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WO2018194068A1 - Aqueous dispersion liquid, aqueous coating material, and coated article - Google Patents

Aqueous dispersion liquid, aqueous coating material, and coated article Download PDF

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Publication number
WO2018194068A1
WO2018194068A1 PCT/JP2018/015905 JP2018015905W WO2018194068A1 WO 2018194068 A1 WO2018194068 A1 WO 2018194068A1 JP 2018015905 W JP2018015905 W JP 2018015905W WO 2018194068 A1 WO2018194068 A1 WO 2018194068A1
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WIPO (PCT)
Prior art keywords
aqueous dispersion
fluoropolymer
group
formula
water
Prior art date
Application number
PCT/JP2018/015905
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French (fr)
Japanese (ja)
Inventor
俊 齋藤
健 守角
Original Assignee
Ａｇｃ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to CN201880025782.0A priority Critical patent/CN110520472B/en
Priority to JP2019513657A priority patent/JPWO2018194068A1/en
Publication of WO2018194068A1 publication Critical patent/WO2018194068A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to an aqueous dispersion containing a fluoropolymer, an aqueous paint, and a coated article.
  • Patent Document 1 discloses an aqueous paint containing an aqueous dispersion containing a fluoropolymer containing units based on fluoroethylene and units based on a monomer having a polyoxyalkylene group.
  • An aqueous dispersion is required to have excellent storage stability.
  • the physical properties required of a coating film formed using an aqueous coating material containing an aqueous dispersion have been further improved, and water repellency (particularly, dynamics that serve as a standard for water attached to the coating film to slide down).
  • a coating film excellent in water repellency is demanded.
  • the present inventors have found that the aqueous dispersion described in Patent Document 1 has good storage stability, but the water repellency of a coating film formed using an aqueous paint containing the aqueous dispersion is insufficient. I found out.
  • the present invention has an object to provide an aqueous dispersion, an aqueous coating material, and a coated article that can form a coating film excellent in water repellency and is excellent in storage stability.
  • the inventors of the present invention include a specific amount of a unit based on a monomer represented by the formula X 1 -Y 1 -Z 1 described below, and CF 3 —CH ⁇ CHF and CF 3 —. It has been found that a desired effect can be obtained by using a fluoropolymer containing a unit based on at least one selected from the group consisting of CF ⁇ CH 2 , and the present invention has been achieved. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the symbols in the formula have the following meanings.
  • X 1 and X 2 are each independently CH 2 ⁇ CHC (O) O—, CH 2 ⁇ C (CH 3 ) C (O) O—, CH 2 ⁇ CHOC (O) —, CH 2 ⁇ CHCH 2 OC (O) —, CH 2 ⁇ CHO— or CH 2 ⁇ CHCH 2 O—.
  • Y 1 is a divalent linking group.
  • Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 .
  • M 1 is an alkylene group having 2 to 4 carbon atoms
  • m is an integer of 6 ⁇ 24
  • L 1 is hydrogen atom, alkyl group of 4 or less, or the formula -SO 3 carbon - represented by A + (Wherein A + is NH 4 + , Na + or K + ), and R 1 is an alkyl group having 1 to 20 carbon atoms.
  • Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms.
  • the group represented by the formula —O (M 1 O) m L 1 is a group represented by the formula —O (CH 2 CH 2 O) m H; The aqueous dispersion according to any one of the above.
  • the content of the unit based on the monomer represented by the formula X 2 -Z 2 is 10 to 50 mol% with respect to the total units contained in the fluoropolymer, The aqueous dispersion according to any one of the above.
  • the fluoropolymer further includes a (meth) acrylate polymer, The aqueous dispersion according to any one of [1] to [9], wherein the fluoropolymer and the (meth) acrylate polymer are core-shell polymers having the fluoropolymer as a core portion and the (meth) acrylate polymer as a shell portion. liquid.
  • a coating film excellent in water repellency (particularly, dynamic water repellency that is a measure for water adhering to the coating to slide down, the same shall apply hereinafter) can be formed, and storage stability can be formed. It is possible to provide an aqueous dispersion, an aqueous coating material, and a coated article excellent in the above.
  • (Meth) acrylate is a general term for “acrylate” and “methacrylate”.
  • the “unit” is a general term for an atomic group derived directly from monomer polymerization and derived from one molecule of the monomer, and an atomic group obtained by chemically converting a part of the atomic group. The content (mol%) of each unit with respect to all units contained in the polymer is obtained by analyzing the polymer by a nuclear magnetic resonance spectrum method, and can be estimated from the charged amount of monomer.
  • “Average particle diameter” is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.).
  • D50 is a particle diameter value of 50 volume% of the cumulative volume calculated from the small particle side in the particle size distribution of the particle measured by the dynamic light scattering method.
  • “Number average molecular weight” is a value measured by gel permeation chromatography using polystyrene as a standard substance. “Number average molecular weight” is also referred to as “Mn”.
  • “Hydroxyl value” is a value measured according to the method of JIS K1557-1 (2007).
  • the “acid value” is a value measured according to the method of JIS K 0070-3 (1992).
  • “Film thickness” is a value measured using an eddy current film thickness meter (trade name “EDY-5000”, manufactured by Sanko Electronics Co., Ltd.).
  • a unit (hereinafter also referred to as “unit F”) based on at least one kind (hereinafter also referred to as “monomer F”), a monomer represented by the formula X 1 -Y 1 -Z 1 (hereinafter referred to as “monomer 1”).
  • a unit based on a monomer represented by the formula X 2 -Z 2 hereinafter also referred to as “monomer 2” (hereinafter referred to as “unit 1”).
  • unit 2 Also referred to as “unit 2”).
  • the content of the unit 1 is 1 to 5 mol% with respect to all units contained in the fluoropolymer.
  • the fluoropolymer is dispersed in water means a state in which the fluoropolymer is dispersed in water as particles.
  • aqueous coating material containing a fluoropolymer containing units based on fluoroethylene for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene
  • fluoroethylene for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene
  • a method of introducing a unit (for example, unit F) based on a monomer having a —CF 3 group such as fluoropropylene into the fluoropolymer can be considered. If the fluoropolymer has —CF 3 groups, it is presumed that —CF 3 groups are arranged on the surface of the coating film to improve the water repellency of the coating film.
  • the fluoropolymer contains the unit F
  • the water dispersibility of the fluoropolymer is lowered, and the storage stability of the aqueous dispersion containing the fluoropolymer is lowered.
  • the water repellency of the coating film and the storage stability of the aqueous dispersion were in a trade-off relationship.
  • the present inventors have obtained an aqueous dispersion excellent in storage stability of an aqueous dispersion by including a specific amount of unit 1 in a fluoropolymer containing units F among units based on fluoropropylene.
  • the water repellency of the coating film formed using an aqueous paint containing this aqueous dispersion was excellent. This is because when monomer F is used among fluoropropylenes, monomer F is well copolymerized with monomer 1, and the hydrophilicity imparted by unit 1 and the water repellency imparted by unit F are balanced. Conceivable. This effect is particularly prominent within the preferred range of the present invention.
  • the coating film formed from the aqueous coating material containing the aqueous dispersion of this invention is also called “this coating film.”
  • the proportion of units based on CF 3 —CF ⁇ CH 2 with respect to the total of both units is preferably 10 to 90 mol%, more preferably 60 to 85 mol%.
  • the content of unit F is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, based on all units contained in the fluoropolymer. If the content of the unit F is 20 mol% or more, the water repellency of the coating film is further improved. When the content of the unit F is 80 mol% or less, the storage stability of the aqueous dispersion is more excellent.
  • the unit 1 contained in the fluoropolymer in the present invention is a unit based on a monomer represented by the formula X 1 -Y 1 -Z 1 .
  • Unit 1 contributes to the improvement of the water dispersibility of the fluoropolymer and improves the storage stability of the aqueous dispersion.
  • the symbols in the formula have the following meanings.
  • Y 1 is a divalent linking group.
  • the divalent linking group is preferably a divalent saturated hydrocarbon group having 2 to 12 carbon atoms.
  • the divalent saturated hydrocarbon group may be linear or branched. Moreover, the divalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure.
  • Z 1 is a group represented by the formula —C (O) OR 1
  • the divalent saturated hydrocarbon group may have a group represented by the formula —SO 3 ⁇ A +. May have an etheric oxygen atom.
  • a + is NH 4 + , Na + or K + .
  • the divalent saturated hydrocarbon group is preferably an alkylene group containing an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
  • Examples of the divalent saturated hydrocarbon group include a group represented by the formula —CH 2 —cycloC 6 H 10 —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 — and a formula —CH.
  • a group represented by 2 CH (Y 11 ) — is preferred.
  • -CycloC 6 H 10 representss a cyclohexylene group, and the bonding site of (-cycloC 6 H 10- ) is not particularly limited, and is usually 1,4-.
  • Y 11 represents an alkyl group having 1 to 10 carbon atoms.
  • Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 , and the formula —O (M 1 O) m L 1 It is preferable that it is group represented by these.
  • M 1 is an alkylene group having 2 to 4 carbon atoms, preferably —CH 2 CH 2 —. When M 1 has 3 or 4 carbon atoms, M 1 may be a linear alkylene group or a branched alkylene group.
  • m is an integer of 6 to 24, and an integer of 10 to 20 is more preferable.
  • L 1 is a hydrogen atom, an alkyl group having 4 or less carbon atoms, or a group represented by the formula —SO 3 ⁇ A + .
  • a + is NH 4 + , Na + or K + .
  • R 1 is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 8 to 15 carbon atoms. The alkyl group may be linear or branched. It is preferable that at least a part of m 1 M 1 is an alkylene group having 2 carbon atoms (CH 2 CH 2 ). When a part of M 1 is an alkylene group having 3 or 4 carbon atoms, m The number of alkylene groups having 2 carbon atoms with respect to M 1 is preferably 50% or more, and more preferably 80% or more. When two or more types of (M 1 O) are present, their bonding order may be random or block.
  • L 1 is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and the alkyl group having 4 or less carbon atoms is preferably a methyl group. L 1 is particularly preferably a hydrogen atom.
  • Monomer 1 may use 2 or more types together.
  • the content of unit 1 is 1 to 5 mol%, preferably 1.0 to 5.0 mol%, based on the total units of the fluoropolymer, from the viewpoint of storage stability of the aqueous dispersion. More than 0 mol% and less than 3.5 mol% is more preferable, and 1.2 mol% to 3.0 mol% is particularly preferable.
  • the unit 2 contained in the fluoropolymer in the present invention is a unit based on a monomer represented by the formula X 2 -Z 2 .
  • X 2 includes CH 2 ⁇ CHOC (O) —, CH 2 ⁇ CHCH 2 OC (O) —, CH 2 ⁇ CHO— and CH 2 ⁇ CHCH 2 O—.
  • CH 2 ⁇ CHOC (O) — and CH 2 ⁇ CHCH 2 OC (O) — are particularly preferred.
  • X 2 is CH 2 ⁇ CHOC (O) — or CH 2 ⁇ CHCH 2 OC (O) —, it is considered that the charging of the fluoropolymer is suppressed by the ester bond that is an included polar group. Therefore, this coating film with high surface smoothness is obtained. As a result, this coating film having particularly excellent water repellency can be obtained.
  • Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms.
  • the monovalent hydrocarbon group may be linear or branched. Moreover, the monovalent hydrocarbon group may consist of a ring structure or may contain a ring structure.
  • the monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.
  • the monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
  • An aralkyl group having 7 to 12 carbon atoms is particularly preferred.
  • alkyl group examples include a methyl group, an ethyl group, a tert-butyl group, a hexyl group, a nonyl group, a decyl group, and a dodecyl group.
  • cycloalkyl group examples include a cyclohexyl group.
  • aralkyl group examples include a benzyl group.
  • aryl group examples include a phenyl group and a naphthyl group.
  • Two or more monomers 2 may be used in combination.
  • monomer 2 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, pivalic acid vinyl ester, neononanoic acid vinyl ester (trade name “Veoba 9” manufactured by HEXION), neodecane Acid vinyl ester (trade name “Beoba 10” manufactured by HEXION), benzoic acid vinyl ester tert-butyl (meth) acrylate, and benzyl (meth) acrylate.
  • the content of unit 2 is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all units contained in the fluoropolymer.
  • the fluoropolymer in the present invention includes all units based on the monomer 2 in which X 2 is CH 2 ⁇ CHOC (O) — or CH 2 ⁇ CHCH 2 OC (O) —.
  • the content is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, based on the unit. In this case, the surface smoothness of the coating film is further improved, and the water repellency is particularly excellent.
  • the unit contains an ester bond which is a polar group and suppresses charging of a particularly highly hydrophobic fluoropolymer.
  • the coating film is formed from the aqueous dispersion of the present invention. It is considered that the particulate fluoropolymer is easily packed densely when formed.
  • the fluoropolymer may contain a unit having a hydroxy group or a carboxy group (hereinafter also referred to as “unit 3”) other than the unit based on the monomer represented by the formula X 1 —Y 1 —Z 1 . .
  • Unit 3 may be a unit based on a monomer having a hydroxy group or a carboxy group (hereinafter also referred to as “monomer 3”), and the hydroxy group of the fluoropolymer containing the unit having a hydroxy group is converted into a carboxy group. It may be a unit obtained by making it.
  • Such units include units in which part or all of the hydroxy groups are converted to carboxy groups by reacting an acid anhydride or the like with a fluoropolymer containing units 3 having a hydroxy group.
  • the monomer 1 having a hydroxy group in which L 1 is a hydrogen atom is not included in the category of the monomer 3.
  • Monomer 3 does not contain a fluorine atom.
  • Examples of the monomer 3 having a carboxy group include unsaturated carboxylic acid and (meth) acrylic acid, and a monomer represented by the formula X 31 -Z 31 (hereinafter also referred to as “monomer 31”) is preferable.
  • X 31 is CH 2 ⁇ CH—, CH (CH 3 ) ⁇ CH— or CH 2 ⁇ C (CH 3 ) —, and preferably CH 2 ⁇ CH— or CH (CH 3 ) ⁇ CH—.
