JP6645575B2 - Aqueous paint composition and painted article - Google Patents

Description

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

Conventionally, products such as metals, inorganics, plastics, wood, paper, leather, and fibers have been subjected to surface coating for the purpose of protecting the surface, imparting designability and functionality, and various paints have been developed. ing.
Japanese Patent No. 421257 discloses a fluorine-containing copolymer composed of 15 to 85 mol% of a fluoroolefin, 0.1 to 20 mol% of a perfluoroalkyl acrylate monomer, and 2 to 50 mol% of a hemiacetal ester. Discloses antifouling paints and varnishes.
Japanese Patent No. 4967190 discloses that 0.1 to 99% of a fluorinated monomer having a polyfluoroalkyl group, 0.1 to 80% of a non-fluorinated monomer having a ketone carbonyl group or an aldehyde carbonyl group and other An aqueous coating composition containing a fluorinated polymer obtained by copolymerizing 1 to 99% of a non-fluorinated monomer and another fluorinated polymer obtained by polymerizing a fluoroolefin is disclosed.
However, these paints have a problem that sufficient antifouling property cannot be obtained especially for oily stains.

Patent No. 421257 Patent No. 4967190

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

The present invention
(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-containing monomer (b); and (2) an aqueous medium. The present invention relates to an aqueous coating composition.
The present invention
(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-containing monomer (b); and (2) an aqueous medium. An aqueous coating composition,
The fluorine-containing monomer (a) has the formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X is a 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. ]
Is a compound represented by
An aqueous coating composition containing a non-fluorine (meth) acrylate or non-fluorine (meth) acrylamide monomer having a linear or branched hydrocarbon group having 1 to 6 carbon atoms, wherein the non-fluorine monomer (b) is I will provide a.

  The aqueous coating composition of the present invention, when coated on a substrate, imparts excellent water and oil repellency, antifouling properties and stain release properties, particularly, excellent antifouling properties and stain release properties against oily stains. it can.

The aqueous coating composition is
(1) a fluorine-containing acrylic polymer; and (2) an aqueous medium.
The aqueous coating composition further comprises:
It may include at least one of (3) a surfactant, and (4) a curing agent.
The aqueous coating composition may further contain (5) other components.

(1) Fluorinated acrylic polymer The fluorinated acrylic polymer is composed of a repeating unit derived from a fluorinated monomer (a) and a non-fluorinated monomer (b) (in particular, a non-fluorinated (meth) acrylate or a non-fluorinated (Meth) acrylamide monomer).
The fluorinated acrylic polymer forms a varnish or vehicle for the aqueous coating composition.

(A) Fluorine-containing monomer The fluorine-containing monomer is generally a polymerizable compound having a fluoroalkyl group or a fluoroalkenyl group and an acrylic acid group, a methacrylic acid group, or an α-substituted acrylic acid group. The “α-substituted acrylic acid group” means a group in which the hydrogen atom at the α-position of the acrylic acid group is substituted with a group such as Cl, Br, I, F, CN, and CF ₃ .
The fluoroalkyl group is preferably a perfluoroalkyl group, and has 1 to 20 carbon atoms. The fluoroalkenyl group is preferably a perfluoroalkenyl group, and has 2 to 6 carbon atoms.

The fluorine-containing monomer has the formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X is a 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. ]
It is a compound shown by these.

In the general formula (I) of the fluorine-containing monomer, X is a hydrogen atom. X is 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, and a CFX ¹ X ² group (where X ¹ and X ² are hydrogen Atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted May be a phenyl group.

  Y is preferably -O-.

Z is, for example, a direct bond, a linear or branched aliphatic group having 1 to 20 carbon atoms (especially, an alkylene group), for example, a formula-(CH ₂ ) _x- (where x is 1 to 10 Or a group represented by the formula —R ² (R ¹ ) N—SO ₂ — or the formula —R ² (R ¹ ) N—CO— (wherein R ¹ represents a carbon atom An alkyl group having 1 to 10 carbon atoms, and R ² is a linear alkylene group or a branched alkylene group having 1 to 10 carbon atoms) or a compound of the formula —CH ₂ CH (OR ³ ) CH ₂ — (Ar —O) _p — (wherein, R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms (eg, formyl or acetyl), Ar is an arylene group optionally having a substituent, and p is 0. or a group represented by the representative) 1 or the formula _{-CH 2 -Ar- (O) q -} . ( formula Group, represented by, Ar is an arylene group having necessary a substituent, q is 0 or _{1) -. (CH 2)} m -SO 2 - (CH 2) n - group or a - (CH _{2) m} -S- (CH _{2) n} - group (where, m is 1 to 10, n is 0, a) may be.
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or a cycloaliphatic group having 6 to 18 carbon atoms,
A —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms),
-CH ₂ CH (OZ ¹ ) CH _2- (Ph-O) _p -group (where Z ¹ is a hydrogen atom or an acetyl group, Ph is a phenylene group, p is 0 or 1),-(CH ₂ ) _n -Ph-O-group (where, Ph is a phenylene radical, n is _{0~10), -. (CH 2} ) m -SO 2 - (CH 2) n - group or - (CH _{2) m} It is preferably a —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, for example, 1 or 2 carbon atoms). Aromatic or cycloaliphatic groups can be substituted or unsubstituted. The S or SO ₂ group may be directly bonded to the Rf group.

