WO2017122700A1 - Aqueous dispersion, production process therefor, water-based coating material, and coated article - Google Patents

Aqueous dispersion, production process therefor, water-based coating material, and coated article Download PDF

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Publication number
WO2017122700A1
WO2017122700A1 PCT/JP2017/000685 JP2017000685W WO2017122700A1 WO 2017122700 A1 WO2017122700 A1 WO 2017122700A1 JP 2017000685 W JP2017000685 W JP 2017000685W WO 2017122700 A1 WO2017122700 A1 WO 2017122700A1
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group
aqueous dispersion
monomer
aqueous
fluoropolymer
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PCT/JP2017/000685
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French (fr)
Japanese (ja)
Inventor
祐二 原
鷲見　直子
高生 廣野
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旭硝子株式会社
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Priority to CN201780006788.9A priority Critical patent/CN108603002B/en
Priority to JP2017561144A priority patent/JP6841238B2/en
Publication of WO2017122700A1 publication Critical patent/WO2017122700A1/en

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • 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
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to an aqueous dispersion containing a fluoropolymer, a method for producing the same, an aqueous paint and a coated article.
  • An aqueous dispersion containing a fluorine-containing polymer obtained by polymerizing CF 2 ⁇ CF 2 or CF 2 ⁇ CFCl, a monomer having a crosslinkable group, CH 2 ⁇ CF 2, or the like has weather resistance, water resistance It is useful as a water-based paint that forms a coating film having excellent properties, chemical resistance, heat resistance, and the like.
  • Patent Document 1 discloses a fluorine-containing polymer obtained by polymerizing a fluoroolefin, a monomer having a polyoxyalkylene group in a side chain, and a monomer having a hydroxyl group in an aqueous medium in the presence of a polymerization initiator.
  • An aqueous dispersion containing coalescence and an aqueous paint prepared from the aqueous dispersion are disclosed.
  • the present inventors are prone to coloration in an aqueous dispersion containing a fluoropolymer using a persulfate as a polymerization initiator, and further, an aqueous paint containing the aqueous dispersion, and an aqueous paint containing the aqueous dispersion. It was found that coloring is likely to occur even in the coating film. Further, it has been found that the pH of the aqueous dispersion containing the fluoropolymer decreases with time, and that the thixotropy of the aqueous paint containing the aqueous dispersion is not stable.
  • the present invention provides an aqueous dispersion containing a fluoropolymer, which can be prepared into an aqueous paint having excellent coloring stability and pH stability, and excellent thixotropic stability, and its efficient
  • the purpose is to provide a manufacturing method.
  • Another object of the present invention is to provide a water-based paint and a coated article excellent in thixotropic stability.
  • the present invention is an aqueous dispersion having the following constitution that solves the above problems, a method for producing the same, an aqueous paint containing the aqueous dispersion, and a coated article having a coating film formed from the aqueous paint.
  • An aqueous dispersion comprising at least one selected component, wherein the content of the component is 0.01 to 0.22 mmol in terms of persulfate per 100 g of the fluoropolymer.
  • the monomer having a crosslinkable group is a monomer having a hydroxyl group, hydrolyzable silyl group, carboxy group, amino group, isocyanate group, epoxy group or oxetanyl group.
  • An aqueous dispersion of any one of [6] The aqueous dispersion according to [5], wherein the monomer having a crosslinkable group is a monomer having a hydroxyl group or a carboxy group.
  • the monomer having a crosslinkable group and a hydrophilic part is a monomer represented by JQ- [O—Y—] n —OH (where J is a vinyloxy group or an allyloxy group) , Q is an alkylene group having 1 to 10 carbon atoms or an alkylene group having a ring structure having 6 to 10 carbon atoms, Y is an alkylene group having 2 to 4 carbon atoms (provided that at least part of n Y is a dimethylene group) , N represents an integer of 2 to 20, and an aqueous dispersion of [7].
  • a method for producing the aqueous dispersion according to any one of [1] to [10], A monomer mixture containing a fluoroolefin and a monomer having a crosslinkable group in an aqueous medium in the presence of a persulfate in an amount of 0.01 to 0.22 mmol with respect to 100 g of the total monomer mixture.
  • the method for producing an aqueous dispersion according to [11], wherein the polymerization in the aqueous medium is emulsion polymerization.
  • aqueous paint comprising the aqueous dispersion of any one of [1] to [10].
  • an aqueous dispersion that can be prepared into an aqueous paint excellent in coloring stability and pH stability and excellent in thixotropic stability, and an efficient production method thereof.
  • water-based paints and coated articles excellent in thixotropic stability can also be provided.
  • unit based on monomer means an atomic group directly formed by polymerization of one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group. It is a generic name. Hereinafter, the unit based on the monomer is also simply referred to as “unit”.
  • the content (mol%) of each unit of the fluoropolymer can be determined by analyzing the fluoropolymer by nuclear magnetic resonance spectroscopy, but can also be estimated from the charged amount of each monomer.
  • the “crosslinkable group” means a group capable of forming a crosslinked structure by reacting with a curing agent, or a group capable of forming a crosslinked structure by reacting with each other.
  • the “curing agent” means a compound having two or more groups capable of reacting with the “crosslinkable group” and capable of forming a crosslinked structure by reacting with the crosslinkable group.
  • (Meth) acrylate is a general term for acrylate and methacrylate.
  • the aqueous dispersion of the present invention is an aqueous dispersion in which a fluoropolymer having a unit based on a fluoroolefin and a unit based on a monomer having a crosslinkable group is dispersed in an aqueous medium. At least one component selected from the group consisting of (hereinafter also referred to as “salt component”), and the content of the salt component is 0.01 to 100 g in terms of persulfate per 100 g of the fluoropolymer. 0.22 mmol.
  • the aqueous dispersion of the present invention is an aqueous dispersion obtained by a polymerization method described in the method for producing an aqueous dispersion described later.
  • the aqueous dispersion of the present invention contains at least an aqueous medium, a fluoropolymer and a salt component, and may contain components used in the polymerization in addition to these.
  • components used in the polymerization include emulsifiers and chain transfer agents described in the method for producing an aqueous dispersion described later.
  • the aqueous medium in the present invention is water or a mixture of water and a water-soluble organic solvent.
  • the water-soluble organic solvent include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
  • the content of the water-soluble organic solvent is preferably 1 to 40 parts by mass and more preferably 3 to 30 parts by mass with respect to 100 parts by mass of water.
  • the fluoropolymer in the present invention is composed of a unit (hereinafter also referred to as “unit 1”) based on a fluoroolefin (hereinafter also referred to as “monomer 1”) and a monomer having a crosslinkable group (hereinafter referred to as “unit 1”). And a unit based on “monomer 2” (hereinafter also referred to as “unit 2”).
  • the fluoropolymer may be a unit based on a monomer other than monomer 1 and monomer 2 (hereinafter also referred to as “monomer 3”) (hereinafter also referred to as “unit 3”). .) May further be included.
  • the content of the fluoropolymer in the aqueous dispersion is preferably 10 to 70% by mass, particularly preferably 20 to 60% by mass, based on the total mass of the aqueous dispersion. If content of a fluoropolymer is more than the said lower limit, superposition
  • the monomer 1 in the present invention is a compound in which one or more hydrogen atoms of the olefin are substituted with fluorine atoms.
  • one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
  • Monomer 1 may use 2 or more types together.
  • the crosslinkable group of the monomer 2 is preferably a hydroxyl group, a hydrolyzable silyl group, a carboxy group, an amino group, an isocyanate group, an epoxy group or an oxetanyl group, and particularly preferably a hydroxyl group or a carboxy group.
  • Examples of the monomer 2 in which the crosslinkable group is a hydroxyl group include hydroxyalkyl vinyl ether (hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), cycloalkane having a hydroxyl group and a vinyloxy group (cyclohexanedi).
  • Methanol monovinyl ether, etc. ethylene glycol monovinyl ether (diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, etc.), hydroxyalkyl allyl ether (hydroxyethyl allyl ether, hydroxybutyl allyl ether, etc.), hydroxyl group and Cycloalkanes having an allyloxy group (such as cyclohexane dimethanol monoallyl ether), hydroxyalkyl vinyl esters (Hydroxyethyl carboxylic acid vinyl ester, hydroxybutyl carboxylic acid vinyl ester, etc.), cycloalkane having a hydroxyl group and a vinyloxycarbonyl group (((hydroxymethylcyclohexyl) methoxy) acetic acid vinyl ester, etc.), hydroxyalkyl carboxylic acid allyl ester (Hydroxyethylcarboxylic acid
  • Monomers 2 having a carboxy group as a crosslinkable group include unsaturated monocarboxylic acids (3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 6-heptenoic acid, 3-octenoic acid, 7-octenoic acid, 2-nonenoic acid, 3-nonenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc.), saturated monocarboxylic acid vinyl ether (vinyloxyvaleric acid, 3-vinyloxypropionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid, 3- (2-vinyloxyethoxycarbonyl) propionic acid, etc.), saturated monocarbox
  • Examples of the monomer 2 (monomer having an amino group) in which the crosslinkable group is an amino group include aminoalkyl vinyl ether, aminoalkyl vinyl ester, aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide, and the like.
  • Examples of the monomer 2 in which the crosslinkable group is an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 2-isocyanate ethyl ethoxy methacrylate, and 2-isocyanate ethyl vinyl ether. Can be mentioned.
  • Monomers 2 having an epoxy group as a crosslinkable group include glycidyl vinyl ether, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl. Examples thereof include vinyl ether and 4-vinyloxymethylcyclohexyl glycidyl ether.
  • the other monomer 2 include a monomer having a crosslinkable group and a hydrophilic site (hereinafter also referred to as “macromonomer”).
  • the hydrophilic part means a part having a hydrophilic group, a part having a hydrophilic bond, or a part composed of a combination of these parts.
  • the hydrophilic group may be ionic, nonionic or amphoteric. From the viewpoint of chemical stability of the aqueous dispersion, a portion having a nonionic or amphoteric hydrophilic group and a portion having another hydrophilic group are combined, or a portion having a hydrophilic group and a hydrophilic group are hydrophilic. It is preferable to combine with a site having a bond.
  • the macromonomer examples include a compound represented by JQ- [O—Y—] n —OR, a compound represented by JQO (C (O) —Z—O—) m R (Wherein, in each formula, J is a vinyloxy group or allyloxy group, Q is an alkylene group having 1 to 10 carbon atoms or an alkylene group having a ring structure having 6 to 10 carbon atoms, Y is 1 to carbon atoms) 4 represents an alkylene group, R represents a hydrogen atom, n represents an integer of 2 to 20, Z represents an alkylene group having 1 to 10 carbon atoms, and m represents an integer of 1 to 30. The same shall apply hereinafter).
  • the group represented by — [O—Y —] — is preferably an oxyethylene group (that is, Y is a dimethylene group).
  • the hydrophilic moiety represented by — [O—Y—] n — represents two or more groups represented by — [O—Y —] — (for example, —OCH 2 CH 2 — and —OCH 2 It may be composed of CH (CH 3 )-).
  • Each group in the case of being composed of two or more groups may be arranged in either block or random form.
  • n Y is an alkylene group having 2 to 4 carbon atoms (where n It is preferable that at least a part of Y is a dimethylene group.)
  • n Y is an alkylene group other than a dimethylene group, —CH 2 CH (CH 3 ) — is preferable, and 50% or more of n Y Is preferably a dimethylene group, more preferably 80 to 100% is a dimethylene group.
  • the macromonomer may be a monomer having a chain obtained by radical polymerization of a hydrophilic ethylenically unsaturated monomer and having a radical polymerizable unsaturated group such as a vinyloxy group or an allyloxy group at one end. Good.
  • Such macromonomers are described in Polym. Bull. , 5.335 (1981). That is, a polymer having a condensable functional group is produced by radical polymerization of an ethylenically unsaturated monomer having a hydrophilic group in the presence of a polymerization initiator having a condensable functional group and a chain transfer agent.
  • Ethylenically unsaturated monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, 2-methoxyethyl (meth) acrylate, diacetone acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth ) Acrylate, hydroxybutyl (meth) acrylate, vinylpyrrolidone and the like.
  • the monomer 2 may use 2 or more types together.
  • the monomer 3 in the present invention is not particularly limited, and is olefin (ethylene, propylene, etc.), alkyl vinyl ether (ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, etc.), cycloalkyl vinyl ether (cyclohexyl vinyl ether, etc.).
  • Alkyl vinyl esters (butanoic acid vinyl ester, octanoic acid vinyl ester, pivalic acid vinyl ester, etc.), alkyl allyl esters (butanoic acid allyl ester, octanoic acid allyl ester, pivalic acid allyl ester, etc.), aromatic vinyl (Styrene, vinyl toluene, etc.), allyl ether (ethyl allyl ether, etc.), (meth) acrylate (methyl (meth) acrylate, butyl (meth) acrylate, etc.) And the like.
  • alkyl vinyl ether, cycloalkyl vinyl ether and alkyl vinyl ester are preferable.
  • the compound represented by JQ- [O—Y—] n —OR described above, or JQO (C (O) —ZO) m examples thereof include compounds represented by R, wherein R is substituted with an alkyl group having 1 to 3 carbon atoms.
  • the ratio of the content (mol%) of unit 1 to the content (mol%) of unit 2 is 0.5 to 800. Is preferable, and 1.5 to 300 is more preferable. When the ratio is within this range, not only the dispersibility in the aqueous dispersion is further improved, but also the weather resistance and water resistance of the resulting coating film are improved.
  • the fluoropolymer in the present invention further contains unit 3, the ratio of the content of unit 3 to the total content of units 1 and 2 (content of unit 3 / content of unit 1 and unit 2) The sum of the contents is preferably 0.1 to 1.5.
  • the content of unit 1 in the fluoropolymer is preferably from 30 to 70 mol%, more preferably from 35 to 65 mol%, still more preferably from 40 to 60 mol%, based on all units of the fluoropolymer. .
  • the content of unit 2 in the fluoropolymer is preferably 0.5 to 30 mol%, more preferably 1.0 to 20 mol%, more preferably 1.5 to 15 mol% is more preferable.
  • the content of unit 3 in the fluoropolymer is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, still more preferably 30 to 60 mol%, based on the total units of the fluoropolymer. .
  • Preferable specific examples of the fluorinated polymer in the present invention include 29.5 to 70 mol% of unit 1, 0.5 to 30 mol% of unit 2 and units of the total amount of all units of the polymer. 3 to 20 to 70 mol%, and more preferable specific examples include units 1 to 34 to 65 mol%, units 2 to 1.0 to 20 mol% and units 3 to 25 to 65 mol%. The polymer which has is mentioned.
  • the fluoropolymer is preferably dispersed in the form of particles in an aqueous medium.
  • the average particle diameter of the fluoropolymer dispersed in the form of particles is preferably 200 nm or less, and particularly preferably 180 nm or less.
  • the lower limit is generally 50 nm.
  • the average particle size is 200 nm or less, the effect of the color stability of the aqueous dispersion becomes remarkable. The reason is not necessarily clear, but it can be considered as follows.
  • the crosslinkable group possessed by the fluoropolymer is a hydroxyl group or a carboxy group, it is considered that the coloring stability of the aqueous dispersion is particularly likely to decrease.
  • the regulation of the content of the salt component in the present invention functions remarkably as a factor for suppressing such a decrease in coloring stability.
  • the average particle size of the fluoropolymer is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.).
  • D50 represents the particle diameter of a volume cumulative 50 volume% calculated from the small particle side in the particle size distribution of the particle measured by the dynamic light scattering method.
  • the salt component in the present invention is a persulfate residue and / or a persulfate decomposition product used as a polymerization initiator when producing a fluoropolymer.
  • the salt component not only causes coloration of the aqueous dispersion by further decomposition during storage, but also causes a decrease in pH of the aqueous dispersion over time.
  • the persulfate in the present invention is preferably ammonium persulfate, potassium persulfate, or sodium persulfate.
  • the content of the salt component in the aqueous dispersion is 0.01 to 0.22 mmol in terms of persulfate, preferably 0.01 to 0.15 mmol, with respect to 100 g of the fluoropolymer. Is more preferably 0.10 mmol, and further preferably 0.01 to 0.05 mmol.
  • the content of the salt component is the total content of persulfate and its decomposition product (including the case where either the persulfate or its decomposition product is not included). If the content of the salt component is at least the above lower limit, the polymerization proceeds rapidly and the monomer is polymerized at a high reaction rate, so that a fluoropolymer can be obtained efficiently.
  • the content of the salt component is not more than the above upper limit value, not only the coloring stability of the aqueous dispersion, the aqueous coating material, and the coating film formed from the aqueous coating material (hereinafter also referred to as the present coating film) is excellent, but also aqueous.
  • the pH stability of the dispersion and water-based paint is improved.
  • the thixotropic stability of the aqueous dispersion and the aqueous paint is improved.
  • the color stability of the aqueous dispersion and the water-based paint over time is improved, the color stability of the coating film is further improved.
  • the thixotropy stability of water-based paints is improved, the “easy to apply and dripping resistance” of water-based paints is improved, and it can be applied uniformly to articles (objects to be coated). Improves. That is, when preparing a water-based paint from an aqueous dispersion, usually a thickener is added to adjust the thixotropy of the water-based paint to an appropriate range.
  • the coating uniformity is not lowered.
  • the method for producing an aqueous dispersion of the present invention is the method for producing an aqueous dispersion of the present invention, wherein a monomer mixture containing monomer 1 and monomer 2 is aqueous in the presence of persulfate.
  • This is a method of polymerizing in a medium.
  • the amount of persulfate used is 0.01 to 0.22 mmol with respect to 100 g of the total amount of the monomer mixture.