  • Z 31 is a carboxy group or a carboxyalkyl group having 1 to 12 carbon atoms, and is preferably a carboxy group or a carboxyalkyl group having 1 to 10 carbon atoms.
  • Examples of the monomer 3 having a hydroxy group include vinyl ether, vinyl ester, allyl ether, allyl ester, (meth) acrylic acid ester and allyl alcohol having a hydroxy group, and a monomer represented by the formula X 32 -Z 32 ( Hereinafter, also referred to as “monomer 32”) or allyl alcohol is preferable.
  • Z 32 is a monovalent saturated hydrocarbon group having 2 to 12 carbon atoms and having a hydroxy group.
  • the monovalent saturated hydrocarbon group may be linear or branched. Moreover, the monovalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure.
  • the monovalent saturated hydrocarbon group is preferably an alkyl group containing an alkyl group having 2 to 6 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
  • the monomer 3 may use 2 or more types together.
  • the hydroxy group or carboxy group of unit 3 becomes a crosslinking point, the crosslinking reaction between the fluoropolymers proceeds through the curing agent, and the strength of the coating film is increased. Since it improves, film physical properties, such as a weather resistance, water resistance, chemical resistance, and heat resistance, improve.
  • the content of unit 3 is preferably from 0.1 to 35 mol%, more preferably from 1 to 20 mol%, particularly preferably from 5 to 15 mol%, based on all units contained in the fluoropolymer.
  • the fluoropolymer preferably contains 20 to 80 mol%, 1 to 5 mol%, and 1 to 50 mol% of the unit F, the unit 1 and the unit 2 in this order with respect to all units of the fluoropolymer.
  • the Mn of the fluoropolymer is preferably 30,000 to 200,000, more preferably 50,000 to 180,000.
  • the hydroxyl value of the fluoropolymer is preferably 1 to 150 mgKOH / g.
  • the acid value of the fluoropolymer is preferably 1 to 150 mgKOH / g.
  • the content of the fluoropolymer in the aqueous dispersion of the present invention is preferably 10 to 70% by mass with respect to the total mass of the aqueous dispersion.
  • the aqueous dispersion of the present invention may contain a (meth) acrylate polymer.
  • the fluoropolymer and the (meth) acrylate polymer are dispersed in water in the aqueous dispersion.
  • “The fluoropolymer and (meth) acrylate polymer are dispersed in water” means a state in which the fluoropolymer and (meth) acrylate polymer are dispersed in water as particles.
  • the fluoropolymer and the (meth) acrylate polymer may be a core-shell polymer having a fluoropolymer as a core part and a (meth) acrylate polymer as a shell part.
  • the core-shell polymer is dispersed in water as particles (core-shell particles).
  • the core-shell particle is a particle having a so-called core-shell structure having a fluoropolymer core and a (meth) acrylate polymer shell located on the surface of the core.
  • the shell portion may cover a part of the surface of the core portion, or may cover the entire core portion.
  • the fluoropolymer and the (meth) acrylate polymer may be independently dispersed in water. In this case, the fluoropolymer is dispersed in the aqueous dispersion as fluoropolymer particles, and the (meth) acrylate polymer is dispersed as (meth) acrylate polymer particles.
  • the (meth) acrylate polymer preferably contains units based on alkyl (meth) acrylate.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate. At least one selected from these groups is preferred.
  • Alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate from the viewpoint of processability of this coating film. More preferred is at least one selected from the group consisting of The content of units based on alkyl (meth) acrylate is preferably 75 to 100 mol% with respect to the total units of the (meth) acrylate polymer.
  • the (meth) acrylate polymer preferably further contains units based on hydroxyalkyl (meth) acrylate. Since the hydroxy group in the unit based on hydroxyalkyl (meth) acrylate functions as a crosslinkable group, the curability of the coating film is improved.
  • Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Is preferred.
  • the (meth) acrylate polymer contains a unit based on hydroxyalkyl (meth) acrylate in an amount of more than 0 mol% and not more than 20 mol% with respect to all units of the (meth) acrylate polymer. Is preferred. Two or more hydroxyalkyl (meth) acrylates may be used in combination.
  • the (meth) acrylate polymer may contain less than 25 mol% of units other than units based on alkyl (meth) acrylate and units based on hydroxy (meth) acrylate with respect to all units contained in the (meth) acrylate polymer. Good.
  • Specific examples of the other monomer include unsaturated carboxylic acid, hydrolyzable silyl group-containing monomer, hydroxyl group-containing alkyl vinyl ether, carboxylic acid vinyl ester, and ⁇ -olefin.
  • the content of the fluoropolymer with respect to the total mass of the fluoropolymer and the (meth) acrylate polymer is preferably 30 to 70% by mass, and from the viewpoint of the balance between weather resistance and processability, 40 to 60% by mass is more preferable. preferable.
  • the aqueous dispersion of the present invention contains particles of fluoropolymer and particles of (meth) acrylate polymer
  • the total content of the particles of fluoropolymer and (meth) acrylate polymer is based on the total mass of the aqueous dispersion. 10 to 70% by mass is preferable.
  • the aqueous dispersion of the present invention contains core-shell particles
  • the content of the core-shell particles is preferably 10 to 70% by mass with respect to the total mass of the aqueous dispersion.
  • the average particle diameter of the fluoropolymer particles, the (meth) acrylate polymer particles, and the core-shell particles is preferably independently from 30 to 300 nm. From the viewpoint of more excellent water repellency of the coating film, 50 to 200 nm is more preferable, and 80 to 150 nm is particularly preferable.
  • the aqueous dispersion of the present invention contains only water or a mixture of water and a water-soluble organic solvent as a coating solvent (dispersion medium).
  • a water-soluble organic solvent in the mixed solution include methanol, ethanol, propanol, butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
  • the content of the water-soluble organic solvent in the mixed solution is preferably 1 to 40 parts by mass with respect to 100 parts by mass of water.
  • the aqueous dispersion of the present invention preferably contains 10 to 90% by mass of water with respect to the total mass of the aqueous dispersion.
  • the aqueous dispersion of the present invention may contain components other than those described above (hereinafter also referred to as “other components”) as long as the effects of the present invention are not impaired.
  • other components include surfactants and molecular weight regulators.
  • a fluoropolymer containing units F, 1 and 2 is obtained by polymerizing fluoroolefin, monomer 1 and monomer 2 in a system containing water.
  • distributed in water is mentioned.
  • monomer 1 and monomer 2 monomer 3 may be further used.
  • Other monomers may be further used.
  • the usage-amount of each component can be suitably determined so that content of each component contained in the aqueous dispersion obtained may become content of each component contained in the aqueous dispersion of this invention mentioned above.
  • a surfactant, a radical polymerization initiator, a chain transfer agent, a chelating agent, a pH adjusting agent and the like may be added.
  • Specific examples of the polymerization method include an emulsion polymerization method and a suspension polymerization method.
  • the polymerization temperature is usually from 0 to 100 ° C.
  • the polymerization pressure is usually 0.2 to 5 MPa.
  • a dispersion in which a fluoropolymer is dispersed in water is obtained, and then an alkyl (meth) acrylate is polymerized to use the fluoropolymer as a core part.
  • an alkyl (meth) acrylate is polymerized to use the fluoropolymer as a core part.
  • a first aqueous dispersion containing water and a fluoropolymer dispersed in water, and a (meth) acrylate polymer containing water dispersed in water is mixed with the second aqueous dispersion to obtain an aqueous dispersion in which the fluoropolymer and the (meth) acrylate polymer are dispersed in water.
  • hydroxyalkyl (meth) acrylate may be used in combination.
  • the aqueous paint of the present invention includes the aqueous dispersion of the present invention, as well as pigments (inorganic colored pigments, organic colored pigments, extender pigments, etc.), curing agents, curing aids, Film-forming aids, thickeners, antifoaming agents, light stabilizers, surface conditioners, dispersants, rust inhibitors, silane coupling agents, antifouling agents, UV absorbers, light stabilizers, color tone adjusters, etc.
  • An additive may further be included.
  • the water-based paint may further contain a polymer other than the fluoropolymer and (meth) acrylate polymer of the present invention.
  • the aqueous paint can be produced by appropriately mixing the aqueous dispersion of the present invention with the above additives.
  • the aqueous paint preferably contains 10 to 80% by mass of the aqueous dispersion of the invention based on the total mass of the aqueous paint.
  • the content of the aqueous dispersion of the present invention in the aqueous paint is more preferably 10 to 60% by mass relative to the total mass of the aqueous paint. If the said content is 10 mass% or more, the weather resistance of this coating film will improve, and if it is 80 mass% or less, the film formability of this aqueous coating material will improve.
  • the water-based paint preferably contains 10 to 90% by mass of a fluoropolymer (the total of these when a (meth) acrylate polymer is included) with respect to the total mass of the water-based paint.
  • the coated article of this invention has a base material and the coating film (this coating film) arrange
  • the substrate include organic materials such as resin, rubber, and wood, inorganic materials such as concrete, glass, ceramics, and stone, iron, iron alloy, aluminum, and aluminum alloy.
  • the film thickness of this coating film is preferably 10 to 100 ⁇ m. If the thickness of the coating film is 10 ⁇ m or more, the water repellency of the coating film is improved, and if it is 100 ⁇ m or less, the weather resistance of the coating film is improved.
  • a coated article can be produced by applying the aqueous paint to the surface of a substrate and drying it to form the coating film.
  • the aqueous paint may be applied directly to the surface of the substrate, or may be applied after a known surface treatment (such as a base treatment) is applied to the surface of the substrate. Furthermore, after forming the undercoat layer on the substrate, it may be applied onto the undercoat layer. Moreover, when this aqueous coating material contains a hardening
  • the application method of the water-based paint include a method using a coating apparatus such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, and a spin coater.
  • the drying temperature and curing temperature after coating are preferably 25 ° C to 300 ° C.
  • Examples 1 to 4 and 7 are examples, and examples 5 and 6 are comparative examples. However, the present invention is not limited to these examples.
  • surface mentioned later shows a mass reference
  • aqueous dispersion 1 containing fluoropolymer particles ( A solid concentration of 48% by mass was obtained.
  • the average particle diameter of the fluoropolymer particles in the aqueous dispersion 1 was 115 nm.
  • the fluoropolymer contained in the aqueous dispersion 1 includes a unit based on HFO-1234ze, a unit based on HFO-1234yf, a unit based on CM-15EOVE, a unit based on EVE, a unit based on V9, and a unit based on CHMVE.
  • the polymer contained 40 mol%, 10 mol%, 2.0 mol%, 10 mol%, 29 mol%, and 9.0 mol% in this order.
  • Examples 1 to 7 A pigment (72 g), a dispersant (5 g), an antifoaming agent (0.5 g), and ion-exchanged water (22.5 g) were mixed to obtain a mill base. Next, an aqueous dispersion 1 (70 g), a curing agent (8 g), a film-forming auxiliary (5 g), and a mill base (25 g) were mixed to obtain an aqueous paint 1. Aqueous paints 2 to 7 were obtained in the same manner as the aqueous paint 1 except that the aqueous dispersion 1 was changed to the aqueous dispersions 2 to 7, respectively.
  • the storage stability of aqueous dispersion was evaluated from the amount of precipitate produced during storage. 50 mL of the aqueous dispersion was placed in a centrifuge tube and allowed to stand at 25 ° C. for 2 weeks, and the amount of the sediment that had settled at the bottom of the centrifuge tube was read from the scale. A: The amount of the precipitate is 0.1 mL or less. B: The amount of the precipitate is more than 0.1 mL and less than 0.5 mL. C: The amount of the precipitate is 0.5 mL or more.
  • the dynamic contact angle of water with respect to the test piece was measured. Using a contact angle meter, drop 10 ⁇ L of pure water onto the surface of a horizontally placed test piece, gradually tilt the test piece, measure the tilt angle at which the droplet starts to slide, and determine the value of the dynamic contact angle. It was.
  • S The dynamic contact angle of water with respect to the test piece is 25 degrees or less.
  • A The dynamic contact angle of water with respect to the test piece is more than 25 degrees and not more than 30 degrees.
  • B The dynamic contact angle of water with respect to the test piece is more than 30 degrees and less than 35 degrees.
  • C The dynamic contact angle of water with respect to the test piece is 35 degrees or more.
  • Table 2 summarizes the evaluation results of the coatings formed from the respective aqueous dispersions and aqueous paints.

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Abstract

Provided is an aqueous dispersion liquid which has excellent storage stability and is capable of forming a coating film that has excellent water repellency. An aqueous dispersion liquid according to the present invention contains water and a fluoropolymer that is dispersed in the water. The fluoropolymer contains a unit based on at least one compound selected from the group consisting of CF3-CH=CHF and CF3-CF=CH2, a unit based on a monomer represented by formula X1-Y1-Z1 and a unit based on a monomer represented by formula X2-Z2; and the content of the unit based on a monomer represented by formula X1-Y1-Z1 is 1 mol% or more relative to all units contained in the fluoropolymer. In the formulae, each of X1 and X2 independently represents CH2=CHO- or the like; Y1 represents a divalent linking group; Z1 represents a group represented by formula -O(M1O)mL1 or the like; M1 represents an alkylene group having 2-4 carbon atoms; L1 represents a hydrogen atom or the like; m represents an integer of 6-24; and Z2 represents a monovalent hydrocarbon group.

Description

水性分散液、水性塗料、および塗装物品Aqueous dispersions, water-based paints, and painted articles
　本発明は、フルオロポリマーを含む水性分散液、水性塗料、および塗装物品に関する。 The present invention relates to an aqueous dispersion containing a fluoropolymer, an aqueous paint, and a coated article.
