TW201809170A - Aqueous coating composition and coated article - Google Patents

Abstract

The present invention provides an aqueous coating composition which comprises (1) a fluorine-containing acrylic polymer having a repeating unit derived from a fluorine-containing monomer (a), and a repeating unit derived from a non-fluorine (meth)acrylate or a (meth)acrylamide monomer (b); and (2) an aqueous medium, wherein the fluorine-containing monomer (a) is a compound represented by the formula: CH2=C(-X)-C(=O)-Y-Z-Rf (I). [In the formula, X is hydrogen atom, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms.].

Description

   Water-based coating composition and coating article   

The present invention relates to an aqueous coating composition having excellent antifouling properties and a coated article having the surface coated with the composition.

In the prior art, products such as metals, inorganics, plastics, wood, paper, leather, and fibers are surface-coated for the purpose of protecting the surface, imparting design and functionality, and developing a variety of coatings.

Japanese Patent No. 4213257 discloses an antifouling paint and varnish using a fluorinated copolymer consisting of 15 to 85 mole% of fluoroolefin and 0.1 to 20 of perfluoroalkyl acrylate monomer. Mole% and hemiacetal esters range from 2 to 50 Mole%.

Japanese Patent No. 4967190 discloses an aqueous coating composition containing: 0.1 to 99% of a fluorine-containing monomer having a polyfluoroalkyl group, 0.1 to 80% of a non-fluorine monomer having a ketocarbonyl or aldehydecarbonyl group, and other non-fluorine monomers. Fluoropolymers obtained by copolymerizing 1 to 99% of fluoromonomers; and other fluoropolymers obtained by polymerizing fluoroolefins.

However, in these coating materials, there is a problem that sufficient antifouling properties cannot be obtained especially for oily stains.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent No. 4213257

Patent Document 2: Japanese Patent No. 4967190

An object of the present invention is to provide an aqueous coating composition having excellent antifouling properties and a coated article whose surface is coated with the composition.

The present invention relates to a (1) fluorine-containing acrylic polymer having repeating units derived from a fluorine-containing monomer (a) and repeating units derived from a non-fluorine monomer (b); and (2) the aqueous property of an aqueous medium Coating composition.

The present invention provides an aqueous coating composition comprising: (1) a fluorine-containing acrylic polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a non-fluorine monomer (b); And (2) an aqueous medium, wherein the fluorine-containing monomer (a) is a compound represented by the following formula (I), and CH ₂ = C (-X) -C (= O) -YZ-Rf (I)

In the formula, X is a hydrogen atom, Y is -O- or -NH-, Z is a directly bonded or divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and the non-fluorine monomer (b) contains Non-fluorinated (meth) acrylate or non-fluorinated (meth) acrylamide monomer having a linear or branched hydrocarbon group having 1 to 6 carbon atoms.

The water-based coating composition of the present invention can provide excellent water and oil repellency, antifouling property, and detergency by being coated on a substrate, and particularly can provide excellent antifouling and detergency properties against oily dirt.

The aqueous coating composition contains (1) a fluorinated acrylic polymer, and (2) an aqueous medium.

The water-based coating composition may further contain at least one of (3) a surfactant and (4) a hardener.

The water-based paint composition may further contain (5) other components.

(1) Fluorinated acrylic polymer

The fluorinated acrylic polymer has a repeating unit derived from a fluorinated monomer (a) and a non-fluorinated monomer (b) (especially a non-fluorinated (meth) acrylate or non-fluorinated (meth) acrylamide monomer) ).

The fluoroacrylic polymer forms a varnish or paint for an aqueous coating composition.

(a) Fluoromonomer

The fluorine-containing monomer is generally a polymerizable compound having a fluoroalkyl group or a fluoroalkenyl group and an acrylic group, a methacrylic group, or an α-substituted acrylic group. The "α-substituted acrylic group" refers to a group in which the hydrogen atom at the α position of the acrylic group is substituted with a group such as Cl, Br, I, F, CN, CF ₃ or the like.

The fluoroalkyl group is preferably a perfluoroalkyl group and has a carbon number of 1 to 20. The fluoroalkenyl group is preferably a perfluoroalkenyl group and has a carbon number of 2 to 6.

The fluorine-containing monomer is a compound represented by the following formula (I), and CH ₂ = C (-X) -C (= O) -YZ-Rf (I)

[In the formula, X is a hydrogen atom, Y is -O- or -NH-, Z is a directly bonded or divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms].

In the general formula (I) of the fluorine-containing monomer, X is a hydrogen atom. X may also be a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² are Hydrogen, fluorine, chlorine, bromine or iodine), cyano, linear or branched fluoroalkyl with 1 to 21 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted Phenyl.

Y is preferably -O-.

Z may be, for example, a direct bond, a linear or branched aliphatic group (especially an alkylene group) having 1 to 20 carbon atoms, for example, a formula-(CH ₂ ) _x- (wherein, x is 1 to 10 ), Or a group represented by the formula -R ² (R ¹ ) N-SO ₂ -or a formula -R ² (R ¹ ) N-CO- (wherein R ¹ is 1 to 10 carbon atoms) Alkyl, R ² is a linear or branched alkylene group having 1 to 10 carbon atoms), or the formula -CH ₂ CH (OR ³ ) CH _2- (Ar-O) _p- (wherein, R ³ represents a hydrogen atom or a fluorenyl group having a carbon number of 1 to 10 (for example, a methyl fluorenyl group or an ethyl fluorenyl group), Ar represents an arylene group having a substituent as required, and p represents a group represented by 0 or 1) Formula -CH ₂ -Ar- (O) _q- (wherein Ar is an arylene group having a substituent as required, q is 0 or 1),-(CH ₂ ) _m -SO _2- ( CH ₂ ) _n -group or-(CH ₂ ) _m -S- (CH ₂ ) _n -group (where m is 1 to 10 and n is 0 to 10).

Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cyclic aliphatic group having 6 to 18 carbon atoms, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (wherein R ¹ is Alkyl group having 1 to 4 carbon atoms), -CH ₂ CH (OZ ¹ ) CH ₂ (Ph-O) _p -group (wherein Z ¹ is a hydrogen atom or ethenyl group, Ph is phenylene group, and p is 0 Or 1),-(CH ₂ ) _n -Ph-O- group (where Ph is phenylene and n is 0 to 10),-(CH ₂ ) _m -SO _2- (CH ₂ ) _n -group or -(CH ₂ ) _m -S- (CH ₂ ) _n -group (where m is 1 to 10 and n is 0 to 10). The aliphatic group is preferably an alkylene group (particularly, having 1 to 4 carbon atoms, such as 1 or 2). The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO ₂ group may be directly bonded to the Rf group.

The Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is 1 to 20, preferably 1 to 6, more preferably 4 to 6, and particularly preferably 6. A fluorine-containing monomer having 1 to 20 carbon atoms in the Rf group may be used, but the fluorine-containing monomer is preferably composed of only a compound having 4 to 6 carbon atoms in the Rf group, particularly 6. Examples of Rf groups are -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₂ CF (CF ₃ ) ₂ , -CF ₂ C (CF ₃ ) ₃ , -CF (CF ₃ ) CF ₂ CF ₂ CF ₃ ,-(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₃ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₄ CF (CF ₃ ) ₂ , -C ₈ F ₁₇ and so on.

In the present invention, the fluorine-containing monomer is preferably free of a fluorine-containing olefin (for example, vinylidene fluoride). The water-based coating composition preferably does not contain a fluorinated olefin (and a repeating unit composed of a fluorinated olefin). The fluorine-containing monomer is preferably composed only of a compound of formula (I).

Specific examples of the fluorine-containing monomer include, for example, the following substances, but they are not limited to these examples.

CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -Rf CH ₂ = C (-H) -C (= O) -OC ₆ H ₄ -Rf CH ₂ = C ( -H) -C (= O) -O- (CH ₂ ) ₂ N (-CH ₃ ) SO ₂ -Rf CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-C ₂ H ₅ ) SO ₂ -Rf CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH ₂ -Rf CH ₂ = C (-H) -C ( = O) -O-CH ₂ CH (-OCOCH ₃ ) CH ₂ -Rf CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -S-Rf CH ₂ = C (- H) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) ₂ -Rf

[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]

(b) Non-fluorine monomer

In the present invention, a (meth) acrylate or (meth) acrylamide monomer having no fluorine atom (that is, a (meth) acrylate having no fluorine atom or a (meth) acrylate having no fluorine atom Group) acrylamide).

The non-fluorine monomer contains or consists only of a non-fluorine (meth) acrylate or a non-fluorine (meth) acrylamide monomer.

The non-fluorinated (meth) acrylate or non-fluorinated (meth) acrylamide monomer has an acyclic (straight-chain or branched) hydrocarbon group having 1 to 6 carbon atoms.

The fluorinated acrylic polymer preferably has no repeat of a non-fluorinated (meth) acrylate or non-fluorinated (meth) acrylamide monomer derived from a linear or branched hydrocarbon group having 7 or more carbon atoms. unit. For example, the fluorinated acrylic polymer is preferably free of stearyl (meth) acrylate. By having no repeating unit derived from a non-fluorinated (meth) acrylate or non-fluorinated (meth) acrylamide monomer derived from a linear or branched hydrocarbon group having 7 or more carbon atoms, a sufficient formation can be achieved Good coating film.

The non-fluorine monomer (b) is preferably a combination of (b1) a non-fluorine crosslinkable monomer and (b2) a non-fluorine non-crosslinkable monomer.

(b1) Non-fluorine crosslinkable monomer

The non-fluorine-crosslinkable monomer is preferably a non-fluorine-crosslinkable (meth) acrylate or (meth) acrylamide monomer.

The non-fluorine-crosslinkable monomer is preferably a (meth) acrylic acid ester or (meth) acrylamide having a reactive group. The reactive group is preferably an active hydrogen-containing group or an active hydrogen-reactive group such as a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group, a keto group, a hydrazine group, and a melamine group. The non-fluorine-crosslinkable monomer is preferably an active hydrogen-containing monomer (for example, a monomer having a hydroxyl group, an amine group, a carboxyl group, a ketone group, a hydrazine group, and / or a melamine group) or an active hydrogen-containing reactive group-containing monomer. The monomer (for example, a monomer having an epoxy group, a chloromethyl group, a blocked isocyanate group, a carboxyl group, and / or a hydrazine group) is more preferably an active hydrogen-containing monomer. Particularly preferably, the reactive group is a hydroxyl group.

The (meth) acrylate or (meth) acrylamide having a reactive group is preferably a compound represented by the formula: CH ₂ = CX ¹ -C (= O) -Y ¹ -Z ¹ -W, [Formula In the above, X ¹ is a halogen atom (such as a chlorine atom, a bromine atom, and an iodine atom) other than a hydrogen atom, a methyl group, or a fluorine atom, Y ¹ is -O- or -NH-, and Z ¹ is directly bonded or divalent. An organic group, W is a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group, a keto group, a hydrazino group, or a melamine group].

The (meth) acrylate or (meth) acrylamide having a hydroxyl group is particularly preferably a compound represented by the formula: CH ₂ = CX ¹ -C (= O) -Y ¹ -Z ¹ -OH, [wherein, X ¹ is a halogen atom (such as a chlorine atom, a bromine atom, and an iodine atom) other than a hydrogen atom, a methyl group, or a fluorine atom, Y ¹ is -O- or -NH-, and Z ¹ is a directly bonded or divalent organic group ].

Z ¹ may be, for example, a linear or branched aliphatic group (especially an alkylene group) having 1 to 20 carbon atoms, for example, represented by the formula-(CH ₂ ) _x- (wherein, x is 1 to 10) Base.

Examples of the non-fluorine-crosslinkable monomer include N-hydroxymethyl (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, and N-hydroxybutyl (methyl) Acrylamide, hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, diacetone (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, (formaldehyde) (Meth) acrylic acid, 2-ethenylacetoxyethyl ester, propylene oxide (meth) acrylate, and the like.

(b2) Non-fluorine non-crosslinkable monomer

The non-fluorine non-crosslinkable monomer is preferably a non-fluorine non-crosslinkable (meth) acrylate or (meth) acrylamide monomer. The non-fluorine non-crosslinkable monomer contains or consists of a (meth) acrylate or (meth) acrylamide monomer having a linear or branched hydrocarbon group having 1 to 6 carbon atoms. The non-fluorine and non-crosslinkable (meth) acrylate or (meth) acrylamide monomer may also contain other hydrocarbon groups, such as a cyclic hydrocarbon group.