  • the monomer mixture may further include a monomer 3 as necessary.
  • the types of the monomer 1, the monomer 2 and the monomer 3 and the definition of the aqueous medium are as described in the aqueous dispersion of the present invention.
  • the suitable aspect of a fluoropolymer is also as having demonstrated with the aqueous dispersion liquid of this invention.
  • the monomer 1, the monomer 2, and the monomer 3 used as necessary are such that the units 1, 2 and 3 of the fluoropolymer to be produced have a desired ratio.
  • the ratio of the content (mol%) of unit 1 to the content (mol%) of unit 2 (content of unit 1 / content of unit 2) is 0.00.
  • examples thereof include fluorine-containing polymers having a molecular weight of 5 to 800, and more preferably fluorine-containing polymers having a molecular weight of 1.5 to 300.
  • the fluoropolymer further contains unit 3, the ratio of the content of unit 3 to the total content of units 1 and 2 (content of unit 3 / content of unit 1 and content of unit 2)
  • examples thereof include fluorine-containing polymers having a sum of the amounts of 0.1 to 1.5.
  • Ratio of the number of moles of monomer 3 to the total number of moles of monomer 1 and monomer 2 (number of moles of monomer 3 / (number of moles of monomer 1 + number of moles of monomer 2)) Is preferably 0.1 to 1.5.
  • the persulfate in the production method of the present invention is preferably ammonium persulfate, potassium persulfate or sodium persulfate.
  • the amount of persulfate used is 0.01 to 0.22 mmol with respect to 100 g of the total monomer mixture.
  • the amount of persulfate used is preferably 0.01 to 0.15 mmol, and preferably 0.01 to 0.10 mmol in terms of persulfate per 100 g of the total monomer mixture. More preferred is 0.01 to 0.05 mmol.
  • the amount of persulfate used is theoretically equal to the content of the salt component.
  • another polymerization initiator may be used in combination with the persulfate.
  • Other polymerization initiators include redox initiators composed of a combination of hydrogen peroxide and sodium hydrogen sulfite, polymerization initiators mixed with inorganic initiators such as ferrous salts and silver nitrate, disuccinic acid peroxide, and diglutar. Examples thereof include organic polymerization initiators such as acid peroxide and azobisbutyronitrile.
  • the amount used is preferably from 1 to 100 mol%, more preferably from 5 to 95 mol%, based on the persulfate.
  • the polymerization in the aqueous medium in the production method of the present invention is preferably emulsion polymerization.
  • an emulsifier is usually used.
  • the emulsifier is preferably a nonionic emulsifier or an anionic emulsifier.
  • Nonionic emulsifiers include alkylphenol ethylene oxide adducts, higher alcohol ethylene oxide adducts, block copolymers of ethylene oxide and propylene oxide, and the like.
  • anionic emulsifier examples include alkyl benzene sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, alkyl sulfate ester salt, alkyl ether sulfate ester salt, and phosphate ester salt.
  • the amount of the emulsifier used may be determined depending on the type of the monomer. If the macromonomer described above has a stabilizing effect on the polymerization system such as the emulsifier, the emulsifier may not be used.
  • the degree of polymerization (molecular weight) of the fluoropolymer may be adjusted using a chain transfer agent. Also, the total concentration of monomers in the aqueous medium can be increased.
  • Chain transfer agents include alkyl mercaptans (tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, etc.), aminoethanethiol, mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, thioglycolic acid 3,3′-dithio-dipropionic acid, 2-ethylhexyl thioglycolate, n-butyl thioglycolate, methoxybutyl thioglycolate, ethyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene And carbon te
  • the amount of the chain transfer agent used is preferably 0 to 2% by mass with respect to the monomer mixture.
  • the polymerization method of the production method of the present invention is not particularly limited, and examples thereof include a batch polymerization method, a dropping polymerization method in which a monomer mixture is dropped, and a continuous polymerization method.
  • the aqueous paint of the present invention is an aqueous paint containing the aqueous dispersion of the present invention, which contains a salt component, and the content of the salt component is 0.01 to 100 g in terms of persulfate per 100 g of the fluoropolymer. 0.22 mmol.
  • the aqueous paint of the present invention is usually obtained by diluting the above aqueous dispersion of the present invention with an aqueous medium or the like and adding an additive as necessary.
  • the aqueous medium used for dilution is the same as the aqueous medium described in the aqueous dispersion of the present invention.
  • the amount of the aqueous medium used for dilution is not particularly limited, but is preferably such that the content of the fluoropolymer in the aqueous coating is 5 to 60% by mass with respect to the total amount of the aqueous coating.
  • the amount of mass% is more preferable. If the content of the fluoropolymer is the above lower limit, a coating film superior in weather resistance can be obtained, and if the content is the above upper limit, the transparency of the coating film is more excellent.
  • the content of the salt component in the water-based paint is 0.01 to 0.22 mmol in terms of persulfate per 100 g of the fluoropolymer, preferably 0.01 to 0.15 mmol, and preferably 0.01 to 0.1. 10 mmol is more preferable, and 0.01 to 0.05 mmol is particularly preferable. If the content of the salt component is within the above range, coloring during storage of the aqueous paint and a decrease in the pH of the aqueous paint over time can be suppressed. In addition, when preparing an aqueous coating material by adding various additives etc. to an aqueous dispersion, a salt component may mix.
  • a salt component derived from the polymerization initiator of the polymer may be mixed.
  • the content of the salt component in the aqueous paint of the present invention is preferably within the above range.
  • the water-based paint of the present invention is a polymer other than the fluorinated polymer, emulsifier, and colorant, in addition to the aqueous dispersion and the aqueous medium used for dilution, as long as the effects of the present invention are not hindered.
  • Curing agents, and other additives may be included.
  • the water-based paint of the present invention can contain a colorant.
  • curing agent in the water-based coating material of this invention the weather resistance, water resistance, chemical resistance, heat resistance, etc. of the obtained coating film further improve.
  • the water-based paint of the present invention may be either a one-pack type or a two-pack type, but when a curing agent is included, it is preferably a two-pack type and the two liquids are mixed immediately before use.
  • the other polymer is not particularly limited, and examples thereof include (meth) acrylic polymers, polyester resins, polyurethane resins, epoxy resins, acrylic silicone resins, melamine resins, urea resins, and vinyl resins. Resins, fluorine resins, phenol resins, alkyd resins and the like can be mentioned.
  • the content of the other polymer in the aqueous paint is preferably 10 to 60% by mass. If the content of the other polymer is set to the above lower limit value, the characteristics of the other polymer can be exhibited. On the other hand, if the content is the above upper limit value, the characteristics of the fluoropolymer are not impaired.
  • An emulsifier may be added to the water-based paint of the present invention for the purpose of improving the emulsion stability.
  • the kind of the emulsifier contained in the aqueous paint is the same as the emulsifier described in the aqueous dispersion of the present invention.
  • the colorant include dyes, organic pigments, and inorganic pigments.
  • the content of the colorant is preferably 1 to 300% by mass with respect to 100 as the total amount of the water-based paint.
  • the curing agent examples include block isocyanates such as hexamethylene isocyanate trimer or emulsion dispersions thereof, melamine resins such as methylated melamine, methylolated melamine, and butyrolated melamine, and urea resins such as methylated urea and butylated urea. Etc.
  • the content of the curing agent is preferably 10 to 150 mol% of the total amount of monomers used.
  • additives include plasticizers, UV absorbers, leveling agents, anti-repellent agents, anti-burr agents, and the like.
  • the coated article of the present invention has a coating film of the aqueous paint of the present invention on the surface of the article.
  • the coated article of the present invention can be produced by applying the aqueous paint of the present invention to the surface of the article and drying to form a coating film.
  • the article is not particularly limited, and examples thereof include a metal plate, a wooden plate, a plastic plate, a glass plate, asphalt, and concrete.
  • Examples of the coating method include a method using a coating apparatus such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, or a spin coater.
  • the thickness of the coating film is preferably 5 to 50 ⁇ m.
  • the thickness of the coating film is the above lower limit value, a fluorescent coating film with high visibility and design is obtained, and if it is the above upper limit value, there is no difference in the degree of curing between the surface layer of the coating film and the inside, and uniform coating is achieved. A membrane is obtained.
  • the drying temperature after coating is preferably about 25 to 300 ° C.
  • the aqueous dispersion of the present invention since the amount of persulfate used in the polymerization is small, the aqueous dispersion of the present invention having a small salt component content can be produced.
  • the aqueous dispersion of the present invention is excellent in coloring stability and pH stability because the content of the salt component is small.
  • the viscosity is often adjusted by adding a thickener or the like so as to obtain an optimum viscosity as a coating material. It is known that the viscosity of water-based paints varies depending on the pH of the aqueous dispersion.
  • the viscosity changes over time, even if the viscosity is adjusted optimally when preparing a water-based paint, In addition, the viscosity changes with the change in pH, and the viscosity at the time of use of the water-based paint deviates from the optimum value. Since the aqueous dispersion of the present invention is excellent in pH stability, when it is used as an aqueous paint, there is little change in viscosity and excellent thixotropy. Further, the water-based paint of the present invention is excellent in thixotropic stability, and the viscosity of the paint is maintained in an optimum range, so that it can be applied uniformly to an article.
  • the water-based paint of the present invention and the coating film formed using the same are also excellent in color stability and uniformity.
  • the coating film formed from the aqueous paint of the present invention prepared from the aqueous dispersion of the present invention containing the fluoropolymer having units 1 and 2 has a weather resistance, water resistance, chemical resistance, heat resistance Excellent in properties.
  • ⁇ Measurement method> [Calculation of the amount of persulfate] (Titration of ammonium iron (II) sulfate with aqueous dispersion) W (g) of the aqueous dispersion was dissolved in 10 g of ion-exchanged water, and this was used as a sample solution. 20 mL of 90 g / L ammonium iron sulfate (II) aqueous solution and 20 mL of phosphoric acid were added to the sample solution to obtain a mixed solution. A 0.02 mol / L potassium permanganate aqueous solution was added dropwise to the mixed solution until the solution turned a slight red color. The titer at that time was A (mL).
  • the concentration C (mass%) of persulfate in the aqueous dispersion was calculated by the following formula (1).
  • the concentration of persulfate in the water-based paint can be calculated in the same manner.
  • C ⁇ (BA) ⁇ f ⁇ Mw ⁇ 0.00005 / W ⁇ ⁇ 100 (1)
  • f 0.02 mol / L
  • Mw molecular weight of persulfate.
  • the persulfate in the sample solution is previously oxidized and reduced with iron iron (II) sulfate, and the excess ammonium iron sulfate (II) is back titrated with potassium permanganate to determine the amount of persulfate. It is a method of measuring.
  • the redox reaction of ammonium iron sulfate (II) and potassium permanganate is represented by the following formula (61).
  • Equation (63) is derived from the titration amount A, titration amount B, and formulas (61) and (62), which are the results of the above titration.
  • C ⁇ (BA) /1000 ⁇ 0.02 ⁇ f ⁇ 5/2 ⁇ Mw/W ⁇ ⁇ 100 (63)
  • equation (6) is derived.
  • Specific values of f are determined using a standardization method (hereinafter referred to as a direct method) performed using a “standard substance” for volumetric analysis or a “standard solution” for volumetric analysis whose factors have already been determined by the direct method. It is determined by the orientation method (referred to as indirect method), and is 1.003 in this measurement.
  • Y (C / X) ⁇ 100 / Mw (7)
  • X Fluoropolymer solid content concentration (mass%) in the aqueous dispersion.
  • the amount of sulfate ion which is a decomposition product of persulfate, was calculated by the following procedure.
  • the amount of sulfate ion in the water-based paint can be calculated in the same manner.
  • a sample solution obtained by diluting the prepared aqueous dispersion 1000 times with ultrapure water was put in an ultrafilter and centrifuged for 60 minutes at 4000 rpm using a rotor having a radius of 13 cm (“H-18” manufactured by Kokusan). .
  • the filtrate was diluted 10 times with ultrapure water to obtain a sample diluted solution.
  • the sulfate ion concentration I ( ⁇ g / mL) in the diluted solution was measured using an ion chromatography system (manufactured by Nippon Dionex Co., Ltd., ICS-3000). From the result, the amount of sulfate ion (persulfate equivalent) Z (mmol) per 100 g of the fluoropolymer solid content in the aqueous dispersion was calculated by the following formula (8).
  • 96 is the molecular weight of sulfate ion.
  • Z 10 ⁇ I / (d ⁇ X ⁇ 96) (8)
  • d Specific gravity of the aqueous dispersion.
  • X Fluoropolymer solid content concentration (mass%) in the aqueous dispersion.
  • aqueous dispersions (immediately after production) obtained in Examples 1 to 6 and Comparative Example 1 were each diluted 10-fold with ion-exchanged water to obtain diluted samples.
  • the diluted sample was placed in a cylindrical cell (30 ⁇ ⁇ 30 mm), and the YI value was measured with a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000).
  • the aqueous dispersions obtained in Examples 1 to 6 and Comparative Example 1 were stored at 50 ° C. for 2 weeks, and the YI values of the aqueous dispersions after storage were measured in the same manner as described above. It shows that it is not colored, so that YI value is low.
  • aqueous dispersions of Examples 1 to 6 and Comparative Example 1 were respectively formed into a film-forming auxiliary texanol (manufactured by Eastman Chemical Co.), an antifoaming agent Dehydran 1620 (manufactured by San Nopco), and an alkali swelling type thickener TT
  • An aqueous paint was prepared by blending with -615 (Rohm and Hearts) and aqueous ammonia. The blending amount of each material was adjusted so that the viscosity of the water-based paint was within the appropriate range for the thixotropy of the water-based paint.
  • the obtained water-based paint was stored at 50 ° C.
  • Example 1 In an autoclave equipped with a stainless steel stirrer with a container volume of 250 mL, 34 g of cyclohexyl vinyl ether (hereinafter referred to as CHVE), 19 g of 2-ethylhexyl vinyl ether (hereinafter referred to as 2EHVE), cyclohexanedimethanol monovinyl ether (hereinafter referred to as CHMVE).
  • CHVE cyclohexyl vinyl ether
  • 2EHVE 2-ethylhexyl vinyl ether
  • CHMVE cyclohexanedimethanol monovinyl ether
  • CMEOVE 1-vinyloxymethyl-4- (polyoxyethylene) cyclohexyl methyl ether
  • CMEOVE 1-vinyloxymethyl-4- (polyoxyethylene) cyclohexyl methyl ether
  • ion-exchanged water 0.26 g of potassium carbonate, ammonium persulfate (hereinafter referred to as “CMEOVE”)
  • DKS NL-100 nonionic emulsifier
  • anionic emulsifier sodium lauryl sulfate
  • Example 2 to 4 and Comparative Example 1 aqueous dispersions were obtained in the same manner as in Example 1 except that the amount of APS used was changed as shown in Table 1.
  • the average particle size of the fluoropolymer in each example was in the range of 140 to 160 nm.
  • Example 5 In a 250 mL stainless steel autoclave with a stirrer vessel, 1.4 g of CHVE, 37 g of ethyl vinyl ether (hereinafter referred to as EVE), 3.8 g of CHMVE, 3.1 g of CMEOVE, 97 g of ion-exchanged water, 0.26 g of potassium carbonate , 0.0025 g of APS, 5.5 g of nonionic emulsifier (DKS NL-100: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 0.1 g of SLS were charged with ice and cooled to 0.5 MPa with nitrogen gas. Pressurize and deaerate.
  • EVE ethyl vinyl ether
  • Example 6 An aqueous dispersion containing a particulate fluoropolymer in the same manner as in Example 3 except that the amount of nonionic emulsifier (DKS NL-100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 2.6 g. A liquid was obtained. The average particle size of the fluoropolymer particles was 210 nm.
  • DKS NL-100 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • the latex yield indicates the ratio (mass%) of the solid content in the post-polymerization reaction liquid with respect to the ratio of the total amount of raw materials other than ion-exchanged water in the raw material (the same applies hereinafter).
  • the content of the salt component (persulfate equivalent) was determined by adding the persulfate amount and the sulfate ion amount.
  • chromaticity (YI value) and pH were measured and thixotropic stability was evaluated.
  • Table 1 shows the measurement results and evaluation results of thixotropic stability. Table 1 shows the absolute value of the difference between the value immediately after production and the value after storage at 50 ° C. for 2 weeks for the YI value and pH.
  • the change width of the value was ⁇ 0.7 or less, which was lower than that of Comparative Example 1, and coloring was suppressed. Moreover, the change width of the YI value before and after storage was small.
  • Examples 1 to 4 the lower the total content (persulfate equivalent) with respect to 100 g of the fluoropolymer in the aqueous dispersion, the lower the YI value and the smaller the change in the YI value before and after storage. It was.
  • Example 5 in which the types and blending amounts of some of the monomers were different, the total content (persulfate equivalent) with respect to 100 g of the fluoropolymer in the aqueous dispersion was 0.01 mmol. Also in Example 5, the YI value immediately after production was ⁇ 11, and the YI value after storage for 2 weeks at 50 ° C. was ⁇ 9.7, which was lower than that of Comparative Example 1. In addition, there was little change in the YI value before and after storage.
  • Example 6 in which the average particle size of the fluoropolymer particles is 200 nm or less, if the average particle size is 200 nm or less, the YI value immediately after production, It was found that both the YI value after storage for 2 weeks at 50 ° C. and the change width of the YI value before and after storage were small, and coloring was suppressed. In Examples 1 to 6, the difference between the pH immediately after production and the pH after storage at 50 ° C. for 2 weeks was smaller than in Comparative Example 1.
