid and the like.

Aromatic carboxylic acids include phthalic acid,
Terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,
6-naphthalenedicarboxylic acid and the like can be mentioned. Examples of trifunctional or higher polycarboxylic acids include citric acid, 1, 3, 5
-Cyclohexanetricarboxylic acid, ethylenediaminetetraacetic acid, trimellitic acid, pyromellitic acid, 3,3 ',
4,4'-benzophenone tetracarboxylic acid and the like can be mentioned.

Examples of the acid anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, citraconic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3 ', 4,4'. -Benzophenone tetracarboxylic dianhydride and the like. Examples of the compound having two or more mercapto groups include an aliphatic dimercapto compound and an aromatic dimercapto compound.

As the aliphatic dimercapto compound, 1,
Examples thereof include aliphatic dimercapto compounds such as 6-dimercaptohexane, dimercaptodiethyl ether, triglycol dimercaptan, and bis- (2-mercaptoethyl) sulfide. Examples of the aromatic dimercapto compound include 3,4-dimercaptotoluene, bis (4-mercaptophenyl) sulfide, 2,5-dimercapto-1,3,4-thiadiazole, 4-tert-butyl-1,2-benzenedithiol. , 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine, 2,4,6-trimercapto-1,3,5-triazine and the like.

Tables 1 to 3 below show examples of combinations of a curing agent with a hydroxy group and the crosslinkable functional group in the antifouling agent of the present invention.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

A curing accelerator can be used in these crosslinking reactions. For example, when a polyisocyanate compound is used as the curing agent, a tin compound or the like can be used as the curing accelerator. Examples of the tin compound include dibutyltin dilaurate, dibutyltin di (maleic acid monoester), dioctyltin dilaurate, dioctyltin di (maleic acid monoester), and dibutyltin diacetate. When an amino resin is used as the curing agent, N, N-dimethylethylsulfamate can be used. In addition, diammonium hydrogen phosphate can be used in the reaction of the oxazoline residue and the polycarboxylic acid compound.

Among the combinations of the crosslinkable functional group and the curing agent mentioned above, those which can be one-liquid room temperature crosslinkable are preferable.
Examples thereof include a combination of a carbonyl group and a polyhydrazide compound, a combination of an active methylene group and a polyamine compound, a combination of an oxazoline residue and a polycarboxylic acid compound, a combination of an oxazoline residue and a polymercaptan compound, and the like.

The amount of the curing agent blended is preferably 1 to 1000 parts by mass with respect to 100 parts by mass of the low-polluting agent. Within this range, the stain resistance, its durability and paint stability are good. It is preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass.

In the present invention, the mechanism by which the coating composition exhibits the excellent resistance to rain streak contamination is not necessarily clear, but is considered as follows. A coating film containing a low-staining agent composed of a polymer having two or more hydroxy groups is
Small octane desorption work in water. This is
It shows that even if the oily component contained in the fouling substance in the urban area once adheres to the surface of the coating film, it can be easily washed away by rain or the like, which means that the stain resistance is excellent.
Furthermore, by introducing a crosslinkable functional group other than a hydroxy group and incorporating a curing agent suitable for it, the hydrophilic component is fixed on the surface of the coating film from the initial stage and the stain resistance can be maintained for a long time.

In the case of an aqueous coating composition, if necessary, a colorant, a film-forming aid, a thickener, a plasticizer, a defoaming agent, an ultraviolet absorber, a leveling agent, an anti-cissing agent, and a skin burr prevention Additives such as agents and pigment dispersants that are usually added to aqueous paints may be mixed. Examples of the colorant include dyes, organic pigments, inorganic pigments, metallic pigments, and the like. In particular, inorganic pigments are preferable because of excellent weather resistance of the coating film.

As the film forming aid, an organic solvent which does not impair the stability of the aqueous coating composition can be used. As a specific example, dipropylene glycol mono n-butyl ether,
Monoalkyl ethers of polyhydric alcohols such as tripropylene glycol mono n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monoethyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoethyl ether monoacetate, etc. Organic acid esters of polyhydric alcohol monoalkyl ethers, 3-ethoxypropionic acid esters,
3-methoxy-3-methyl-butyl acetate and the like can be mentioned. As the plasticizer, conventionally known ones can be used, and specific examples thereof include low molecular weight plasticizers such as dioctyl phthalate and high molecular weight plasticizers such as vinyl polymer plasticizers and polyester plasticizers.