The non-fluorine and non-crosslinkable (meth) acrylate or (meth) acrylamide monomer is preferably a compound represented by the formula: CH ₂ = CX ² -C (= O) -Y ² -Z ² , [ In the formula, X ² is a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom) other than a hydrogen atom, a methyl group, or a fluorine atom, Y ² is -O- or -NH-, and Z ² is a hydrocarbon group].

Z ² may be a hydrocarbon group having 1 to 30 carbon atoms. Z ^{2 is} preferably a hydrocarbon group having 1 to 6 carbon atoms (for example, a linear or branched alkyl group).

The non-fluorine non-crosslinkable (meth) acrylate or (meth) acrylamide monomer may be a (meth) acrylate having a linear or branched hydrocarbon group having 1 to 6 carbon atoms. For example, the non-fluorine and non-crosslinkable monomer may be an acrylate represented by the formula: CH ₂ = CA ¹¹ COOA ¹² , [wherein A ¹¹ is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom (for example, a chlorine atom, Bromine atom and iodine atom), and A ¹² is a linear or branched hydrocarbon group having 1 to 6 carbon atoms].

The linear or branched hydrocarbon group having 1 to 6 carbon atoms is preferably an alkyl group represented by C _n H _{2n + 1} (n = 1 to 6).

The non-fluorine non-crosslinkable monomer (b2) may contain a (meth) acrylate monomer having a cyclic hydrocarbon group.

The cyclic hydrocarbon group-containing (meth) acrylate monomer is preferably a compound represented by the formula: CH ₂ = CA ²¹ -C (= O) -OA ²² , [wherein A ²¹ is a hydrogen atom or a methyl group, A ²² is a cyclic hydrocarbon group having 4 to 30 carbon atoms].

The cyclic hydrocarbon group-containing (meth) acrylate monomer is a monomer whose homopolymer has a high glass transition point (for example, 50 ° C. or higher, and particularly 80 ° C. or higher).

A ^{21 is} particularly preferably methyl.

A ²² may be a cyclic hydrocarbon group having a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include saturated or unsaturated, monocyclic, polycyclic, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is 4 to 30, preferably 6 to 20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 30 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and an aromatic aliphatic group having 7 to 30 carbon atoms. The number of carbon atoms in the cyclic hydrocarbon group is preferably 15 or less, and particularly preferably 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are cyclohexyl, third butylcyclohexyl, isofluorenyl, dicyclopentyl, dicyclopentenyl, and adamantyl.

Specific examples of the cyclic hydrocarbon group-containing (meth) acrylate monomer include cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, and benzyl (meth) acrylate Ester, isoamyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentene (meth) acrylate, dicyclopentyloxyethyl (meth) acrylate, (meth) acrylic acid Tricyclopentyl ester, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate Wait.

The presence of the cyclic hydrocarbon group-containing acrylate monomer improves the water and oil repellency imparted by the copolymer.

(c) Other monomers

It is preferable that the monomers (c) other than the monomers (a) and (b) do not contain fluorine. Other monomers (c) include halogenated olefins, (meth) acrylic acid, (meth) acrylamide, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, and poly (meth) acrylate. Propylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether.

The halogenated olefin monomer (halogenated olefin) preferably has no fluorine atom. The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, and particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefins are halogenated ethylene, such as vinyl chloride, vinyl bromide, and vinyl iodoethylene; and vinylidene halide, such as vinylidene chloride, vinylidene bromide, and vinylidene vinylidene. Vinyl chloride and vinylidene chloride are preferred, and vinyl chloride is particularly preferred.

The monomers (a) to (c) may be each alone or a mixture of two or more of them.

In the aqueous coating composition of the present invention, the fluorine-containing polymer is preferably only a fluorine-containing acrylic polymer. The fluorine-containing acrylic polymer preferably does not have a polyethylene oxide group, and particularly preferably does not have a polyalkylene oxide group.

The amount of the monomer (a) relative to the polymer is 0.1 to 50% by weight, preferably 5 to 30% by weight, and may be, for example, 10 to 25% by weight.

The amount of the monomer (b) relative to the polymer is 10 to 95% by weight or more, preferably 30 to 90% by weight, and may be, for example, 50 to 85% by weight.

The weight ratio of the monomer (a) to the monomer (b) is 1: 1 to 1:30, preferably 1: 2 to 1:20, and may be, for example, 1: 3 to 1:10.

The weight ratio of the non-fluorine crosslinkable monomer (b1) to the non-fluorine non-crosslinkable monomer (b2) is 5:95 to 90:10, preferably 10:90 to 50:50, and may be, for example, 15: 85 to 40: 60.

The amount of the monomer (c) relative to the polymer is 0 to 20% by weight, preferably 1 to 15% by weight, and may be 2 to 15% by weight, for example. The amount of the carboxylic acid group-containing (meth) acrylate (for example, acrylic acid) is 0 to 10% by weight, and may be 0.5 to 8% by weight, for example.

The amount of the fluorine-containing acrylic polymer (solid content) is about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, and particularly preferably about 5 to 35% by weight relative to the water-based coating composition. Amount of%.

The fluorinated acrylic polymer may exist in the form of a solution dissolved in an organic solvent, but is preferably in the form of an aqueous dispersion.

The fluorine-containing acrylic polymer may have a weight average molecular weight of 5,000 to 500,000. The weight average molecular weight is a value calculated in terms of polystyrene by gel permeation chromatography.

The fluorine-containing acrylic polymer may be a random copolymer or a block copolymer, and is preferably a random copolymer.

The glass transition point (Tg) of the fluorine-containing acrylic polymer is usually -30 to 80 ° C, preferably -20 to 50 ° C. The glass transition point can be measured by a differential scanning calorimeter (DSC) method.

The hydroxyl value of the fluorine-containing acrylic polymer is preferably 2 to 200 mgKOH / g, and more preferably 4 to 100 mgKOH / g.

In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate, and the "(meth) acrylamide" generally refers to acrylamide or methacrylamide. The "(meth) acrylate" and "(meth) acrylamide" may further include a group other than a hydrogen atom and a methyl group at the α-position (such as a monovalent organic group (such as a hydrocarbon group having 2 to 10 carbon atoms) Or halogen atom (such as chlorine atom and bromine atom)).

Each of the monomer (a), the monomer (b) (the monomer (b1) and the monomer (b2)), and the monomer (c) may be a single species or a combination of two or more species.