The Rf group is preferably a perfluoroalkyl group. The number of carbon atoms of the Rf group is 1 to 20, preferably 1 to 6, more preferably 4 to 6, especially 6. Although a fluorine-containing monomer having 1 to 20 carbon atoms in the Rf group may be used, the fluorine-containing monomer may be composed of only a compound in which the Rf group has 4 to 6, particularly 6 carbon atoms. preferable. Examples of Rf _{groups, -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, a -C ₈ F ₁₇ and the like.

  In the present invention, the fluorine-containing monomer preferably does not contain a fluorine-containing olefin (for example, vinylidene fluoride). The aqueous coating composition preferably does not contain a fluorinated olefin (and a repeating unit formed from the fluorinated olefin). Preferably, the fluorinated monomer comprises only the compound of formula (I).

Specific examples of the fluorinated monomer include, for example, the following, but are not limited thereto.
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (−H) −C (= O) −O−C 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 ester having no fluorine atom or having no fluorine atom ( (Meth) acrylamide) is used.
The non-fluorine monomer contains or consists of non-fluorine (meth) acrylate or non-fluorine (meth) acrylamide monomer.
The non-fluorine (meth) acrylate or non-fluorine (meth) acrylamide monomer has a non-cyclic (linear or branched) hydrocarbon group having 1 to 6 carbon atoms.
The fluorine-containing acrylic polymer must not have a repeating unit derived from a non-fluorine (meth) acrylate or non-fluorine (meth) acrylamide monomer having a linear or branched hydrocarbon group having 7 or more carbon atoms. Is preferred. For example, it is preferable that the fluorine-containing acrylic polymer does not contain stearyl (meth) acrylate. By not having a repeating unit derived from a non-fluorine (meth) acrylate or non-fluorine (meth) acrylamide monomer having a linear or branched hydrocarbon group having 7 or more carbon atoms, a sufficiently good coating can be obtained. A film can be formed.

  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 (meth) acrylate or (meth) acrylamide having a reactive group. The reactive group is preferably an active hydrogen-containing group or an active hydrogen reactive group, for example, a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group, a carboxyl group, a ketone group, a hydrazide group and a melamine group. . The non-fluorine crosslinkable monomer is an active hydrogen-containing monomer (for example, a monomer having a hydroxyl group, an amino group, a carboxyl group, a ketone group, a hydrazide group and / or a melamine group) or a monomer containing an active hydrogen-reactive group. It is preferably a monomer (for example, a monomer having an epoxy group, a chloromethyl group, a blocked isocyanate group, a carboxyl group and / or a hydrazide group), and more preferably an active hydrogen-containing monomer. Particularly preferred reactive groups are hydroxyl groups.

The (meth) acrylate or (meth) acrylamide having a reactive group has the formula:
CH ₂ = CX ¹ -C (= O) -Y ¹ -Z ¹ -W
[In the formula, X ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom),
Y ¹ is —O— or —NH—;
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 amino group, a carboxyl group, a ketone group, a hydrazide group or a melamine group. ]
Preferably, the compound is

The (meth) acrylate or (meth) acrylamide having a hydroxyl group has the formula:
CH ₂ = CX ¹ -C (= O) -Y ¹ -Z ¹ -OH
[In the formula, X ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom),
Y ¹ is —O— or —NH—;
Z ¹ is a direct bond or a divalent organic group. ]
It is particularly preferred that the compound is
Z ¹ is, for example, a linear or branched aliphatic group having 1 to 20 carbon atoms (particularly, an alkylene group), for example, a formula — (CH ₂ ) _x — (where x is 1 to 10). ) May be used.
Examples of the non-fluorine crosslinkable monomer include N-methylol (meth) acrylamide, N-2-propanol (meth) acrylamide, N-butyrol (meth) acrylamide, hydroxyethyl (meth) acrylate, and hydroxybutyl (meth). ) Acrylate, diacetone (meth) acrylamide, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, glycidyl (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 non-crosslinkable (meth) acrylate or (meth) acrylamide monomer may include another hydrocarbon group, for example, a cyclic hydrocarbon group.

The non-fluorine non-crosslinkable (meth) acrylate or (meth) acrylamide monomer has the formula:
CH ₂ = CX ² -C (= O) -Y ² -Z ²
Wherein X ² is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom);
Y ² is —O— or —NH—;
Z ² is a hydrocarbon group. ]
Preferably, the compound is
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 ester having a linear or branched hydrocarbon group having 1 to 6 carbon atoms. For example, a non-fluorine non-crosslinkable monomer has the formula:
CH ₂ = CA ¹¹ COOA ¹²
[In the formula, A ¹¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, a chlorine atom, a bromine atom and an iodine atom),
A ¹² is a linear or branched hydrocarbon group having 1 to 6 carbon atoms. ]
May be an acrylate represented by Linear or branched hydrocarbon group having 1 to 6 carbon atoms _is preferably an alkyl group represented by _{C n H 2n + 1 (n} = 1~6).

