WO2014112252A1 - Fluorinated polymer, aqueous dispersion of fluorinated polymer, and method for producing said aqueous dispersion - Google Patents

Fluorinated polymer, aqueous dispersion of fluorinated polymer, and method for producing said aqueous dispersion Download PDF

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WO2014112252A1
WO2014112252A1 PCT/JP2013/083241 JP2013083241W WO2014112252A1 WO 2014112252 A1 WO2014112252 A1 WO 2014112252A1 JP 2013083241 W JP2013083241 W JP 2013083241W WO 2014112252 A1 WO2014112252 A1 WO 2014112252A1
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monomer
fluoropolymer
group
mol
meth
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PCT/JP2013/083241
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French (fr)
Japanese (ja)
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吉井　公彦
突廻　恵介
良彰 高橋
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Jsr株式会社
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Publication of WO2014112252A1 publication Critical patent/WO2014112252A1/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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the present invention relates to a fluoropolymer, a fluoropolymer aqueous dispersion, and a method for producing the same.
  • Fluorine-containing polymers have excellent heat resistance, weather resistance, electrical insulation, etc., and are coating agents that impart antifouling and chemical resistance to various substrates such as glass, metal, resin, wood, and slate. It is used. Adhesion to the base material is particularly important for practical use of the fluorinated polymer, but it is essentially inferior to the base material compared to non-fluorine organic resins. When it was going to improve adhesiveness by mix
  • JP-A-10-120858 discloses an aqueous dispersion in which a copolymer of vinylidene fluoride, hexafluoropropene, and chlorotrifluoroethylene is dispersed in an aqueous medium. It is said that the mechanical stability of has been improved.
  • JP 2009-227754 A discloses a production method in which vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene are copolymerized in an aqueous medium in the presence of a specific fluorine-containing surfactant, Similarly, the mechanical stability of the aqueous dispersion is improved.
  • the adhesion when these systems are applied on various substrates such as glass and hard aluminum, and it is difficult to say that a coating film having sufficient adhesion can be obtained.
  • Japanese Patent Application Laid-Open No. 08-120221 discloses a technique of blending an organosilicon oligomer with an aqueous dispersion of a fluoropolymer obtained by polymerizing fluoroolefins and the like.
  • WO 98/23680 discloses a technique for blending an aqueous dispersion of a copolymer of a fluoroolefin and a vinyl monomer and an organosilicon oligomer.
  • 2003-286440 discloses an aqueous dispersion of a composite polymer particle of a fluorine-containing polymer and a methacrylic polymer, and a composite polymer particle of an organosilicon compound and a methacrylic polymer. Formulation with an aqueous dispersion is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 05-170909 discloses a method for producing an aqueous dispersion in which an alkoxysilane monomer is subjected to a condensation reaction in the presence of an aqueous dispersion of fluoropolymer particles. However, in these techniques, the adhesion and weather resistance of the coating film are not sufficient, and nothing is mentioned about the transparency of the coating film.
  • an organosilicon compound having an olefinically unsaturated bond and a hydrolyzable group, synthesized in an organic solvent, fluoroolefins, 20 mol% or more vinyl ethers It is said that a coating film excellent in weather resistance, water resistance and the like can be formed, and adhesion evaluation is performed on a coating film formed by adding organotin.
  • organotin which is a compound with a large environmental load, was added immediately before coating, and evaluation was not possible.
  • Japanese Patent Application Laid-Open No. 10-147738 also describes a polymer composed of a fluoroolefin monomer in an organic solvent, a methacrylic acid ester monomer, and an olefinic monomer having a hydrolyzable silyl group. . It is stated that the (meth) acrylic acid ester is preferably 20 mol% or more, and the adhesion and weather resistance are not sufficient.
  • JP 09-194538 A a fluoroolefin, an organosilicon compound containing an unsaturated bond and an alkoxysilyl group, an unsaturated carboxylic acid, 30 mol% or more of a fatty acid vinyl ester and / or an alkyl vinyl ether, Although an aqueous fluororesin dispersion made of is described, the adhesion to the substrate is not evaluated and is not mentioned.
  • some aspects of the present invention provide a fluorine-containing heavy metal that can form a coating film that has excellent adhesion to the substrate and that has excellent transparency, weather resistance, and water resistance by solving the above-described problems. It is intended to provide a combined polymer (aqueous dispersion), a fluoropolymer aqueous dispersion capable of forming a coating film having excellent stain resistance in addition to these characteristics, and a method for producing the same.
  • the present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
  • One aspect of the fluoropolymer according to the present invention is: When the total amount of all monomers is 100 mol%, (A) 10 to 99 mol% of a monomer having a fluorine atom, (B) 1 to 90 mol% of a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group, (C) 15 mol% or less of monomers other than the component (A) and the component (B), It is characterized by being polymerized.