  • the aqueous paint using the aqueous dispersions of Examples 1 to 6 showed less decrease in thixotropy when stored at 50 ° C. for 2 weeks.
  • the amount of persulfate (APS) in Example 5 was half (0.005 mmol)
  • the latex yield was 90%. The fluoropolymer could not be obtained efficiently.
  • the water-based paint containing the aqueous dispersion of the present invention can be used, for example, for the coating of wood or the like used in construction or the like or metals used in devices.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-005299 filed on Jan. 14, 2016 are incorporated herein as the disclosure of the specification of the present invention. It is.

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Abstract

Provided are: an aqueous dispersion capable of giving a water-based coating material which is excellent in terms of coloration stability and pH stability and has highly stable thixotropic properties; a process for producing the aqueous dispersion; a water-based coating material; and a coated article. The aqueous dispersion comprises an aqueous medium and, dispersed therein, a fluoropolymer comprising units based on a fluoroolefin and units based on a monomer having a crosslinkable group, and contains at least one ingredient selected from the group consisting of persulfuric acid salts and products of decomposition thereof, the content of the ingredient being 0.01-0.22 mmol in terms of persulfuric acid salt amount per 100 g of the fluoropolymer.

Description

水性分散液、その製造方法、水性塗料および塗装物品Aqueous dispersion, method for producing the same, water-based paint and coated article
　本発明は、含フッ素重合体を含む水性分散液、その製造方法、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, a method for producing the same, an aqueous paint and a coated article.
　ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌと、架橋性基を有する単量体またはＣＨ２＝ＣＦ２等とを重合させて得られた含フッ素重合体を含む水性分散液は、耐候性、耐水性、耐薬品性、耐熱性等に優れた塗膜を形成する水性塗料として有用である。
　特許文献１には、重合開始剤の存在下、水性媒体中で、フルオロオレフィン、側鎖にポリオキシアルキレン基を有する単量体および水酸基を有する単量体を重合させて得られた含フッ素重合体を含む水性分散液、該水性分散液から調製された水性塗料が開示されている。 An aqueous dispersion containing a fluorine-containing polymer obtained by polymerizing CF 2 ═CF 2 or CF 2 ═CFCl, a monomer having a crosslinkable group, CH 2 ═CF 2, or the like has weather resistance, water resistance It is useful as a water-based paint that forms a coating film having excellent properties, chemical resistance, heat resistance, and the like.
Patent Document 1 discloses a fluorine-containing polymer obtained by polymerizing a fluoroolefin, a monomer having a polyoxyalkylene group in a side chain, and a monomer having a hydroxyl group in an aqueous medium in the presence of a polymerization initiator. An aqueous dispersion containing coalescence and an aqueous paint prepared from the aqueous dispersion are disclosed.
特開平７－１７９８０９号公報Japanese Unexamined Patent Publication No. 7-179809
　本発明者等は、重合開始剤として過硫酸塩を用いた含フッ素重合体を含む水性分散液において着色が生じやすいこと、さらには、該水性分散液を含む水性塗料、該水性塗料から形成される塗膜においても着色が生じやすいことを知見した。また、該含フッ素重合体を含む水性分散液のｐＨは経時的に低くなること、さらには、該水性分散液を含む水性塗料のチクソ性が安定しないことを知見した。
　そこで、本発明は、着色安定性およびｐＨ安定性に優れており、かつ、チクソ性の安定性に優れた水性塗料に調製できる、含フッ素重合体を含む水性分散液、および、その効率的な製造方法の提供を目的とする。また、チクソ性の安定性に優れた水性塗料および塗装物品の提供も目的とする。 The present inventors are prone to coloration in an aqueous dispersion containing a fluoropolymer using a persulfate as a polymerization initiator, and further, an aqueous paint containing the aqueous dispersion, and an aqueous paint containing the aqueous dispersion. It was found that coloring is likely to occur even in the coating film. Further, it has been found that the pH of the aqueous dispersion containing the fluoropolymer decreases with time, and that the thixotropy of the aqueous paint containing the aqueous dispersion is not stable.
Accordingly, the present invention provides an aqueous dispersion containing a fluoropolymer, which can be prepared into an aqueous paint having excellent coloring stability and pH stability, and excellent thixotropic stability, and its efficient The purpose is to provide a manufacturing method. Another object of the present invention is to provide a water-based paint and a coated article excellent in thixotropic stability.
　本発明は、上記課題を解決した以下の構成を有する水性分散液、その製造方法、該水性分散液を含む水性塗料、および該水性塗料から形成された塗膜を有する塗装物品である。
　［１］フルオロオレフィンに基づく単位および架橋性基を有する単量体に基づく単位を有する含フッ素重合体が水性媒体に分散した水性分散液であって、過硫酸塩およびその分解物からなる群から選ばれる少なくとも１種の成分を含み、該成分の含有量が、該含フッ素重合体の１００ｇに対して過硫酸塩換算で０．０１～０．２２ｍｍｏｌであることを特徴とする水性分散液。
　［２］前記含フッ素重合体が水性媒体中に粒子状に分散してなり、該粒子の平均粒子径が２００ｎｍ以下である、［１］の水性分散液。
　［３］前記水性分散液中の含フッ素重合体の濃度が１０～７０質量％である、［１］または［２］の水性分散液。 The present invention is an aqueous dispersion having the following constitution that solves the above problems, a method for producing the same, an aqueous paint containing the aqueous dispersion, and a coated article having a coating film formed from the aqueous paint.
[1] An aqueous dispersion in which a fluoropolymer having a unit based on a fluoroolefin and a unit based on a monomer having a crosslinkable group is dispersed in an aqueous medium, comprising a persulfate and a decomposition product thereof. An aqueous dispersion comprising at least one selected component, wherein the content of the component is 0.01 to 0.22 mmol in terms of persulfate per 100 g of the fluoropolymer.
[2] The aqueous dispersion according to [1], wherein the fluoropolymer is dispersed in the form of particles in an aqueous medium, and the average particle diameter of the particles is 200 nm or less.
[3] The aqueous dispersion according to [1] or [2], wherein the concentration of the fluoropolymer in the aqueous dispersion is 10 to 70% by mass.
　［４］前記フルオロオレフィンが、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌである、［１］～［３］のいずれかの水性分散液。
　［５］前記架橋性基を有する単量体が、水酸基、加水分解性シリル基、カルボキシ基、アミノ基、イソシアネート基、エポキシ基またはオキセタニル基を有する単量体である、［１］～［４］のいずれかの水性分散液。
　［６］前記架橋性基を有する単量体が、水酸基またはカルボキシ基を有する単量体である、［５］の水性分散液。 [4] The aqueous dispersion according to any one of [1] to [3], wherein the fluoroolefin is CF 2 = CF 2 or CF 2 = CFCl.
[5] The monomer having a crosslinkable group is a monomer having a hydroxyl group, hydrolyzable silyl group, carboxy group, amino group, isocyanate group, epoxy group or oxetanyl group. ] An aqueous dispersion of any one of
[6] The aqueous dispersion according to [5], wherein the monomer having a crosslinkable group is a monomer having a hydroxyl group or a carboxy group.
　［７］前記架橋性基を有する単量体が、架橋性基と親水性部位を有する単量体である、［１］～［６］のいずれかの水性分散液。
　［８］前記架橋性基と親水性部位を有する単量体が、Ｊ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＨで表される単量体である（ただし、Ｊはビニルオキシ基またはアリルオキシ基、Ｑは炭素数１～１０のアルキレン基または炭素数６～１０の環構造を有するアルキレン基、Ｙは２～４のアルキレン基（ただし、ｎ個のＹの少なくとも一部はジメチレン基である）、ｎは２～２０の整数、を表す。）、［７］の水性分散液。
　［９］－［Ｏ－Ｙ－］ｎ－が、オキシプロピレン基を有していてもよいポリオキシエチレン鎖である、［８］の水性分散液。
　［１０］前記含フッ素重合体が、さらに、架橋性基を有する単量体以外のフッ素原子を有しない単量体に基づく単位を有する、［１］～［９］のいずれかの水性分散液。 [7] The aqueous dispersion according to any one of [1] to [6], wherein the monomer having a crosslinkable group is a monomer having a crosslinkable group and a hydrophilic portion.
[8] The monomer having a crosslinkable group and a hydrophilic part is a monomer represented by JQ- [O—Y—] n —OH (where J is a vinyloxy group or an allyloxy group) , Q is an alkylene group having 1 to 10 carbon atoms or an alkylene group having a ring structure having 6 to 10 carbon atoms, Y is an alkylene group having 2 to 4 carbon atoms (provided that at least part of n Y is a dimethylene group) , N represents an integer of 2 to 20, and an aqueous dispersion of [7].
[9] The aqueous dispersion according to [8], wherein — [O—Y—] n — is a polyoxyethylene chain which may have an oxypropylene group.
[10] The aqueous dispersion according to any one of [1] to [9], wherein the fluoropolymer further has a unit based on a monomer having no fluorine atom other than the monomer having a crosslinkable group .
　［１１］前記［１］～［１０］のいずれかの水性分散液の製造方法であって、
　フルオロオレフィンおよび架橋性基を有する単量体を含む単量体混合物を、前記単量体混合物の総和１００ｇに対して０．０１～０．２２ｍｍｏｌの量の過硫酸塩の存在下で、水性媒体中で重合させることを特徴とする水性分散液の製造方法。
　［１２］前記水性媒体中における重合が乳化重合である、［１１］の水性分散液の製造方法。
　［１３］前記［１］～［１０］のいずれかの水性分散液を含む水性塗料。
　［１４］含フッ素重合体以外の重合体をさらに含有する、［１３］の水性塗料。
　［１５］物品の表面に［１３］または［１４］の水性塗料から形成された塗膜を有する塗装物品。 [11] A method for producing the aqueous dispersion according to any one of [1] to [10],
A monomer mixture containing a fluoroolefin and a monomer having a crosslinkable group in an aqueous medium in the presence of a persulfate in an amount of 0.01 to 0.22 mmol with respect to 100 g of the total monomer mixture. A method for producing an aqueous dispersion, characterized by polymerizing in an aqueous solution.
[12] The method for producing an aqueous dispersion according to [11], wherein the polymerization in the aqueous medium is emulsion polymerization.
[13] An aqueous paint comprising the aqueous dispersion of any one of [1] to [10].
[14] The water-based paint according to [13], further containing a polymer other than the fluoropolymer.
[15] A coated article having a coating film formed from the water-based paint of [13] or [14] on the surface of the article.
　本発明によれば、着色安定性およびｐＨ安定性に優れており、かつ、チクソ性の安定性に優れた水性塗料に調製できる、水性分散液、および、その効率的な製造方法を提供できる。また、チクソ性の安定性に優れた水性塗料および塗装物品も提供できる。 According to the present invention, it is possible to provide an aqueous dispersion that can be prepared into an aqueous paint excellent in coloring stability and pH stability and excellent in thixotropic stability, and an efficient production method thereof. In addition, water-based paints and coated articles excellent in thixotropic stability can also be provided.
　本明細書において、「単量体に基づく単位」とは、単量体１分子が重合することで直接形成される原子団と、該原子団の一部を化学変換することで得られる原子団との総称である。なお、単量体に基づく単位は、以下、単に「単位」ともいう。
　含フッ素重合体が有する各単位の含有量（モル％）は、含フッ素重合体を核磁気共鳴スペクトル法により分析して求められるが、各単量体の仕込量からも推算できる。
　「架橋性基」とは、硬化剤と反応することにより架橋構造を形成可能な基、または架橋性基同士が反応して架橋構造を形成可能な基を意味する。
　「硬化剤」とは、「架橋性基」と反応可能な基を２個以上有し、架橋性基と反応することにより架橋構造を形成可能な化合物を意味する。
　「（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。 In this specification, “unit based on monomer” means an atomic group directly formed by polymerization of one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group. It is a generic name. Hereinafter, the unit based on the monomer is also simply referred to as “unit”.
The content (mol%) of each unit of the fluoropolymer can be determined by analyzing the fluoropolymer by nuclear magnetic resonance spectroscopy, but can also be estimated from the charged amount of each monomer.
The “crosslinkable group” means a group capable of forming a crosslinked structure by reacting with a curing agent, or a group capable of forming a crosslinked structure by reacting with each other.
The “curing agent” means a compound having two or more groups capable of reacting with the “crosslinkable group” and capable of forming a crosslinked structure by reacting with the crosslinkable group.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
　本発明の水性分散液は、フルオロオレフィンに基づく単位および架橋性基を有する単量体に基づく単位を有する含フッ素重合体が水性媒体に分散した水性分散液であり、過硫酸塩およびその分解物からなる群から選ばれる少なくとも１種の成分（以下、「塩成分」ともいう。）を含み、塩成分の含有量が、含フッ素重合体の１００ｇに対して過硫酸塩換算で０．０１～０．２２ｍｍｏｌである。
　本発明の水性分散液は、後述の水性分散液の製造方法で説明する重合法により得られた水性分散液である。したがって、本発明の水性分散液は、水性媒体、含フッ素重合体および塩成分を少なくとも含んでおり、これら以外に重合の際に用いた成分を含んでいてもよい。重合の際に用いる成分としては、後述の水性分散液の製造方法で説明する乳化剤、連鎖移動剤等が挙げられる。 The aqueous dispersion of the present invention is an aqueous dispersion in which a fluoropolymer having a unit based on a fluoroolefin and a unit based on a monomer having a crosslinkable group is dispersed in an aqueous medium. At least one component selected from the group consisting of (hereinafter also referred to as “salt component”), and the content of the salt component is 0.01 to 100 g in terms of persulfate per 100 g of the fluoropolymer. 0.22 mmol.
The aqueous dispersion of the present invention is an aqueous dispersion obtained by a polymerization method described in the method for producing an aqueous dispersion described later. Accordingly, the aqueous dispersion of the present invention contains at least an aqueous medium, a fluoropolymer and a salt component, and may contain components used in the polymerization in addition to these. Examples of components used in the polymerization include emulsifiers and chain transfer agents described in the method for producing an aqueous dispersion described later.
　本発明における水性媒体としては、水、または水と水溶性有機溶媒の混合物である。
　水溶性有機溶媒としては、ｔｅｒｔ－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等が挙げられる。
　水性媒体が水溶性有機溶媒を含有すると、重合時の水性媒体への単量体の分散性、および生成した含フッ素重合体の分散性が向上し、生産性が向上する。
　水溶性有機溶媒の含有量は、水１００質量部に対して、１～４０質量部が好ましく、３～３０質量部がより好ましい。 The aqueous medium in the present invention is water or a mixture of water and a water-soluble organic solvent.
Examples of the water-soluble organic solvent include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
When the aqueous medium contains a water-soluble organic solvent, the dispersibility of the monomer in the aqueous medium during polymerization and the dispersibility of the produced fluoropolymer are improved, and the productivity is improved.
The content of the water-soluble organic solvent is preferably 1 to 40 parts by mass and more preferably 3 to 30 parts by mass with respect to 100 parts by mass of water.
　本発明における含フッ素重合体は、フルオロオレフィン（以下、「単量体１」ともいう。）に基づく単位（以下、「単位１」ともいう。）および架橋性基を有する単量体（以下、「単量体２」ともいう。）に基づく単位（以下、「単位２」ともいう。）を有する。
　含フッ素重合体は、必要に応じて、単量体１および単量体２以外の単量体（以下、「単量体３」ともいう。）に基づく単位（以下、「単位３」ともいう。）をさらに有していてもよい。 The fluoropolymer in the present invention is composed of a unit (hereinafter also referred to as “unit 1”) based on a fluoroolefin (hereinafter also referred to as “monomer 1”) and a monomer having a crosslinkable group (hereinafter referred to as “unit 1”). And a unit based on “monomer 2” (hereinafter also referred to as “unit 2”).
The fluoropolymer may be a unit based on a monomer other than monomer 1 and monomer 2 (hereinafter also referred to as “monomer 3”) (hereinafter also referred to as “unit 3”). .) May further be included.
　水性分散液中の含フッ素重合体の含有量は、水性分散液の全質量に対して、１０～７０質量％が好ましく、２０～６０質量％が特に好ましい。含フッ素重合体の含有量が上記下限値以上であれば、重合が速やかに進行し高い反応率が得られる。一方、上限値以下であれば、水性分散液中での含フッ素重合体の分散安定性と、その着色安定性がより優れる。 The content of the fluoropolymer in the aqueous dispersion is preferably 10 to 70% by mass, particularly preferably 20 to 60% by mass, based on the total mass of the aqueous dispersion. If content of a fluoropolymer is more than the said lower limit, superposition | polymerization will advance rapidly and a high reaction rate will be obtained. On the other hand, if it is below the upper limit, the dispersion stability of the fluoropolymer in the aqueous dispersion and the coloration stability thereof are more excellent.
　本発明における単量体１は、オレフィンの水素原子の１個以上がフッ素原子で置換された化合物である。単量体１においては、フッ素原子で置換されていない水素原子の１個以上が塩素原子で置換されていてもよい。
　単量体１としては、ＣＦ２＝ＣＦ２、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨＦ、ＣＨ２＝ＣＦ２、ＣＦ２＝ＣＦＣＦ３およびＣＦ２＝ＣＨＣＦ３が好ましく、得られる塗膜の耐候性の点から、ＣＦ２＝ＣＦ２およびＣＦ２＝ＣＦＣｌがより好ましく、ＣＦ２＝ＣＦＣｌが特に好ましい。
　単量体１は、２種以上を併用してもよい。 The monomer 1 in the present invention is a compound in which one or more hydrogen atoms of the olefin are substituted with fluorine atoms. In the monomer 1, one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
As monomer 1, CF 2 = CF 2 , CF 2 = CFCl, CF 2 = CHF, CH 2 = CF 2 , CF 2 = CFCF 3 and CF 2 = CHCF 3 are preferred, and the weather resistance of the resulting coating film In view of the above, CF 2 = CF 2 and CF 2 = CFCl are more preferable, and CF 2 = CFCl is particularly preferable.