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

The cyclic hydrocarbon group-containing (meth) acrylate ester monomer has the formula:
^{_{CH 2 = CA 21 -C (=}} O) -O-A 22
Wherein A ²¹ is a hydrogen atom or a methyl group;
A ²² is a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms. ]
It is preferable that the compound is represented by
The cyclic hydrocarbon group-containing (meth) acrylate ester monomer is a monomer having a high glass transition point of the homopolymer (for example, 50 ° C. or higher, particularly 80 ° C. or higher).

A ²¹ is particularly preferably a methyl group.
A ²² is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). Examples of the cyclic hydrocarbon group include a saturated or unsaturated monocyclic group, polycyclic group, bridged ring group, and the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group has 4 to 30 carbon atoms, and preferably 6 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 30, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and an araliphatic group having 7 to 30 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example, 12 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.

Specific examples of the cyclic hydrocarbon group-containing (meth) acrylate ester monomer include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate And 2-ethyl-2-adamantyl (meth) acrylate.
The presence of the cyclic hydrocarbon group-containing acrylate ester monomer increases the water repellency and oil repellency provided by the copolymer.

(C) Other Monomer The monomer (c) other than the monomers (a) and (b) preferably does not contain fluorine. Other monomers (c) include halogenated olefins, (meth) acrylic acid, (meth) acrylamide, ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxy polyethylene. Glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and vinyl alkyl ether are included.

  It is preferable that the halogenated olefin monomer (halogenated olefin) does not have a fluorine atom. The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted by 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of halogenated olefins are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides, such as vinylidene chloride, vinylidene bromide, vinylidene iodide. Vinyl chloride and vinylidene chloride are preferred, with vinyl chloride being particularly preferred.

  Each of the monomers (a) to (c) may be used alone or as a mixture of two or more.

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

The amount of the monomer (a) may be 0.1 to 50% by weight, preferably 5 to 30% by weight, for example, 10 to 25% by weight, based on the polymer.
The amount of the monomer (b) may be 10 to 95% by weight or more, preferably 30 to 90% by weight, for example, 50 to 85% by weight, based on the polymer.
The weight ratio of monomer (a) to monomer (b) may be from 1: 1 to 1:30, preferably from 1: 2 to 1:20, for example from 1: 3 to 1:10.
The weight ratio of the non-fluorine non-crosslinkable monomer (b1) to the non-fluorine non-crosslinkable monomer (b2) is 5:95 to 90:10, preferably 10:90 to 50:50, for example, 15:85. 40:60.
The amount of the monomer (c) may be 0 to 20% by weight, preferably 1 to 15% by weight, for example 2 to 15% by weight, based on the polymer. The amount of the carboxylic acid group-containing (meth) acrylate (for example, acrylic acid) may be 0 to 10% by weight, for example 0.5 to 8% by weight.

The amount of the fluorinated acrylic polymer (solid content) is about 0.01 to 60% by weight, preferably about 0.1 to 40% by weight, particularly preferably about 5 to 35% by weight, based on the aqueous coating composition. May be.
The fluorinated acrylic polymer may be present in the form of a solution dissolved in an organic solvent, but is preferably present in the form of an aqueous dispersion.

The weight average molecular weight of the fluorinated acrylic polymer may be from 5,000 to 500,000. The weight average molecular weight is a value determined in terms of polystyrene by gel permeation chromatography.
The fluorine-containing acrylic polymer may be a random copolymer or a block copolymer, but is preferably a random copolymer.

  The glass transition point (Tg) of the fluorinated acrylic polymer is generally -30 to 80C, preferably -20 to 50C. The glass transition point is measured by a differential scanning calorimeter (DSC) method.

  The fluorinated acrylic polymer preferably has a hydroxyl value of 2 to 200 mgKOH / g, and more preferably 4 to 100 mgKOH / g.

In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” generally means acrylamide or methacrylamide. “(Meth) acrylate” and “(meth) acrylamide” refer to a group other than a hydrogen atom and a methyl group at the α-position (for example, a monovalent organic group (for example, a hydrocarbon group having 2 to 10 carbon atoms) ) Or a halogen atom (eg, a chlorine atom and a bromine atom).
Each of the monomer (a), the monomer (b) (the monomer (b1) and the monomer (b2)), and the monomer (c) may be used alone or A combination of more than one kind may be used.

(2) Aqueous medium The aqueous coating composition comprises a fluorinated acrylic polymer and an aqueous medium. In the present specification, the term "aqueous medium" refers to a medium consisting of only water and an organic solvent in addition to water (the amount of the organic solvent is 80 parts by weight or less, for example, 0.1 to 100 parts by weight of water, 50 parts by weight, especially 5 to 30 parts by weight).
The amount of aqueous medium may be 20-99% by weight, for example 40-95% by weight, based on the aqueous coating composition.

  The aqueous medium may be added after the fluorinated acrylic polymer is produced by polymerization. For example, after a monomer is polymerized in the presence of an organic solvent to produce a fluorinated acrylic polymer, water is added and the organic solvent is distilled off. The organic solvent does not have to be distilled off. The surfactant may be added before or after the polymerization, or may not be added. Even when the surfactant is not added, an aqueous dispersion in which the fluorine-containing acrylic polymer is well dispersed in the aqueous medium can be obtained.