As the coating method of the coating material of the present invention, a commonly used coating method can be adopted without particular limitation, and coating with a brush or roller brush, air spray coating, coating with a curtain flow coater, coating with a roll coater, etc. can be used. Can be mentioned.

When the combination of carbonyl group and polyhydrazide compound, active methylene group and polyamine compound, oxazoline residue and polycarboxylic acid compound, oxazoline residue and polymercaptan compound is used, the coating film obtained by coating is at room temperature. And dried to obtain a cured coating film. It is possible to obtain a cured coating film by baking at a high temperature and drying in a short time both in the above crosslinking reaction and in other crosslinking reactions. The baking temperature is not particularly limited, but is preferably not higher than the heat resistant temperature of the substrate to be coated. Usually, a temperature of 250 ° C. or lower is preferable.

The coating composition using the coating composition of the present invention may be applied to a new base material or article before installation.
Moreover, you may paint after setting a base material or an article.
It is also suitable for repair painting to paint on already painted substrates and articles. Further, it is particularly suitable for coating base materials and articles used outdoors.

A coating material using the coating composition of the present invention is applied to an inorganic base material such as concrete, natural stone or glass, or a metal base material such as iron, stainless steel, aluminum, copper, brass or titanium. It can be preferably applied as an application. Also, FR
It can also be applied to organic-inorganic composite materials such as P, resin reinforced concrete and fiber reinforced concrete. Further, it can be applied to a substrate having a coating layer formed of another resin composition.

The coating composition using the coating composition of the present invention can be applied to, for example, automobiles, trains, aircrafts, bridge members, steel towers, tanks and pipes in the fields of transportation, construction, civil engineering and electric / electronics. , Building exterior panels, doors,
Industrial materials such as window materials, gates, other building materials, median strips, guardrails, other road materials, communication equipment, electric / electronic parts, etc. can be mentioned.

A coated article having a coating film formed by using the coating composition of the present invention has excellent stain resistance. In particular, it has excellent resistance to rain streaks. In the present invention, the octane desorption work calculated from the contact angle of octane in water of the coating film is 3.0 × 10 ⁻² J / m ²
Coated articles that are less than are particularly preferred. Desorption work is 2.0
A coated article having a coating film of less than × 10 ⁻² J / m ² is more preferable. The desorption work of the coating is essentially the same as the desorption work for coatings formed from the anti-staining agents described above and is defined as the "coating" replaced by the "coating". .

[0126]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples and examples, but the present invention is not limited thereto. In the following, parts and% are based on mass unless otherwise specified. The weight average molecular weight is a value measured by gel permeation chromatography using polystyrene as a standard substance. Table 4 shows the abbreviations of the compounds used in each of the following examples.

[0127]

[Table 4]

[Synthesis of Antifouling Agent] [Synthesis Example 1] 512.0 g of methanol and 83.6 g of MA were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
Chain transfer agent DSH (9.7 g) and polymerization initiator AIBN
Of 2.4 g, and stirring under a nitrogen atmosphere,
Polymerization was carried out at 0 ° C. for 18 hours. Furthermore, GA's 173.9
g, and reacted at 0.5 MPa and 100 ° C. for 3 hours,
A solution of polymer 1 having a solid content of 30% was obtained. The weight average molecular weight of the polymer 1 was 5,000. Methanol was distilled off from the solution of polymer 1 with a rotary evaporator to obtain polymer 1.

[Synthesis Example 2] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
240.0 g, MAm 24.0 g, chain transfer agent DS
9.7 g of H and 2.4 g of AIBN polymerization initiator were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 2 having a solid content of 30%. The weight average molecular weight of the polymer 2 was 5,000. Methanol was distilled off from the solution of the polymer 2 with a rotary evaporator to obtain the polymer 2.