　環境保護の観点から、塗料分野では、水を塗料溶媒とする水性塗料が注目されている。さらに、耐候性、耐薬品性、耐溶剤性等の塗膜物性の観点から、フルオロポリマーを含む水性塗料が期待されている。特許文献１には、フルオロエチレンに基づく単位、およびポリオキシアルキレン基を有するモノマーに基づく単位等を含むフルオロポリマーを含む水性分散液を含む水性塗料が開示されている。 From the viewpoint of environmental protection, water-based paints using water as a paint solvent are attracting attention in the paint field. Furthermore, from the viewpoint of coating film properties such as weather resistance, chemical resistance, and solvent resistance, water-based paints containing fluoropolymers are expected. Patent Document 1 discloses an aqueous paint containing an aqueous dispersion containing a fluoropolymer containing units based on fluoroethylene and units based on a monomer having a polyoxyalkylene group.
特許第３４１４４６５号公報Japanese Patent No. 3414465
　水性分散液には、優れた貯蔵安定性が求められている。また、近年、水性分散液を含む水性塗料を用いて形成されてなる塗膜に求められる物性はさらに向上しており、撥水性（特に、塗膜に付着した水が滑落する目安となる動的撥水性）に優れた塗膜が求められている。
　本発明者らは、特許文献１に記載の水性分散液は、貯蔵安定性が良好であるが、これを含む水性塗料を用いて形成されてなる塗膜の撥水性が不十分であるのを知見した。 An aqueous dispersion is required to have excellent storage stability. In recent years, the physical properties required of a coating film formed using an aqueous coating material containing an aqueous dispersion have been further improved, and water repellency (particularly, dynamics that serve as a standard for water attached to the coating film to slide down). A coating film excellent in water repellency is demanded.
The present inventors have found that the aqueous dispersion described in Patent Document 1 has good storage stability, but the water repellency of a coating film formed using an aqueous paint containing the aqueous dispersion is insufficient. I found out.
　本発明は、上記課題に鑑みて、撥水性に優れた塗膜を形成でき、貯蔵安定性に優れた水性分散液、水性塗料、および塗装物品の提供を課題とする。 In view of the above problems, the present invention has an object to provide an aqueous dispersion, an aqueous coating material, and a coated article that can form a coating film excellent in water repellency and is excellent in storage stability.
　本発明者らは、上記課題について鋭意検討した結果、後述する式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位を特定量含み、かつ、ＣＦ３－ＣＨ＝ＣＨＦおよびＣＦ３－ＣＦ＝ＣＨ２からなる群から選択される少なくとも一種に基づく単位を含むフルオロポリマーを用いれば、所望の効果が得られるのを見出し、本発明に至った。
　すなわち、本発明者らは、以下の構成により上記課題が解決できるのを見出した。 As a result of intensive studies on the above problems, the inventors of the present invention include a specific amount of a unit based on a monomer represented by the formula X 1 -Y 1 -Z 1 described below, and CF 3 —CH═CHF and CF 3 —. It has been found that a desired effect can be obtained by using a fluoropolymer containing a unit based on at least one selected from the group consisting of CF═CH 2 , and the present invention has been achieved.
That is, the present inventors have found that the above problem can be solved by the following configuration.
［１］　水および水中に分散しているフルオロポリマーを含む水性分散液であって、
　前記フルオロポリマーが、ＣＦ３－ＣＨ＝ＣＨＦおよびＣＦ３－ＣＦ＝ＣＨ２からなる群から選択される少なくとも一種に基づく単位、式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位、および式Ｘ２－Ｚ２で表されるモノマーに基づく単位を含み、
　前記式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位の含有量が、前記フルオロポリマーが含む全単位に対して、１～５モル％であることを特徴とする水性分散液。
　式中の記号は、以下の意味を示す。
　Ｘ１およびＸ２はそれぞれ独立に、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－、ＣＨ２＝ＣＨＯＣ（Ｏ）－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－またはＣＨ２＝ＣＨＣＨ２Ｏ－である。
　Ｙ１は、２価の連結基である。
　Ｚ１は、式－Ｏ（Ｍ１Ｏ）ｍＬ１で表される基、または式－Ｃ（Ｏ）ＯＲ１で表される基である。ただし、Ｍ１は炭素数２～４のアルキレン基であり、ｍは６～２４の整数であり、Ｌ１は水素原子、炭素数４以下のアルキル基または式－ＳＯ３ －Ａ＋で表される基であり（式中、Ａ＋はＮＨ４ ＋、Ｎａ＋またはＫ＋である）、Ｒ１は炭素数１～２０のアルキル基である。
　Ｚ２は、炭素数１～２４の１価の炭化水素基である。 [1] An aqueous dispersion containing water and a fluoropolymer dispersed in water,
The fluoropolymer, CF 3 -CH = CHF and CF 3 at least one in-based unit is selected from the group consisting of -CF = CH 2, unit based on a monomer represented by the formula X 1 -Y 1 -Z 1, And units based on monomers of the formula X 2 -Z 2 ,
An aqueous dispersion characterized in that the content of units based on the monomer represented by the formula X 1 -Y 1 -Z 1 is 1 to 5 mol% with respect to the total units contained in the fluoropolymer.
The symbols in the formula have the following meanings.
X 1 and X 2 are each independently CH 2 ═CHC (O) O—, CH 2 ═C (CH 3 ) C (O) O—, CH 2 ═CHOC (O) —, CH 2 ═CHCH 2 OC (O) —, CH 2 ═CHO— or CH 2 ═CHCH 2 O—.
Y 1 is a divalent linking group.
Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 . However, M 1 is an alkylene group having 2 to 4 carbon atoms, m is an integer of 6 ~ 24, L 1 is hydrogen atom, alkyl group of 4 or less, or the formula -SO 3 carbon - represented by A + (Wherein A + is NH 4 + , Na + or K + ), and R 1 is an alkyl group having 1 to 20 carbon atoms.
Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms.
［２］　前記フルオロポリマーが、ＣＦ３－ＣＨ＝ＣＨＦに基づく単位とＣＦ３－ＣＦ＝ＣＨ２に基づく単位とを含む、［１］に記載の水性分散液。
［３］　前記フルオロポリマー中のＣＦ３－ＣＨ＝ＣＨＦに基づく単位とＣＦ３－ＣＦ＝ＣＨ２に基づく単位との合計の含有量が、フルオロポリマーが含む全単位に対して、２０～８０モル％である、［１］または［２］に記載の水性分散液。
［４］　前記Ｙ１が炭素数２～１２の２価の飽和炭化水素基である、［１］～［３］のいずれかに記載の水性分散液。
［５］　前記式－Ｏ（Ｍ１Ｏ）ｍＬ１で表される基が、式－Ｏ（ＣＨ２ＣＨ２Ｏ）ｍＨで表される基である、［１］～［４］のいずれかに記載の水性分散液。
［６］　前記Ｘ２が、ＣＨ２＝ＣＨＯＣ（Ｏ）－またはＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－である、［１］～［５］のいずれかに記載の水性分散液。
［７］　前記式Ｘ２－Ｚ２で表されるモノマーに基づく単位の含有量が、前記フルオロポリマーが含む全単位に対して、１０～５０モル％である、［１］～［６］のいずれかに記載の水性分散液。
［８］　前記フルオロポリマーが、前記式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位以外の、ヒドロキシ基またはカルボキシ基を有する単位をさらに含む、［１］～［７］のいずれかに記載の水性分散液。
［９］　前記ヒドロキシ基またはカルボキシ基を有する単位の含有量が、フルオロポリマーが含む全単位に対して、１～２０モル％である、［８］に記載の水性分散液。 [2] the fluoropolymer, and a unit based on units and CF 3 -CF = CH 2 based on CF 3 -CH = CHF, aqueous dispersion according to [1].
[3] the total content of the CF 3 based on -CH = CHF units and CF 3 -CF = CH 2 in based units of the fluoropolymer is, relative to the total units containing fluoropolymers, 20 to 80 moles %, The aqueous dispersion according to [1] or [2].
[4] The aqueous dispersion according to any one of [1] to [3], wherein Y 1 is a divalent saturated hydrocarbon group having 2 to 12 carbon atoms.
[5] The group represented by the formula —O (M 1 O) m L 1 is a group represented by the formula —O (CH 2 CH 2 O) m H; The aqueous dispersion according to any one of the above.
[6] The aqueous dispersion according to any one of [1] to [5], wherein X 2 is CH 2 ═CHOC (O) — or CH 2 ═CHCH 2 OC (O) —.
[7] The content of the unit based on the monomer represented by the formula X 2 -Z 2 is 10 to 50 mol% with respect to the total units contained in the fluoropolymer, The aqueous dispersion according to any one of the above.
[8] Any of [1] to [7], wherein the fluoropolymer further includes a unit having a hydroxy group or a carboxy group other than the unit based on the monomer represented by the formula X 1 -Y 1 -Z 1 An aqueous dispersion according to the above.
[9] The aqueous dispersion according to [8], wherein the content of the unit having a hydroxy group or a carboxy group is 1 to 20 mol% with respect to all units contained in the fluoropolymer.
［１０］　前記水性分散液が、水に分散している（メタ）アクリレートポリマーをさらに含む、［１］～［９］のいずれかに記載の水性分散液。
［１１］　前記フルオロポリマーが、（メタ）アクリレートポリマーをさらに含み、
　前記フルオロポリマーおよび前記（メタ）アクリレートポリマーが、前記フルオロポリマーをコア部とし前記（メタ）アクリレートポリマーをシェル部とするコアシェルポリマーである、［１］～［９］のいずれかに記載の水性分散液。
［１２］　前記水性分散液が含むポリマーの粒子の平均粒子径が、３０～３００ｎｍである、［１］～［１１］のいずれかに記載の水性分散液。
［１３］　前記［１］～［１２］のいずれかに記載の水性分散液を含む、水性塗料。
［１４］　前記水性塗料がさらに硬化剤を含む、［１３］に記載の水性塗料。
［１５］　基材と、前記基材上に配置され、［１３］または［４］に記載の水性塗料を用いて形成されてなる塗膜と、を有する、塗装物品。 [10] The aqueous dispersion according to any one of [1] to [9], wherein the aqueous dispersion further comprises a (meth) acrylate polymer dispersed in water.
[11] The fluoropolymer further includes a (meth) acrylate polymer,
The aqueous dispersion according to any one of [1] to [9], wherein the fluoropolymer and the (meth) acrylate polymer are core-shell polymers having the fluoropolymer as a core portion and the (meth) acrylate polymer as a shell portion. liquid.
[12] The aqueous dispersion according to any one of [1] to [11], wherein the polymer particles contained in the aqueous dispersion have an average particle size of 30 to 300 nm.
[13] An aqueous paint containing the aqueous dispersion according to any one of [1] to [12].
[14] The aqueous paint according to [13], wherein the aqueous paint further contains a curing agent.
[15] A coated article having a base material and a coating film disposed on the base material and formed using the water-based paint described in [13] or [4].
　以下に示すように、本発明によれば、撥水性（特に、塗膜に付着した水が滑落する目安となる動的撥水性。以下同様。）に優れた塗膜を形成でき、貯蔵安定性に優れた水性分散液、水性塗料、および塗装物品を提供できる。 As shown below, according to the present invention, a coating film excellent in water repellency (particularly, dynamic water repellency that is a measure for water adhering to the coating to slide down, the same shall apply hereinafter) can be formed, and storage stability can be formed. It is possible to provide an aqueous dispersion, an aqueous coating material, and a coated article excellent in the above.
　本発明における用語の意味は以下の通りである。
　「（メタ）アクリレート」とは、「アクリレート」および「メタクリレート」の総称である。
　「単位」とは、モノマーの重合により直接形成された、上記モノマー１分子に由来する原子団と、上記原子団の一部を化学変換して得られる原子団との総称である。ポリマーが含む全単位に対する、それぞれの単位の含有量（モル％）は、ポリマーを核磁気共鳴スペクトル法により分析して求められ、モノマーの仕込量からも推測できる。
　「平均粒子径」は、ＥＬＳ－８０００（大塚電子株式会社製）を用いて動的光散乱法により求められるＤ５０の値である。なお、Ｄ５０は、動的光散乱法により測定した粒子の粒度分布において、小さな粒子側から起算した体積累計５０体積％の粒子直径値である。
　「数平均分子量」は、ポリスチレンを標準物質としてゲルパーミエーションクロマトグラフィーで測定される値である。「数平均分子量」は、「Ｍｎ」ともいう。
　「水酸基価」は、ＪＩＳ　Ｋ　１５５７－１（２００７）の方法に準じて測定される値である。
　「酸価」は、ＪＩＳ　Ｋ　００７０－３（１９９２）の方法に準じて測定される値である。
　「膜厚」は、渦電流式膜厚計（商品名「ＥＤＹ－５０００」、サンコウ電子社製）を用いて測定される値である。 The meanings of terms in the present invention are as follows.
“(Meth) acrylate” is a general term for “acrylate” and “methacrylate”.
The “unit” is a general term for an atomic group derived directly from monomer polymerization and derived from one molecule of the monomer, and an atomic group obtained by chemically converting a part of the atomic group. The content (mol%) of each unit with respect to all units contained in the polymer is obtained by analyzing the polymer by a nuclear magnetic resonance spectrum method, and can be estimated from the charged amount of monomer.
“Average particle diameter” is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.). In addition, D50 is a particle diameter value of 50 volume% of the cumulative volume calculated from the small particle side in the particle size distribution of the particle measured by the dynamic light scattering method.
“Number average molecular weight” is a value measured by gel permeation chromatography using polystyrene as a standard substance. “Number average molecular weight” is also referred to as “Mn”.
“Hydroxyl value” is a value measured according to the method of JIS K1557-1 (2007).
The “acid value” is a value measured according to the method of JIS K 0070-3 (1992).
“Film thickness” is a value measured using an eddy current film thickness meter (trade name “EDY-5000”, manufactured by Sanko Electronics Co., Ltd.).