(3) Surfactant When the aqueous coating composition is an aqueous dispersion, it may contain a surfactant. The surfactant includes at least one of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. Further, the surfactant may include an amphoteric surfactant. In addition, a surfactant may not be contained.
The aqueous coating composition, when it is an aqueous dispersion, generally contains a surfactant. Aqueous coating compositions generally do not include surfactants when they are aqueous solutions.

The nonionic surfactant is a nonionic surfactant having an oxyalkylene group. The number of carbon atoms of the alkylene group in the oxyalkylene group is preferably 2 to 10. Generally, the number of oxyalkylene groups in the molecule of the nonionic surfactant is preferably 2 to 100.
Nonionic surfactants include alkylene oxide adducts of linear and / or branched aliphatic (saturated and / or unsaturated) groups, linear and / or branched fatty acids (saturated and / or unsaturated). Polyalkylene glycol ester, polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), alkylene oxide adduct of acetylene glycol, and the like. Among these, the structure of the alkylene oxide-added portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or POE / POP copolymer (even if it is a random copolymer or a block copolymer). May be preferable).
Further, the nonionic surfactant preferably has a structure containing no aromatic group due to environmental problems (biodegradability, environmental hormones, etc.).

  The cationic surfactant is preferably a compound having no amide group.

  The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, an alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative, an amine salt type surfactant such as imidazoline, an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, Examples include quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, and benzethonium chloride.

  Specific examples of the cationic surfactant include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl) trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Di (hydropolyoxyethylene) ammonium chloride, benzyldodecyldi (hydropolyoxyethylene) ammonium chloride, N- [2- (diethylamino) ethyl] oleamide hydrochloride are included.

Examples of the anionic surfactant include a fatty acid salt (the fatty acid has, for example, 8 to 30 carbon atoms), a sulfonate (for example, an alkyl sulfonic acid, an alkylbenzene sulfonate (the alkyl group has 8 to 30 carbon atoms, for example). 30)), and sulfate salts (for example, alkyl sulfate salts (the alkyl group has, for example, 8 to 30 carbon atoms)).
Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, polyethanol triethanolamine lauryl ether sulfate, sodium cocoyl sarcosine, Sodium N-cocoyl methyl taurine, sodium polyoxyethylene coco alkyl ether sulfate, sodium dietherhexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate and the like are included.

  Examples of the amphoteric surfactant include alanines, imidazolinium betaines, amido betaines, betaine acetate and the like.Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethyl Betaine aminoacetate, betaine fatty acid amidopropyldimethylaminoacetate and the like.

Each of the nonionic surfactant, the cationic surfactant, the anionic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more kinds.
Preferably, the surfactant is an anionic surfactant and / or a nonionic 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 based on 100 parts by weight of the monomer.
In the present invention, even when a surfactant is not used, a dispersion of a fluorine-containing acrylic polymer, particularly, an aqueous dispersion can be formed.

[Production method of fluorine-containing acrylic polymer]
The fluorine-containing acrylic polymer in the present invention can be produced by any ordinary polymerization method, and the conditions of the polymerization reaction can be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

  In the solution polymerization, a method is used in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after stirring with nitrogen, the mixture is heated and stirred at 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. No. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

  The organic solvent is one that is inert to the monomer and dissolves them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate), a ketone (for example, carbon It may be a ketone having 2 to 30 atoms, specifically, methyl ethyl ketone, diisobutyl ketone), or an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol). Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, Examples thereof include diisobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, and trichlorotrifluoroethane. The organic solvent is used in an amount of 10 to 2000 parts by weight, for example, 50 to 1000 parts by weight based on 100 parts by weight of the total of the monomers.

  In the emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen replacement, polymerization is performed by stirring at 50 to 80 ° C. for 1 to 10 hours. The polymerization initiator is benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, azo Water-soluble substances such as bisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide , T-butyl peroxypivalate, diisopropyl peroxydicarbonate and the like are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

  In order to obtain a polymer aqueous dispersion having excellent storage stability, a monomer is finely divided into water and polymerized using an emulsifying apparatus capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent that makes the monomers sufficiently compatible with each other, for example, a water-soluble organic solvent or a low molecular weight monomer. By adding a compatibilizer, emulsifiability and copolymerizability 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, and ethanol, and 1 to 50 parts by weight with respect to 100 parts by weight of water. , For example, in the range of 10 to 40 parts by weight. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like. 1 to 50 parts by weight, based on 100 parts by weight of the total amount of the monomer, For example, it may be used in the range of 10 to 40 parts by weight.

  In the polymerization, a chain transfer agent may be used. 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 include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly, alkyl mercaptans (for example, having 1 to 30 carbon atoms)), and inorganic salts such as sodium hypophosphite and sodium bisulfite. And so on. The chain transfer agent may be used in an amount of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight based on 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 (in particular, an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. The aqueous coating composition comprises a polymer (the active component of the surface treatment agent) and a medium (particularly a liquid medium, for example, an organic solvent and / or water). The amount of medium can be, for example, from 5 to 99.9% by weight, in particular from 10 to 80% by weight, based on the aqueous coating composition.
In aqueous coating compositions, the concentration of the polymer may be from 0.01 to 95% by weight, for example from 5 to 50% by weight.