Monomer 1 may use 2 or more types together.
　本発明における単量体２の架橋性基は、水酸基、加水分解性シリル基、カルボキシ基、アミノ基、イソシアネート基、エポキシ基またはオキセタニル基が好ましく、水酸基またはカルボキシ基が特に好ましい。 In the present invention, the crosslinkable group of the monomer 2 is preferably a hydroxyl group, a hydrolyzable silyl group, a carboxy group, an amino group, an isocyanate group, an epoxy group or an oxetanyl group, and particularly preferably a hydroxyl group or a carboxy group.
　架橋性基が水酸基である単量体２（水酸基を有する単量体）としては、ヒドロキシアルキルビニルエーテル（ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル等。）、水酸基とビニルオキシ基を有するシクロアルカン（シクロへキサンジメタノールモノビニルエーテル等。）、エチレングリコールモノビニルエーテル（ジエチレングリコールモノビニルエーテル、トリエチレングリコールモノビニルエーテル、テトラエチレングリコールモノビニルエーテル等。）、ヒドロキシアルキルアリルエーテル（ヒドロキシエチルアリルエーテル、ヒドロキシブチルアリルエーテル等）、水酸基とアリルオキシ基を有するシクロアルカン（シクロへキサンジメタノールモノアリルエーテル等）、ヒドロキシアルキルビニルエステル（ヒドロキシエチルカルボン酸ビニルエステル、ヒドロキシブチルカルボン酸ビニルエステル等。）、水酸基とビニルオキシカルボニル基を有するシクロアルカン（（（ヒドロキシメチルシクロヘキシル）メトキシ）酢酸ビニルエステル等。）、ヒドロキシアルキルカルボン酸アリルエステル（ヒドロキシエチルカルボン酸アリルエステル、ヒドロキシブチルカルボン酸アリルエステル等。）、水酸基とアリルオキシカルボニル基を有するシクロアルカン（（（ヒドロキシメチルシクロヘキシル）メトキシ）酢酸アリルエステル等。）、ヒドロキシアルキル（メタ）アクリレート（ヒドロキシエチル（メタ）アクリレート等。）が挙げられる。水酸基を有する単量体としては、ヒドロキシアルキルビニルエーテルおよびヒドロキシアルキルアリルエーテルが好ましく、ヒドロキシアルキルビニルエーテルが特に好ましい。 Examples of the monomer 2 in which the crosslinkable group is a hydroxyl group (a monomer having a hydroxyl group) include hydroxyalkyl vinyl ether (hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), cycloalkane having a hydroxyl group and a vinyloxy group (cyclohexanedi). Methanol monovinyl ether, etc.), ethylene glycol monovinyl ether (diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, etc.), hydroxyalkyl allyl ether (hydroxyethyl allyl ether, hydroxybutyl allyl ether, etc.), hydroxyl group and Cycloalkanes having an allyloxy group (such as cyclohexane dimethanol monoallyl ether), hydroxyalkyl vinyl esters (Hydroxyethyl carboxylic acid vinyl ester, hydroxybutyl carboxylic acid vinyl ester, etc.), cycloalkane having a hydroxyl group and a vinyloxycarbonyl group (((hydroxymethylcyclohexyl) methoxy) acetic acid vinyl ester, etc.), hydroxyalkyl carboxylic acid allyl ester (Hydroxyethylcarboxylic acid allyl ester, hydroxybutylcarboxylic acid allyl ester, etc.), cycloalkane having a hydroxyl group and an allyloxycarbonyl group (((hydroxymethylcyclohexyl) methoxy) acetic acid allyl ester, etc.), hydroxyalkyl (meth) acrylate (Hydroxyethyl (meth) acrylate, etc.). As the monomer having a hydroxyl group, hydroxyalkyl vinyl ether and hydroxyalkyl allyl ether are preferable, and hydroxyalkyl vinyl ether is particularly preferable.
　架橋性基がカルボキシ基である単量体２（カルボキシ基を有する単量体）としては、不飽和モノカルボン酸（３－ブテン酸、４－ペンテン酸、２－ヘキセン酸、３－ヘキセン酸、５－ヘキセン酸、２－ヘプテン酸、３－ヘプテン酸、６－ヘプテン酸、３－オクテン酸、７－オクテン酸、２－ノネン酸、３－ノネン酸、８－ノネン酸、９－デセン酸、１０－ウンデセン酸、アクリル酸、メタクリル酸、クロトン酸、桂皮酸等。）、飽和モノカルボン酸ビニルエーテル（ビニルオキシ吉草酸、３－ビニルオキシプロピオン酸、３－（２－ビニルオキシブトキシカルボニル）プロピオン酸、３－（２－ビニルオキシエトキシカルボニル）プロピオン酸等。）、飽和モノカルボン酸アリルエーテル（アリルオキシ吉草酸、３－アリルオキシプロピオン酸、３－（２－アリロキシブトキシカルボニル）プロピオン酸、３－（２－アリロキシエトキシカルボニル）プロピオン酸等。）、飽和多価カルボン酸モノビニルエステル（アジピン酸モノビニル、コハク酸モノビニル、フタル酸ビニル、ピロメリット酸ビニル等。）、不飽和ジカルボン酸またはその分子内酸無水物（イタコン酸、マレイン酸、フマル酸、マレイン酸無水物、イタコン酸無水物等。）、不飽和カルボン酸モノエステル（イタコン酸モノエステル、マレイン酸モノエステル、フマル酸モノエステル等。）が挙げられる。カルボキシ基を有する単量体としては、不飽和モノカルボン酸が好ましく、１０－ウンデセン酸およびクロトン酸が好ましい。 Monomers 2 having a carboxy group as a crosslinkable group (monomers having a carboxy group) include unsaturated monocarboxylic acids (3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 6-heptenoic acid, 3-octenoic acid, 7-octenoic acid, 2-nonenoic acid, 3-nonenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc.), saturated monocarboxylic acid vinyl ether (vinyloxyvaleric acid, 3-vinyloxypropionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid, 3- (2-vinyloxyethoxycarbonyl) propionic acid, etc.), saturated monocarboxylic acid allyl ether (allyloxyvaleric acid, 3-allyloxypropio) Acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, etc.), saturated polycarboxylic acid monovinyl ester (monovinyl adipate, monovinyl succinate, vinyl phthalate) , Vinyl pyromellitic acid vinyl, etc.), unsaturated dicarboxylic acid or its intramolecular acid anhydride (itaconic acid, maleic acid, fumaric acid, maleic acid anhydride, itaconic acid anhydride etc.), unsaturated carboxylic acid monoester ( Itaconic acid monoester, maleic acid monoester, fumaric acid monoester, etc.). As the monomer having a carboxy group, an unsaturated monocarboxylic acid is preferable, and 10-undecenoic acid and crotonic acid are preferable.
　架橋性基が加水分解性シリル基である単量体２（加水分解性シリル基を有する単量体）としては、（ＣＨ２＝ＣＨＣ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＯＣ２Ｈ５）３、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ（ＣＨ２）３ＳｉＣＨ３（ＯＣ２Ｈ５）２、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３ＳｉＣ２Ｈ５（ＯＣＨ３）２、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２（ＯＣ２Ｈ５）、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＨ、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ（ＣＨ２）３Ｓｉ（ＯＣＯＣＨ３）３、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３ＳｉＣ２Ｈ５（ＯＣＯＣＨ３）２、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３ＳｉＣＨ３（Ｎ（ＣＨ３）ＣＯＣＨ３）２、ＣＨ２＝ＣＨＣ（Ｏ）Ｏ（ＣＨ２）３ＳｉＣＨ３［ＯＮ（ＣＨ３）Ｃ２Ｈ５］２、ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ（ＣＨ２）３ＳｉＣ６Ｈ５［ＯＮ（ＣＨ３）Ｃ２Ｈ５］２等の加水分解性シラン基を有する（メタ）アクリレート、ＣＨ２＝ＣＨＳｉ［ＯＮ＝Ｃ（ＣＨ３）（Ｃ２Ｈ５）］３、ＣＨ２＝ＣＨＳｉ（ＯＣＨ３）３、ＣＨ２＝ＣＨＳｉ（ＯＣ２Ｈ５）３、ＣＨ２＝ＣＨＳｉＣＨ３（ＯＣＨ３）２、ＣＨ２＝ＣＨＳｉ（ＯＣＯＣＨ３）３、ＣＨ２＝ＣＨＳｉ（ＣＨ３）２（ＯＣ２Ｈ５）、ＣＨ２＝ＣＨＳｉ（ＣＨ３）２ＳｉＣＨ３（ＯＣＨ３）２、ＣＨ２＝ＣＨＳｉＣ２Ｈ５（ＯＣＯＣＨ３）２、ＣＨ２＝ＣＨＳｉＣＨ３［ＯＮ（ＣＨ３）Ｃ２Ｈ５］２、ＣＨ２＝ＣＨＳｉＣｌ３等のビニルシラン、加水分解性シラン基を有するビニルエーテルが挙げられる。加水分解性シリル基を有する単量体は、部分的に加水分解された縮合物であってもよい。 As the monomer 2 (monomer having a hydrolyzable silyl group) in which the crosslinkable group is a hydrolyzable silyl group, (CH 2 ═CHC (O) O (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 = CHC (O) O (CH 2) 3 Si (OC 2 H 5) 3, CH 2 = C (CH 3) C (O) O (CH 2) 3 Si (OCH 3) 3, CH 2 = C (CH 3) C ( O) O (CH 2) 3 Si (OC 2 H 5) 3, CH 2 = CHC (O) O (CH 2) 3 SiCH 3 (OC 2 H 5) 2, CH 2 = C (CH 3) C ( O) O (CH 2) 3 SiC 2 H 5 (OCH 3) 2, CH 2 = C (CH 3) C (O) O (CH 2) 3 Si (CH 3) 2 (OC 2 H 5), CH 2 = C (CH 3) C (O) O (CH 2) 3 Si (CH 3) 2 OH, CH 2 = CHC (O) O (CH 2) 3 Si (OCOCH 3) 3, CH 2 = C (CH 3) C (O) O (CH 2) 3 SiC 2 H 5 (OCOCH 3) 2, CH 2 = C (CH 3 ) C (O) O (CH 2 ) 3 SiCH 3 (N (CH 3 ) COCH 3 ) 2 , CH 2 = CHC (O) O (CH 2 ) 3 SiCH 3 [ON (CH 3 ) Having a hydrolyzable silane group such as C 2 H 5 ] 2 , CH 2 ═C (CH 3 ) C (O) O (CH 2 ) 3 SiC 6 H 5 [ON (CH 3 ) C 2 H 5 ] 2 (meth) acrylate, CH 2 = CHSi [ON = C (CH 3) (C 2 H 5)] 3, CH 2 = CHSi (OCH 3) 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSiCH 3 (OCH 3) 2 , CH 2 = CH i (OCOCH 3) 3, CH 2 = CHSi (CH 3) 2 (OC 2 H 5), CH 2 = CHSi (CH 3) 2 SiCH 3 (OCH 3) 2, CH 2 = CHSiC 2 H 5 (OCOCH 3 ) 2 , CH 2 = CHSiCH 3 [ON (CH 3 ) C 2 H 5 ] 2 , CH 2 = CHSiCl 3 and the like, and vinyl ethers having hydrolyzable silane groups. The monomer having a hydrolyzable silyl group may be a partially hydrolyzed condensate.
　架橋性基がアミノ基である単量体２（アミノ基を有する単量体）としては、アミノアルキルビニルエーテル、アミノアルキルビニルエステル、アミノメチルスチレン、ビニルアミン、アクリルアミド、ビニルアセトアミド、ビニルホルムアミド等が挙げられる。
　架橋性基がイソシアネート基である単量体２（イソシアネート基を有する単量体）としては、２－イソシアネートエチルメタクリレート、２－イソシアネートエチルアクリレート、２－イソシアネートエチルエトキシメタクリレート、２－イソシアネートエチルビニルエーテル等が挙げられる。
　架橋性基がエポキシ基である単量体２（エポキシ基を有する単量体）としては、グリシジルビニルエーテル、グリシジルメタクリレート、３，４－エポキシシクロへキシルメチルメタクリレート、３，４－エポキシシクロへキシルメチルビニルエーテル、４－ビニロキシメチルシクロへキシルグリシジルエーテル等が挙げられる。 Examples of the monomer 2 (monomer having an amino group) in which the crosslinkable group is an amino group include aminoalkyl vinyl ether, aminoalkyl vinyl ester, aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, vinylformamide, and the like. .
Examples of the monomer 2 in which the crosslinkable group is an isocyanate group (monomers having an isocyanate group) include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 2-isocyanate ethyl ethoxy methacrylate, and 2-isocyanate ethyl vinyl ether. Can be mentioned.
Monomers 2 having an epoxy group as a crosslinkable group (monomers having an epoxy group) include glycidyl vinyl ether, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl. Examples thereof include vinyl ether and 4-vinyloxymethylcyclohexyl glycidyl ether.
　他の単量体２の好ましい例示としては、架橋性基と親水性部位を有する単量体（以下、「マクロモノマー」ともいう。）が挙げられる。
　親水性部位とは、親水性基を有する部位か親水性の結合を有する部位、またはこれらの部位の組合せからなる部位を意味する。親水性基としては、イオン性、ノニオン性、両性のいずれであってもよい。
　水性分散液の化学的安定性の点からは、ノニオン性または両性の親水性基を有する部位と他の親水性基を有する部位とを組合せるか、または親水性基を有する部位と親水性の結合を有する部位とを組合せるのが好ましい。 Preferable examples of the other monomer 2 include a monomer having a crosslinkable group and a hydrophilic site (hereinafter also referred to as “macromonomer”).
The hydrophilic part means a part having a hydrophilic group, a part having a hydrophilic bond, or a part composed of a combination of these parts. The hydrophilic group may be ionic, nonionic or amphoteric.
From the viewpoint of chemical stability of the aqueous dispersion, a portion having a nonionic or amphoteric hydrophilic group and a portion having another hydrophilic group are combined, or a portion having a hydrophilic group and a hydrophilic group are hydrophilic. It is preferable to combine with a site having a bond.
　マクロモノマーの具体例としては、Ｊ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＲで表される化合物、Ｊ－Ｑ－Ｏ（Ｃ（Ｏ）－Ｚ－Ｏ－）ｍＲで表される化合物等が挙げられる（ただし、それぞれの式中、Ｊはビニルオキシ基またはアリルオキシ基、Ｑは炭素数１～１０のアルキレン基または炭素数６～１０の環構造を有するアルキレン基、Ｙは炭素数１～４のアルキレン基、Ｒは水素原子、ｎは２～２０の整数、Ｚは炭素数１～１０のアルキレン基、ｍは１～３０の整数を示す。以下同様）。
　－［Ｏ－Ｙ－］－で表される基は、オキシエチレン基（すなわち、Ｙがジメチレン基である。）が好ましい。また、－［Ｏ－Ｙ－］ｎ－で表される親水性部位は、２種以上の－［Ｏ－Ｙ－］－で表される基（たとえば、－ＯＣＨ２ＣＨ２－と－ＯＣＨ２ＣＨ（ＣＨ３）－）で構成されていてもよい。２種以上の基で構成される場合のそれぞれの基は、ブロック、ランダムのいずれの型で配列されていてもよい。
　マクロモノマーとしては、Ｊ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＨで表される化合物（ただし、Ｊ、Ｑ、ｎは上記の通り。Ｙは炭素数２～４のアルキレン基（ただし、ｎ個のＹの少なくとも一部はジメチレン基である。）が好ましい。Ｙがジメチレン基以外のアルキレン基である場合は、－ＣＨ２ＣＨ（ＣＨ３）－が好ましい。ｎ個のＹの５０％以上がジメチレン基であることが好ましく、８０～１００％がジメチレン基であることがより好ましい。 Specific examples of the macromonomer include a compound represented by JQ- [O—Y—] n —OR, a compound represented by JQO (C (O) —Z—O—) m R (Wherein, in each formula, J is a vinyloxy group or allyloxy group, Q is an alkylene group having 1 to 10 carbon atoms or an alkylene group having a ring structure having 6 to 10 carbon atoms, Y is 1 to carbon atoms) 4 represents an alkylene group, R represents a hydrogen atom, n represents an integer of 2 to 20, Z represents an alkylene group having 1 to 10 carbon atoms, and m represents an integer of 1 to 30. The same shall apply hereinafter).
The group represented by — [O—Y —] — is preferably an oxyethylene group (that is, Y is a dimethylene group). The hydrophilic moiety represented by — [O—Y—] n — represents two or more groups represented by — [O—Y —] — (for example, —OCH 2 CH 2 — and —OCH 2 It may be composed of CH (CH 3 )-). Each group in the case of being composed of two or more groups may be arranged in either block or random form.
As the macromonomer, a compound represented by JQ- [O—Y—] n —OH (where J, Q, and n are as described above, Y is an alkylene group having 2 to 4 carbon atoms (where n It is preferable that at least a part of Y is a dimethylene group.) When Y is an alkylene group other than a dimethylene group, —CH 2 CH (CH 3 ) — is preferable, and 50% or more of n Y Is preferably a dimethylene group, more preferably 80 to 100% is a dimethylene group.