　本発明の水性分散液は、水および水中に分散しているフルオロポリマーを含む水性分散液であって、フルオロポリマーが、ＣＦ３－ＣＨ＝ＣＨＦおよびＣＦ３－ＣＦ＝ＣＨ２からなる群から選択される少なくとも一種（以下、「モノマーＦ」ともいう。）に基づく単位（以下、「単位Ｆ」ともいう。）、式Ｘ１－Ｙ１－Ｚ１で表されるモノマー（以下、「モノマー１」ともいう。）に基づく単位（以下、「単位１」ともいう。）、および式Ｘ２－Ｚ２で表されるモノマー（以下、「モノマー２」ともいう。）に基づく単位（以下、「単位２」ともいう。）を含む。
　また、フルオロポリマーにおいて、単位１の含有量は、フルオロポリマーが含む全単位に対して、１～５モル％である。
　なお、本発明の水性分散液において、「フルオロポリマーが水中に分散している」とは、フルオロポリマーが粒子として水中に分散している状態を意味する。 Aqueous dispersions of the present invention is an aqueous dispersion comprising a fluoropolymer is dispersed in water and water, fluoropolymer, selected from the group consisting of CF 3 -CH = CHF and CF 3 -CF = CH 2 A unit (hereinafter also referred to as “unit F”) based on at least one kind (hereinafter also referred to as “monomer F”), a monomer represented by the formula X 1 -Y 1 -Z 1 (hereinafter referred to as “monomer 1”). And a unit based on a monomer represented by the formula X 2 -Z 2 (hereinafter also referred to as “monomer 2”) (hereinafter referred to as “unit 1”). Also referred to as “unit 2”).
In the fluoropolymer, the content of the unit 1 is 1 to 5 mol% with respect to all units contained in the fluoropolymer.
In the aqueous dispersion of the present invention, “the fluoropolymer is dispersed in water” means a state in which the fluoropolymer is dispersed in water as particles.
　本発明者らは、フルオロエチレン（例えば、ビニリデンフルオリド、テトラフルオロエチレン、クロロトリフルオロエチレン）に基づく単位を含むフルオロポリマーを含む水性塗料を用いて塗膜を形成した場合、その塗膜の撥水性に改良の余地があるのを知見した。
　この問題に対して、フルオロプロピレン等の－ＣＦ３基を有するモノマーに基づく単位（例えば、単位Ｆ）をフルオロポリマーに導入する方法が考えられる。フルオロポリマーが－ＣＦ３基を有すれば、その塗膜の表面には－ＣＦ３基が配列して、塗膜の撥水性が向上すると推測される。しかし、フルオロポリマーが単位Ｆを含む場合、フルオロポリマーの水分散性が低下して、フルオロポリマーを含む水性分散液の貯蔵安定性が低下する。このように、塗膜の撥水性と、水性分散液の貯蔵安定性とは、トレードオフの関係にあった。
　この問題に対して、本発明者らは、フルオロプロピレンに基づく単位の中でも単位Ｆを含むフルオロポリマーに特定量の単位１を含ませれば、水性分散液の貯蔵安定性に優れた水性分散液が得られ、この水性分散液を含む水性塗料を用いて形成される塗膜の撥水性も優れるのを見出した。これは、フルオロプロピレンの中でもモノマーＦを用いた場合において、モノマーＦがモノマー１と良好に共重合し、単位１によって付与される親水性と単位Ｆによって付与される撥水性とがバランスするためと考えられる。なお、この効果は、本発明の好適な範囲において、特に顕著に発現する。
　以下において、本発明の水性分散液を含む水性塗料から形成されてなる塗膜を「本塗膜」ともいう。 When the present invention forms a coating film using an aqueous coating material containing a fluoropolymer containing units based on fluoroethylene (for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene), It was found that there is room for improvement in aqueous properties.
To solve this problem, a method of introducing a unit (for example, unit F) based on a monomer having a —CF 3 group such as fluoropropylene into the fluoropolymer can be considered. If the fluoropolymer has —CF 3 groups, it is presumed that —CF 3 groups are arranged on the surface of the coating film to improve the water repellency of the coating film. However, when the fluoropolymer contains the unit F, the water dispersibility of the fluoropolymer is lowered, and the storage stability of the aqueous dispersion containing the fluoropolymer is lowered. Thus, the water repellency of the coating film and the storage stability of the aqueous dispersion were in a trade-off relationship.
In order to solve this problem, the present inventors have obtained an aqueous dispersion excellent in storage stability of an aqueous dispersion by including a specific amount of unit 1 in a fluoropolymer containing units F among units based on fluoropropylene. It was found that the water repellency of the coating film formed using an aqueous paint containing this aqueous dispersion was excellent. This is because when monomer F is used among fluoropropylenes, monomer F is well copolymerized with monomer 1, and the hydrophilicity imparted by unit 1 and the water repellency imparted by unit F are balanced. Conceivable. This effect is particularly prominent within the preferred range of the present invention.
Below, the coating film formed from the aqueous coating material containing the aqueous dispersion of this invention is also called "this coating film."
　本発明におけるフルオロポリマーに含まれる単位Ｆは、モノマーＦに基づく単位である。つまり、本発明におけるフルオロポリマーは、ＣＦ３－ＣＨ＝ＣＨＦに基づく単位およびＣＦ３－ＣＦ＝ＣＨ２に基づく単位の一方のみを含んでいてもよいし、両単位を含んでいてもよい。単位Ｆは、重合性の観点、および平均粒子径が小さいフルオロポリマーが得られ、フルオロポリマー粒子の密パッキングにより撥水性により優れる観点から、ＣＦ３－ＣＨ＝ＣＨＦに基づく単位およびＣＦ３－ＣＦ＝ＣＨ２に基づく単位の両方を含んでいることが好ましい。上記２つの単位を有する場合、両単位の合計に対するＣＦ３－ＣＦ＝ＣＨ２に基づく単位の割合は、１０～９０モル％が好ましく、６０～８５モル％がより好ましい。
　単位Ｆの含有量は、フルオロポリマーが含む全単位に対して、２０～８０モル％が好ましく、３０～７０モル％がより好ましい。単位Ｆの含有量が２０モル％以上であれば、本塗膜の撥水性がより向上する。単位Ｆの含有量が８０モル％以下であれば、水性分散液の貯蔵安定性がより優れる。 The unit F contained in the fluoropolymer in the present invention is a unit based on the monomer F. That is, the fluoropolymer of the present invention may also contain one of units based on units and CF 3 -CF = CH 2 based on CF 3 -CH = CHF only, may contain both units. Unit F is polymerizable aspects, and the average particle diameter is smaller fluoropolymer is obtained, fluoro terms of more excellent water repellency by dense packing of the polymer particles, CF 3 -CH = units based on CHF and CF 3 -CF = Preferably, both units based on CH 2 are included. In the case of having the above two units, the proportion of units based on CF 3 —CF═CH 2 with respect to the total of both units is preferably 10 to 90 mol%, more preferably 60 to 85 mol%.
The content of unit F is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, based on all units contained in the fluoropolymer. If the content of the unit F is 20 mol% or more, the water repellency of the coating film is further improved. When the content of the unit F is 80 mol% or less, the storage stability of the aqueous dispersion is more excellent.
　本発明におけるフルオロポリマーに含まれる単位１は、式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位である。単位１は、フルオロポリマーの水分散性の向上に寄与し、水性分散液の貯蔵安定性を向上させる。
　式中の記号は、以下の意味を示す。
　Ｘ１は、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－、ＣＨ２＝ＣＨＯＣ（Ｏ）－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－またはＣＨ２＝ＣＨＣＨ２Ｏ－であり、ＣＦ３－ＣＨ＝ＣＨＦまたはＣＦ３－ＣＦ＝ＣＨ２との交互重合性に優れる観点から、ＣＨ２＝ＣＨＯ－、ＣＨ２＝ＣＨＣＨ２Ｏ－またはＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－であることが好ましい。 The unit 1 contained in the fluoropolymer in the present invention is a unit based on a monomer represented by the formula X 1 -Y 1 -Z 1 . Unit 1 contributes to the improvement of the water dispersibility of the fluoropolymer and improves the storage stability of the aqueous dispersion.
The symbols in the formula have the following meanings.
X 1 represents CH 2 ═CHC (O) O—, CH 2 ═C (CH 3 ) C (O) O—, CH 2 ═CHOC (O) —, CH 2 ═CHCH 2 OC (O) —, CH 2 = CHO- or CH 2 = CHCH 2 O-, and from the viewpoint of excellent alternating polymerizability with CF 3 -CH = CHF or CF 3 -CF = CH 2 , CH 2 = CHO-, CH 2 = CHCH 2 O— or CH 2 ═CHCH 2 OC (O) — is preferred.
　Ｙ１は、２価の連結基である。２価の連結基としては、炭素数２～１２の２価の飽和炭化水素基が好ましい。２価の飽和炭化水素基は、直鎖状であってもよく分岐鎖状であってもよい。また、２価の飽和炭化水素基は、環構造からなっていてもよく、環構造を含んでいてもよい。なお、Ｚ１が式－Ｃ（Ｏ）ＯＲ１で表される基である場合、２価の飽和炭化水素基は、式－ＳＯ３ －Ａ＋で表される基を有していてもよく、エーテル性酸素原子を有していてもよい。式中、Ａ＋はＮＨ４ ＋、Ｎａ＋またはＫ＋である。
　２価の飽和炭化水素基は、炭素数２～１２のアルキレン基または炭素数６～８のシクロアルキレン基を含むアルキレン基が好ましい。
　２価の飽和炭化水素基としては、式－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２－で表される基、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ２－および式－ＣＨ２ＣＨ（Ｙ１１）－で表される基が好ましい。－ｃｙｃｌｏＣ６Ｈ１０－はシクロへキシレン基を示し、（－ｃｙｃｌｏＣ６Ｈ１０－)の結合部位は、特に限定されず、通常１，４－である。また、Ｙ１１は炭素数１～１０のアルキル基を表す。 Y 1 is a divalent linking group. The divalent linking group is preferably a divalent saturated hydrocarbon group having 2 to 12 carbon atoms. The divalent saturated hydrocarbon group may be linear or branched. Moreover, the divalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure. When Z 1 is a group represented by the formula —C (O) OR 1 , the divalent saturated hydrocarbon group may have a group represented by the formula —SO 3 − A +. May have an etheric oxygen atom. In the formula, A + is NH 4 + , Na + or K + .
The divalent saturated hydrocarbon group is preferably an alkylene group containing an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
Examples of the divalent saturated hydrocarbon group include a group represented by the formula —CH 2 —cycloC 6 H 10 —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 — and a formula —CH. A group represented by 2 CH (Y 11 ) — is preferred. -CycloC 6 H 10 -represents a cyclohexylene group, and the bonding site of (-cycloC 6 H 10- ) is not particularly limited, and is usually 1,4-. Y 11 represents an alkyl group having 1 to 10 carbon atoms.
　Ｚ１は、式－Ｏ（Ｍ１Ｏ）ｍＬ１で表される基、または、式－Ｃ（Ｏ）ＯＲ１で表される基であり、式－Ｏ（Ｍ１Ｏ）ｍＬ１で表される基であることが好ましい。
　Ｍ１は、炭素数２～４のアルキレン基であり、－ＣＨ２ＣＨ２－が好ましい。なお、Ｍ１の炭素数が３または４である場合、Ｍ１、直鎖状のアルキレン基であってもよく分岐鎖状のアルキレン基であってもよい。
　ｍは、６～２４の整数であり、１０～２０の整数がより好ましい。
　Ｌ１は、水素原子、炭素数４以下のアルキル基または式－ＳＯ３ －Ａ＋で表される基である。式中、Ａ＋は、ＮＨ４ ＋、Ｎａ＋またはＫ＋である。
　Ｒ１は、炭素数１～２０のアルキル基であり、炭素数８～１５のアルキル基が好ましい。アルキル基は、直鎖状でもよく、分岐鎖状でもよい。
　ｍ個存在するＭ１の少なくとも一部は炭素数２のアルキレン基（ＣＨ２ＣＨ２）であることが好ましく、Ｍ１の一部が炭素数３または４のアルキレン基である場合は、ｍ個のＭ１に対する炭素数２のアルキレン基の数は、５０％以上が好ましく、８０％以上がより好ましい。２種以上の（Ｍ１Ｏ）が存在する場合、それらの結合順はランダム型でもブロック型でもよい。（Ｍ１Ｏ）ｍとしては、（ＣＨ２ＣＨ２Ｏ）ｍが特に好ましい。
　Ｌ１は、水素原子または炭素数４以下のアルキル基であることが好ましく、炭素数４以下のアルキル基としてはメチル基が好ましい。Ｌ１は水素原子であることが特に好ましい。 Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 , and the formula —O (M 1 O) m L 1 It is preferable that it is group represented by these.
M 1 is an alkylene group having 2 to 4 carbon atoms, preferably —CH 2 CH 2 —. When M 1 has 3 or 4 carbon atoms, M 1 may be a linear alkylene group or a branched alkylene group.
m is an integer of 6 to 24, and an integer of 10 to 20 is more preferable.
L 1 is a hydrogen atom, an alkyl group having 4 or less carbon atoms, or a group represented by the formula —SO 3 − A + . In the formula, A + is NH 4 + , Na + or K + .
R 1 is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 8 to 15 carbon atoms. The alkyl group may be linear or branched.
It is preferable that at least a part of m 1 M 1 is an alkylene group having 2 carbon atoms (CH 2 CH 2 ). When a part of M 1 is an alkylene group having 3 or 4 carbon atoms, m The number of alkylene groups having 2 carbon atoms with respect to M 1 is preferably 50% or more, and more preferably 80% or more. When two or more types of (M 1 O) are present, their bonding order may be random or block. As (M 1 O) m , (CH 2 CH 2 O) m is particularly preferable.
L 1 is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and the alkyl group having 4 or less carbon atoms is preferably a methyl group. L 1 is particularly preferably a hydrogen atom.