(2) Aqueous medium

The aqueous coating composition contains a fluorine-containing acrylic polymer and an aqueous medium. In the present specification, the "aqueous medium" refers to a medium composed of only water and an organic solvent other than water (the amount of the organic solvent is 80 parts by weight or less based on 100 parts by weight of water, for example, 0.1 to 50 parts by weight Parts, especially 5 to 30 parts by weight) of the medium.

The amount of the aqueous medium is 20 to 99% by weight relative to the aqueous coating composition, and may be 40 to 95% by weight, for example.

The aqueous medium may be added after the fluorine-containing acrylic polymer is produced by polymerization. For example, a monomer is polymerized in the presence of an organic solvent to produce a fluorinated acrylic polymer, water is then added, and the organic solvent is distilled off. The organic solvent may be removed without distillation. The surfactant may be added before or after the polymerization, or may not be added. Even without adding a surfactant, an aqueous dispersion liquid in which a fluorine-containing acrylic polymer is well dispersed in an aqueous medium can be obtained.

(3) Surfactant

When the aqueous coating composition is an aqueous dispersion, a surfactant may be contained. The surfactant includes at least one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. The surfactant may also include an amphoteric surfactant. Moreover, you may not contain a surfactant.

When the aqueous coating composition is an aqueous dispersion, a surfactant is usually contained. When the aqueous coating composition is an aqueous solution, it usually does not contain a surfactant.

The nonionic surfactant is a nonionic surfactant having an oxyalkylene group. The carbon number of the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is usually preferably 2 to 100.

Non-ionic surfactants can be linear and / or branched aliphatic (saturated and / or unsaturated) radical epoxy alkyl adducts, linear and / or branched fatty acids (saturated And / or unsaturated) polyalkylene glycol esters, polyoxyethylene (POE) / polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide alkylene glycols Adducts, etc. Among these, it is preferable that the structure of the alkylene oxide addition portion and the polyalkylene glycol portion is polyoxyethylene (POE), polyoxypropylene (POP), or POE / POP copolymer (random copolymer). , Block copolymers).

In addition, in terms of environmental problems (biodegradability, environmental hormones, etc.), the nonionic surfactant is preferably a structure that does not contain an aromatic group.

The cationic surfactant is preferably a compound which does not have an amidino group.

The cationic surfactant can be an amine salt, a quaternary ammonium salt, or an oxyethylene addition ammonium salt. Specific examples of the cationic surfactant are not particularly limited, and examples thereof include amine salt surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines, and alkyltrimethyl Grade 4 ammonium salt type surfactants such as ammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzylammonium chloride, etc. .

Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, cetyltrimethylammonium bromide, and trimethyloctadecyl chloride Ammonium, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi (hydropolyoxyethylene) ammonium chloride, benzyl Dodecyl di (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride.

Examples of the anionic surfactant include fatty acid salts (for example, the carbon number of the fatty acid is 8 to 30), sulfonates (for example, alkylsulfonic acid, and alkylbenzene sulfonate (for example, the carbon number of the alkyl group) 8 to 30)), a sulfate salt (for example, an alkyl sulfate salt (the carbon number of the alkyl group is, for example, 8 to 30).

Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene lauryl ether triethanolamine, coconut Sodium oleosinate, sodium N-cocomethyltaurate, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexylsulfosuccinate, sodium alpha-olefin sulfonate, sodium lauryl phosphate, Polyoxyethylene lauryl ether sodium phosphate and so on.

Examples of the amphoteric surfactants include alanine, imidazolinium betaine, amidobetaine, betaine acetate, and the like. Specific examples include lauryl betaine, stearyl betaine, and lauryl carboxylate. Methylhydroxyethylimidazolinium betaine, lauryl dimethylaminoacetic acid betaine, fatty amidopropyldimethylaminobetaine, and the like.

Each of the nonionic surfactant, the cationic surfactant, the anionic surfactant, and the amphoteric surfactant may be one or a combination of two or more.

The surfactant is preferably an anionic surfactant and / or a non-ionic surfactant. A combination of an anionic surfactant and a nonionic surfactant is preferred.

The surfactant may be used in a range of 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer.

In the present invention, it is possible to form a dispersion liquid of a fluorine-containing acrylic polymer without using a surfactant, particularly an aqueous dispersion liquid.

[Manufacturing method of fluorine-containing acrylic polymer]

The fluorinated acrylic polymer of the present invention can be produced by any one of ordinary polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization.

In the solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, heating and stirring in a range of 30 to 120 ° C. for 1 to 10 hours may be employed. Examples of the polymerization initiator include azobisisobutyronitrile, benzamidine peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydrogen peroxide, and neopentyl peroxide. Acid third butyl ester, diisopropyl peroxydicarbonate and the like. The amount of the polymerization initiator used is in the range of 0.01 to 20 parts by weight, for example in the range of 0.01 to 10 parts by weight, with respect to 100 parts by weight of the monomer.

Organic solvents are substances that are inert to the monomer and can dissolve them, and can be, for example, esters (for example, esters having 2 to 30 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (for example, 2 to 30 carbon atoms) Ketones, specifically methyl ethyl ketone, diisobutyl ketone), alcohols (for example, alcohols having 1 to 30 carbon atoms, specifically isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-two Alkane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloride Ethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. The amount of the organic solvent used is in a range of 10 to 2000 parts by weight, for example, in a range of 50 to 1,000 parts by weight, with respect to 100 parts by weight of the total of the monomers.

In the emulsion polymerization, a method of emulsifying a monomer in water in the presence of a polymerization initiator and an emulsifier, and stirring the polymer in a range of 50 to 80 ° C. for 1 to 10 hours after nitrogen substitution may be employed. As the polymerization initiator, benzamidine peroxide, lauryl peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropylfluorenyl peroxide, and acetamyl peroxide can be used. Oxides, azobisisobutylphosphonium-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate and other water-soluble ones or azobisisobutyronitrile, benzoyl peroxide溶, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxide and other oil-soluble ones. The amount of the polymerization initiator used is in the range of 0.01 to 10 parts by weight relative to 100 parts by weight of the monomer.