[Synthesis Example 3] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
216.0 g, MAm 24.0 g, chain transfer agent DS
9.7 g of H and 2.4 g of AIBN polymerization initiator were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 3 having a solid content of 30%. The weight average molecular weight of the polymer 3 was 5,000. Methanol was distilled off from the solution of the polymer 3 with a rotary evaporator to obtain the polymer 3.

[Synthesis Example 4] 512.0 g of methanol, 75.2 g of MA, 24.0 g of DOAm, and chain transfer agent DSH were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
Was charged and 2.4 g of the polymerization initiator AIBN was charged, and the mixture was polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere. Furthermore, add 156.5 g of GA to 0.5
The reaction was carried out at 100 ° C. for 3 hours at MPa to obtain a solution of polymer 4 having a solid content of 30%. The weight average molecular weight of the polymer 4 is 5
It was 000. Methanol was distilled off from the solution of polymer 4 with a rotary evaporator to obtain polymer 4.

[Synthesis Example 5] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
216.0 g, DOAm 24.0 g, chain transfer agent D
9.7 g of SH and 2.4 g of AIBN polymerization initiator were charged and polymerized at 60 ° C. for 18 hours with stirring under a nitrogen atmosphere to obtain a solution of polymer 5 having a solid content of 30%. The weight average molecular weight of the polymer 5 was 5,000. Methanol was distilled off from the solution of polymer 5 with a rotary evaporator to obtain polymer 5.

[Synthesis Example 6] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
216.0 g, AAEMA 24.0 g, chain transfer agent DSH 9.7 g and polymerization initiator AIBN 2.4 g.
And stir in a nitrogen atmosphere while stirring at 60 ° C for 18
Polymerization was carried out for a time to obtain a solution of polymer 6 having a solid content of 30%.
The weight average molecular weight of the polymer 6 was 5,000. Methanol was distilled off from the solution of the polymer 6 with a rotary evaporator to obtain the polymer 6.

[Synthesis Example 7] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
216.0 g of MA, 24.0 g of MA, chain transfer agent DSH
Was added and 2.4 g of AIBN as a polymerization initiator were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 7 having a solid content of 30%. The weight average molecular weight of the polymer 7 was 5,000. Methanol was distilled off from the solution of the polymer 7 with a rotary evaporator to obtain the polymer 7.

[Synthesis Example 8] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
216.0 g, IPO 24.0 g, chain transfer agent DS
9.7 g of H and 2.4 g of AIBN polymerization initiator were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 8 having a solid content of 30%. The weight average molecular weight of the polymer 8 was 5,000. Methanol was distilled off from the solution of the polymer 8 with a rotary evaporator to obtain the polymer 8.

[Synthesis Example 9] 512.0 g of methanol and GLM were placed in an autoclave having an internal volume of 1 L equipped with a stirrer.
168.0 g, DOAm 24.0 g, PME-40
0, 48.0 g, chain transfer agent DSH 9.7 g and polymerization initiator AIBN 2.4 g were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to give a solid content of 30
% Polymer 9 solution was obtained. The weight average molecular weight of the polymer 9 was 5,000. Methanol was distilled off from the solution of the polymer 9 with a rotary evaporator to obtain the polymer 9.

[Synthesis Example 10] Internal volume of 1 L equipped with a stirrer
512.0 g of methanol, GL
168.0g of M, 24.0g of DOAm, 4 of NVP
8.0 g, chain transfer agent DSH 9.7 g and polymerization initiator AIBN 2.4 g were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 10 having a solid content of 30%. Got The weight average molecular weight of the polymer 10 was 5,000. Methanol was distilled off from the solution of the polymer 10 with a rotary evaporator to obtain the polymer 10.

[Synthesis Example 11] Internal volume of 1 L equipped with a stirrer
512.0 g of methanol, GL
168.0g of M, 24.0g of DOAm, 4 of NVA
8.0 g, chain transfer agent DSH 9.7 g and polymerization initiator AIBN 2.4 g were charged and polymerized at 60 ° C. for 18 hours with stirring under a nitrogen atmosphere to obtain a solution of polymer 11 having a solid content of 30%. Got The weight average molecular weight of the polymer 11 was 5,000. Methanol was distilled off from the solution of the polymer 11 with a rotary evaporator to obtain the polymer 11.