　モノマー１は、２種以上を併用してもよい。
　モノマー１の具体例としては、ＣＨ２＝ＣＨＯ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ、ＣＨ２＝ＣＨＣＨ２Ｏ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１ＣＨ３、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ（Ｃ４Ｈ９）－Ｏ（ＣＨ２ＣＨ２Ｏ）ｎ１Ｈ、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－ＣＨ（ＳＯ３ －Ａ＋）ＣＨ２－Ｃ（Ｏ）Ｏ（ＣＨ２）ｎ２ＣＨ３が挙げられる（式中のｎ１は１０～２０の整数を、ｎ２は１～２０の整数を示す。）。
　単位１の含有量は、水性分散液の貯蔵安定性の観点から、フルオロポリマーが有する全単位に対して、１～５モル％であり、１．０～５．０モル％が好ましく、１．０モル％超３．５モル％未満がより好ましく、１．２モル％～３．０モル％が特に好ましい。 Monomer 1 may use 2 or more types together.
Specific examples of the monomer 1, CH 2 = CHO-CH 2 -cycloC 6 H 10 -CH 2 -O (CH 2 CH 2 O) n1 H, CH 2 = CHCH 2 O-CH 2 -cycloC 6 H 10 - CH 2 —O (CH 2 CH 2 O) n1 H, CH 2 ═CHOCH 2 CH 2 —O (CH 2 CH 2 O) n1 H, CH 2 ═CHOCH 2 CH 2 CH 2 CH 2 —O (CH 2 CH 2 O) n1 H, CH 2 = CHOCH 2 CH 2 -O (CH 2 CH 2 O) n1 CH 3, CH 2 = CHCH 2 OCH 2 CH 2 -O (CH 2 CH 2 O) n1 H, CH 2 = CHCH 2 OCH 2 CH (C 4 H 9 ) —O (CH 2 CH 2 O) n1 H, CH 2 ═CHCH 2 OC (O) —CH (SO 3 − A + ) CH 2 —C (O) O ( C 2) n2 CH 3 and the like (the integer n1 is 10-20 in the formula, n2 is an integer of 1-20.).
The content of unit 1 is 1 to 5 mol%, preferably 1.0 to 5.0 mol%, based on the total units of the fluoropolymer, from the viewpoint of storage stability of the aqueous dispersion. More than 0 mol% and less than 3.5 mol% is more preferable, and 1.2 mol% to 3.0 mol% is particularly preferable.
　本発明におけるフルオロポリマーに含まれる単位２は、式Ｘ２－Ｚ２で表されるモノマーに基づく単位である。
　Ｘ２は、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－、ＣＨ２＝ＣＨＯＣ（Ｏ）－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－またはＣＨ２＝ＣＨＣＨ２Ｏ－である。本塗膜の耐候性に優れる観点から、Ｘ２としては、ＣＨ２＝ＣＨＯＣ（Ｏ）－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－およびＣＨ２＝ＣＨＣＨ２Ｏ－が好ましく、ＣＨ２＝ＣＨＯＣ（Ｏ）－およびＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－が特に好ましい。
　Ｘ２がＣＨ２＝ＣＨＯＣ（Ｏ）－またはＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－である場合、包含される極性基であるエステル結合により、フルオロポリマーの帯電が抑制されると考えられる。したがって、表面平滑性が高い本塗膜が得られる。その結果、撥水性に特に優れた本塗膜が得られる。 The unit 2 contained in the fluoropolymer in the present invention is a unit based on a monomer represented by the formula X 2 -Z 2 .
X 2 represents CH 2 ═CHC (O) O—, CH 2 ═C (CH 3 ) C (O) O—, CH 2 ═CHOC (O) —, CH 2 ═CHCH 2 OC (O) —, CH 2 = CHO- or CH 2 = CHCH 2 O-. From the viewpoint of excellent weather resistance of the coating film, X 2 includes CH 2 ═CHOC (O) —, CH 2 ═CHCH 2 OC (O) —, CH 2 ═CHO— and CH 2 ═CHCH 2 O—. CH 2 ═CHOC (O) — and CH 2 ═CHCH 2 OC (O) — are particularly preferred.
When X 2 is CH 2 ═CHOC (O) — or CH 2 ═CHCH 2 OC (O) —, it is considered that the charging of the fluoropolymer is suppressed by the ester bond that is an included polar group. Therefore, this coating film with high surface smoothness is obtained. As a result, this coating film having particularly excellent water repellency can be obtained.
　Ｚ２は炭素数１～２４の１価の炭化水素基である。１価の炭化水素基は、直鎖状であってもよく分岐鎖状であってもよい。また、１価の炭化水素基は、環構造からなっていてもよく、環構造を含んでいてもよい。また、１価の炭化水素基は、１価の飽和炭化水素基であってもよく１価の不飽和炭化水素基であってもよい。
　１価の炭化水素基は、アルキル基、シクロアルキル基、アリール基、アラルキル基が好ましく、炭素数２～１２のアルキル基、炭素数６～１０のシクロアルキル基、炭素数６～１０のアリール基、炭素数７～１２のアラルキル基が特に好ましい。
　アルキル基の具体例としては、メチル基、エチル基、ｔｅｒｔ－ブチル基、ヘキシル基、ノニル基、デシル基、ドデシル基等が挙げられる。
　シクロアルキル基の具体例としては、シクロヘキシル基が挙げられる。
　アラルキル基の具体例としては、ベンジル基が挙げられる。
　アリール基の具体例としては、フェニル基およびナフチル基が挙げられる。 Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms. The monovalent hydrocarbon group may be linear or branched. Moreover, the monovalent hydrocarbon group may consist of a ring structure or may contain a ring structure. The monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.
The monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. An aralkyl group having 7 to 12 carbon atoms is particularly preferred.
Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a hexyl group, a nonyl group, a decyl group, and a dodecyl group.
Specific examples of the cycloalkyl group include a cyclohexyl group.
Specific examples of the aralkyl group include a benzyl group.
Specific examples of the aryl group include a phenyl group and a naphthyl group.
　モノマー２は、２種以上を併用してもよい。
　モノマー２の具体例としては、エチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル、酢酸ビニル、ピバル酸ビニルエステル、ネオノナン酸ビニルエステル（ＨＥＸＩＯＮ社製、商品名「ベオバ９」）、ネオデカン酸ビニルエステル（ＨＥＸＩＯＮ社製、商品名「ベオバ１０」）、安息香酸ビニルエステルｔｅｒｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレートが挙げられる。 Two or more monomers 2 may be used in combination.
Specific examples of monomer 2 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, pivalic acid vinyl ester, neononanoic acid vinyl ester (trade name “Veoba 9” manufactured by HEXION), neodecane Acid vinyl ester (trade name “Beoba 10” manufactured by HEXION), benzoic acid vinyl ester tert-butyl (meth) acrylate, and benzyl (meth) acrylate.
　単位２の含有量は、フルオロポリマーが含む全単位に対して、１～５０モル％が好ましく、５～４０モル％がより好ましい。
　また、本発明におけるフルオロポリマーは、単位２のうち、Ｘ２がＣＨ２＝ＣＨＯＣ（Ｏ）－またはＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－であるモノマー２に基づく単位を、フルオロポリマーが含む全単位に対して、１０～５０モル％含むことが好ましく、１５～４０モル％含むことがより好ましい。この場合、本塗膜の表面平滑性がより向上し、撥水性が特に優れる。その理由は必ずしも明確ではないが、上記単位は、極性基であるエステル結合を包含し、特に疎水性の高いフルオロポリマーの帯電を抑制するため、その結果、本発明の水性分散液から塗膜が形成される際に、粒子状のフルオロポリマーが密にパッキングしやすいためと考えられる。 The content of unit 2 is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all units contained in the fluoropolymer.
In the fluoropolymer in the present invention, the fluoropolymer includes all units based on the monomer 2 in which X 2 is CH 2 ═CHOC (O) — or CH 2 ═CHCH 2 OC (O) —. The content is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, based on the unit. In this case, the surface smoothness of the coating film is further improved, and the water repellency is particularly excellent. The reason for this is not necessarily clear, but the unit contains an ester bond which is a polar group and suppresses charging of a particularly highly hydrophobic fluoropolymer. As a result, the coating film is formed from the aqueous dispersion of the present invention. It is considered that the particulate fluoropolymer is easily packed densely when formed.
　フルオロポリマーは、前記式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位以外の、ヒドロキシ基またはカルボキシ基を有する単位（以下、「単位３」ともいう。）を含んでいてもよい。単位３は、ヒドロキシ基またはカルボキシ基を有するモノマー（以下、「モノマー３」ともいう。）に基づく単位であってもよく、ヒドロキシ基を有する単位を含むフルオロポリマーのヒドロキシ基を、カルボキシ基に変換させて得られる単位であってもよい。このような単位としては、ヒドロキシ基を有する単位３を含むフルオロポリマーに、酸無水物等を反応させて、ヒドロキシ基の一部または全部がカルボキシ基に変換された単位等が挙げられる。ただし、Ｌ１が水素原子であるヒドロキシ基を有するモノマー１は、モノマー３の範疇には含まれないものとする。なお、モノマー３はフッ素原子を含まない。 The fluoropolymer may contain a unit having a hydroxy group or a carboxy group (hereinafter also referred to as “unit 3”) other than the unit based on the monomer represented by the formula X 1 —Y 1 —Z 1 . . Unit 3 may be a unit based on a monomer having a hydroxy group or a carboxy group (hereinafter also referred to as “monomer 3”), and the hydroxy group of the fluoropolymer containing the unit having a hydroxy group is converted into a carboxy group. It may be a unit obtained by making it. Examples of such units include units in which part or all of the hydroxy groups are converted to carboxy groups by reacting an acid anhydride or the like with a fluoropolymer containing units 3 having a hydroxy group. However, the monomer 1 having a hydroxy group in which L 1 is a hydrogen atom is not included in the category of the monomer 3. Monomer 3 does not contain a fluorine atom.
　カルボキシ基を有するモノマー３としては、不飽和カルボン酸および（メタ）アクリル酸が挙げられ、式Ｘ３１－Ｚ３１で表されるモノマー（以下、「モノマー３１」ともいう。）が好ましい。
　Ｘ３１は、ＣＨ２＝ＣＨ－、ＣＨ（ＣＨ３）＝ＣＨ－またはＣＨ２＝Ｃ（ＣＨ３）－であり、ＣＨ２＝ＣＨ－またはＣＨ（ＣＨ３）＝ＣＨ－であることが好ましい。
　Ｚ３１は、カルボキシ基または炭素数１～１２のカルボキシアルキル基であり、カルボキシ基または炭素数１～１０のカルボキシアルキル基であることが好ましい。 Examples of the monomer 3 having a carboxy group include unsaturated carboxylic acid and (meth) acrylic acid, and a monomer represented by the formula X 31 -Z 31 (hereinafter also referred to as “monomer 31”) is preferable.
X 31 is CH 2 ═CH—, CH (CH 3 ) ═CH— or CH 2 ═C (CH 3 ) —, and preferably CH 2 ═CH— or CH (CH 3 ) ═CH—. .
Z 31 is a carboxy group or a carboxyalkyl group having 1 to 12 carbon atoms, and is preferably a carboxy group or a carboxyalkyl group having 1 to 10 carbon atoms.
　ヒドロキシ基を有するモノマー３としては、ヒドロキシ基を有する、ビニルエーテル、ビニルエステル、アリルエーテル、アリルエステル、（メタ）アクリル酸エステルおよびアリルアルコールが挙げられ、式Ｘ３２－Ｚ３２で表されるモノマー（以下、「モノマー３２」ともいう。）またはアリルアルコールが好ましい。
　Ｘ３２は、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－、ＣＨ２＝ＣＨＯＣ（Ｏ）－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－またはＣＨ２＝ＣＨＣＨ２Ｏ－であり、ＣＨ２＝ＣＨＯ－またはＣＨ２＝ＣＨＣＨ２Ｏ－であることが好ましい。
　Ｚ３２は、ヒドロキシ基を有する炭素数２～１２の１価の飽和炭化水素基である。１価の飽和炭化水素基は、直鎖状であってもよく分岐状であってもよい。また、１価の飽和炭化水素基は、環構造からなっていてもよく、環構造を含んでいてもよい。
　１価の飽和炭化水素基は、炭素数２～６のアルキル基または炭素数６～８のシクロアルキレン基を含むアルキル基であることが好ましい。 Examples of the monomer 3 having a hydroxy group include vinyl ether, vinyl ester, allyl ether, allyl ester, (meth) acrylic acid ester and allyl alcohol having a hydroxy group, and a monomer represented by the formula X 32 -Z 32 ( Hereinafter, also referred to as “monomer 32”) or allyl alcohol is preferable.
X 32 represents CH 2 ═CHC (O) O—, CH 2 ═C (CH 3 ) C (O) O—, CH 2 ═CHOC (O) —, CH 2 ═CHCH 2 OC (O) —, CH 2 = CHO- or CH 2 = CHCH 2 is O-, CH 2 = CHO- or preferably CH 2 = CHCH 2 O- in which.
Z 32 is a monovalent saturated hydrocarbon group having 2 to 12 carbon atoms and having a hydroxy group. The monovalent saturated hydrocarbon group may be linear or branched. Moreover, the monovalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure.
The monovalent saturated hydrocarbon group is preferably an alkyl group containing an alkyl group having 2 to 6 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
　モノマー３１としては、ＣＨ２＝ＣＨＣＯＯＨ、ＣＨ（ＣＨ３）＝ＣＨＣＯＯＨ、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＨ、式ＣＨ２＝ＣＨ（ＣＨ２）ｎ３ＣＯＯＨで表される化合物（ただし、ｎ３は１～１０の整数を示す。）等が挙げられる。
　モノマー３２としては、ＣＨ２＝ＣＨＯ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２Ｏ－ＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ、ＣＨ２＝ＣＨＣＨ２ＯＣＨ２ＣＨ２ＣＨ２ＣＨ２ＯＨ等が挙げられる。
　モノマー３は、２種以上を併用してもよい。 As the monomer 31, a compound represented by CH 2 ═CHCOOH, CH (CH 3 ) ═CHCOOH, CH 2 ═C (CH 3 ) COOH, formula CH 2 ═CH (CH 2 ) n3 COOH (where n3 is 1) Represents an integer of ˜10).