　また、マクロモノマーは、親水性のエチレン性不飽和単量体がラジカル重合した鎖を有し、片末端にビニルオキシ基またはアリルオキシ基等のラジカル重合性不飽和基を有する単量体であってもよい。
　かかるマクロモノマーは、Ｐｏｌｙｍ．Ｂｕｌｌ．，５．３３５（１９８１）に記載される方法により製造できる。すなわち、縮合可能な官能基を有する重合開始剤および連鎖移動剤の存在下に親水性基を有するエチレン性不飽和単量体をラジカル重合させて縮合可能な官能基を有する重合体を製造する。次いで、この重合体の官能基にグリシジルビニルエーテル、グリシジルアリルエーテル等の化合物を反応させ、末端にラジカル重合性不飽和基を導入する方法である。
　エチレン性不飽和単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、２－メトキシエチル（メタ）アクリレート、ジアセトンアクリルアミド、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートおよびビニルピロリドン等が挙げられる。
　単量体２は、２種以上を併用してもよい。 Further, the macromonomer may be a monomer having a chain obtained by radical polymerization of a hydrophilic ethylenically unsaturated monomer and having a radical polymerizable unsaturated group such as a vinyloxy group or an allyloxy group at one end. Good.
Such macromonomers are described in Polym. Bull. , 5.335 (1981). That is, a polymer having a condensable functional group is produced by radical polymerization of an ethylenically unsaturated monomer having a hydrophilic group in the presence of a polymerization initiator having a condensable functional group and a chain transfer agent. Next, the functional group of this polymer is reacted with a compound such as glycidyl vinyl ether or glycidyl allyl ether to introduce a radical polymerizable unsaturated group at the terminal.
Ethylenically unsaturated monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, 2-methoxyethyl (meth) acrylate, diacetone acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth ) Acrylate, hydroxybutyl (meth) acrylate, vinylpyrrolidone and the like.
The monomer 2 may use 2 or more types together.
　本発明における単量体３は、特に限定されず、オレフィン（エチレン、プロピレン等。）、アルキルビニルエーテル（エチルビニルエーテル、プロピルビニルエーテル、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等。）、シクロアルキルビニルエーテル（シクロヘキシルビニルエーテル等。）、アルキルビニルエステル（ブタン酸ビニルエステル、オクタン酸ビニルエステル、ピバリン酸ビニルエステル等。）、アルキルアリルエステル（ブタン酸アリルエステル、オクタン酸アリルエステル、ピバリン酸アリルエステル等。）、芳香族ビニル（スチレン、ビニルトルエン等。）、アリルエーテル（エチルアリルエーテル等。）、（メタ）アクリレート（メチル（メタ）アクリレート、ブチル（メタ）アクリレート等。）が挙げられる。単量体３としては、アルキルビニルエーテル、シクロアルキルビニルエーテルおよびアルキルビニルエステルが好ましい。 The monomer 3 in the present invention is not particularly limited, and is olefin (ethylene, propylene, etc.), alkyl vinyl ether (ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, etc.), cycloalkyl vinyl ether (cyclohexyl vinyl ether, etc.). ), Alkyl vinyl esters (butanoic acid vinyl ester, octanoic acid vinyl ester, pivalic acid vinyl ester, etc.), alkyl allyl esters (butanoic acid allyl ester, octanoic acid allyl ester, pivalic acid allyl ester, etc.), aromatic vinyl (Styrene, vinyl toluene, etc.), allyl ether (ethyl allyl ether, etc.), (meth) acrylate (methyl (meth) acrylate, butyl (meth) acrylate, etc.) And the like. As the monomer 3, alkyl vinyl ether, cycloalkyl vinyl ether and alkyl vinyl ester are preferable.
　また、他の単量体３としては、前述した、Ｊ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＲで表される化合物、またはＪ－Ｑ－Ｏ（Ｃ（Ｏ）－Ｚ－Ｏ）ｍＲで表される化合物であって、Ｒが炭素数１～３のアルキル基に置換された化合物を挙げられる。 Further, as the other monomer 3, the compound represented by JQ- [O—Y—] n —OR described above, or JQO (C (O) —ZO) m Examples thereof include compounds represented by R, wherein R is substituted with an alkyl group having 1 to 3 carbon atoms.
　本発明における含フッ素重合体は、単位１としてＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌに基づく単位を有し、単位２としてヒドロキシアルキルビニルエーテルまたはＣＨ２＝ＣＨＯ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＨで表される化合物に基づく単位を有する重合体であるか、単位１としてＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌに基づく単位を有し、単位２としてヒドロキシアルキルビニルエステルまたはＣＨ２＝ＣＨＣＨ２Ｏ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＨで表される化合物に基づく単位を有する重合体であるのが好ましい。 Fluoropolymer in the present invention has a unit based on CF 2 = CF 2 or CF 2 = CFCl units 1, hydroxy units 2 alkyl vinyl ether or CH 2 = CHO-Q- [O -Y-] n A polymer having units based on a compound represented by —OH, or having units based on CF 2 ═CF 2 or CF 2 ═CFCl as units 1 and hydroxyalkyl vinyl esters or CH 2 ═CHCH as units 2 It is preferably a polymer having units based on a compound represented by 2 O—Q— [O—Y—] n —OH.
　本発明における含フッ素重合体において、単位２の含有量（モル％）に対する単位１の含有量（モル％）の割合（単位１の含有量／単位２の含有量）は、０．５～８００が好ましく、１．５～３００がより好ましい。該割合が、この範囲にあれば、水性分散液における分散性がより向上するだけでなく、得られる塗膜の耐候性、耐水性がより良好になる。
　本発明における含フッ素重合体が単位３をさらに含む場合においては、単位１と単位２の総含有量に対する単位３の含有量の割合（単位３の含有量／単位１の含有量と単位２の含有量の和）は、０．１～１．５が好ましい。
　含フッ素重合体中の単位１の含有量は、含フッ素重合体が有する全単位に対して、３０～７０モル％が好ましく、３５～６５モル％がより好ましく、４０～６０モル％がさらに好ましい。
　含フッ素重合体中の単位２の含有量は、含フッ素重合体が有する全単位に対して、０．５～３０モル％が好ましく、１．０～２０モル％がより好ましく、１．５～１５モル％がさらに好ましい。
　含フッ素重合体中の単位３の含有量は、含フッ素重合体が有する全単位に対して、２０～７０モル％が好ましく、２５～６５モル％がより好ましく、３０～６０モル％がさらに好ましい。 In the fluoropolymer of the present invention, the ratio of the content (mol%) of unit 1 to the content (mol%) of unit 2 (content of unit 1 / content of unit 2) is 0.5 to 800. Is preferable, and 1.5 to 300 is more preferable. When the ratio is within this range, not only the dispersibility in the aqueous dispersion is further improved, but also the weather resistance and water resistance of the resulting coating film are improved.
In the case where the fluoropolymer in the present invention further contains unit 3, the ratio of the content of unit 3 to the total content of units 1 and 2 (content of unit 3 / content of unit 1 and unit 2) The sum of the contents is preferably 0.1 to 1.5.
The content of unit 1 in the fluoropolymer is preferably from 30 to 70 mol%, more preferably from 35 to 65 mol%, still more preferably from 40 to 60 mol%, based on all units of the fluoropolymer. .
The content of unit 2 in the fluoropolymer is preferably 0.5 to 30 mol%, more preferably 1.0 to 20 mol%, more preferably 1.5 to 15 mol% is more preferable.
The content of unit 3 in the fluoropolymer is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, still more preferably 30 to 60 mol%, based on the total units of the fluoropolymer. .
　本発明における含フッ素重合体の好適な具体的としては、重合体の全単位の合計量に対して、単位１を２９．５～７０モル％、単位２を０．５～３０モル％および単位３を２０～７０モル％有する重合体が挙げられ、更に好適な具体例としては、単位１を３４～６５モル％、単位２を１．０～２０モル％および単位３を２５～６５モル％有する重合体が挙げられる。 Preferable specific examples of the fluorinated polymer in the present invention include 29.5 to 70 mol% of unit 1, 0.5 to 30 mol% of unit 2 and units of the total amount of all units of the polymer. 3 to 20 to 70 mol%, and more preferable specific examples include units 1 to 34 to 65 mol%, units 2 to 1.0 to 20 mol% and units 3 to 25 to 65 mol%. The polymer which has is mentioned.
　本発明の水性分散液において、含フッ素重合体は水性媒体中に粒子状に分散しているのが好ましい。粒子状に分散した含フッ素重合体の平均粒子径は、２００ｎｍ以下が好ましく、１８０ｎｍ以下が特に好ましい。下限値は、一般に５０ｎｍである。平均粒子径が２００ｎｍ以下である場合、水性分散液の着色安定性の効果が顕著となる。その理由は必ずしも明確ではないが、以下のように考えられる。
　水性分散液に分散する含フッ素重合体の粒子の平均粒子径が小さい程、含フッ素重合体の粒子と塩成分に由来する着色成分との相互作用（光散乱等。）が強くなると考えられる。さらに含フッ素重合体が有する架橋性基が水酸基またはカルボキシ基である場合は、特に水性分散液の着色安定性が低下しやすいと考えられる。しかし、本発明における塩成分の含有量の規定が、かかる着色安定性の低下を抑制する要因として顕著に機能する。その結果、含フッ素重合体の粒子の平均粒子径が小さい場合でも、本発明の水性分散液は着色安定性に優れていると考えられる。
　なお、含フッ素重合体の平均粒子径は、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。ここで、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％の粒子直径を表す。 In the aqueous dispersion of the present invention, the fluoropolymer is preferably dispersed in the form of particles in an aqueous medium. The average particle diameter of the fluoropolymer dispersed in the form of particles is preferably 200 nm or less, and particularly preferably 180 nm or less. The lower limit is generally 50 nm. When the average particle size is 200 nm or less, the effect of the color stability of the aqueous dispersion becomes remarkable. The reason is not necessarily clear, but it can be considered as follows.
It is believed that the smaller the average particle size of the fluoropolymer particles dispersed in the aqueous dispersion, the stronger the interaction (light scattering, etc.) between the fluoropolymer particles and the coloring component derived from the salt component. Furthermore, when the crosslinkable group possessed by the fluoropolymer is a hydroxyl group or a carboxy group, it is considered that the coloring stability of the aqueous dispersion is particularly likely to decrease. However, the regulation of the content of the salt component in the present invention functions remarkably as a factor for suppressing such a decrease in coloring stability. As a result, even when the average particle size of the fluoropolymer particles is small, it is considered that the aqueous dispersion of the present invention is excellent in coloring stability.
The average particle size of the fluoropolymer is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.). Here, D50 represents the particle diameter of a volume cumulative 50 volume% calculated from the small particle side in the particle size distribution of the particle measured by the dynamic light scattering method.
　本発明における塩成分は、含フッ素重合体を製造する際に重合開始剤として用いた過硫酸塩の残存物および／または過硫酸塩の分解物である。重合の際に重合開始剤の使用量が多いと、水性分散液中の塩成分の含有量が多くなり、使用量が少ないと、その含有量が少なくなる。塩成分は、貯蔵時に更に分解するなどして水性分散液の着色の原因となるだけでなく、水性分散液のｐＨの経時的な低下の原因ともなる。
　本発明における過硫酸塩は、過硫酸アンモニウム塩、過硫酸カリウム塩、または過硫酸ナトリウム塩が好ましい。 The salt component in the present invention is a persulfate residue and / or a persulfate decomposition product used as a polymerization initiator when producing a fluoropolymer. When the amount of the polymerization initiator used is large during the polymerization, the content of the salt component in the aqueous dispersion increases, and when the amount used is small, the content decreases. The salt component not only causes coloration of the aqueous dispersion by further decomposition during storage, but also causes a decrease in pH of the aqueous dispersion over time.
The persulfate in the present invention is preferably ammonium persulfate, potassium persulfate, or sodium persulfate.
　水性分散液中の塩成分の含有量は、含フッ素重合体の１００ｇに対して、過硫酸塩換算で０．０１～０．２２ｍｍｏｌであり、０．０１～０．１５ｍｍｏｌが好ましく、０．０１～０．１０ｍｍｏｌがより好ましく、０．０１～０．０５ｍｍｏｌがさらに好ましい。なお、塩成分の含有量とは、過硫酸塩およびその分解物の合計含有量である（過硫酸塩およびその分解物のいずれか一方を含まない場合も含む。）。
　塩成分の含有量が上記下限値以上であれば、重合が速やかに進行し、単量体が高い反応率で重合するため、効率的に含フッ素重合体が得られる。
　塩成分の含有量が上記上限値以下であれば、水性分散液、水性塗料および水性塗料から形成される塗膜（以下、本塗膜ともいう。）の着色安定性が優れるだけでなく、水性分散液および水性塗料のｐＨ安定性が良好になる。その結果、水性分散液および水性塗料のチクソ性の安定性が良好となる。 The content of the salt component in the aqueous dispersion is 0.01 to 0.22 mmol in terms of persulfate, preferably 0.01 to 0.15 mmol, with respect to 100 g of the fluoropolymer. Is more preferably 0.10 mmol, and further preferably 0.01 to 0.05 mmol. The content of the salt component is the total content of persulfate and its decomposition product (including the case where either the persulfate or its decomposition product is not included).
If the content of the salt component is at least the above lower limit, the polymerization proceeds rapidly and the monomer is polymerized at a high reaction rate, so that a fluoropolymer can be obtained efficiently.
If the content of the salt component is not more than the above upper limit value, not only the coloring stability of the aqueous dispersion, the aqueous coating material, and the coating film formed from the aqueous coating material (hereinafter also referred to as the present coating film) is excellent, but also aqueous. The pH stability of the dispersion and water-based paint is improved. As a result, the thixotropic stability of the aqueous dispersion and the aqueous paint is improved.
　さらに、水性分散液および水性塗料の経時による着色安定性が良好になるため、本塗膜の着色安定性がさらに良好になる。また、水性塗料のチクソ性の安定性が良好になるため、水性塗料の「塗りやすさ・垂れにくさ」が向上し、物品（被塗装物）に対し均一に塗装でき、本塗膜の均一性が向上する。
　つまり、水性分散液から水性塗料を調製する際には、通常、増粘剤を添加して水性塗料のチクソ性を適切な範囲に調整する。増粘剤の作用は、水性分散液のｐＨの影響を受けるため、水性分散液のｐＨが経時的に変化すると水性塗料のチクソ性も変化してしまい、調整した範囲から外れて、塗装の際の均一性が低下してしまうが、本発明の水性分散液および水性塗料では、塗装の均一性が低下しない。 Furthermore, since the color stability of the aqueous dispersion and the water-based paint over time is improved, the color stability of the coating film is further improved. In addition, since the thixotropy stability of water-based paints is improved, the “easy to apply and dripping resistance” of water-based paints is improved, and it can be applied uniformly to articles (objects to be coated). Improves.
That is, when preparing a water-based paint from an aqueous dispersion, usually a thickener is added to adjust the thixotropy of the water-based paint to an appropriate range. Since the action of the thickener is affected by the pH of the aqueous dispersion, if the pH of the aqueous dispersion changes over time, the thixotropy of the aqueous paint will also change, deviating from the adjusted range, and However, in the aqueous dispersion and the aqueous paint of the present invention, the coating uniformity is not lowered.
　本発明の水性分散液の製造方法は、前記本発明の水性分散液の製造方法であって、単量体１および単量体２を含む単量体混合物を、過硫酸塩の存在下、水性媒体中で重合させる方法である。
　過硫酸塩の使用量は、単量体混合物の総量１００ｇに対して０．０１～０．２２ｍｍｏｌである。
　単量体混合物は、必要に応じて、単量体３をさらに含んでもよい。
　ここで、単量体１、単量体２および単量体３のそれぞれ種類および水性媒体の定義は、前述の本発明の水性分散液で説明したとおりである。また、含フッ素重合体の好適態様も、本発明の水性分散液で説明した通りである。 The method for producing an aqueous dispersion of the present invention is the method for producing an aqueous dispersion of the present invention, wherein a monomer mixture containing monomer 1 and monomer 2 is aqueous in the presence of persulfate. This is a method of polymerizing in a medium.
The amount of persulfate used is 0.01 to 0.22 mmol with respect to 100 g of the total amount of the monomer mixture.
The monomer mixture may further include a monomer 3 as necessary.
Here, the types of the monomer 1, the monomer 2 and the monomer 3 and the definition of the aqueous medium are as described in the aqueous dispersion of the present invention. Moreover, the suitable aspect of a fluoropolymer is also as having demonstrated with the aqueous dispersion liquid of this invention.
　たとえば、単量体１、単量体２、および必要に応じて使用される単量体３は、製造される含フッ素重合体の単位１と単位２と単位３が所望の割合になるように使用できる。
　含フッ素重合体の好適な具体例としては、単位２の含有量（モル％）に対する単位１の含有量（モル％）の割合（単位１の含有量／単位２の含有量）が、０．５～８００である含フッ素重合体が挙げられ、より好適には１．５～３００である含フッ素重合体が挙げられる。
　また、含フッ素重合体が単位３をさらに含む場合においては、単位１と単位２の総含有量に対する単位３の含有量の割合（単位３の含有量／単位１の含有量と単位２の含有量の和）が、０．１～１．５である含フッ素重合体が挙げられる。
　単量体１と単量体２の総モル数に対する単量体３のモル数の割合（単量体３のモル数／（単量体１のモル数＋単量体２のモル数））は、０．１～１．５が好ましい。 For example, the monomer 1, the monomer 2, and the monomer 3 used as necessary are such that the units 1, 2 and 3 of the fluoropolymer to be produced have a desired ratio. Can be used.
As a preferred specific example of the fluoropolymer, the ratio of the content (mol%) of unit 1 to the content (mol%) of unit 2 (content of unit 1 / content of unit 2) is 0.00. Examples thereof include fluorine-containing polymers having a molecular weight of 5 to 800, and more preferably fluorine-containing polymers having a molecular weight of 1.5 to 300.