[Synthesis Example 12] Internal volume of 1 L equipped with a stirrer
512.0 g of methanol, GL
M 168.0, DOAm 24.0g, MMA 4
8.0 g, chain transfer agent DSH 9.7 g and polymerization initiator AIBN 2.4 g were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 12 having a solid content of 30%. Got The weight average molecular weight of the polymer 12 was 5,000. Methanol was distilled off from the solution of the polymer 12 with a rotary evaporator to obtain the polymer 12.

[Synthesis Example 13] Internal volume of 1 L equipped with a stirrer
Into the autoclave, 512.0 g of acetone, GLM
12.0g, DOAm 24.0g, MMA 20
4.0 g, chain transfer agent DSH 9.7 g and polymerization initiator AIBN 2.4 g were charged and polymerized at 60 ° C. for 18 hours while stirring under a nitrogen atmosphere to obtain a solution of polymer 13 having a solid content of 30%. Got The weight average molecular weight of the polymer 13 was 5,000. Acetone was distilled off from the solution of the polymer 13 with a rotary evaporator to obtain the polymer 13.

[Evaluation of octane elimination work of each polymer] Using the obtained polymers 1 to 13, a coating film was formed on the surface of an aluminum plate. The contact angle of octane in water to the coating was measured. Octane desorption work was determined from the measured contact angle. The results are shown in Table 5.

[0142]

[Table 5]

[Preparation of Base Paint] [Preparation Example 1: Base white paint 1] Stainless steel with stirrer
Ion exchange in a manufactured autoclave (internal volume of 200 mL)
105.3 g of water, nonionic emulsifier N-1110 (day
The present emulsifier: manufactured by N-1110. ) Of 2.0
g, 0.2 g of sodium dodecyl sulfate, ammonium persulfate
0.07 g of 25% by mass aqueous solution of potassium, potassium carbonate
0.22 g, sodium bisulfite 0.02 g, ethi
21.2g of vinyl ether, cyclohexyl vinyl
21.0 g of ether, CH_Two= CHOCH_TwoC₆H
₁₀CH_Two3.4 g of OH and CH_Two= CHOCH_Two
C₆H₁₀CH_TwoO (C_TwoH_FourO) _kH (k is the average value
It is about 15. ) Of 8.2 g, and cooled with ice,
Pressurize nitrogen gas to 0.35 MPa, then purge
The pressure was returned to 0.1 MPa.

After repeating this pressurization and purging twice, deaeration was performed to 1.3 × 10 ⁴ Pa using a vacuum pump to remove residual air, and chlorotrifluoroethylene 5 was added.
Charge 6.7 g, carry out a polymerization reaction at 30 ° C. for 12 hours,
An aqueous dispersion 1 of fluororesin 1 was obtained. The average particle diameter of the fluororesin 1 in the aqueous dispersion 1 was 140 nm, and the solid content concentration was 50% by mass.

71 parts of the above aqueous dispersion 1, film-forming auxiliary Cs
-12 (manufactured by Chisso Co.) 3.6 parts, thickener Reobis CR
(Hoechst Synthetic Co., Ltd.) 0.3 parts, titanium oxide CR-9
7 (manufactured by Ishihara Sangyo Co., Ltd.), 15.4 parts, pigment dispersant Nopcos Perth 44-C (manufactured by San Nopco) 0.8 parts, defoamer FS Antifoam 90 (manufactured by Dow Corning) 0.6 parts and Mix 10.3 parts of deionized water,
Base white paint 1 was obtained. The concentration of the fluorine-containing resin 1 in the base white paint 1 was 34.8%.