The monomer 32, CH 2 = CHOCH 2 -cycloC 6 H 10 -CH 2 OH, CH 2 = CHCH 2 O-CH 2 -cycloC 6 H 10 -CH 2 OH, CH 2 = CHOCH 2 CH 2 OH, CH 2 = CHCH 2 OCH 2 CH 2 OH, CH 2 = CHOCH 2 CH 2 CH 2 CH 2 OH, CH 2 = CHCH 2 OCH 2 CH 2 CH 2 CH 2 OH , and the like.
The monomer 3 may use 2 or more types together.
　本発明の水性塗料が硬化剤を含む場合には、単位３のヒドロキシ基またはカルボキシ基が架橋点となって、フルオロポリマー間の架橋反応が硬化剤を介して進行し、本塗膜の強度が向上するので、耐候性、耐水性、耐薬品性、耐熱性等の塗膜物性が向上する。
　単位３の含有量は、フルオロポリマーが含む全単位に対して、０．１～３５モル％が好ましく、１～２０モル％がより好ましく、５～１５モル％が特に好ましい。 When the water-based paint of the present invention contains a curing agent, the hydroxy group or carboxy group of unit 3 becomes a crosslinking point, the crosslinking reaction between the fluoropolymers proceeds through the curing agent, and the strength of the coating film is increased. Since it improves, film physical properties, such as a weather resistance, water resistance, chemical resistance, and heat resistance, improve.
The content of unit 3 is preferably from 0.1 to 35 mol%, more preferably from 1 to 20 mol%, particularly preferably from 5 to 15 mol%, based on all units contained in the fluoropolymer.
　フルオロポリマーは、フルオロポリマーが有する全単位に対して、単位Ｆと単位１と単位２とを、この順に２０～８０モル％、１～５モル％、１～５０モル％含むことが好ましい。
　フルオロポリマーのＭｎは、３０，０００～２００，０００が好ましく、５０，０００～１８０，０００がより好ましい。
　フルオロポリマーが水酸基価を有する場合、フルオロポリマーの水酸基価は、１～１５０ｍｇＫＯＨ／ｇであるのが好ましい。
　フルオロポリマーが酸価を有する場合、フルオロポリマーの酸価は、１～１５０ｍｇＫＯＨ／ｇであるのが好ましい。
　本発明の水性分散液におけるフルオロポリマーの含有量は、水性分散液の全質量に対して、１０～７０質量％が好ましい。 The fluoropolymer preferably contains 20 to 80 mol%, 1 to 5 mol%, and 1 to 50 mol% of the unit F, the unit 1 and the unit 2 in this order with respect to all units of the fluoropolymer.
The Mn of the fluoropolymer is preferably 30,000 to 200,000, more preferably 50,000 to 180,000.
When the fluoropolymer has a hydroxyl value, the hydroxyl value of the fluoropolymer is preferably 1 to 150 mgKOH / g.
When the fluoropolymer has an acid value, the acid value of the fluoropolymer is preferably 1 to 150 mgKOH / g.
The content of the fluoropolymer in the aqueous dispersion of the present invention is preferably 10 to 70% by mass with respect to the total mass of the aqueous dispersion.
　本発明の水性分散液は、（メタ）アクリレートポリマーを含んでもよい。この場合、水性分散液において、フルオロポリマーおよび（メタ）アクリレートポリマーが水中に分散している。なお、「フルオロポリマーおよび（メタ）アクリレートポリマーが水中に分散している」とは、フルオロポリマーおよび（メタ）アクリレートポリマーが粒子として水中に分散している状態を意味する。 The aqueous dispersion of the present invention may contain a (meth) acrylate polymer. In this case, the fluoropolymer and the (meth) acrylate polymer are dispersed in water in the aqueous dispersion. “The fluoropolymer and (meth) acrylate polymer are dispersed in water” means a state in which the fluoropolymer and (meth) acrylate polymer are dispersed in water as particles.
　フルオロポリマーおよび（メタ）アクリレートポリマーは、フルオロポリマーをコア部とし（メタ）アクリレートポリマーをシェル部とするコアシェルポリマーであってもよい。この場合、コアシェルポリマーは、粒子（コアシェル粒子）として、水中に分散している。
　コアシェル粒子は、フルオロポリマーのコア部と、このコア部の表面に位置する（メタ）アクリレートポリマーのシェル部とを有する、いわゆるコアシェル構造の粒子である。シェル部は、コア部の表面の一部を被覆していてもよいし、コア部の全体を被覆していてもよい。
　また、フルオロポリマーおよび（メタ）アクリレートポリマーは、それぞれ独立して、水中に分散していてもよい。この場合、フルオロポリマーはフルオロポリマーの粒子として、（メタ）アクリレートポリマーは（メタ）アクリレートポリマーの粒子として、水性分散液中に分散している。 The fluoropolymer and the (meth) acrylate polymer may be a core-shell polymer having a fluoropolymer as a core part and a (meth) acrylate polymer as a shell part. In this case, the core-shell polymer is dispersed in water as particles (core-shell particles).
The core-shell particle is a particle having a so-called core-shell structure having a fluoropolymer core and a (meth) acrylate polymer shell located on the surface of the core. The shell portion may cover a part of the surface of the core portion, or may cover the entire core portion.
Moreover, the fluoropolymer and the (meth) acrylate polymer may be independently dispersed in water. In this case, the fluoropolymer is dispersed in the aqueous dispersion as fluoropolymer particles, and the (meth) acrylate polymer is dispersed as (meth) acrylate polymer particles.
　（メタ）アクリレートポリマーは、アルキル（メタ）アクリレートに基づく単位を含むことが好ましい。
　アルキル（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレートおよびシクロヘキシル（メタ）アクリレートが挙げられ、これらの群から選択される少なくとも１種が好ましい。アルキル（メタ）アクリレートは、本塗膜の加工性の観点から、メチル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレート、およびシクロヘキシル（メタ）アクリレートからなる群から選択される少なくとも１種がより好ましい。
　アルキル（メタ）アクリレートに基づく単位の含有量は、（メタ）アクリレートポリマーが有する全単位に対して、７５～１００モル％が好ましい。 The (meth) acrylate polymer preferably contains units based on alkyl (meth) acrylate.
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate. At least one selected from these groups is preferred. Alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate from the viewpoint of processability of this coating film. More preferred is at least one selected from the group consisting of
The content of units based on alkyl (meth) acrylate is preferably 75 to 100 mol% with respect to the total units of the (meth) acrylate polymer.
　（メタ）アクリレートポリマーは、さらにヒドロキシアルキル（メタ）アクリレートに基づく単位を含むことが好ましい。ヒドロキシアルキル（メタ）アクリレートに基づく単位におけるヒドロキシ基が、架橋性基として機能するため、本塗膜の硬化性が向上する。
　ヒドロキシアルキル（メタ）アクリレートの具体例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートが挙げられ、２－ヒドロキシエチル（メタ）アクリレートが好ましい。
　（メタ）アクリレートポリマーは、本塗膜の硬度の観点から、（メタ）アクリレートポリマーが有する全単位に対して、ヒドロキシアルキル（メタ）アクリレートに基づく単位を、０モル％超２０モル％以下含むことが好ましい。
　ヒドロキシアルキル（メタ）アクリレートは、２種以上を併用してもよい。 The (meth) acrylate polymer preferably further contains units based on hydroxyalkyl (meth) acrylate. Since the hydroxy group in the unit based on hydroxyalkyl (meth) acrylate functions as a crosslinkable group, the curability of the coating film is improved.
Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Is preferred.
From the viewpoint of the hardness of the coating film, the (meth) acrylate polymer contains a unit based on hydroxyalkyl (meth) acrylate in an amount of more than 0 mol% and not more than 20 mol% with respect to all units of the (meth) acrylate polymer. Is preferred.
Two or more hydroxyalkyl (meth) acrylates may be used in combination.
　（メタ）アクリレートポリマーは、アルキル（メタ）アクリレートに基づく単位およびヒドロキシ（メタ）アクリレートに基づく単位以外の単位を、（メタ）アクリレートポリマーが含む全単位に対して、２５モル％未満含んでいてもよい。他のモノマーの具体例としては、不飽和カルボン酸、加水分解性シリル基含有モノマー、水酸基含有アルキルビニルエーテル、カルボン酸ビニルエステル、α－オレフィンが挙げられる。 The (meth) acrylate polymer may contain less than 25 mol% of units other than units based on alkyl (meth) acrylate and units based on hydroxy (meth) acrylate with respect to all units contained in the (meth) acrylate polymer. Good. Specific examples of the other monomer include unsaturated carboxylic acid, hydrolyzable silyl group-containing monomer, hydroxyl group-containing alkyl vinyl ether, carboxylic acid vinyl ester, and α-olefin.
　本発明における、フルオロポリマーと（メタ）アクリレートポリマーとの総質量に対するフルオロポリマーの含有量は、３０～７０質量％が好ましく、耐候性と加工性のバランスの観点から、４０～６０質量％がより好ましい。
　本発明の水性分散液がフルオロポリマーの粒子および（メタ）アクリレートポリマーの粒子を含む場合、フルオロポリマーの粒子および（メタ）アクリレートポリマーの粒子の含有量の合計は、水性分散液の全質量に対して、１０～７０質量％が好ましい。
　本発明の水性分散液がコアシェル粒子を含む場合、コアシェル粒子の含有量は、水性分散液の全質量に対して、１０～７０質量％が好ましい。 In the present invention, the content of the fluoropolymer with respect to the total mass of the fluoropolymer and the (meth) acrylate polymer is preferably 30 to 70% by mass, and from the viewpoint of the balance between weather resistance and processability, 40 to 60% by mass is more preferable. preferable.
When the aqueous dispersion of the present invention contains particles of fluoropolymer and particles of (meth) acrylate polymer, the total content of the particles of fluoropolymer and (meth) acrylate polymer is based on the total mass of the aqueous dispersion. 10 to 70% by mass is preferable.
When the aqueous dispersion of the present invention contains core-shell particles, the content of the core-shell particles is preferably 10 to 70% by mass with respect to the total mass of the aqueous dispersion.
　本発明の水性分散液中において、フルオロポリマーの粒子、（メタ）アクリレートポリマーの粒子、およびコアシェル粒子の平均粒子径は、それぞれ独立に、３０～３００ｎｍが好ましく、各粒子が密にパッキングして本塗膜の撥水性がより優れる観点から、５０～２００ｎｍがより好ましく、８０～１５０ｎｍが特に好ましい。 In the aqueous dispersion of the present invention, the average particle diameter of the fluoropolymer particles, the (meth) acrylate polymer particles, and the core-shell particles is preferably independently from 30 to 300 nm. From the viewpoint of more excellent water repellency of the coating film, 50 to 200 nm is more preferable, and 80 to 150 nm is particularly preferable.
　本発明の水性分散液は、塗料溶媒（分散媒）として、水のみか、水と水溶性有機溶媒との混合液を含む。
　混合液における水溶性有機溶媒の具体例としては、メタノール、エタノール、プロパノール、ブタノール、プロピレングリコール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールが挙げられる。混合液における水溶性有機溶剤の含有量は、水１００質量部に対して１～４０質量部が好ましい。
　本発明の水性分散液は、水性分散液の全質量に対して、水を１０～９０質量％含むことが好ましい。 The aqueous dispersion of the present invention contains only water or a mixture of water and a water-soluble organic solvent as a coating solvent (dispersion medium).
Specific examples of the water-soluble organic solvent in the mixed solution include methanol, ethanol, propanol, butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol. The content of the water-soluble organic solvent in the mixed solution is preferably 1 to 40 parts by mass with respect to 100 parts by mass of water.
The aqueous dispersion of the present invention preferably contains 10 to 90% by mass of water with respect to the total mass of the aqueous dispersion.
　本発明の水性分散液には、本発明の効果を損なわない範囲で、上記以外の成分（以下、「他の成分」ともいう。）が含まれていてもよい。
　他の成分の具体例としては、界面活性剤、分子量調整剤が挙げられる。 The aqueous dispersion of the present invention may contain components other than those described above (hereinafter also referred to as “other components”) as long as the effects of the present invention are not impaired.
Specific examples of other components include surfactants and molecular weight regulators.
　本発明の水性分散液の製造方法の一態様としては、水を含む系にて、フルオロオレフィンとモノマー１とモノマー２とを重合させて、単位Ｆと単位１と単位２とを含むフルオロポリマーが水中に分散している水性分散液を得る方法が挙げられる。
　本製造方法では、フルオロオレフィン、モノマー１およびモノマー２に加えて、モノマー３をさらに使用してもよい。また、他のモノマーをさらに使用してもよい。
　それぞれの成分については、本発明の水性分散液において説明した通りなので、その説明を省略する。また、それぞれの成分の使用量は、得られる水性分散液中に含まれる各成分の含有量が、上述した本発明の水性分散液中に含まれる各成分の含有量となるように適宜決定できる。
　重合では、界面活性剤、ラジカル重合開始剤、連鎖移動剤、キレート化剤、ｐＨ調整剤等を添加してよい。
　重合法の具体例としては、乳化重合法、懸濁重合法が挙げられる。
　重合の温度は、通常、０～１００℃である。重合の圧力は、通常、０．２～５ＭＰａである。 As one aspect of the method for producing an aqueous dispersion of the present invention, a fluoropolymer containing units F, 1 and 2 is obtained by polymerizing fluoroolefin, monomer 1 and monomer 2 in a system containing water. The method of obtaining the aqueous dispersion liquid disperse | distributed in water is mentioned.
In this production method, in addition to the fluoroolefin, monomer 1 and monomer 2, monomer 3 may be further used. Other monomers may be further used.
About each component, since it is as having demonstrated in the aqueous dispersion liquid of this invention, the description is abbreviate | omitted. Moreover, the usage-amount of each component can be suitably determined so that content of each component contained in the aqueous dispersion obtained may become content of each component contained in the aqueous dispersion of this invention mentioned above. .
In the polymerization, a surfactant, a radical polymerization initiator, a chain transfer agent, a chelating agent, a pH adjusting agent and the like may be added.