In order to obtain an aqueous polymer dispersion having excellent storage stability, it is preferable to use an emulsifying device such as a high-pressure homogenizer or an ultrasonic homogenizer which can impart a strong crushing energy, to make the monomer micronized and polymerized in water. In addition, as the emulsifier, various anionic, cationic, or nonionic emulsifiers can be used, and they can be used in a range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. In the case where the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low-molecular-weight monomer, to make these monomers sufficiently compatible. By adding a compatibilizer, emulsification and copolymerization can be improved.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, and the like. It is used in the range of, for example, 10 to 40 parts by weight. Examples of the low-molecular-weight monomer include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. 100 parts by weight can be used in a range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

A chain transfer agent can be used in the polymerization. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of the chain transfer agent are thiol group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (especially (for example, alkyl thiols having 1 to 30 carbon atoms)), sodium hypophosphite, and sodium bisulfite And other inorganic salts. The use amount of the chain transfer agent may be within a range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the monomers.

The aqueous coating composition of the present invention may be in the form of a solution, an emulsion (especially an aqueous dispersion) or an aerosol, and is preferably an aqueous dispersion. The aqueous coating composition contains a polymer (the active ingredient of the surface treatment agent) and a medium (especially a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, relative to the aqueous coating composition.

In the aqueous coating composition, the concentration of the polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

The fluorinated acrylic polymer is preferably produced by an emulsion polymerization method or a solution polymerization method.

After the fluorine-containing acrylic polymer is produced by polymerization, water (or an aqueous medium) is preferably added to disperse the fluorine-containing acrylic polymer in water.

Water (or an aqueous medium) may be added after the fluorine-containing acrylic polymer is produced by polymerization. For example, a monomer can be polymerized in the presence of an organic solvent to produce a fluorinated acrylic polymer. Then, water is added to the polymer mixture, and the organic solvent is distilled off to disperse the fluorinated acrylic polymer in water. The organic solvent may be removed without distillation. The surfactant may be added before or after the polymerization, or may not be added. Even without adding a surfactant, a good aqueous dispersion can be obtained.

The aqueous coating composition may contain (4) a hardener (active hydrogen-reactive compound or active hydrogen-containing compound). The hardener (4) is usually added after the production of the fluoroacrylic polymer.

(4) Hardener

In order to harden the fluorinated acrylic polymer well, the water-based coating composition preferably contains a curing agent (crosslinking agent). Due to the non-fluorine-crosslinkable (meth) acrylate or (meth) acrylamide monosystem containing monomers containing active hydrogen or monomers containing reactive hydrogen reactive groups, fluorine-containing acrylic polymers have active hydrogen or Active hydrogen reactive group. The hardener is an active hydrogen-reactive compound or an active hydrogen-containing compound that is intended to react with an active hydrogen or an active hydrogen-reactive group of a fluorine-containing acrylic polymer.

Examples of the active hydrogen-reactive compound are a polyisocyanate compound, an epoxy compound, a chloromethyl group-containing compound, a carboxyl group-containing compound, and a hydrazine compound.

Examples of the compound containing active hydrogen are a compound containing a hydroxyl group, a compound containing an amine group and a compound containing a carboxyl group, a compound containing a ketone group, a hydrazine compound, and a melamine compound.

The curing agent is preferably a polyisocyanate compound.

The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.

Examples of the aliphatic polyisocyanate are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene Diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, or 2,2,4-trimethylhexaene Methylene diisocyanate, aliphatic diisocyanate of 2,6-diisocyanate methylhexanoate, and lysine triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-tris Isocyanate undecane, 1,8-diisocyanate-4- isocyanate methyloctane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-di Aliphatic triisocyanate such as isocyanate-5-isocyanate methyloctane and the like.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanate and alicyclic triisocyanate. Specific examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3 , 5-triisocyanate cyclohexane.

Examples of the aromatic aliphatic polyisocyanate are aromatic aliphatic diisocyanate and aromatic aliphatic triisocyanate. Specific examples of the aromatic aliphatic polyisocyanate include 1,3- or 1,4-xylyl diisocyanate or a mixture thereof, and 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) Benzene (tetramethylxylyl diisocyanate) or a mixture thereof, 1,3,5-triisocyanate methylbenzene.

Examples of the aromatic polyisocyanate include an aromatic diisocyanate, an aromatic triisocyanate, and an aromatic tetraisocyanate. Specific examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4 '-Diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-toluene diisocyanate or mixtures thereof, triphenylmethane-4,4', 4 "-triisocyanate and 4,4'-di Phenylmethane-2,2 ', 5,5'-tetraisocyanate, etc.

Examples of the polyisocyanate derivative include the dimer, trimer, bisuret, urethanate, carbodiimide, uretdione, and uretimine of the polyisocyanate compound described above. ), Isocyanurate, imine two Various derivatives such as dione.

These polyisocyanates can be used singly or in combination of two or more kinds.

As the polyisocyanate compound, a compound obtained by blocking an isocyanate group of the polyisocyanate compound with a blocking agent, that is, a blocked polyisocyanate compound can also be used.

Blocking agents are those which block free isocyanate groups. The blocked polyisocyanate compound can be easily reacted with a hydroxyl group, for example, by regenerating the isocyanate group by heating to 100 ° C or higher, preferably 130 ° C or higher. Examples of the blocking agent include a phenol-based compound, a lactam-based compound, an aliphatic alcohol-based compound, an oxime-based compound, and the like.

Polyisocyanate compounds can be used individually or in combination of 2 or more types.

The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyalkylene oxide group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether, and sorbitol polyglycidyl ether.

The chloromethyl-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl-containing compound are chloromethyl polystyrene and the like.

The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include (poly) acrylic acid and (poly) methacrylic acid.

A keto group-containing compound is a compound having a keto group. Examples of the ketone group-containing compound are (poly) diacetone acrylamide, diacetone alcohol, and the like.

The hydrazine compound is a compound having a hydrazine group. Examples of the hydrazine compound include hydrazine, carbohydrazine, hydrazine adipate, and the like.

Examples of the melamine compound include a melamine resin, a methyl etherified melamine resin, and the like.

In the coating composition of the present invention, the equivalent ratio (NCO / OH) of the hydroxyl group in the fluorine-containing acrylic polymer to the isocyanate group in the polyisocyanate compound is preferably 0.5 to 2.0, and more preferably 0.8 to 1.5.

(5) Other ingredients

The water-based coating composition may contain components (5) other than the components (1) to (4). Other ingredients (5) are usually added after the production of the fluoroacrylic polymer. Examples of other ingredients are non-fluorine water repellent compounds.