[Preparation Example 2: Base white paint 2] 15.0 g of DOAm, 50.0 g of MMA, 30.0 g of n-butyl methacrylate, 5.0 g of MA, 1.0 g of N-1110, lauryl sulfate. Pre-emulsion 1 was prepared by stirring and mixing 0.3 g of sodium and 100 g of ion-exchanged water. Then, 170 g of the aqueous dispersion 1 was charged into a glass flask having an internal volume of 300 mL, and the temperature was adjusted to 7
After warming to 0 ° C, pre-emulsion 1 30
g 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 2 of the fluoroacrylic resin 1 containing the fluororesin 1 and the (meth) acrylic acid ester-based component in a mass ratio of 17: 3 was obtained. The solid content concentration of the aqueous dispersion 2 was 50%. 71 parts of the obtained aqueous dispersion 2, 3.6 parts of Cs-12, 0.3 part of Rheobis CR, 15.4 parts of CR-97, 0.8 part of Nopcospar 44-C, FS Antifoam. 9
0.6 parts of 0 and 10.3 parts of ion-exchanged water were mixed and adjusted to pH 7.0 with aqueous ammonia to obtain base white paint 2. The concentration of the fluoroacrylic resin 1 in the base white paint 2 was 34.8%.

[Preparation Example 3: Base white paint 3] In a stainless steel autoclave (internal volume 2.5 L) equipped with a stirrer,
1100 g of ion-exchanged water, 4.75 g of fluorine-based anionic emulsifier FC-143 (Sumitomo 3M), N-1
Then, 2.2 parts of 110 and 47.0 g of tert-butyl alcohol were charged, and deaeration with a vacuum pump and pressurization with nitrogen gas were repeated. Next, 72.0 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 was 1.34 MPa. While maintaining the temperature at 70 ° C., 2 mL of a 25 mass% aqueous solution of ammonium persulfate was added to initiate polymerization. 50/25/2 of tetrafluoroethylene / propylene / ethylene with decreasing pressure
A mixed gas of 5 (mol%) was charged to maintain the pressure.
Also, 30 m of a 25 mass% aqueous solution of ammonium persulfate
L was added continuously. After 8 hours, the supply of the mixed gas was stopped, the autoclave was cooled to room temperature with water, and then the unpolymerized monomer was purged to obtain an aqueous dispersion 3 of the fluororesin 3.
The total amount of the mixed gas charged afterward was 861.5 g. The solid content concentration of the aqueous dispersion 3 was 43.1%.

A part of the aqueous dispersion 3 was placed in a centrifugal separator to allow it to settle, and then filtered through a glass filter, followed by 5 under reduced pressure.
After removing water over time, crush with a hammer mill,
A powder of fluorinated resin 3 was obtained. As a result of composition analysis by ¹³ C-NMR spectrum, the composition of the fluorine-containing resin 3 was such that the ratio of polymer units based on tetrafluoroethylene / propylene / ethylene was 52/28/20 (mol%). The melting point was 96.2 ° C.

In a glass flask having an internal volume of 300 mL,
170 g of the above aqueous dispersion 3 was charged, the inside of the flask was sufficiently replaced with nitrogen, and the temperature was raised to 70 ° C. to prepare the pre-emulsion 1
26 g was added dropwise over 1 hour. After further stirring and dispersing 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 4 of the fluoroacrylic resin 2 containing the fluororesin 3 and the (meth) acrylic acid ester-based component in a mass ratio of 17: 3 was obtained. The solid content concentration of the aqueous dispersion 4 was 43.8%.

71 parts of the resulting aqueous dispersion 4, Cs-1
2, 3.6 parts of Reobis CR, 15.4 parts of CR-97, 0.8 parts of Nopcos Perth 44-C, FS
0.6 parts of anti-foam 90 and 1 part of deionized water
0.3 part was mixed and adjusted to pH 7.0 with aqueous ammonia to obtain base white paint 3. The concentration of the fluoroacrylic resin 2 in the base white paint 3 was 30.5%.

[Examples 1 to 19] Polymers 1 to 13, PVAL, a curing agent, in the proportions shown in Table 6, Table 7 and Table 8
And, if necessary, a curing accelerator, base white paint 1 to 3
To obtain an aqueous coating composition. The pH was adjusted to 7.0 with ammonia or hydrochloric acid. 200 x 95
An aluminum plate having a size of × 8 mm was coated with the aqueous coating composition using an applicator so that the dry film thickness was 20 μm, and dried under the conditions shown in Tables 6, 7, and 8 to obtain a coated plate. Got The evaluation results of the aqueous coating composition and the coated plate are shown in Table 6, Table 7 and Table 8. Examples 1 to 15 are Examples, and Examples 16 to 19 are Comparative Examples.