When the fluoropolymer further contains unit 3, the ratio of the content of unit 3 to the total content of units 1 and 2 (content of unit 3 / content of unit 1 and content of unit 2) Examples thereof include fluorine-containing polymers having a sum of the amounts of 0.1 to 1.5.
Ratio of the number of moles of monomer 3 to the total number of moles of monomer 1 and monomer 2 (number of moles of monomer 3 / (number of moles of monomer 1 + number of moles of monomer 2)) Is preferably 0.1 to 1.5.
　本発明の製造方法における過硫酸塩は、過硫酸アンモニウム塩、過硫酸カリウム塩または過硫酸ナトリウム塩が好ましい。
　過硫酸塩の使用量は、単量体混合物の総和１００ｇに対して０．０１～０．２２ｍｍｏｌである。また、過硫酸塩の使用量は、単量体混合物の総和１００ｇに対して過硫酸塩換算で、０．０１～０．１５ｍｍｏｌであることが好ましく、０．０１～０．１０ｍｍｏｌであることがより好ましく、０．０１～０．０５ｍｍｏｌであることがさらに好ましい。
　なお、過硫酸塩の使用量は、理論的に、塩成分の含有量と等しくなる。
　過硫酸塩の使用量が多いと、得られた水性分散液において、塩成分の含有量が多くなり、水性分散液の貯蔵時等の着色安定性が損なわれるだけでなく、水性分散液のｐＨが経時的に低下しやすい。一方、過硫酸塩の使用量が少ないと、重合の進行が遅くなり、単量体が高い反応率で重合しない。その結果、効率的に含フッ素重合体が得られず、場合によっては重合が全く進行しなくなる。過硫酸塩の使用量が上記の範囲であれば、得られる水性分散液の着色安定性、ｐＨ安定性および重合時の生産性がより良好となる。 The persulfate in the production method of the present invention is preferably ammonium persulfate, potassium persulfate or sodium persulfate.
The amount of persulfate used is 0.01 to 0.22 mmol with respect to 100 g of the total monomer mixture. The amount of persulfate used is preferably 0.01 to 0.15 mmol, and preferably 0.01 to 0.10 mmol in terms of persulfate per 100 g of the total monomer mixture. More preferred is 0.01 to 0.05 mmol.
The amount of persulfate used is theoretically equal to the content of the salt component.
When the amount of persulfate used is large, the content of the salt component in the obtained aqueous dispersion increases, and not only the color stability during storage of the aqueous dispersion is impaired, but also the pH of the aqueous dispersion. Tends to decrease over time. On the other hand, when the amount of persulfate used is small, the progress of the polymerization is delayed and the monomer is not polymerized at a high reaction rate. As a result, a fluorine-containing polymer cannot be obtained efficiently, and in some cases, polymerization does not proceed at all. If the amount of persulfate used is in the above range, the color stability, pH stability and productivity during polymerization of the aqueous dispersion obtained will be better.
　本発明の製造方法では、過硫酸塩と組合せて、他の重合開始剤を併用してもよい。
　他の重合開始剤としては、過酸化水素と亜硫酸水素ナトリウム等との組み合わせからなるレドックス開始剤、第一鉄塩、硝酸銀等の無機系開始剤を混合させた重合開始剤、ジコハク酸パーオキシド、ジグルタール酸パーオキシド、アゾビスブチロニトリル等の有機系重合開始剤等が挙げられる。
　他の重合開始剤を併用する場合の使用量は、過硫酸塩に対して、１～１００モル％が好ましく、５～９５モル％がより好ましい。 In the production method of the present invention, another polymerization initiator may be used in combination with the persulfate.
Other polymerization initiators include redox initiators composed of a combination of hydrogen peroxide and sodium hydrogen sulfite, polymerization initiators mixed with inorganic initiators such as ferrous salts and silver nitrate, disuccinic acid peroxide, and diglutar. Examples thereof include organic polymerization initiators such as acid peroxide and azobisbutyronitrile.
When used in combination with other polymerization initiators, the amount used is preferably from 1 to 100 mol%, more preferably from 5 to 95 mol%, based on the persulfate.
　本発明の製造方法における水性媒体中での重合は、乳化重合であることが好ましい。乳化重合においては、通常、乳化剤が使用される。
　乳化剤は、ノニオン性乳化剤またはアニオン性乳化剤が好ましい。
　ノニオン性乳化剤としては、アルキルフェノールエチレンオキシド付加物、高級アルコールエチレンオキシド付加物、エチレンオキシドとプロピレンオキシドのブロックコポリマー等が挙げられる。
　アニオン性乳化剤としては、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、高級脂肪酸塩、アルキル硫酸エステル塩、アルキルエーテル硫酸エステル塩、リン酸エステル塩等が挙げられる。
　乳化剤の使用量は、単量体の種類によって決定すればよく、前述したマクロモノマーが乳化剤のような重合系の安定化効果を有する場合には、乳化剤を使用しなくてもよい。 The polymerization in the aqueous medium in the production method of the present invention is preferably emulsion polymerization. In emulsion polymerization, an emulsifier is usually used.
The emulsifier is preferably a nonionic emulsifier or an anionic emulsifier.
Nonionic emulsifiers include alkylphenol ethylene oxide adducts, higher alcohol ethylene oxide adducts, block copolymers of ethylene oxide and propylene oxide, and the like.
Examples of the anionic emulsifier include alkyl benzene sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, alkyl sulfate ester salt, alkyl ether sulfate ester salt, and phosphate ester salt.
The amount of the emulsifier used may be determined depending on the type of the monomer. If the macromonomer described above has a stabilizing effect on the polymerization system such as the emulsifier, the emulsifier may not be used.
　本発明の製造方法では、連鎖移動剤を用いて含フッ素重合体の重合度（分子量）を調節してよい。また、水性媒体中の単量体の濃度の合計を高めることもできる。
　連鎖移動剤としては、アルキルメルカプタン（ｔｅｒｔ－ドデシルメルカプタン、ｎ－ドデシルメルカプタン、ステアリルメルカプタン等。）、アミノエタンチオール、メルカプトエタノール、３－メルカプトプロピオン酸、２－メルカプトプロピオン酸、チオリンゴ酸、チオグリコール酸、３，３’－ジチオ－ジプロピオン酸、チオグリコール酸２－エチルヘキシル、チオグリコール酸ｎ－ブチル、チオグリコール酸メトキシブチル、チオグリコール酸エチル、２，４－ジフェニル－４－メチル－１－ペンテン、四塩化炭素等が挙げられる。
　連鎖移動剤の使用量は、単量体混合物に対して０～２質量％が好ましい。
　本発明の製造方法の重合方式は、特に限定されず、バッチ重合法、単量体混合物を滴下する滴下重合法、連続重合法等による方式が挙げられる。 In the production method of the present invention, the degree of polymerization (molecular weight) of the fluoropolymer may be adjusted using a chain transfer agent. Also, the total concentration of monomers in the aqueous medium can be increased.
Chain transfer agents include alkyl mercaptans (tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, etc.), aminoethanethiol, mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, thioglycolic acid 3,3′-dithio-dipropionic acid, 2-ethylhexyl thioglycolate, n-butyl thioglycolate, methoxybutyl thioglycolate, ethyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene And carbon tetrachloride.
The amount of the chain transfer agent used is preferably 0 to 2% by mass with respect to the monomer mixture.
The polymerization method of the production method of the present invention is not particularly limited, and examples thereof include a batch polymerization method, a dropping polymerization method in which a monomer mixture is dropped, and a continuous polymerization method.
　本発明の水性塗料は、本発明の水性分散液を含む水性塗料であり、塩成分を含み、塩成分の含有量が、含フッ素重合体の１００ｇに対して過硫酸塩換算で０．０１～０．２２ｍｍｏｌである。
　本発明の水性塗料は、通常、上記の本発明の水性分散液を水性媒体等により希釈し、必要により添加剤を含ませて得られる。
　希釈に用いられる水性媒体は、本発明の水性分散液で説明した水性媒体と同様である。
　希釈に用いられる水性媒体の使用量は、特に限定されないが、水性塗料中の含フッ素重合体の含有量が、水性塗料の全量に対し、５～６０質量％となる量が好ましく、１０～５０質量％となる量がより好ましい。含フッ素重合体の含有量が上記下限値であれば耐候性により優れた塗膜が得られ、上記上限値であれば塗膜の透明性がより優れる。 The aqueous paint of the present invention is an aqueous paint containing the aqueous dispersion of the present invention, which contains a salt component, and the content of the salt component is 0.01 to 100 g in terms of persulfate per 100 g of the fluoropolymer. 0.22 mmol.
The aqueous paint of the present invention is usually obtained by diluting the above aqueous dispersion of the present invention with an aqueous medium or the like and adding an additive as necessary.
The aqueous medium used for dilution is the same as the aqueous medium described in the aqueous dispersion of the present invention.
The amount of the aqueous medium used for dilution is not particularly limited, but is preferably such that the content of the fluoropolymer in the aqueous coating is 5 to 60% by mass with respect to the total amount of the aqueous coating. The amount of mass% is more preferable. If the content of the fluoropolymer is the above lower limit, a coating film superior in weather resistance can be obtained, and if the content is the above upper limit, the transparency of the coating film is more excellent.
　水性塗料における塩成分の含有量は、含フッ素重合体の１００ｇに対して過硫酸塩換算で０．０１～０．２２ｍｍｏｌであり、０．０１～０．１５ｍｍｏｌが好ましく、０．０１～０．１０ｍｍｏｌがより好ましく、０．０１～０．０５ｍｍｏｌが特に好ましい。塩成分の含有量が上記の範囲内であれば、水性塗料の保管時における着色や水性塗料のｐＨの経時的な低下を抑制できる。
　なお、水性分散液に種々の添加剤等を添加して水性塗料を調製する場合、塩成分が混入する場合がある。例えば、含フッ素重合体を追加したり、他の重合体を添加したりする際に、それら重合体の重合開始剤に由来する塩成分が混入する場合がある。しかし、添加剤等から塩成分が混入した場合においても、本発明の水性塗料における塩成分の含有量は上記の範囲が好ましい。 The content of the salt component in the water-based paint is 0.01 to 0.22 mmol in terms of persulfate per 100 g of the fluoropolymer, preferably 0.01 to 0.15 mmol, and preferably 0.01 to 0.1. 10 mmol is more preferable, and 0.01 to 0.05 mmol is particularly preferable. If the content of the salt component is within the above range, coloring during storage of the aqueous paint and a decrease in the pH of the aqueous paint over time can be suppressed.
In addition, when preparing an aqueous coating material by adding various additives etc. to an aqueous dispersion, a salt component may mix. For example, when adding a fluorinated polymer or adding another polymer, a salt component derived from the polymerization initiator of the polymer may be mixed. However, even when a salt component is mixed from an additive or the like, the content of the salt component in the aqueous paint of the present invention is preferably within the above range.
　本発明の水性塗料は、必要に応じて、本発明の作用効果を妨げない範囲で、水性分散液および希釈に用いる水性媒体以外に、含フッ素重合体以外の他の重合体、乳化剤、着色剤、硬化剤、その他の添加剤を含んでもよい。
　たとえば、本発明の水性塗料には、着色剤を含ませることができる。
　また、本発明の水性塗料に硬化剤を含ませることにより、得られる塗膜の、耐候性、耐水性、耐薬品性、耐熱性等がさらに向上する。本発明の水性塗料は、一液型であってもよく、二液型であってもよいが、硬化剤を含ませる場合、二液型とし、使用直前に両液を混合するのが好ましい。 The water-based paint of the present invention, if necessary, is a polymer other than the fluorinated polymer, emulsifier, and colorant, in addition to the aqueous dispersion and the aqueous medium used for dilution, as long as the effects of the present invention are not hindered. , Curing agents, and other additives may be included.
For example, the water-based paint of the present invention can contain a colorant.
Moreover, by including a hardening | curing agent in the water-based coating material of this invention, the weather resistance, water resistance, chemical resistance, heat resistance, etc. of the obtained coating film further improve. The water-based paint of the present invention may be either a one-pack type or a two-pack type, but when a curing agent is included, it is preferably a two-pack type and the two liquids are mixed immediately before use.
　該他の重合体としては、特に限定されず、例えば、（メタ）アクリル系重合体、ポリエステル系樹脂、ポリウレタン系樹脂、エポキシ系樹脂、アクリルシリコーン系樹脂、メラミン系樹脂、ユリア系樹脂、ビニル系樹脂、フッ素系樹脂、フェノール系樹脂、アルキド系樹脂等が挙げられる。
　該他の重合体を含有する場合において、水性塗料中の他の重合体の含有量は、１０～６０質量％が好ましい。他の重合体の含有量を上記下限値とすれば、他の重合体が有する特性を発揮でき、一方、上記上限値であれば、含フッ素重合体が有する特性を損ねない。 The other polymer is not particularly limited, and examples thereof include (meth) acrylic polymers, polyester resins, polyurethane resins, epoxy resins, acrylic silicone resins, melamine resins, urea resins, and vinyl resins. Resins, fluorine resins, phenol resins, alkyd resins and the like can be mentioned.
In the case of containing the other polymer, the content of the other polymer in the aqueous paint is preferably 10 to 60% by mass. If the content of the other polymer is set to the above lower limit value, the characteristics of the other polymer can be exhibited. On the other hand, if the content is the above upper limit value, the characteristics of the fluoropolymer are not impaired.
　本発明の水性塗料には、乳化安定性を向上させる目的で、乳化剤を添加してもよい。水性塗料中に含有される乳化剤の種類は、本発明の水性分散液で説明した乳化剤と同様である。
　着色剤としては、染料、有機顔料、無機顔料等が挙げられる。
　着色剤の含有量は、水性塗料の総量１００に対して１～３００質量％が好ましい。
　硬化剤としては、例えば、ヘキサメチレンイソシアネート三量体等のブロックイソシアネートまたはその乳化分散体、メチル化メラミン、メチロール化メラミン、ブチロール化メラミン等のメラミン樹脂、メチル化尿素、ブチル化尿素等の尿素樹脂等が挙げられる。
　硬化剤の含有量は、使用する単量体の総量、１０～１５０モル％が好ましい。 An emulsifier may be added to the water-based paint of the present invention for the purpose of improving the emulsion stability. The kind of the emulsifier contained in the aqueous paint is the same as the emulsifier described in the aqueous dispersion of the present invention.
Examples of the colorant include dyes, organic pigments, and inorganic pigments.
The content of the colorant is preferably 1 to 300% by mass with respect to 100 as the total amount of the water-based paint.
Examples of the curing agent include block isocyanates such as hexamethylene isocyanate trimer or emulsion dispersions thereof, melamine resins such as methylated melamine, methylolated melamine, and butyrolated melamine, and urea resins such as methylated urea and butylated urea. Etc.
The content of the curing agent is preferably 10 to 150 mol% of the total amount of monomers used.
　その他の添加剤としては、可塑剤、紫外線吸収剤、レベリング剤、ハジキ防止剤、皮バリ防止剤等が挙げられる。 Other additives include plasticizers, UV absorbers, leveling agents, anti-repellent agents, anti-burr agents, and the like.
　本発明の塗装物品は、物品の表面に本発明の水性塗料の塗膜を有する。
　本発明の塗装物品は、物品の表面に本発明の水性塗料を塗布し、乾燥して塗膜を形成することにより製造できる。
　物品としては、特に制限されず、金属板、木板、プラスチック板、ガラス板、アスファルト、コンクリート等が挙げられる。
　塗布方法としては、刷毛、ローラー、ディッピング、スプレー、ロールコーター、ダイコター、アプリケーター、またはスピンコーター等の塗装装置を用いて行う方法が挙げられる。
　塗膜の厚みは、５～５０μｍが好ましい。塗膜の厚みが上記下限値であれば、視認性、意匠性の高い蛍光塗膜が得られ、上記上限値であれば、塗膜の表層と内部の硬化度合いに差がなく、均一な塗膜が得られる。
　塗布後の乾燥温度は、２５～３００℃程度が好ましい。 The coated article of the present invention has a coating film of the aqueous paint of the present invention on the surface of the article.
The coated article of the present invention can be produced by applying the aqueous paint of the present invention to the surface of the article and drying to form a coating film.
The article is not particularly limited, and examples thereof include a metal plate, a wooden plate, a plastic plate, a glass plate, asphalt, and concrete.
Examples of the coating method include a method using a coating apparatus such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, or a spin coater.
The thickness of the coating film is preferably 5 to 50 μm. If the thickness of the coating film is the above lower limit value, a fluorescent coating film with high visibility and design is obtained, and if it is the above upper limit value, there is no difference in the degree of curing between the surface layer of the coating film and the inside, and uniform coating is achieved. A membrane is obtained.
The drying temperature after coating is preferably about 25 to 300 ° C.
　本発明の水性分散液の製造方法によれば、重合の際に用いる過硫酸塩の使用量が少ないため、塩成分の含有量が少ない本発明の水性分散液を製造できる。
　本発明の水性分散液は、塩成分の含有量が少ないため、着色安定性、ｐＨ安定性に優れる。前述したとおり、水性分散液から水性塗料を調製する際は、増粘剤等を添加することにより、塗料として最適な粘度となるように粘度を調整する場合が多い。水性塗料の粘度は水性分散液のｐＨにより変化することが知られており、そのｐＨが経時的に変化してしまうと、水性塗料を調製する際に粘度を最適に調整しても、経時的にｐＨの変化に伴って粘度が変化し、水性塗料の使用時の粘度が最適値から外れてしまう。本発明の水性分散液は、ｐＨ安定性に優れるため、水性塗料とした場合に、粘度の変化が少なく、チクソ性に優れる。
　また、本発明の水性塗料は、チクソ性の安定性に優れており、塗料の粘度が最適な範囲に保持されるため、物品に対し均一に塗装できる。
　したがって、本発明の水性塗料およびこれを用いて形成される塗膜も、着色安定性、均一性に優れる。
　また、単位１および単位２を有する含フッ素重合体を含む本発明の水性分散液から調製される、本発明の水性塗料から形成される塗膜は、耐候性、耐水性、耐薬品性、耐熱性等に優れる。 According to the method for producing an aqueous dispersion of the present invention, since the amount of persulfate used in the polymerization is small, the aqueous dispersion of the present invention having a small salt component content can be produced.