Non-fluorine water repellent compound

The water-based paint composition may contain a water-repellent compound (non-fluorine-repellent compound) which does not contain a fluorine atom.

The non-fluorinated water-repellent compound may be a non-fluorinated acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a polysiloxane compound.

The non-fluorinated acrylate polymer is a homopolymer composed of one non-fluorinated (meth) acrylate monomer, a copolymer composed of at least two non-fluorinated (meth) acrylate monomers, or at least one A copolymer of a non-fluorine (meth) acrylate monomer and at least one other non-fluorine monomer (ethylenically unsaturated compound, for example, ethylene, vinyl-based monomer).

The non-fluorinated (meth) acrylate monomer constituting the non-fluorinated acrylate polymer is a compound represented by the formula: CH ₂ = CA-T, [wherein A is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom. (Such as a chlorine atom, a bromine atom, and an iodine atom), T is a hydrogen atom, a chain or cyclic hydrocarbon group having 1 to 30 carbons, or a chain or cyclic organic group having 1 to 31 carbons having an ester bond] .

Examples of the chain or cyclic hydrocarbon group having 1 to 30 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic aliphatic group having 4 to 30 carbon atoms, and an aromatic group having 6 to 30 carbon atoms. Group hydrocarbon group, aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms.

Examples of the chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (here, Q is a carbon number of 1 to 30) A linear or branched aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 30 carbon atoms).

Examples of the non-fluorinated (meth) acrylate monomer include, for example, alkyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxypolyethylene glycol (Meth) acrylate, methoxy polypropylene glycol (meth) acrylate.

The non-fluorinated (meth) acrylate monomer is preferably an alkyl (meth) acrylate. The number of carbon atoms of the alkyl group may be 1 to 30, such as 6 to 30 (such as 10 to 30). Specific examples of the non-fluorine (meth) acrylate monomer include lauryl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate.

The non-fluorinated acrylate polymer can be produced by the same polymerization method as the fluorinated acrylic polymer.

The saturated or unsaturated hydrocarbon-based compound is preferably a saturated hydrocarbon. In the saturated or unsaturated hydrocarbon-based compound, the carbon number may be 15 or more, preferably 20 to 300, for example, 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon-based compound include paraffin and the like.

Polysiloxanes are usually used as water repellent users. The polysiloxane compound is not limited as long as it is a compound that exhibits water repellency.

The amount of the non-fluorinated water repellent compound may be 500 parts by weight or less, such as 5 to 200 parts by weight, and particularly 5 to 100 parts by weight, with respect to 100 parts by weight of the fluorinated acrylic polymer.

In the water-based coating composition of the present invention, known pigments such as color pigments, extender pigments, bright pigments, and rust preventive pigments can be blended as necessary.

In addition, the water-based coating composition of the present invention may be compounded with ordinary coating additives such as a hardening catalyst, an ultraviolet absorber, a light stabilizer, an antioxidant, a surface conditioner, and an antifoaming agent as necessary. In the present invention, it is preferable not to use a compound containing a hydrazine group.

The water-based coating composition is preferably free of silicon atoms. The water-based coating composition is preferably a fluorine-free olefin.

The aqueous coating composition of the present invention can be applied to an object to be treated (that is, an article) by a conventionally known method. Generally, the aqueous coating composition can be diluted by dispersing it in an organic solvent or water, and adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, and the like. Drying method. In addition, if necessary, it can be applied together with a suitable cross-linking agent for curing. Auxiliaries such as insect repellents, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixatives, anti-wrinkle agents, and film-forming aids can also be added to the aqueous coating composition of the present invention in combination. The concentration of the polymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.

Examples of the object (substrate) to be treated with the aqueous coating composition (water-based coating) of the present invention include construction wood, wall materials, concrete, plastic products, stone, glass, paper, tree, leather, and fur. , Asbestos, brick, cement, metals and oxides, ceramics and plaster. Preferred are construction wood, wall materials and plastic products.

Examples of the base material include car bodies such as automobiles and two-wheeled vehicles, and parts thereof. Metal substrates such as cold-rolled steel plates, galvanized steel plates, galvanized steel plates, stainless steel plates, tin-plated steel plates, aluminum plates, aluminum alloy plates, and various plastic substrates that form car bodies and the like.

The aqueous coating composition can be applied by any method known for treating a coating liquid. The water-based coating composition can be attached or sprayed. In order to show the oil repellency, the substrate to be treated is preferably dried at, for example, 60 to 120 ° C, and particularly 80 ° C.

A film containing a fluorine-containing acrylic polymer is formed on a substrate using an aqueous coating composition. The membrane is continuous and usually has no pores. The thickness of the film may be 0.01 to 5 mm, such as 0.1 to 3 mm.

The coated article has a substrate and a film containing a fluorine-containing acrylic polymer.

    [Example]    

Hereinafter, the present invention will be specifically described using examples, comparative examples, and test examples. However, these descriptions do not limit the inventor.

In the following, unless otherwise specified, parts or% means parts by weight or% by weight.

The characteristics are measured as follows.

Polymer stability

The aqueous dispersion obtained in the production example was left to stand at room temperature for one week, and the stability was evaluated visually.

Antifouling test

Refer to ASTM (American Society for Testing and Materials: D6758-00 and JG / T304-2011 for antifouling tests). On the PET film coated with the sample, dirt was attached using a water-based whiteboard pen (ZEBRA blue and red) and an oily marker pen (Sharpie blue and black). After 10 minutes, wipe with various wiping methods in the following table to evaluate the residual condition of dirt.

Water-based dirt is wiped with a dry cloth or paper.

Oily dirt is wiped with the following wiping method.

The evaluation of the residual condition of the dirt is as follows.