The evaluation items shown in the table below were measured according to the following methods. Gloss: A specular gloss of 60 degrees was measured according to JIS Z8741. The larger the value, the better the gloss. Octane desorption work: The contact angle of octane with respect to a coating film in water was measured. Octane desorption work was determined from the measured contact angle.

Slope surface resistance: Painted plate (size: 200 ×
(95 × 8 mm) was bent at a portion of 100 mm, and the coated surface was exposed so that the upper part was at an angle of 30 degrees from the horizontal plane and the lower part was vertical, and exposed outdoors in Kawasaki City, Kanagawa Prefecture. The L * value of the 30 ° slope was measured after 3 months and 1 year of exposure of this coated plate. Difference in L * value before and after the test ΔL *
Was calculated and described as an absolute value. The L * value is SQ2
000 (manufactured by Nippon Denshoku Industries Co., Ltd.), JIS Z87
It measured according to 30. The smaller the value, the better the slope contamination resistance.

Rain streak resistance: The appearance of rain streak on the vertical surface of the outdoor exposed plate evaluated for slope pollution was evaluated. If the rain streaks were not conspicuous, the marks were marked with O, those with some conspicuity were marked with Δ, and those with conspicuous marks were marked with X. Accelerated weather resistance: The gloss retention after 4000 hours of the carbon arc lamp type accelerated weather resistance test described in JIS K5400 9.8.1 was measured. Gloss retention of 80% or more is ○,
The gloss retention rate of less than 80% was described as x.

[0157]

[Table 6]

[0158]

[Table 7]

[0159]

[Table 8]

In addition, in Examples 3 to 7 and Examples 9 to 15, those stored at 50 ° C. for 2 weeks were similarly coated and evaluated. Each coated plate was coated with the water-based coating composition before storage described in Tables 6 to 8 for physical properties such as gloss, slope stain resistance, rain line stain resistance and accelerated weathering resistance. It showed the same performance as the plate.

[0161]

EFFECTS OF THE INVENTION According to the present invention, the surface has a high gloss and is excellent in stain resistance, rain streak resistance, stain cleaning property, stain wiping property, stain release property, etc., and their sustainability. It is possible to obtain a coating composition capable of forming a coating film excellent in weatherability and excellent in weather resistance. Also, coated articles having coatings having these excellent properties are obtained.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 5/16 C09D 5/16 133/00 133/00 201/06 201/06 F term (reference) 4J038 CD091 CD111 CD121 CD132 CE052 CF032 CG001 CG142 CG172 CH122 CJ291 CR072 DA161 DB001 DD001 DG001 DL031 EA011 GA03 GA12 NA05 PC02 PC03 PC06 PC08 PC09 PC10 4J100 AE09P AE18P AG08P AL08P AM21P AN04P BA02P CA01 CA04 JA01

Claims (8)

[Claims] 1. A recurring unit (A) containing one or more recurring units (A) having two or more hydroxy groups, and optionally a recurring unit (B) other than the recurring unit (A), and the recurring unit (A). A stain-reducing agent comprising a polymer having a content ratio (A) of more than 10% (A). 2. The antifouling agent according to claim 1, wherein at least one of the repeating units (B) is a repeating unit (b1) having a crosslinkable functional group. 3. The octane desorption work calculated from the contact angle of octane in water of the coating film formed from the antifouling agent is less than 3.0 × 10 ⁻² J / m ^2. The low-polluting agent according to 1 or 2. 4. A coating composition comprising a coating resin and the antifouling agent according to any one of claims 1 to 3. 5. The coating composition according to claim 4, wherein the coating composition further contains a cross-linking agent capable of cross-linking the stain-reducing agent. 6. The coating composition according to claim 4, wherein the coating resin is a fluorine-containing resin. 7. A coated article having a coating film formed by using the coating composition according to any one of claims 4 to 6. 8. The octane desorption work calculated from the contact angle of octane in water of the coating film is 3.0 × 1.
Coated article of claim 7 which is less than 0 ^-2 J / ^{m 2.}