It is preferable to produce the fluorinated acrylic polymer by an emulsion polymerization method or a solution polymerization method.
After the fluorinated acrylic polymer is produced by polymerization, it is preferable to add water (or an aqueous medium) to disperse the fluorinated acrylic polymer in water.
Water (or aqueous medium) may be added after the fluorinated acrylic polymer is produced by polymerization. For example, after a monomer is polymerized in the presence of an organic solvent to produce a fluorinated acrylic polymer, water is added to the polymer mixture, and the organic solvent is distilled off to form a fluorinated acrylic polymer. May be dispersed in water. The organic solvent does not have to be distilled off. 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 curing agent (active hydrogen reactive compound or active hydrogen containing compound). Generally, after producing the fluorinated acrylic polymer, the curing agent (4) is added.

(4) Curing agent The aqueous coating composition preferably contains a curing agent (crosslinking agent) so that the fluorinated acrylic polymer is cured well. Since the non-fluorine-crosslinkable (meth) acrylate or (meth) acrylamide monomer is an active hydrogen-containing monomer or an active hydrogen-reactive group-containing monomer, the fluorine-containing acrylic polymer reacts with active hydrogen or active hydrogen. It has a functional group. The curing agent is an active hydrogen reactive compound or an active hydrogen containing compound so as to react with the active hydrogen or the active hydrogen reactive group of the fluorinated 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 hydrazide compound.
Examples of active hydrogen-containing compounds are hydroxyl-containing compounds, amino-containing compounds and carboxyl-containing compounds, ketone-containing compounds, hydrazide compounds and melamine compounds.

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 acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, aromatic polyisocyanate, and derivatives of these polyisocyanates.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate of 2,6-diisocyanatomethylcaproate, and lysine ester triisocyanate, 1,4,8-triisocyanate Octane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trime Aliphatic triisocyanates such as Le-1,8-diisocyanato-5-isocyanatomethyl octane, and the like.

  Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane.

  Examples of araliphatic polyisocyanates are araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (tetramethyl Xylylene diisocyanate) or a mixture thereof, 1,3,5-triisocyanatomethylbenzene.

Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, aromatic tetraisocyanates. Specific examples of the aromatic polyisocyanate,
m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6 -Tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4 ', 4 "-triisocyanate and 4,4'-diphenylmethane-2,2', 5,5'-tetraisocyanate.

  Examples of the polyisocyanate derivative include various derivatives of the above-mentioned polyisocyanate compound, such as dimer, trimer, biuret, allophanate, carbodiimide, uretdione, uretoimine, isocyanurate, and iminooxadiazinedione.

These polyisocyanates can be used alone or in combination of two or more.
As the polyisocyanate compound, a blocked polyisocyanate compound which is a compound obtained by blocking an isocyanate group of a polyisocyanate compound with a blocking agent can also be used.

  The blocking agent blocks a free isocyanate group. When the blocked polyisocyanate compound is heated to, for example, 100 ° C. or more, preferably 130 ° C. or more, the isocyanate group is regenerated and can easily react with the hydroxyl group. Examples of the blocking agent include phenol compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and the like.

  The polyisocyanate compounds can be used alone or in combination of two or more.

The epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether.
A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene.
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.

The ketone group-containing compound is a compound having a ketone group. Examples of the ketone group-containing compound include (poly) diacetoneacrylamide, diacetone alcohol and the like.
A hydrazide compound is a compound having a hydrazide group. Examples of hydrazide compounds are hydrazine, carbohydrazide, adipic hydrazide and the like.
Examples of the melamine compound include a melamine resin and a methyl etherified melamine resin.

  In the coating composition of the present invention, the equivalent ratio (NCO / OH) of the hydroxyl group in the fluorinated acrylic polymer to the isocyanate group in the polyisocyanate compound is preferably 0.5 to 2.0, and 0.1 to 2.0. More preferably, it is 8 to 1.5.

(5) Other components The aqueous coating composition may contain another component (5) other than the above components (1) to (4). Generally, the other component (5) is added after the production of the fluorinated acrylic polymer. Examples of other components are non-fluorine water repellent compounds.

The non-fluorine water-repellent compound aqueous coating composition may contain a water-repellent compound containing no fluorine atom (non-fluorine water-repellent compound).
The non-fluorine water-repellent compound may be a non-fluorine acrylate polymer, a saturated or unsaturated hydrocarbon compound, or a silicone compound.

The non-fluorine acrylate polymer is a homopolymer composed of one kind of non-fluorine (meth) acrylate monomer, or a copolymer composed of at least two kinds of non-fluorine (meth) acrylate monomer, or A copolymer composed of at least one non-fluorine (meth) acrylate monomer and at least one other non-fluorine monomer (ethylenically unsaturated compound, for example, ethylene or vinyl monomer) is there.
The non-fluorine (meth) acrylate monomer constituting the non-fluorine acrylate polymer has a formula:
CH ₂ = CA-T
Wherein A is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (eg, 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 carbon atoms, or a chain or cyclic organic group having 1 to 31 carbon atoms having an ester bond. ]
It is a compound shown by these.