Manufacturing example 1

In a 500 ml reaction flask, CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH = CH ₂ (n = 2.0) (C6SFA) 15 g, methyl methacrylate 28 g, butyl acrylate 22 g, 27 g of hydroxyethyl acrylate, 3 g of methacrylic acid, 0.5 g of 3-chloro-2-hydroxypropyl methacrylate, and 0.5 g of glycerol methacrylate were dissolved in 150 g of 2-propanol, and nitrogen was substituted in the reaction flask. Then, a solution of 0.4 g of azobisisobutyronitrile and 9 g of water was added, and the mixture was heated to 80 ° C. and reacted for 20 hours. Then, neutralization was performed, 150 g of pure water was added, and 2-propanol was distilled off at 60 ° C. with stirring to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Manufacturing example 2

In a 500 ml reaction flask, 150 g of pure water, 3 g of alkyl sulfonate, and 3.0 g of polyoxyethylene alkyl ether were added. After nitrogen substitution, 2,2-azobis (2-fluorenylpropane) dihydrochloride 0.4 was added. g and 9 g of water, heated to 80 ° C, mixed with CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH = CH ₂ (n = 2.0) (C6SFA) 5 g, 32 g of methyl methacrylate, 37 g of butyl acrylate, 21 g of hydroxyethyl acrylate, and 3 g of methacrylic acid. After completion of the dropwise addition, the mixture was allowed to react for 20 hours to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Manufacturing example 3

In a 500 ml reaction flask, CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH = CH ₂ (n = 2.0) (C6SFA) 15 g, methyl methacrylate 25 g, butyl acrylate 22 g, 27 g of hydroxyethyl acrylate, 5 g of methacrylic acid, 0.5 g of 3-chloro-2-hydroxypropyl methacrylate, and 0.5 g of glycerol methacrylate were dissolved in 150 g of 2-propanol, and nitrogen was substituted in the reaction flask. Then, a solution of 0.4 g of azobisisobutyronitrile and 9 g of water was added, and the mixture was heated to 80 ° C. and reacted for 20 hours. Then, neutralization was performed, 150 g of pure water was added, and 2-propanol was distilled off at 60 ° C. with stirring to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Manufacturing Example 4

In a 500 ml reaction flask, CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH = CH ₂ (n = 2.0) (C6SFA) 15 g, methyl methacrylate 25 g, butyl acrylate 22 g, 27 g of hydroxyethyl acrylate, 5 g of methacrylic acid, 3 g of diacetone acrylamide, 0.5 g of 3-chloro-2-hydroxypropyl methacrylate, and 0.5 g of glycerol methacrylate are dissolved in 150 g of 2-propanol. After the inside of the reaction flask was replaced with nitrogen, a solution of 0.4 g of azobisisobutyronitrile and 9 g of water was added, and the mixture was heated to 80 ° C. and allowed to react for 20 hours. Then, neutralization was performed, 150 g of pure water was added, and 2-propanol was distilled off at 60 ° C. with stirring to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Comparative Manufacturing Example 1

In a 500 ml reaction flask, 15 g of CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (C6SFClA), 25 g of methyl methacrylate, and butyl acrylate 22 g of ester, 27 g of hydroxyethyl acrylate, 5 g of methacrylic acid, 0.5 g of 3-chloro-2-hydroxypropyl methacrylate, and 0.5 g of glycerol methacrylate were dissolved in 150 g of 2-propanol. After nitrogen substitution, a solution of 0.4 g of azobisisobutyronitrile and 9 g of water was added, and the mixture was heated to 80 ° C. and allowed to react for 20 hours. Then, neutralization was performed, 150 g of pure water was added, and 2-propanol was distilled off at 60 ° C. with stirring to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Comparative Manufacturing Example 2

In a 500 ml reaction flask, CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ (n = 2.0) (C6SFMA) 15 g, methyl methacrylate 25 g, acrylic acid 22 g of butyl ester, 27 g of hydroxyethyl acrylate, 5 g of methacrylic acid, 0.5 g of 3-chloro-2-hydroxypropyl methacrylate, and 0.5 g of glycerol methacrylate were dissolved in 150 g of 2-propanol. After nitrogen substitution was performed inside, a solution of 0.4 g of azobisisobutyronitrile and 9 g of water was added, and the mixture was heated to 80 ° C. and allowed to react for 20 hours. Then, neutralization was performed, 150 g of pure water was added, and 2-propanol was distilled off at 60 ° C. with stirring to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Comparative Manufacturing Example 3

In a 500 ml reaction flask, 33 g of methyl methacrylate, 35 g of butyl acrylate, 27 g of hydroxyethyl acrylate, and 3 g of methacrylic acid were dissolved in 150 g of 2-propanol. After replacing nitrogen in the reaction flask, azo was added. A solution of 0.4 g of diisobutyronitrile and 9 g of water was heated to 80 ° C. and allowed to react for 20 hours. Then, it was adjusted to pH 7 with triethylamine. 150 g of pure water, 3 g of alkyl sulfonate, and 3.0 g of polyoxyethylene alkyl ether were added, and 2-propanol was distilled off at 60 ° C. with stirring to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer was basically the same as the composition of the charged monomer.

Example 1

A PET film (6 cm x 15 cm) was prepared, and 2 g of diethyl adipate (film-forming aid) was added to 95 g of the aqueous dispersion of the polymer obtained in Production Example 1 whose pH was adjusted to 7 to 9, and left to stand for 24 After 6 hours, hexamethylene diisocyanate (HDI) -based isocyanate (isocyanate-based hardener) was added so that the molar ratio was NCO / OH = 1.05, and a smooth transparent film was coated on the PET film using a coating rod. . The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

Example 2

A PET film (6 cm x 15 cm) was prepared, and 2 g of diethyl adipate (film-forming aid) was added to 95 g of the aqueous dispersion of the polymer obtained in Production Example 2 whose pH was adjusted to 7 to 9, and allowed to stand for 24 hours. After an hour, HDI-based isocyanate (isocyanate-based hardener) was added so that the molar ratio was NCO / OH = 1.05, and a smooth transparent film was coated on the PET film using a coating bar. The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

Example 3

A PET film (6 cm x 15 cm) was prepared, and 2 g of diethyl adipate (film-forming aid) was added to 95 g of the aqueous dispersion of the polymer obtained in Production Example 3 whose pH was adjusted to 7 to 9, and left to stand for 24 After an hour, HDI-based isocyanate (isocyanate-based hardener) was added so that the molar ratio was NCO / OH = 1.05, and a smooth transparent film was coated on the PET film using a coating bar. The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

Example 4

A PET film (6 cm x 15 cm) was prepared, and 2 g of diethyl adipate (film-forming aid) was added to 95 g of the aqueous dispersion of the polymer obtained in Production Example 4 whose pH was adjusted to 7 to 9, and allowed to stand for 24 hours. After 3 hours, 3 g of dihydrazine adipate (hydrazine-based hardener) was added, and a smooth transparent film was coated on the PET film using a coating bar. The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