The aqueous dispersion of the present invention is excellent in coloring stability and pH stability because the content of the salt component is small. As described above, when preparing an aqueous coating material from an aqueous dispersion, the viscosity is often adjusted by adding a thickener or the like so as to obtain an optimum viscosity as a coating material. It is known that the viscosity of water-based paints varies depending on the pH of the aqueous dispersion. If the pH changes over time, even if the viscosity is adjusted optimally when preparing a water-based paint, In addition, the viscosity changes with the change in pH, and the viscosity at the time of use of the water-based paint deviates from the optimum value. Since the aqueous dispersion of the present invention is excellent in pH stability, when it is used as an aqueous paint, there is little change in viscosity and excellent thixotropy.
Further, the water-based paint of the present invention is excellent in thixotropic stability, and the viscosity of the paint is maintained in an optimum range, so that it can be applied uniformly to an article.
Therefore, the water-based paint of the present invention and the coating film formed using the same are also excellent in color stability and uniformity.
In addition, the coating film formed from the aqueous paint of the present invention prepared from the aqueous dispersion of the present invention containing the fluoropolymer having units 1 and 2 has a weather resistance, water resistance, chemical resistance, heat resistance Excellent in properties.
　以下の実施例により本発明を具体的に説明するが、本発明は本実施例に限定されない。
　後述の各例で用いた測定方法を以下に示す。 The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.
The measurement method used in each example described later is shown below.
＜測定方法＞
［過硫酸塩量の算出］
（水性分散液を加えた硫酸アンモニウム鉄（ＩＩ）の滴定）
　水性分散液のＷ（ｇ）をイオン交換水の１０ｇに溶解し、これを試料溶液とした。
　試料溶液に、９０ｇ／Ｌ硫酸アンモニウム鉄（ＩＩ）水溶液の２０ｍＬおよびリン酸の２０ｍＬを加えて、混合液を得た。該混合液に０．０２ｍｏｌ／Ｌ過マンガン酸カリウム水溶液を、溶液が微紅色を呈するまで滴下した。その際の滴定量をＡ（ｍＬ）とした。 <Measurement method>
[Calculation of the amount of persulfate]
(Titration of ammonium iron (II) sulfate with aqueous dispersion)
W (g) of the aqueous dispersion was dissolved in 10 g of ion-exchanged water, and this was used as a sample solution.
20 mL of 90 g / L ammonium iron sulfate (II) aqueous solution and 20 mL of phosphoric acid were added to the sample solution to obtain a mixed solution. A 0.02 mol / L potassium permanganate aqueous solution was added dropwise to the mixed solution until the solution turned a slight red color. The titer at that time was A (mL).
（硫酸アンモニウム鉄（ＩＩ）の滴定）
　イオン交換水の１０ｇに、９０ｇ／Ｌ硫酸アンモニウム鉄（ＩＩ）水溶液の２０ｍＬおよびリン酸の２０ｍＬを加えて、混合液を得た。該混合液に０．０２ｍｏｌ／Ｌ過マンガン酸カリウム水溶液を、溶液が微紅色を呈するまで滴下した。その際の滴定量をＢ（ｍＬ）とした。 (Titration of ammonium iron (II) sulfate)
To 10 g of ion-exchanged water, 20 mL of 90 g / L ammonium iron sulfate (II) aqueous solution and 20 mL of phosphoric acid were added to obtain a mixed solution. A 0.02 mol / L potassium permanganate aqueous solution was added dropwise to the mixed solution until the solution turned a slight red color. The titer at that time was B (mL).
（過硫酸塩量の算出方法）
　まず、下式（１）により、水性分散液中の過硫酸塩の濃度Ｃ（質量％）を算出した。なお、水性塗料における過硫酸塩の濃度も同様にして算出できる。
　Ｃ＝｛（Ｂ－Ａ）×ｆ×Ｍｗ×０．００００５／Ｗ｝×１００　・・・（１）
　　ｆ：０．０２ｍｏｌ／Ｌ過マンガン酸カリウム水溶液の濃度の程度を示すもので当該過マンガン酸カリウム水溶液中に含まれている過マンガン酸カリウム量を補正する値。
　　Ｍｗ：過硫酸塩の分子量。 (Calculation method of persulfate amount)
First, the concentration C (mass%) of persulfate in the aqueous dispersion was calculated by the following formula (1). The concentration of persulfate in the water-based paint can be calculated in the same manner.
C = {(BA) × f × Mw × 0.00005 / W} × 100 (1)
f: 0.02 mol / L A value indicating the degree of concentration of the potassium permanganate aqueous solution, which corrects the amount of potassium permanganate contained in the potassium permanganate aqueous solution.
Mw: molecular weight of persulfate.
　ここで、上記の滴定は、予め試料溶液中の過硫酸塩を硫酸アンモニウム鉄（ＩＩ）と酸化還元反応させ、過剰の硫酸アンモニウム鉄（ＩＩ）を過マンガン酸カリウムで逆滴定して過硫酸塩量を測定する方法である。
　硫酸アンモニウム鉄（ＩＩ）と過マンガン酸カリウムの酸化還元反応は下式（６１）で示される。
　５ＦｅＳＯ４（ＮＨ４）２ＳＯ４＋ＫＭｎＯ４→５Ｆｅ３＋＋１０ＳＯ４ ２－＋１０ＮＨ４ ＋＋Ｋ＋＋ＭｎＯ４ ６－　・・・（６１）
　硫酸アンモニウム鉄（ＩＩ）と過硫酸塩の酸化還元反応は下式（６２）で示される。
　２ＦｅＳＯ４（ＮＨ４）２ＳＯ４＋ＱＳ２Ｏ８→２Ｆｅ３＋＋４ＳＯ４ ２－＋４ＮＨ４ ＋＋２ＳＯ４ ２－＋Ｑ　・・・（６２）
　Ｑ：アミン類、アルカリ金属類等のカウンターカチオン。
　上記の滴定の結果である、滴定量Ａ、滴定量Ｂ、および式（６１）、式（６２）より下式（６３）が導かれる。
　Ｃ＝｛（Ｂ－Ａ）／１０００×０．０２×ｆ×５／２×Ｍｗ／Ｗ｝×１００・・・　（６３）
　式（６３）の定数を計算することで式（６）が導きだされる。
　ｆの具体的な数値は、容量分析用「標準物質」を用いて行う標定法（以後、直接法という）や、すでに直接法でファクターを決めてある容量分析用「標準液」を用いて行う標定法（間接法という）により求められ、本測定においては１．００３である。 Here, in the above titration, the persulfate in the sample solution is previously oxidized and reduced with iron iron (II) sulfate, and the excess ammonium iron sulfate (II) is back titrated with potassium permanganate to determine the amount of persulfate. It is a method of measuring.
The redox reaction of ammonium iron sulfate (II) and potassium permanganate is represented by the following formula (61).
5FeSO 4 (NH 4 ) 2 SO 4 + KMnO 4 → 5Fe 3+ + 10SO 4 2 + + 10NH 4 + + K + + MnO 4 6− (61)
The oxidation-reduction reaction between ammonium iron (II) sulfate and persulfate is represented by the following formula (62).
2FeSO 4 (NH 4 ) 2 SO 4 + QS 2 O 8 → 2Fe 3+ + 4SO 4 2 + + 4NH 4 + + 2SO 4 2 + Q (62)
Q: Counter cations such as amines and alkali metals.
The following formula (63) is derived from the titration amount A, titration amount B, and formulas (61) and (62), which are the results of the above titration.
C = {(BA) /1000×0.02×f×5/2×Mw/W} × 100 (63)
By calculating the constant of equation (63), equation (6) is derived.
Specific values of f are determined using a standardization method (hereinafter referred to as a direct method) performed using a “standard substance” for volumetric analysis or a “standard solution” for volumetric analysis whose factors have already been determined by the direct method. It is determined by the orientation method (referred to as indirect method), and is 1.003 in this measurement.
　次いで、下式（７）により、水性分散液中の含フッ素重合体固形分１００ｇ当たりの残存過硫酸塩の量Ｙ（ｍｍｏｌ）を算出した。
　Ｙ＝（Ｃ／Ｘ）×１００／Ｍｗ　・・・（７）
　　Ｘ：水性分散液中の含フッ素重合体固形分濃度（質量％）。 Next, the amount Y (mmol) of the residual persulfate per 100 g of the fluoropolymer solid content in the aqueous dispersion was calculated by the following formula (7).
Y = (C / X) × 100 / Mw (7)
X: Fluoropolymer solid content concentration (mass%) in the aqueous dispersion.
［硫酸イオン量の算出］
　以下の手順で、過硫酸塩の分解物である硫酸イオンの量を算出した。なお、水性塗料における硫酸イオンの量も同様にして算出できる。
　製造した水性分散液を超純水で１０００倍希釈した試料溶液を限外ろ過器に入れ、半径１３ｃｍのローター（コクサン社製「Ｈ－１８」）を用い、４０００ｒｐｍの条件で６０分間遠心分離した。ろ液を超純水で１０倍希釈し、試料希釈液を得た。
　次いで、イオンクロマトグラフィーシステム（日本ダイオネクス（株）製、ＩＣＳ－３０００）を用いて、該希釈液中の硫酸イオン濃度Ｉ（μｇ／ｍＬ）を測定した。
　その結果から、下式（８）により、水性分散液中の含フッ素重合体固形分１００ｇ当たりの硫酸イオン量（過硫酸塩換算）Ｚ（ｍｍｏｌ）を算出した。なお、式中の９６は、硫酸イオンの分子量である。
　Ｚ＝１０×Ｉ／（ｄ×Ｘ×９６）　・・・（８）
　　ｄ：水性分散液の比重。
　　Ｘ：水性分散液中の含フッ素重合体固形分濃度（質量％）。 [Calculation of sulfate ion content]
The amount of sulfate ion, which is a decomposition product of persulfate, was calculated by the following procedure. The amount of sulfate ion in the water-based paint can be calculated in the same manner.
A sample solution obtained by diluting the prepared aqueous dispersion 1000 times with ultrapure water was put in an ultrafilter and centrifuged for 60 minutes at 4000 rpm using a rotor having a radius of 13 cm (“H-18” manufactured by Kokusan). . The filtrate was diluted 10 times with ultrapure water to obtain a sample diluted solution.
Subsequently, the sulfate ion concentration I (μg / mL) in the diluted solution was measured using an ion chromatography system (manufactured by Nippon Dionex Co., Ltd., ICS-3000).
From the result, the amount of sulfate ion (persulfate equivalent) Z (mmol) per 100 g of the fluoropolymer solid content in the aqueous dispersion was calculated by the following formula (8). In the formula, 96 is the molecular weight of sulfate ion.
Z = 10 × I / (d × X × 96) (8)
d: Specific gravity of the aqueous dispersion.
X: Fluoropolymer solid content concentration (mass%) in the aqueous dispersion.
［色度（ＹＩ値）の測定］
　実施例１～６および比較例１で得られた水性分散液（製造直後）をそれぞれイオン交換水で１０倍に希釈して希釈試料とした。希釈試料を円筒セル（３０φ×３０ｍｍ）に入れ測色色差計（日本電色工業（株）製、ＺＥ－２０００）でＹＩ値を測定した。
　また、実施例１～６および比較例１で得られた水性分散液を５０℃で２週間保存し、保存後の水性分散液についても、上記と同様にして、ＹＩ値を測定した。
　ＹＩ値が低い程、着色していないことを示す。 [Measurement of chromaticity (YI value)]
The aqueous dispersions (immediately after production) obtained in Examples 1 to 6 and Comparative Example 1 were each diluted 10-fold with ion-exchanged water to obtain diluted samples. The diluted sample was placed in a cylindrical cell (30φ × 30 mm), and the YI value was measured with a colorimetric color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000).
In addition, the aqueous dispersions obtained in Examples 1 to 6 and Comparative Example 1 were stored at 50 ° C. for 2 weeks, and the YI values of the aqueous dispersions after storage were measured in the same manner as described above.
It shows that it is not colored, so that YI value is low.
［ｐＨの測定］
　実施例１～６および比較例１で得られた水性分散液（製造直後）の２５℃におけるｐＨを測定した。
　また、実施例１～６および比較例１で得られた水性分散液を５０℃で２週間保存し、保存後の水性分散液についても２５℃におけるｐＨを測定した。 [Measurement of pH]
The pH at 25 ° C. of the aqueous dispersions (immediately after production) obtained in Examples 1 to 6 and Comparative Example 1 was measured.
Further, the aqueous dispersions obtained in Examples 1 to 6 and Comparative Example 1 were stored at 50 ° C. for 2 weeks, and the pH of the aqueous dispersion after storage was measured at 25 ° C.
［チクソ性の安定性の評価］
　実施例１～６および比較例１の水性分散液をそれぞれ、造膜助剤のテキサノール（イーストマンケミカル社製）、消泡剤のデヒドラン１６２０（サンノプコ社製）、アルカリ膨潤型増粘剤のＴＴ－６１５（ローム アンド ハーツ社製）およびアンモニア水と配合して水性塗料を調製した。各材料の配合量は、水性塗料の粘度をチクソ性が水性塗料として適正範囲になるよう調整した。
　得られた水性塗料を５０℃で２週間保存し、保存前、保存後それぞれの水性塗料のチクソ性から以下の基準でチクソ性の安定性を評価した。
　○：保存によるチクソ性の低下なし。
　△：保存によりチクソ性がやや低下した。
　×：保存によりチクソ性が明らかに低下した。
　水性塗料のチクソ性：ＪＩＳ　Ｋ　５６００－２－３に規定されるコーン・プレート粘度計法に準拠し、Ｎｏ．４のローターを使用し、２５℃において、回転数５ｒｐｍ時、回転数５０ｒｐｍ時それぞれの水性塗料のおける粘度を測定し、それらの粘度の比であるＴＩ値（＝回転数５ｒｐｍ時の粘度［ｍＰａ・ｓ］／回転数５０ｒｐｍ時の粘度［ｍＰａ・ｓ］）を算出し、これをチクソ性の指標とした。 [Evaluation of thixotropic stability]
The aqueous dispersions of Examples 1 to 6 and Comparative Example 1 were respectively formed into a film-forming auxiliary texanol (manufactured by Eastman Chemical Co.), an antifoaming agent Dehydran 1620 (manufactured by San Nopco), and an alkali swelling type thickener TT An aqueous paint was prepared by blending with -615 (Rohm and Hearts) and aqueous ammonia. The blending amount of each material was adjusted so that the viscosity of the water-based paint was within the appropriate range for the thixotropy of the water-based paint.
The obtained water-based paint was stored at 50 ° C. for 2 weeks, and the stability of thixotropy was evaluated according to the following criteria from the thixotropy of each water-based paint before and after storage.
○: No decrease in thixotropy due to storage.
(Triangle | delta): Thixotropic property fell a little by storage.
X: The thixotropy was clearly reduced by storage.
Thixotropic properties of water-based paints: In accordance with the cone plate viscometer method defined in JIS K 5600-2-3, No. 4 rotor was used, and the viscosity of each water-based paint was measured at 25 ° C. at a rotation speed of 5 rpm and at a rotation speed of 50 rpm, and the TI value (= viscosity at a rotation speed of 5 rpm [mPa] S] / viscosity at 50 rpm (mPa · s]) was calculated and used as an index of thixotropy.