Specific examples of the polymerization method include an emulsion polymerization method and a suspension polymerization method.
The polymerization temperature is usually from 0 to 100 ° C. The polymerization pressure is usually 0.2 to 5 MPa.
　本発明における水性分散液の製造方法の別の態様としては、フルオロポリマーが水中に分散している分散液を得て、つぎに、アルキル（メタ）アクリレートを重合させて、フルオロポリマーをコア部とし（メタ）アクリレートポリマーをシェル部とするコアシェルポリマーが水中に分散している水性分散液を得る態様が挙げられる。
　また、本発明における水性分散液の製造方法の別の態様としては、水を含みフルオロポリマーが水中に分散している第１の水性分散液と、水を含み（メタ）アクリレートポリマーが水中に分散している第２の水性分散液とを混合して、フルオロポリマーおよび（メタ）アクリレートポリマーが水中に分散している水性分散液を得る態様が挙げられる。
　なお、アルキル（メタ）アクリレートに加えて、ヒドロキシアルキル（メタ）アクリレートをさらに併用してもよい。
　各成分については、本発明の水性分散液において説明した通りなので、その説明を省略する。また、本製造方法で使用し得る成分、重合法および重合条件は、上述した水性分散液の製造方法で述べた通りなので、その説明を省略する。 As another aspect of the method for producing an aqueous dispersion in the present invention, a dispersion in which a fluoropolymer is dispersed in water is obtained, and then an alkyl (meth) acrylate is polymerized to use the fluoropolymer as a core part. The aspect which obtains the aqueous dispersion in which the core shell polymer which makes a (meth) acrylate polymer a shell part has disperse | distributed in water is mentioned.
In another embodiment of the method for producing an aqueous dispersion according to the present invention, a first aqueous dispersion containing water and a fluoropolymer dispersed in water, and a (meth) acrylate polymer containing water dispersed in water. The second aqueous dispersion is mixed with the second aqueous dispersion to obtain an aqueous dispersion in which the fluoropolymer and the (meth) acrylate polymer are dispersed in water.
In addition to alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate may be used in combination.
About each component, since it was as having demonstrated in the aqueous dispersion liquid of this invention, the description is abbreviate | omitted. In addition, since the components, polymerization method, and polymerization conditions that can be used in this production method are as described in the method for producing an aqueous dispersion described above, the description thereof is omitted.
　本発明の水性塗料（以下、「本水性塗料」という。）は、本発明の水性分散液を含むほか、顔料（無機着色顔料、有機着色顔料、体質顔料等）、硬化剤、硬化助剤、造膜助剤、増粘剤、消泡剤、光安定剤、表面調整剤、分散剤、防錆剤、シランカップリング剤、防汚剤、紫外線吸収剤、光安定剤、色調調整剤等の添加剤をさらに含んでいてもよい。
　また、本水性塗料は、本発明のフルオロポリマーおよび（メタ）クリレートポリマー以外のポリマーをさらに含んでいてもよい。本水性塗料は、本発明の水性分散液と上記添加剤等とを適宜混合して製造できる。 The aqueous paint of the present invention (hereinafter referred to as “the present aqueous paint”) includes the aqueous dispersion of the present invention, as well as pigments (inorganic colored pigments, organic colored pigments, extender pigments, etc.), curing agents, curing aids, Film-forming aids, thickeners, antifoaming agents, light stabilizers, surface conditioners, dispersants, rust inhibitors, silane coupling agents, antifouling agents, UV absorbers, light stabilizers, color tone adjusters, etc. An additive may further be included.
In addition, the water-based paint may further contain a polymer other than the fluoropolymer and (meth) acrylate polymer of the present invention. The aqueous paint can be produced by appropriately mixing the aqueous dispersion of the present invention with the above additives.
　本水性塗料は、本水性塗料の全質量に対して、本発明の水性分散液を１０～８０質量％含むことが好ましい。本水性塗料における本発明の水性分散液の含有量は、本水性塗料の全質量に対して、１０～６０質量％がより好ましい。上記含有量が１０質量％以上であれば、本塗膜の耐候性が向上し、８０質量％以下であれば、本水性塗料の成膜性が向上する。
　本水性塗料は、本水性塗料の全質量に対して、フルオロポリマー（（メタ）アクリレートポリマーを含む場合には、これらの合計）を１０～９０質量％含むことが好ましい。 The aqueous paint preferably contains 10 to 80% by mass of the aqueous dispersion of the invention based on the total mass of the aqueous paint. The content of the aqueous dispersion of the present invention in the aqueous paint is more preferably 10 to 60% by mass relative to the total mass of the aqueous paint. If the said content is 10 mass% or more, the weather resistance of this coating film will improve, and if it is 80 mass% or less, the film formability of this aqueous coating material will improve.
The water-based paint preferably contains 10 to 90% by mass of a fluoropolymer (the total of these when a (meth) acrylate polymer is included) with respect to the total mass of the water-based paint.
　本発明の塗装物品は、基材と、上記基材上に配置され、本水性塗料を用いて形成されてなる塗膜（本塗膜）と、を有する。
　基材の具体例としては、樹脂、ゴム、木材等の有機質材料、コンクリート、ガラス、セラミックス、石材等の無機質材料、鉄、鉄合金、アルミニウム、アルミニウム合金が挙げられる。
　本塗膜の膜厚は、１０～１００μｍが好ましい。本塗膜の膜厚が１０μｍ以上であれば、本塗膜の撥水性が向上し、１００μｍ以下であれば、本塗膜の耐候性が向上する。 The coated article of this invention has a base material and the coating film (this coating film) arrange | positioned on the said base material and formed using this aqueous coating material.
Specific examples of the substrate include organic materials such as resin, rubber, and wood, inorganic materials such as concrete, glass, ceramics, and stone, iron, iron alloy, aluminum, and aluminum alloy.
The film thickness of this coating film is preferably 10 to 100 μm. If the thickness of the coating film is 10 μm or more, the water repellency of the coating film is improved, and if it is 100 μm or less, the weather resistance of the coating film is improved.
　塗装物品は、基材の表面に本水性塗料を塗布し、乾燥させて本塗膜を形成すると製造できる。本水性塗料は、基材の表面に直接塗布してもよく、基材の表面に公知の表面処理（下地処理等）を施した上に塗布してもよい。さらに、基材に下塗り層を形成した後、下塗り層上に塗布してもよい。また、本水性塗料が硬化剤を含む場合、必要に応じて硬化させて本塗膜を形成してもよい。
　本水性塗料の塗布方法の具体例としては、刷毛、ローラー、ディッピング、スプレー、ロールコーター、ダイコーター、アプリケーター、スピンコーター等の塗装装置を使用する方法が挙げられる。
　塗布後の乾燥温度と硬化温度は、２５℃～３００℃が好ましい。 A coated article can be produced by applying the aqueous paint to the surface of a substrate and drying it to form the coating film. The aqueous paint may be applied directly to the surface of the substrate, or may be applied after a known surface treatment (such as a base treatment) is applied to the surface of the substrate. Furthermore, after forming the undercoat layer on the substrate, it may be applied onto the undercoat layer. Moreover, when this aqueous coating material contains a hardening | curing agent, you may make it harden | cure as needed and may form this coating film.
Specific examples of the application method of the water-based paint include a method using a coating apparatus such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, and a spin coater.
The drying temperature and curing temperature after coating are preferably 25 ° C to 300 ° C.
　以下、例を挙げて本発明を詳細に説明する。例１～例４および例７は実施例、例５および例６は比較例である。ただし本発明はこれらの例に限定されない。なお、後述する表中における各成分の配合量は、質量基準を示す。 Hereinafter, the present invention will be described in detail with examples. Examples 1 to 4 and 7 are examples, and examples 5 and 6 are comparative examples. However, the present invention is not limited to these examples. In addition, the compounding quantity of each component in the table | surface mentioned later shows a mass reference | standard.
〔水性塗料の製造に使用した成分〕
（フルオロポリマー）
　以下のモノマーを用い、後述する例により得られるフルオロポリマーを使用した。
　モノマーＦ：ＣＦ３－ＣＨ＝ＣＨＦ（ＨＦＯ－１２３４ｚｅ）、ＣＦ３－ＣＦ＝ＣＨ２（ＨＦＯ－１２３４ｙｆ）
　モノマーＸ：ＣＦ２＝ＣＦ２（ＴＦＥ）
　モノマー１：ＣＨ２＝ＣＨＯＣＨ２－ｃｙｃｌｏＣ６Ｈ１０－ＣＨ２Ｏ（ＣＨ２ＣＨ２Ｏ）１５Ｈ（ＣＭ－１５ＥＯＶＥ）
　モノマー２：シクロヘキシルビニルエーテル（ＣＨＶＥ）、エチルビニルエーテル（ＥＶＥ）、ネオノナン酸ビニルエステル（Ｖ９）（ＨＥＸＩＯＮ社製。商品名「ベオバ９」）
　モノマー３：シクロヘキサンジメタノールモノビニルエーテル（ＣＨＭＶＥ）
（界面活性剤）
　ＤＫＳ　ＮＬ－１００：ポリオキシエチレンアルキルエーテル（第一工業製薬社製、ノニオン性界面活性剤）
　ＳＬＳ：ラウリル硫酸ナトリウム（日光ケミカルズ（株）社製、アニオン性界面活性剤） [Ingredients used in the manufacture of water-based paints]
(Fluoropolymer)
The following monomers were used and the fluoropolymer obtained by the example mentioned later was used.
Monomer F: CF 3 —CH═CHF (HFO-1234ze), CF 3 —CF═CH 2 (HFO-1234yf)
Monomer X: CF 2 = CF 2 (TFE)
Monomer 1: CH 2 ═CHOCH 2 —cycloC 6 H 10 —CH 2 O (CH 2 CH 2 O) 15 H (CM-15EOVE)
Monomer 2: Cyclohexyl vinyl ether (CHVE), ethyl vinyl ether (EVE), neononanoic acid vinyl ester (V9) (manufactured by HEXION, trade name “Beova 9”)
Monomer 3: Cyclohexanedimethanol monovinyl ether (CHMVE)
(Surfactant)
DKS NL-100: Polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd., nonionic surfactant)
SLS: Sodium lauryl sulfate (manufactured by Nikko Chemicals Co., Ltd., anionic surfactant)
（添加剤）
　硬化剤：Ｂａｙｈｙｄｕｒ３１００（商品名、Ｂａｙｅｒ社製、イソシアネート系硬化剤）
　顔料：Ｄ９１８（商品名、堺化学工業社製）
　分散剤：ＢＹＫ－１９０（商品名、ＢＹＫ－Ｃｈｅｍｉｅ社製）
　消泡剤：デヒドラン　１６２０（商品名、ＢＡＳＦ社製）
　造膜助剤：ＣＳ－１２（商品名、Ａｌｄｒｉｃｈ社製） (Additive)
Curing agent: Bayhydr 3100 (trade name, manufactured by Bayer, isocyanate curing agent)
Pigment: D918 (trade name, manufactured by Sakai Chemical Industry Co., Ltd.)
Dispersant: BYK-190 (trade name, manufactured by BYK-Chemie)
Antifoaming agent: Dehydran 1620 (trade name, manufactured by BASF)
Film-forming aid: CS-12 (trade name, manufactured by Aldrich)
［製造例１］
　真空脱気したオートクレーブ（内容積２．７Ｌ）内に、ＨＦＯ－１２３４ｚｅ（３０６ｇ）、ＨＦＯ－１２３４ｙｆ（７６ｇ）、ＣＭ－１５ＥＯＶＥ（１１１ｇ）、ＥＶＥ（４８ｇ）、Ｖ９（３５８ｇ）、ＣＨＭＶＥ（１０３ｇ）、イオン交換水（１，０００ｇ）、炭酸カリウム（１．５ｇ）、ＤＫＳ　ＮＬ－１００（５０．１ｇ）、ＳＬＳ（１．０ｇ）を撹拌下で導入して昇温し、５０℃に保持した。
　続いて、オートクレーブ内に、過硫酸アンモニウムの０．４質量％水溶液（５０ｍＬ）を連続的に添加しながら２４時間重合した後、オートクレーブ内溶液をろ過し、フルオロポリマーの粒子を含む水性分散液１（固形分濃度４８質量％）を得た。水性分散液１の、フルオロポリマーの粒子の平均粒子径は１１５ｎｍであった。
　なお、水性分散液１が含むフルオロポリマーは、ＨＦＯ－１２３４ｚｅに基づく単位、ＨＦＯ－１２３４ｙｆに基づく単位、ＣＭ－１５ＥＯＶＥに基づく単位、ＥＶＥに基づく単位、Ｖ９に基づく単位、およびＣＨＭＶＥに基づく単位を、この順に４０モル％、１０モル％、２．０モル％、１０モル％、２９モル％、および９．０モル％含むポリマーであった。 [Production Example 1]
In a vacuum degassed autoclave (inner volume 2.7 L), HFO-1234ze (306 g), HFO-1234yf (76 g), CM-15EOOVE (111 g), EVE (48 g), V9 (358 g), CHMVE (103 g) , Ion-exchanged water (1,000 g), potassium carbonate (1.5 g), DKS NL-100 (50.1 g) and SLS (1.0 g) were introduced with stirring, and the temperature was raised and maintained at 50 ° C. .
Subsequently, polymerization was performed for 24 hours while continuously adding a 0.4% by mass aqueous solution of ammonium persulfate (50 mL) into the autoclave, and then the solution in the autoclave was filtered to obtain an aqueous dispersion 1 containing fluoropolymer particles ( A solid concentration of 48% by mass was obtained. The average particle diameter of the fluoropolymer particles in the aqueous dispersion 1 was 115 nm.
The fluoropolymer contained in the aqueous dispersion 1 includes a unit based on HFO-1234ze, a unit based on HFO-1234yf, a unit based on CM-15EOVE, a unit based on EVE, a unit based on V9, and a unit based on CHMVE. The polymer contained 40 mol%, 10 mol%, 2.0 mol%, 10 mol%, 29 mol%, and 9.0 mol% in this order.