Comparative Example 1

Prepare a PET film (6 cm x 15 cm), adjust 95 g of the aqueous dispersion of the polymer obtained in Comparative Manufacturing Example 1 immediately after polymerization to pH 7 to 9, and add 2 g of diethyl adipate (film-forming aid) After standing for 24 hours, HDI-based isocyanate (isocyanate-based hardener) was added so that the molar ratio became NCO / OH = 1.05, and a smooth transparent film was coated on the PET film using a coating bar. The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

Comparative Example 2

A PET film (6 cm x 15 cm) was prepared, 95 g of the aqueous dispersion of the polymer obtained in Comparative Production Example 2 immediately after polymerization was adjusted to pH 7 to 9, and 2 g of diethyl adipate (film-forming aid) was added. After standing for 24 hours, HDI-based isocyanate (isocyanate-based hardener) was added so that the molar ratio was NCO / OH = 1.05, and a smooth transparent film was coated on the PET film using a coating bar. The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

Comparative Example 3

A PET film (6 cm x 15 cm) was prepared, and 2 g of diethyl adipate (film-forming aid) was added to 95 g of an aqueous dispersion of the polymer obtained in Comparative Production Example 3 whose pH was adjusted to 7 to 9, and allowed to stand. After 24 hours, HDI-based isocyanate (isocyanate-based hardener) was added so that the molar ratio was NCO / OH = 1.05, and a smooth transparent film was coated on the PET film using a coating bar. The coated PET film was cured at 80 ° C. for 3 hours or naturally dried at room temperature for 7 days for evaluation tests. The results are shown in Table 1.

The meanings of the abbreviations are as follows.

    [Industrial availability]    

The water-based coating composition of the present invention can be used as a coating for covering, for example, wood for construction, wall materials, and plastic products.

Claims (14)

An aqueous coating composition comprising: (1) a fluorine-containing acrylic polymer having a repeating unit derived from a fluorine-containing monomer (a) and a repeating unit derived from a non-fluorine monomer (b); and (2) An aqueous medium in which the fluorine-containing monomer (a) is a compound represented by the following formula (I), and CH ₂ = C (-X) -C (= O) -YZ-Rf (I) where X is hydrogen Atom, Y is -O- or -NH-, Z is a directly bonded or divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and the non-fluorine monomer (b) has a carbon number of 1 to 6 Non-fluorinated (meth) acrylic acid ester or non-fluorinated (meth) acrylamide monomer.     The water-based coating composition according to item 1 of the scope of patent application, wherein in the fluorine-containing monomer (a), Z is a linear or branched alkylene group having 1 to 20 carbon atoms, and Rf's The carbon number is 1 to 6.         The water-based coating composition according to item 1 or 2 of the scope of patent application, wherein the fluorine-containing monomer (a) does not contain a fluorine-containing olefin.         The water-based coating composition according to any one of claims 1 to 3, wherein the non-fluorine monomer (b) contains (b1) a non-fluorine crosslinkable monomer and (b2) a non-fluorine non-crosslinkable The non-fluorine crosslinkable monomer (b1) and the non-fluorine non-crosslinkable monomer (b2) are non-fluorine (meth) acrylate or (meth) acrylamide monomers.     The water-based coating composition according to item 4 of the scope of patent application, wherein the non-fluorine-crosslinkable monomer (b1) is a formula: CH ₂ = CX ¹ -C (= O) -Y ¹ -Z ¹ -W In the formula, X ¹ is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom, such as a chlorine atom, a bromine atom, and an iodine atom, Y ¹ is -O- or -NH-, and Z ¹ is a direct bond. Or a divalent organic group, W is a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group, a hydrazine group, or a melamine group; the non-fluorine and non-crosslinkable monomer (b2) has the formula: CH ₂ = acrylate represented by CA ¹¹ COOA ¹² , where A ¹¹ is a halogen atom other than a hydrogen atom, a methyl group, or a fluorine atom, such as a chlorine atom, a bromine atom, and an iodine atom, and A ¹² is a carbon number of 1 to 6 Linear or branched hydrocarbon group. The water-based coating composition according to any one of claims 1 to 5, wherein Z ¹ is a linear or branched alkylene group having 1 to 20 carbon atoms, W is a hydroxyl group, and contains fluorine The acrylic polymer system does not have a repeating unit derived from a non-fluorine (meth) acrylate or (meth) acrylamide monomer having a linear or branched hydrocarbon group having 7 or more carbon atoms.     The water-based coating composition according to any one of claims 1 to 6, wherein the water-based coating composition contains at least one of (3) a surfactant and (4) a hardener, with respect to 100 of the monomer. Parts by weight, the amount of the surfactant (3) is 0.5 to 20 parts by weight, the hardener (4) is a polyisocyanate compound, and the equivalent ratio of hydroxyl groups in the fluoroacrylic polymer to isocyanate groups in the polyisocyanate compound (NCO / OH) is 0.5 to 2.0.         The water-based coating composition according to any one of claims 1 to 7, wherein the amount of the monomer (a) in the fluorine-containing acrylic polymer is 0.1 to 50% by weight based on the polymer, and The weight ratio of the body (a) to the monomer (b) is 1: 1 to 1:30, and the amount of the fluorine-containing acrylic polymer (solid content) is 0.01 to 60% by weight based on the aqueous coating composition.         The water-based coating composition according to any one of claims 1 to 8 of the patent application scope, which contains a water-repellent compound containing no fluorine atom.         The water-based coating composition according to any one of claims 1 to 9, wherein the fluorine-containing polymer is only the aforementioned fluorine-containing acrylic polymer.         The water-based coating composition according to any one of claims 1 to 10, wherein the water-based coating composition contains no silicon atom, the water-based coating composition contains no fluoroolefin, and the fluorinated acrylic polymer does not have a polymer. Alkylene oxide.         A method for producing an aqueous coating composition according to any one of claims 1 to 11 of the scope of application for a patent, which comprises producing a fluorine-containing acrylic polymer by an emulsion polymerization method or a solution polymerization method.         The manufacturing method according to item 12 of the scope of patent application, comprising the step of adding water to disperse the fluorinated acrylic polymer in water after the fluorinated acrylic polymer is manufactured.         A method for manufacturing a coated article, comprising applying the water-based coating composition according to any one of claims 1 to 11 on the article.