＜実施例１＞
　容器積２５０ｍＬのステンレス製攪拌機付きオートクレーブ中に、シクロヘキシルビニルエーテル（以下、ＣＨＶＥという。）の３４ｇ、２－エチルヘキシルビニルエーテル（以下、２ＥＨＶＥという。）の１９ｇ、シクロヘキサンジメタノールモノビニルエーテル（以下、ＣＨＭＶＥという。）の２．８ｇ、１－ビニロキシメチル－４－（ポリオキシエチレン）シクロヘキシルメチルエーテル（以下、ＣＭＥＯＶＥという。）の１．７ｇ、イオン交換水の９３ｇ、炭酸カリウムの０．２６ｇ、過硫酸アンモニウム（以下、ＡＰＳという。）の０．０１２ｇ、ノニオン性乳化剤（ＤＫＳ　ＮＬ－１００：第一工業製薬（株）製）の５．２ｇ、アニオン性乳化剤（ラウリル硫酸ナトリウム。以下、ＳＬＳという。）の０．１ｇを仕込み、氷で冷却して、窒素ガスを０．５ＭＰａになるよう加圧し脱気した。この加圧脱気を２回繰り返した後－０．８ＭＰａまで脱気して溶存空気を除去した後、ＣＦ２＝ＣＦＣｌ（以下、ＣＴＦＥという。）の４７ｇを圧入し、５０℃で３６時間、重合反応を行った。重合反応後、２００メッシュのナイロン布で水性分散液を濾過した。次いで、イオン交換水を用いて、固形分濃度が５２質量％になるように調整して、粒子状の含フッ素重合体を含む水性分散液を得た。含フッ素重合体の粒子の平均粒子径は、１５０ｎｍであった。
　なお、上記ＣＭＥＯＶＥは、ＣＨＭＶＥのエチレンオキシド付加物であって、１分子あたりのオキシエチレン基の数は平均約１５である。 <Example 1>
In an autoclave equipped with a stainless steel stirrer with a container volume of 250 mL, 34 g of cyclohexyl vinyl ether (hereinafter referred to as CHVE), 19 g of 2-ethylhexyl vinyl ether (hereinafter referred to as 2EHVE), cyclohexanedimethanol monovinyl ether (hereinafter referred to as CHMVE). 2.8 g of 1-vinyloxymethyl-4- (polyoxyethylene) cyclohexyl methyl ether (hereinafter referred to as CMEOVE), 93 g of ion-exchanged water, 0.26 g of potassium carbonate, ammonium persulfate (hereinafter referred to as “CMEOVE”) 0.012 g of nonionic emulsifier (DKS NL-100: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 0.2 g of anionic emulsifier (sodium lauryl sulfate, hereinafter referred to as SLS). Charge 1g and cool with ice Then, nitrogen gas was pressurized to 0.5 MPa and degassed. After repeating this pressure degassing twice, deaeration to −0.8 MPa to remove dissolved air, and then 47 g of CF 2 = CFCl (hereinafter referred to as CTFE) was injected and the mixture was injected at 50 ° C. for 36 hours. A polymerization reaction was performed. After the polymerization reaction, the aqueous dispersion was filtered with a 200 mesh nylon cloth. Subsequently, using ion-exchange water, it adjusted so that solid content concentration might be 52 mass%, and obtained the aqueous dispersion liquid containing a particulate fluoropolymer. The average particle size of the fluoropolymer particles was 150 nm.
The above CMEOVE is an ethylene oxide adduct of CHMVE, and the average number of oxyethylene groups per molecule is about 15.
＜実施例２～４および比較例１＞
　実施例２～４および比較例１では、ＡＰＳの使用量を表１に示すとおりに変更した以外は、実施例１と同様に水性分散液を得た。それぞれの例における含フッ素重合体の平均粒子径は、いずれも１４０～１６０ｎｍの範囲内であった。 <Examples 2 to 4 and Comparative Example 1>
In Examples 2 to 4 and Comparative Example 1, aqueous dispersions were obtained in the same manner as in Example 1 except that the amount of APS used was changed as shown in Table 1. The average particle size of the fluoropolymer in each example was in the range of 140 to 160 nm.
＜実施例５＞
　容器積２５０ｍＬのステンレス製攪拌機付きオートクレーブ中にＣＨＶＥの１．４ｇ、エチルビニルエーテル（以下、ＥＶＥという。）３７ｇ、ＣＨＭＶＥの３．８ｇ、ＣＭＥＯＶＥの３．１ｇ、イオン交換水９７ｇ、炭酸カリウム０．２６ｇ、ＡＰＳの０．００２５ｇ、ノニオン性乳化剤（ＤＫＳ　ＮＬ－１００：第一工業製薬（株）製）５．５ｇ、ＳＬＳの０．１ｇを仕込み、氷で冷却して、窒素ガスを０．５ＭＰａになるよう加圧し脱気する。この加圧脱気を２回繰り返した後－０．８ＭＰａまで脱気して溶存空気を除去した後、ＣＴＦＥの６４ｇを圧入し、５０℃で３６時間、重合反応を行った。重合反応後、２００メッシュのナイロン布で水性分散液を濾過した。次いで、イオン交換水を用いて、固形分濃度が５２質量％になるように調整して、水性分散液を得た。 <Example 5>
In a 250 mL stainless steel autoclave with a stirrer vessel, 1.4 g of CHVE, 37 g of ethyl vinyl ether (hereinafter referred to as EVE), 3.8 g of CHMVE, 3.1 g of CMEOVE, 97 g of ion-exchanged water, 0.26 g of potassium carbonate , 0.0025 g of APS, 5.5 g of nonionic emulsifier (DKS NL-100: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 0.1 g of SLS were charged with ice and cooled to 0.5 MPa with nitrogen gas. Pressurize and deaerate. This pressure degassing was repeated twice and then degassed to -0.8 MPa to remove dissolved air, and then 64 g of CTFE was injected and polymerization reaction was carried out at 50 ° C. for 36 hours. After the polymerization reaction, the aqueous dispersion was filtered with a 200 mesh nylon cloth. Subsequently, using ion exchange water, it adjusted so that solid content concentration might be 52 mass%, and the aqueous dispersion liquid was obtained.
＜実施例６＞
　ノニオン性乳化剤（ＤＫＳ　ＮＬ－１００：第一工業製薬（株）製）の仕込み量を２．６ｇに変えた以外は、実施例３と同様にして、粒子状の含フッ素重合体を含む水性分散液を得た。含フッ素重合体の粒子の平均粒子径は、２１０ｎｍであった。 <Example 6>
An aqueous dispersion containing a particulate fluoropolymer in the same manner as in Example 3 except that the amount of nonionic emulsifier (DKS NL-100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was changed to 2.6 g. A liquid was obtained. The average particle size of the fluoropolymer particles was 210 nm.
　各水性分散液について、ラテックス収率、過硫酸塩量および硫酸イオン量を算出した。ラテックス収率は、原料中のイオン交換水以外の原料総量の割合に対する重合反応後液中の固形分量の割合（質量％）を示す（以下同様）。塩成分の含有量（過硫酸塩換算）は、過硫酸塩量および硫酸イオン量を合算して求めた。また、得られた水性分散液について、色度（ＹＩ値）およびｐＨを測定し、チクソ性の安定性を評価した。
　各例における原料の使用量、含フッ素重合体の１００ｇに対する塩成分の含有量（過硫酸塩（ＡＰＳ）およびその分解物の合計含有量（過硫酸塩換算））の算出結果、ＹＩ値およびｐＨの測定結果、並びにチクソ性の安定性の評価結果を表１に示す。また、ＹＩ値、ｐＨについて、製造直後の値と５０℃２週間保存後の値との差の絶対値を表１に示す。 For each aqueous dispersion, the latex yield, the amount of persulfate and the amount of sulfate ion were calculated. The latex yield indicates the ratio (mass%) of the solid content in the post-polymerization reaction liquid with respect to the ratio of the total amount of raw materials other than ion-exchanged water in the raw material (the same applies hereinafter). The content of the salt component (persulfate equivalent) was determined by adding the persulfate amount and the sulfate ion amount. Moreover, about the obtained aqueous dispersion, chromaticity (YI value) and pH were measured and thixotropic stability was evaluated.
The amount of raw materials used in each example, the calculation result of the salt component content (persulfate (APS) and the total content of its decomposition products (persulfate equivalent)) per 100 g of the fluoropolymer, YI value and pH Table 1 shows the measurement results and evaluation results of thixotropic stability. Table 1 shows the absolute value of the difference between the value immediately after production and the value after storage at 50 ° C. for 2 weeks for the YI value and pH.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　水性分散液中の含フッ素重合体の１００ｇに対する過硫酸塩（ＡＰＳ）およびその分解物の合計含有量（過硫酸塩換算）が０．２４ｍｍｏｌであった比較例１では、製造直後のＹＩ値が－５．８、５０℃で２週間保存後のＹＩ値が１．４であり、その変化幅は７．２であった。
　これに対し、該合計含有量（過硫酸塩換算）が０．２２ｍｍｏｌ以下であった実施例１～４では、製造直後のＹＩ値が－６．４以下、５０℃で２週間保存後のＹＩ値の変化幅が－０．７以下と、比較例１に比べ低く、着色が抑制されていた。また、保存前後でのＹＩ値の変化幅も少なかった。実施例１～４の中でも、水性分散液中の含フッ素重合体の１００ｇに対する合計含有量（過硫酸塩換算）が低い実施例程、ＹＩ値が低く、保存前後でのＹＩ値の変化が小さかった。 In Comparative Example 1 in which the total content (persulfate equivalent) of persulfate (APS) and its decomposition product with respect to 100 g of the fluoropolymer in the aqueous dispersion was 0.24 mmol, the YI value immediately after production was The YI value after storage at −5.8 and 50 ° C. for 2 weeks was 1.4, and the range of change was 7.2.
On the other hand, in Examples 1 to 4 in which the total content (persulfate equivalent) was 0.22 mmol or less, the YI value immediately after production was −6.4 or less, and the YI after storage at 50 ° C. for 2 weeks. The change width of the value was −0.7 or less, which was lower than that of Comparative Example 1, and coloring was suppressed. Moreover, the change width of the YI value before and after storage was small. Among Examples 1 to 4, the lower the total content (persulfate equivalent) with respect to 100 g of the fluoropolymer in the aqueous dispersion, the lower the YI value and the smaller the change in the YI value before and after storage. It was.
　一部の単量体の種類および配合量が異なる実施例５では、水性分散液中の含フッ素重合体の１００ｇに対する合計含有量（過硫酸塩換算）が０．０１ｍｍｏｌであった。実施例５も、製造直後のＹＩ値が－１１、５０℃で２週間保存後のＹＩ値が－９．７と、比較例１に比べ低かった。また、保存前後でのＹＩ値の変化も少なかった。
　また、含フッ素重合体の粒子の平均粒子径が２００ｎｍ以下である実施例３と、２００ｎｍ以上である実施例６との対比より、平均粒子径が２００ｎｍ以下であると、製造直後のＹＩ値、５０℃で２週間保存後のＹＩ値、保存前後のＹＩ値の変化幅がいずれも小さく、着色が抑制されることが分かった。
　実施例１～６では、製造直後のｐＨと５０℃で２週間保存後のｐＨとの差が比較例１よりも小さかった。
　実施例１～６の水性分散液を用いた水性塗料は、比較例１を用いた水性塗料に比べて、５０℃で２週間保存したときのチクソ性の低下が少なかった。
　なお、実施例５における過硫酸塩（ＡＰＳ）量を半量（０．００５ｍｍｏｌ）とする以外は同様にして、含フッ素重合体を含む水性分散液を製造した場合には、ラテックス収率が９０％未満であり、含フッ素重合体が効率よく得られなかった。 In Example 5 in which the types and blending amounts of some of the monomers were different, the total content (persulfate equivalent) with respect to 100 g of the fluoropolymer in the aqueous dispersion was 0.01 mmol. Also in Example 5, the YI value immediately after production was −11, and the YI value after storage for 2 weeks at 50 ° C. was −9.7, which was lower than that of Comparative Example 1. In addition, there was little change in the YI value before and after storage.
Further, in comparison with Example 3 in which the average particle size of the fluoropolymer particles is 200 nm or less and Example 6 in which the average particle size is 200 nm or more, if the average particle size is 200 nm or less, the YI value immediately after production, It was found that both the YI value after storage for 2 weeks at 50 ° C. and the change width of the YI value before and after storage were small, and coloring was suppressed.
In Examples 1 to 6, the difference between the pH immediately after production and the pH after storage at 50 ° C. for 2 weeks was smaller than in Comparative Example 1.
Compared with the aqueous paint using Comparative Example 1, the aqueous paint using the aqueous dispersions of Examples 1 to 6 showed less decrease in thixotropy when stored at 50 ° C. for 2 weeks.
In the same manner except that the amount of persulfate (APS) in Example 5 was half (0.005 mmol), when an aqueous dispersion containing a fluoropolymer was produced, the latex yield was 90%. The fluoropolymer could not be obtained efficiently.
　本発明の水性分散液を含む水性塗料は、例えば、建築等に用いられる木材、装置等に用いられる金属等の塗装に使用できる。
　なお、２０１６年０１月１４日に出願された日本特許出願２０１６－００５２９９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。 The water-based paint containing the aqueous dispersion of the present invention can be used, for example, for the coating of wood or the like used in construction or the like or metals used in devices.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-005299 filed on Jan. 14, 2016 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (15)

  1. 　フルオロオレフィンに基づく単位および架橋性基を有する単量体に基づく単位を有する含フッ素重合体が水性媒体に分散した水性分散液であって、
    　過硫酸塩およびその分解物からなる群から選ばれる少なくとも１種の成分を含み、
    　該成分の含有量が、該含フッ素重合体の１００ｇに対して過硫酸塩換算で０．０１～０．２２ｍｍｏｌであることを特徴とする水性分散液。     An aqueous dispersion in which a fluoropolymer having a unit based on a fluoroolefin and a unit based on a monomer having a crosslinkable group is dispersed in an aqueous medium,
    Including at least one component selected from the group consisting of persulfates and decomposition products thereof;
    An aqueous dispersion, wherein the content of the component is 0.01 to 0.22 mmol in terms of persulfate per 100 g of the fluoropolymer.
  2. 　前記含フッ素重合体が水性媒体中に粒子状に分散してなり、該粒子の平均粒子径が２００ｎｍ以下である、請求項１に記載の水性分散液。 The aqueous dispersion according to claim 1, wherein the fluoropolymer is dispersed in the form of particles in an aqueous medium, and the average particle diameter of the particles is 200 nm or less.
  3. 　前記水性分散液中の含フッ素重合体の濃度が１０～７０質量％である、請求項１または２に記載の水性分散液。 The aqueous dispersion according to claim 1 or 2, wherein the concentration of the fluoropolymer in the aqueous dispersion is 10 to 70% by mass.
  4. 　前記フルオロオレフィンが、ＣＦ２＝ＣＦ２またはＣＦ２＝ＣＦＣｌである、請求項１～３のいずれか一項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 3, wherein the fluoroolefin is CF 2 = CF 2 or CF 2 = CFCl.
  5. 　前記架橋性基を有する単量体が、水酸基、加水分解性シリル基、カルボキシ基、アミノ基、イソシアネート基、エポキシ基またはオキセタニル基を有する単量体である、請求項１～４のいずれか一項に記載の水性分散液。 The monomer having a crosslinkable group is a monomer having a hydroxyl group, a hydrolyzable silyl group, a carboxy group, an amino group, an isocyanate group, an epoxy group or an oxetanyl group. The aqueous dispersion according to item.
  6. 　前記架橋性基を有する単量体が、水酸基またはカルボキシ基を有する単量体である、請求項５に記載の水性分散液。 The aqueous dispersion according to claim 5, wherein the monomer having a crosslinkable group is a monomer having a hydroxyl group or a carboxy group.
  7. 　前記架橋性基を有する単量体が、架橋性基と親水性部位を有する単量体である、請求項１～６のいずれか一項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 6, wherein the monomer having a crosslinkable group is a monomer having a crosslinkable group and a hydrophilic portion.
  8. 　前記架橋性基と親水性部位を有する単量体が、Ｊ－Ｑ－［Ｏ－Ｙ－］ｎ－ＯＨで表される単量体である（ただし、Ｊはビニルオキシ基またはアリルオキシ基、Ｑは炭素数１～１０のアルキレン基または炭素数６～１０の環構造を有するアルキレン基、Ｙは２～４のアルキレン基（ただし、ｎ個のＹの少なくとも一部はジメチレン基である）、ｎは２～２０の整数、を表す。）、請求項７に記載の水性分散液。 The monomer having a crosslinkable group and a hydrophilic portion is a monomer represented by JQ- [O—Y—] n —OH (where J is a vinyloxy group or allyloxy group, Q is An alkylene group having 1 to 10 carbon atoms or an alkylene group having a ring structure having 6 to 10 carbon atoms, Y is an alkylene group having 2 to 4 (provided that at least a part of n Y is a dimethylene group), and n is The aqueous dispersion according to claim 7, which represents an integer of 2 to 20.
  9. 　－［Ｏ－Ｙ－］ｎ－が、オキシプロピレン基を有していてもよいポリオキシエチレン鎖である、請求項８に記載の水性分散液。 9. The aqueous dispersion according to claim 8, wherein — [O—Y—] n — is a polyoxyethylene chain which may have an oxypropylene group.
  10. 　前記含フッ素重合体が、さらに、架橋性基を有する単量体以外のフッ素原子を有しない単量体に基づく単位を有する、請求項１～９のいずれか一項に記載の水性分散液。 The aqueous dispersion according to any one of claims 1 to 9, wherein the fluoropolymer further has units based on a monomer having no fluorine atom other than the monomer having a crosslinkable group.
  11. 　請求項１～１０のいずれか一項に記載の水性分散液の製造方法であって、
    　フルオロオレフィンおよび架橋性基を有する単量体を含む単量体混合物を、前記単量体混合物の総和１００ｇに対して０．０１～０．２２ｍｍｏｌの量の過硫酸塩の存在下で、水性媒体中で重合させることを特徴とする水性分散液の製造方法。     A method for producing an aqueous dispersion according to any one of claims 1 to 10,
    A monomer mixture containing a fluoroolefin and a monomer having a crosslinkable group in an aqueous medium in the presence of a persulfate in an amount of 0.01 to 0.22 mmol with respect to 100 g of the total monomer mixture. A method for producing an aqueous dispersion, characterized by polymerizing in an aqueous solution.
  12. 　前記水性媒体中における重合が乳化重合である、請求項１１に記載の水性分散液の製造方法。 The method for producing an aqueous dispersion according to claim 11, wherein the polymerization in the aqueous medium is emulsion polymerization.
  13. 　請求項１～１０のいずれか一項に記載の水性分散液を含む水性塗料。 An aqueous paint comprising the aqueous dispersion according to any one of claims 1 to 10.
  14. 　含フッ素重合体以外の重合体をさらに含有する、請求項１３に記載の水性塗料。 The water-based paint according to claim 13, further comprising a polymer other than the fluorine-containing polymer.
  15. 　物品の表面に請求項１３または１４に記載の水性塗料から形成された塗膜を有する塗装物品。 A coated article having a coating film formed from the water-based paint according to claim 13 or 14 on the surface of the article.
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