［製造例２～７］
　使用するモノマーの種類と量を表１に示すように変更した以外は、合成例１と同様にして、水性分散液２～７をそれぞれ得た。
　製造例１～７で得られた水性分散液の物性をまとめて、表１に示す。 [Production Examples 2 to 7]
Aqueous dispersions 2 to 7 were obtained in the same manner as in Synthesis Example 1 except that the types and amounts of monomers used were changed as shown in Table 1.
The physical properties of the aqueous dispersions obtained in Production Examples 1 to 7 are summarized in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［例１～７］
　顔料（７２ｇ）、分散剤（５ｇ）、消泡剤（０．５ｇ）、およびイオン交換水（２２．５ｇ）を混合し、ミルベースを得た。
　次に、水性分散液１（７０ｇ）、硬化剤（８ｇ）、造膜助剤（５ｇ）、およびミルベース（２５ｇ）を混合し、水性塗料１を得た。水性分散液１を水性分散液２～７にそれぞれ変更した以外は、水性塗料１と同様にして、水性塗料２～７を得た。 [Examples 1 to 7]
A pigment (72 g), a dispersant (5 g), an antifoaming agent (0.5 g), and ion-exchanged water (22.5 g) were mixed to obtain a mill base.
Next, an aqueous dispersion 1 (70 g), a curing agent (8 g), a film-forming auxiliary (5 g), and a mill base (25 g) were mixed to obtain an aqueous paint 1. Aqueous paints 2 to 7 were obtained in the same manner as the aqueous paint 1 except that the aqueous dispersion 1 was changed to the aqueous dispersions 2 to 7, respectively.
（試験板の作製）
　縦１２０ｍｍ、横６０ｍｍ、厚さ１５ｍｍのスレート板の表面に、ＳＫプライマーを、アプリケーターにて乾燥膜厚が１０μｍになるように塗装し、１００℃で２１０秒間乾燥させて下塗り膜を形成した。
　次に、下塗り膜の上に、水性塗料１～７を、それぞれアプリケーターにて乾燥膜厚が５０μｍになるように塗装し、２５℃で６０分養生した後、８０℃で２０分乾燥させて塗膜を形成し、塗膜付きスレート板を得た。得られた塗膜付きスレート板を試験片として、下記評価方法にしたがって評価した。 (Preparation of test plate)
An SK primer was applied to the surface of a slate plate having a length of 120 mm, a width of 60 mm, and a thickness of 15 mm with an applicator so that the dry film thickness was 10 μm, and dried at 100 ° C. for 210 seconds to form an undercoat film.
Next, each of the water-based paints 1 to 7 is applied on the undercoat film with an applicator so that the dry film thickness is 50 μm, cured at 25 ° C. for 60 minutes, and then dried at 80 ° C. for 20 minutes. A film was formed to obtain a slate plate with a coating film. The obtained coated slate plate was used as a test piece and evaluated according to the following evaluation method.
（水性分散液の貯蔵安定性）
　それぞれの水性分散液について、貯蔵時に生じる沈殿物の量から貯蔵安定性を評価した。水性分散液５０ｍＬを遠沈管に入れ、２５℃で２週間静置し、遠沈管の底部に沈んだ沈殿物の量を目盛から読みとった。
　Ａ：沈殿物の量が、０．１ｍＬ以下である。
　Ｂ：沈殿物の量が、０．１ｍＬ超０．５ｍＬ未満である。
　Ｃ：沈殿物の量が、０．５ｍＬ以上である。 (Storage stability of aqueous dispersion)
For each aqueous dispersion, the storage stability was evaluated from the amount of precipitate produced during storage. 50 mL of the aqueous dispersion was placed in a centrifuge tube and allowed to stand at 25 ° C. for 2 weeks, and the amount of the sediment that had settled at the bottom of the centrifuge tube was read from the scale.
A: The amount of the precipitate is 0.1 mL or less.
B: The amount of the precipitate is more than 0.1 mL and less than 0.5 mL.
C: The amount of the precipitate is 0.5 mL or more.
（塗膜の撥水性）
　それぞれの試験片について、試験片に対する水の動的接触角を測定した。
接触角計を用いて、水平に配置した試験片の表面に１０μＬの純水を滴下し、試験片を徐々に傾斜させて、液滴が滑り始める傾斜角度を測定し、動的接触角の値とした。
　Ｓ：試験片に対する水の動的接触角が、２５度以下である。
　Ａ：試験片に対する水の動的接触角が、２５度超３０度以下である。
　Ｂ：試験片に対する水の動的接触角が、３０度超３５度未満である。
　Ｃ：試験片に対する水の動的接触角が、３５度以上である。 (Water repellency of coating film)
For each test piece, the dynamic contact angle of water with respect to the test piece was measured.
Using a contact angle meter, drop 10 μL of pure water onto the surface of a horizontally placed test piece, gradually tilt the test piece, measure the tilt angle at which the droplet starts to slide, and determine the value of the dynamic contact angle. It was.
S: The dynamic contact angle of water with respect to the test piece is 25 degrees or less.
A: The dynamic contact angle of water with respect to the test piece is more than 25 degrees and not more than 30 degrees.
B: The dynamic contact angle of water with respect to the test piece is more than 30 degrees and less than 35 degrees.
C: The dynamic contact angle of water with respect to the test piece is 35 degrees or more.
　それぞれの水性分散液および水性塗料から形成してなる塗膜の評価結果をまとめて、表２に示す。 Table 2 summarizes the evaluation results of the coatings formed from the respective aqueous dispersions and aqueous paints.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、フルオロポリマーが含む全単位に対して、単位Ｆ、および所定量の単位１を含むフルオロポリマーを用いると、水性分散液の貯蔵安定性に優れ、かつ撥水性に優れた塗膜を形成できることが示された。
　なお、２０１７年０４月１８日に出願された日本特許出願２０１７－０８２０３３号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 As shown in Table 2, when the fluoropolymer containing unit F and a predetermined amount of unit 1 is used for all units contained in the fluoropolymer, the aqueous dispersion is excellent in storage stability and water repellency. It has been shown that a coating can be formed.
It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-082033 filed on Apr. 18, 2017 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (15)

  1. 　水および水中に分散しているフルオロポリマーを含む水性分散液であって、
    　前記フルオロポリマーが、ＣＦ３－ＣＨ＝ＣＨＦおよびＣＦ３－ＣＦ＝ＣＨ２からなる群から選択される少なくとも一種に基づく単位、式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位、および式Ｘ２－Ｚ２で表されるモノマーに基づく単位を含み、
    　前記式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位の含有量が、前記フルオロポリマーが含む全単位に対して、１～５モル％であることを特徴とする水性分散液。
    　式中の記号は、以下の意味を示す。
    　Ｘ１およびＸ２はそれぞれ独立に、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－、ＣＨ２＝ＣＨＯＣ（Ｏ）－、ＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－、ＣＨ２＝ＣＨＯ－またはＣＨ２＝ＣＨＣＨ２Ｏ－である。
    　Ｙ１は、２価の連結基である。
    　Ｚ１は、式－Ｏ（Ｍ１Ｏ）ｍＬ１で表される基、または式－Ｃ（Ｏ）ＯＲ１で表される基である。ただし、Ｍ１は炭素数２～４のアルキレン基であり、ｍは６～２４の整数であり、Ｌ１は水素原子、炭素数４以下のアルキル基または式－ＳＯ３ －Ａ＋で表される基であり（式中、Ａ＋はＮＨ４ ＋、Ｎａ＋またはＫ＋である）、Ｒ１は炭素数１～２０のアルキル基である。
    　Ｚ２は、炭素数１～２４の１価の炭化水素基である。     An aqueous dispersion comprising water and a fluoropolymer dispersed in water,
    The fluoropolymer, CF 3 -CH = CHF and CF 3 at least one in-based unit is selected from the group consisting of -CF = CH 2, unit based on a monomer represented by the formula X 1 -Y 1 -Z 1, And units based on monomers of the formula X 2 -Z 2 ,
    An aqueous dispersion characterized in that the content of units based on the monomer represented by the formula X 1 -Y 1 -Z 1 is 1 to 5 mol% with respect to the total units contained in the fluoropolymer.
    The symbols in the formula have the following meanings.
    X 1 and X 2 are each independently CH 2 ═CHC (O) O—, CH 2 ═C (CH 3 ) C (O) O—, CH 2 ═CHOC (O) —, CH 2 ═CHCH 2 OC (O) —, CH 2 ═CHO— or CH 2 ═CHCH 2 O—.
    Y 1 is a divalent linking group.
    Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 . However, M 1 is an alkylene group having 2 to 4 carbon atoms, m is an integer of 6 ~ 24, L 1 is hydrogen atom, alkyl group of 4 or less, or the formula -SO 3 carbon - represented by A + (Wherein A + is NH 4 + , Na + or K + ), and R 1 is an alkyl group having 1 to 20 carbon atoms.
    Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms.
  2. 　前記フルオロポリマーが、ＣＦ３－ＣＨ＝ＣＨＦに基づく単位とＣＦ３－ＣＦ＝ＣＨ２に基づく単位とを含む、請求項１に記載の水性分散液。 Said fluoropolymer, and a unit based on units and CF 3 -CF = CH 2 based on CF 3 -CH = CHF, aqueous dispersion of claim 1.
  3. 　前記フルオロポリマー中のＣＦ３－ＣＨ＝ＣＨＦに基づく単位とＣＦ３－ＣＦ＝ＣＨ２に基づく単位との合計の含有量が、フルオロポリマーが含む全単位に対して、２０～８０モル％である、請求項１または２に記載の水性分散液。 The total content of the CF 3 -CH = CHF to based units and CF 3 -CF = CH 2 in based units of the fluoropolymer is, relative to the total units containing fluoropolymers, 20 to 80 mol% The aqueous dispersion according to claim 1 or 2.
  4. 　前記Ｙ１が炭素数２～１２の２価の飽和炭化水素基である、請求項１～３のいずれか１項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 3, wherein Y 1 is a divalent saturated hydrocarbon group having 2 to 12 carbon atoms.
  5. 　前記式－Ｏ（Ｍ１Ｏ）ｍＬ１で表される基が、式－Ｏ（ＣＨ２ＣＨ２Ｏ）ｍＨで表される基である、請求項１～４のいずれか１項に記載の水性分散液。 The group represented by the formula -O (M 1 O) m L 1 is a group represented by the formula -O (CH 2 CH 2 O) m H. The aqueous dispersion described.
  6. 　前記Ｘ２が、ＣＨ２＝ＣＨＯＣ（Ｏ）－またはＣＨ２＝ＣＨＣＨ２ＯＣ（Ｏ）－である、請求項１～５のいずれか１項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 5, wherein X 2 is CH 2 = CHOC (O)-or CH 2 = CHCH 2 OC (O)-.
  7. 　前記式Ｘ２－Ｚ２で表されるモノマーに基づく単位の含有量が、前記フルオロポリマーが含む全単位に対して、１０～５０モル％である、請求項１～６のいずれか１項に記載の水性分散液。 The content of units based on the monomer represented by the formula X 2 -Z 2 is 10 to 50 mol% with respect to the total units contained in the fluoropolymer, according to any one of claims 1 to 6. The aqueous dispersion described.
  8. 　前記フルオロポリマーが、前記式Ｘ１－Ｙ１－Ｚ１で表されるモノマーに基づく単位以外の、ヒドロキシ基またはカルボキシ基を有する単位をさらに含む、請求項１～７のいずれか１項に記載の水性分散液。 8. The fluoropolymer according to any one of claims 1 to 7, wherein the fluoropolymer further includes a unit having a hydroxy group or a carboxy group other than a unit based on the monomer represented by the formula X 1 -Y 1 -Z 1. Aqueous dispersion.
  9. 　前記ヒドロキシ基またはカルボキシ基を有する単位の含有量が、フルオロポリマーが含む全単位に対して、１～２０モル％である、請求項８に記載の水性分散液。 The aqueous dispersion according to claim 8, wherein the content of the unit having a hydroxy group or a carboxy group is 1 to 20 mol% with respect to all units contained in the fluoropolymer.
  10. 　前記水性分散液が、水に分散している（メタ）アクリレートポリマーをさらに含む、請求項１～９のいずれか１項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 9, wherein the aqueous dispersion further comprises a (meth) acrylate polymer dispersed in water.
  11. 　前記フルオロポリマーが、（メタ）アクリレートポリマーをさらに含み、
    　前記フルオロポリマーおよび前記（メタ）アクリレートポリマーが、前記フルオロポリマーをコア部とし前記（メタ）アクリレートポリマーをシェル部とするコアシェルポリマーである、請求項１～９のいずれか１項に記載の水性分散液。     The fluoropolymer further comprises a (meth) acrylate polymer;
    The aqueous dispersion according to any one of claims 1 to 9, wherein the fluoropolymer and the (meth) acrylate polymer are core-shell polymers having the fluoropolymer as a core portion and the (meth) acrylate polymer as a shell portion. liquid.
  12. 　前記水性分散液が含むポリマーの粒子の平均粒子径が、３０～３００ｎｍである、請求項１～１１のいずれか１項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 11, wherein an average particle size of the polymer particles contained in the aqueous dispersion is 30 to 300 nm.
  13. 　請求項１～１２のいずれか１項に記載の水性分散液を含む、水性塗料。 An aqueous paint containing the aqueous dispersion according to any one of claims 1 to 12.
  14. 　前記水性塗料がさらに硬化剤を含む、請求項１３に記載の水性塗料。 The water-based paint according to claim 13, wherein the water-based paint further contains a curing agent.
  15. 　基材と、前記基材上に配置され、請求項１３または１４に記載の水性塗料を用いて形成されてなる塗膜と、を有する、塗装物品。 A coated article comprising: a base material; and a coating film disposed on the base material and formed using the water-based paint according to claim 13 or 14.
PCT/JP2018/015905 2017-04-18 2018-04-17 Aqueous dispersion liquid, aqueous coating material, and coated article WO2018194068A1 (en)

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