  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 cycloaliphatic group having 4 to 30 carbon atoms, and 6 to 30 carbon atoms. 30 aromatic hydrocarbon groups and araliphatic hydrocarbon groups having 7 to 30 carbon atoms.

  Examples of the chain or cyclic organic group having an ester bond and having 1 to 31 carbon atoms are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 30 carbon atoms). 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 araliphatic hydrocarbon group having 7 to 30 carbon atoms). .

  Examples of non-fluorine (meth) acrylate monomers include, for example, alkyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) Acrylates are included.

The non-fluorine (meth) acrylate monomer is preferably an alkyl (meth) acrylate ester. The number of carbon atoms in the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). Specific examples of the non-fluorine (meth) acrylate monomer are 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 compound is preferably a saturated hydrocarbon. The carbon number of the saturated or unsaturated hydrocarbon compound may be 15 or more, preferably 20 to 300, for example, 25 to 100. Specific examples of the saturated or unsaturated hydrocarbon compound include paraffin.
The silicone compound is generally used as a water repellent. The silicone compound is not limited as long as it is a compound exhibiting water repellency.
The amount of the non-fluorine water-repellent compound may be 500 parts by weight or less, for example, 5 to 200 parts by weight, particularly 5 to 100 parts by weight based on 100 parts by weight of the fluorinated acrylic polymer.

  Known pigments such as coloring pigments, extender pigments, brilliant pigments, and rust-preventive pigments can be added to the aqueous coating composition of the present invention, if necessary.

The aqueous coating composition of the present invention may further contain, if necessary, general coating additives such as a curing catalyst, an ultraviolet absorber, a light stabilizer, an antioxidant, a surface conditioner, and an antifoaming agent. It is also possible. In the present invention, it is preferable not to use a hydrazino group-containing compound.
Preferably, the aqueous coating composition does not contain any silicon atoms. Preferably, the aqueous coating composition does not contain a fluoroolefin.

  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. Usually, the aqueous coating composition is dispersed and diluted in an organic solvent or water, and is applied to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, and the like, followed by drying. Taken. If necessary, the composition may be applied together with an appropriate crosslinking agent and cured. Further, to the aqueous coating composition of the present invention, an auxiliary agent, for example, an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, a film forming auxiliary and the like are used in combination. It is also possible. The concentration of the polymer in the treatment liquid to be brought into 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.

  The objects (substrates) to be treated with the water-based paint composition (water-based paint) of the present invention include architectural wood, wall materials, concrete, plastic products, stone, glass, paper, wood, leather, fur, and asbestos. , Bricks, cements, metals and oxides, ceramic products, and plasters. Building wood, wall materials and plastic products are preferred.

  Examples of the substrate include a vehicle body such as an automobile and a motorcycle, and parts thereof. Metal base materials such as cold-rolled steel sheets, galvanized steel sheets, zinc alloy-plated steel sheets, stainless steel sheets, tin-plated steel sheets, etc., aluminum sheets, aluminum alloy sheets, etc., which form a vehicle body; various plastic base materials, etc. .

The aqueous coating composition can be applied by any of the methods known for treating coatings with liquids. The aqueous coating composition may be applied or sprayed. The treated substrate is dried and preferably heated, for example, at 60 to 120 ° C., particularly 80 ° C. in order to develop oil repellency.
The film containing the fluorinated acrylic polymer is formed on the substrate by the aqueous coating composition. The membrane is continuous and generally free of pores. The thickness of the membrane may be 0.01-5 mm, for example 0.1-3 mm.
The coated article has a substrate and a film containing a fluorinated acrylic polymer.

Next, the present invention will be specifically described with reference to Examples, Comparative Examples, and Test Examples. However, these descriptions do not limit the present invention.
In the following, parts or% represent parts by weight or% by weight, unless otherwise specified.
The characteristics were measured as follows.

The stability of the aqueous dispersion obtained by the polymer production preparation example was allowed to stand at room temperature for one week, and the stability was visually evaluated.

Antifouling test
An antifouling test was performed with reference to ASTM (American Society for Testing and Materials) D6758-00 and JG / T304-2011. Stain was applied to the sample coated PET film using an aqueous whiteboard pen (ZEBRA blue and red) and an oily marker pen (Sharpie blue and black). After 10 minutes, wiping was performed by each wiping method shown in the following table, and the degree of remaining stain was evaluated.

Water stains are wiped off with a dry cloth or paper.
Oily dirt is wiped off by the following wiping method.

The evaluation of the remaining degree of dirt is as follows.

Production Example 1
500ml reaction flask _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOCH = CH 2 (n = 2.0) (C6SFA) 15g, methyl methacrylate 28 g, butyl acrylate 22 g, hydroxyl ethyl methacrylate 27 g, Dissolve 3 g of methacrylic acid, 0.5 g of 3-chloro-2-hydroxypropyl methacrylate, and 0.5 g of glycerol methacrylate in 150 g of 2-propanol, replace the inside of the reaction flask with nitrogen, and then dissolve 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. Thereafter, the mixture was neutralized, 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 almost matched the composition of the charged monomers.

Production Example 2
A 500 ml reaction flask was charged with 150 g of pure water, 3 g of alkyl sulfonate, and 3.0 g of polyoxyethylene alkyl ether. After purging with nitrogen, a solution of 0.4 g of 2,2-azobis (2-amidinopropane) dihydrochloride and 9 g of water was added. The mixture was heated to 80 ° C., and CF ₃ CF ₂ — (CF ₂ CF ₂ ) _n —CH ₂ CH ₂ OCOCH ＝ CH ₂ (n = 2.0) (C6SFA) 5 g, methyl methacrylate 32 g, butyl acrylate 37 g , 21 g of hydroxylethyl methacrylate and 3 g of methacrylic acid were mixed and slowly added dropwise. After the completion of the dropwise addition, the reaction was carried out for 20 hours to obtain an aqueous dispersion. The solid content was adjusted to 40%, and the composition of the polymer almost matched the composition of the charged monomers.

Production Example 3
500ml reaction flask _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOCH = CH 2 (n = 2.0) (C6SFA) 15g, methyl methacrylate 25 g, butyl acrylate 22 g, hydroxyl ethyl methacrylate 27 g, 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 replacing the inside of the reaction flask with nitrogen, a solution of 0.4 g of azobisisobutyronitrile and 9 g of water was dissolved. Was added and the mixture was heated to 80 ° C. and reacted for 20 hours. Thereafter, the mixture was neutralized, 150 g of pure water was added thereto, 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 almost matched the composition of the charged monomers.

Production Example 4
500ml reaction flask _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOCH = CH 2 (n = 2.0) (C6SFA) 15g, methyl methacrylate 25 g, butyl acrylate 22 g, hydroxyl ethyl methacrylate 27 g, Dissolve 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 in 150 g of 2-propanol, and after replacing the inside of the reaction flask with nitrogen, 0.4 g of azobisisobutyronitrile And a solution of 9 g of water were added, heated to 80 ° C., and reacted for 20 hours. Thereafter, the mixture was neutralized, 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 almost matched the composition of the charged monomers.

Comparative Production Example 1
_CF 3 _CF 2 in 500ml reaction flask _{- (CF 2 CF 2) n} -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) (C6SFClA) 15g, methyl methacrylate 25 g, butyl acrylate 22 g, hydroxylethyl 27 g of methacrylate, 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 after replacing the inside of the reaction flask with nitrogen, 0.4 g of azobisisobutyronitrile and water 9 g of the solution was added, heated to 80 ° C., and reacted for 20 hours. Thereafter, the mixture was neutralized, 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 almost matched the composition of the charged monomers.

Comparative Production Example 2
500ml reaction flask _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (CH 3) = CH 2 (n = 2.0) (C6SFMA) 15g, methyl methacrylate 25 g, butyl acrylate 22 g, hydroxyl 27 g of ethyl methacrylate, 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 after replacing the inside of the reaction flask with nitrogen, 0.4 g of azobisisobutyronitrile and A solution of 9 g of water was added, heated to 80 ° C., and reacted for 20 hours. Thereafter, the mixture was neutralized, 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 almost matched the composition of the charged monomers.

Comparative Production Example 3
33 g of methyl methacrylate, 35 g of butyl acrylate, 27 g of hydroxylethyl methacrylate and 3 g of methacrylic acid were dissolved in 150 g of 2-propanol in a 500 ml reaction flask, and the inside of the reaction flask was replaced with nitrogen. The solution was added, heated to 80 ° C., and reacted for 20 hours. Thereafter, the pH 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 almost matched the composition of the charged monomers.

Example 1
A PET film (6 cm × 15 cm) was prepared, and 2 g of diethyl adipate (a film-forming auxiliary) was added to 95 g of the aqueous dispersion of the polymer obtained in Production Example 1 in which the pH was adjusted to 7 to 9, and the mixture was allowed to stand for 24 hours. After that, hexamethylene diisocyanate (HDI) -based isocyanate (isocyanate-based solidifying agent) was added so that the molar ratio NCO / OH was 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 and subjected to an evaluation test. Table 1 shows the results.

Example 2
A PET film (6 cm × 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 Production Example 2 in which the pH was adjusted to 7 to 9, and the mixture was allowed to stand for 24 hours. After this, HDI-based isocyanate (isocyanate-based solidifying agent) was added so that the molar ratio NCO / OH was 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 and subjected to an evaluation test. Table 1 shows the results.

Example 3
A PET film (6 cm × 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 Production Example 3 in which the pH was adjusted to 7 to 9, and the mixture was allowed to stand for 24 hours. After this, HDI-based isocyanate (isocyanate-based solidifying agent) was added so that the molar ratio NCO / OH was 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 and subjected to an evaluation test. Table 1 shows the results.

Example 4
A PET film (6 cm × 15 cm) was prepared, and 2 g of diethyl adipate (a film forming aid) was added to 95 g of an aqueous dispersion of the polymer obtained in Production Example 4 in which the pH was adjusted to 7 to 9, and the mixture was allowed to stand for 24 hours. After placing, 3 g of adipic dihydrazide (hydrazide-based solidifying agent) was added, 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 and subjected to an evaluation test. Table 1 shows the results.

Comparative Example 1
A PET film (6 cm × 15 cm) was prepared. Immediately after polymerization, 95 g of an aqueous dispersion of the polymer obtained in Comparative Production Example 1 was adjusted to a pH of 7 to 9, and 2 g of diethyl adipate (film forming aid) was prepared. After adding for 24 hours, HDI-based isocyanate (isocyanate-based solidifying agent) was added at a molar ratio of 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 and subjected to an evaluation test. Table 1 shows the results.

Comparative Example 2
A PET film (6 cm × 15 cm) was prepared. Immediately after polymerization, 95 g of an aqueous dispersion of the polymer obtained in Comparative Production Example 2 was adjusted to pH 7 to 9, and 2 g of diethyl adipate (film forming aid) was used. After adding for 24 hours, HDI-based isocyanate (isocyanate-based solidifying agent) was added at a molar ratio of 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 and subjected to an evaluation test. Table 1 shows the results.

Comparative Example 3
A PET film (6 cm × 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 Comparative Production Example 3 having a pH of 7 to 9 for 24 hours. After standing, HDI-based isocyanate (isocyanate-based solidifying agent) was added so that the molar ratio NCO / OH became 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 and subjected to an evaluation test. Table 1 shows the results.

The meanings of the abbreviations are as follows.

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

Claims (13)

(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-containing monomer (b); and (2) an aqueous medium. An aqueous coating composition,
The fluorine-containing monomer (a) has the formula:
CH ₂ = C (−X) −C (= O) −Y−Z−Rf (I)
[Wherein, X is a 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. ]
Is a compound represented by
The non-fluorine monomer (b) includes a combination of (b1) a non-fluorine crosslinkable monomer and (b2) a non-fluorine non-crosslinkable monomer,
The non-fluorine crosslinkable monomer (b1) has the formula:
CH ₂ = CX ¹ -C (= O) -Y ¹ -Z ¹ -OH
Wherein X ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom;
Y ¹ is —O— or —NH—;
Z ¹ is — (CH ₂ ) _x — (where x is 1 to 10). ]
Is a (meth) acrylate or (meth) acrylamide monomer having a hydroxyl group,
The non-fluorine non-crosslinkable monomer (b2) is a non-fluorine (meth) acrylate or non-fluorine (meth) acrylamide monomer having a linear or branched hydrocarbon group having 1 to 6 carbon atoms,
An aqueous coating composition wherein the amount of the fluorinated monomer (a) is 5 to 50% by weight based on the fluorinated acrylic polymer.   The aqueous coating composition according to claim 1, wherein in the fluorine-containing monomer (a), Z is a linear or branched alkylene group having 1 to 20 carbon atoms, and Rf has 1 to 6 carbon atoms. .   The aqueous coating composition according to claim 1, wherein the fluorine-containing monomer (a) does not contain a fluorine-containing olefin. The non-fluorine non-crosslinkable monomer (b2) has the formula:
CH ₂ = CA ¹¹ COOA ¹²
Wherein, A ¹¹ is a hydrogen atom, a methyl group, or a halogen atom other than fluorine atom,
A ¹² is a linear or branched hydrocarbon group having 1 to 6 carbon atoms. ]
The aqueous coating composition according to claim 3, which is an acrylate represented by the formula:   5. The fluorine-containing acrylic polymer 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. 2. The aqueous coating composition according to item 1. The aqueous coating composition is
(3) a surfactant, and (4) at least one of a curing agent,
The amount of the surfactant (3) is 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer,
The curing agent (4) is a polyisocyanate compound, and an equivalent ratio (NCO / OH) of a hydroxyl group in the fluorinated acrylic polymer to an isocyanate group in the polyisocyanate compound is 0.5 to 2.0. The aqueous coating composition according to any one of claims 1 to 5.   In the fluorinated acrylic polymer, the amount of the monomer (a) is 5 to 30% by weight based on the fluorinated acrylic polymer, and the weight ratio of the monomer (a) to the monomer (b) is Is 1: 1 to 1:30, and the amount of the fluorinated acrylic polymer (solid content) is 0.01 to 60% by weight based on the aqueous coating composition. 2. The aqueous coating composition according to item 1.   The aqueous coating composition according to any one of claims 1 to 7, comprising a water-repellent compound containing no fluorine atom.   The aqueous coating composition according to any one of claims 1 to 8, wherein the polymer containing fluorine is only the fluorine-containing acrylic polymer.   The aqueous coating composition according to any one of claims 1 to 9, wherein the aqueous coating composition does not contain a silicon atom, the aqueous coating composition does not contain a fluoroolefin, and the fluorinated acrylic polymer has no polyalkylene oxide group. Paint composition.   The method for producing an aqueous coating composition according to any one of claims 1 to 10, wherein the fluorinated acrylic polymer is produced by an emulsion polymerization method or a solution polymerization method.   The method according to claim 11, comprising adding water after producing the fluorinated acrylic polymer and dispersing the fluorinated acrylic polymer in water.   A method for producing a coated article, comprising applying the aqueous coating composition according to any one of claims 1 to 10 to an article.