  • One aspect of the fluoropolymer according to the present invention is: In 100 mol% of all repeating units, (A) 10 to 99 mol% of repeating units derived from a monomer having a fluorine atom; (B) 1 to 90 mol% of repeating units derived from a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group; (C) 15 mol% or less of repeating units derived from monomers other than the component (A) and the component (B); It is characterized by containing.
  • the monomer (A) having a fluorine atom may be at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
  • the component (C) may be at least one selected from the group consisting of (meth) acrylic acid ester monomers, vinyl ether monomers, and allyl ether monomers that do not contain silicon.
  • One aspect of the fluoropolymer aqueous dispersion according to the present invention is: The fluorine-containing polymer of any one of Application Examples 1 to 4 is dispersed in an aqueous medium.
  • One aspect of the fluoropolymer aqueous dispersion according to the present invention is: In the presence of the fluoropolymer of any one of Application Examples 1 to 4, Furthermore, it is obtained by reacting (D) a monomer having an ethylenically unsaturated group.
  • One aspect of the method for producing an aqueous fluoropolymer dispersion according to the present invention is as follows: When the total amount of all monomers is 100 mol%, (A) 10 to 99 mol% of a monomer having a fluorine atom; (B) 1 to 90 mol% of a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group, (C) 15 mol% or less of monomers other than the component (A) and the component (B), Characterized in that it comprises a step (a) of emulsion polymerization in an aqueous medium to obtain a fluoropolymer.
  • the fluoropolymer (aqueous dispersion) according to the present invention it is possible to form a coating film having excellent adhesion to the substrate and excellent transparency, weather resistance and water resistance. Furthermore, by using the fluoropolymer aqueous dispersion according to the present invention, a coating film having good stain resistance in addition to these characteristics can be formed. When the fluoropolymer aqueous dispersion according to the present invention is used as a coating agent for various substrates, the effect is remarkably exhibited.
  • ⁇ (meth) acrylate is a concept encompassing both “ ⁇ acrylate” and “ ⁇ methacrylate”.
  • (meth) acrylic acid is a concept encompassing both “acrylic acid” and “methacrylic acid”.
  • the fluorine-containing polymer according to the present embodiment comprises a monomer having (A) a fluorine atom (hereinafter referred to as “(A) single unit) when the total amount of all monomers is 100 mol%. 10-99 mol%, (B) a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group (hereinafter referred to as “(B) single monomer”) 1 to 90 mol%, (C) 15 mol% or less of monomer other than the component (A) and the component (B) (hereinafter also referred to as “(C) monomer”). And are polymerized.
  • the repeating unit derived from a monomer having (A) a fluorine atom in 100 mol% of all repeating units. 10 to 99 mol% of units, (B) 1 to 90 mol% of repeating units derived from a vinyl monomer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and (C In other words, it contains 15 mol% or less of repeating units derived from monomers other than the component (A) and the component (B).
  • each monomer will be described in detail.
  • the monomer having a fluorine atom contributes to the improvement of heat resistance and weather resistance when a polymer obtained is mainly used as a coating film.
  • the olefin compound which has a fluorine atom the (meth) acrylic acid ester which has a fluorine atom, etc. are mentioned, for example.
  • the olefin compound having a fluorine atom include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, dichlorodifluoroethylene, and hexafluoropropylene.
  • Examples of the (meth) acrylic acid ester having a fluorine atom include a compound represented by the following general formula (1): (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (tri Fluoromethyl) fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl and the like. These (A) monomers may be used individually by 1 type, and may use 2 or more types together.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is a C 1-18 hydrocarbon group having a fluorine atom.
  • R 2 in the general formula (1) examples include fluorinated alkyl groups having 1 to 12 carbon atoms, fluorinated aryl groups having 6 to 16 carbon atoms, and fluorinated aralkyl groups having 7 to 18 carbon atoms. However, it is preferably a fluorinated alkyl group having 1 to 12 carbon atoms.
  • R 2 in the general formula (1) include, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1, 3,3,3-hexafluoropropan-2-yl group, ⁇ - (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4- Hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H, 1H, 11H-perfluoroundecyl group, perfluorooctyl group, etc.
  • the monomer having a fluorine atom is preferably an olefin compound having a fluorine atom, and is at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. Is more preferable.
  • the monomer is preferably used in an amount of 10 to 99 mol% with respect to 100 mol% of the monomer constituting the fluoropolymer.
  • the content rate of a monomer is the said range, the weather resistance and heat resistance of a coating film can be improved more, and the adhesiveness to a base material can be improved more.
  • (B) Vinyl-based monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group is a group obtained when a polymer obtained is mainly used as a coating film. Contributes to improved material adhesion.
  • Specific examples of the hydrolyzable group include a halogen element, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group, and are alkoxy groups. It is preferable.
  • vinyl monomers containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group include vinyltrimethoxysilane, vinyldimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, and vinyldioxide.
  • the monomer is preferably used in an amount of 1 to 90 mol% with respect to 100 mol% of the monomer constituting the fluoropolymer. (B) If the content ratio of the monomer is within the above range, the substrate adhesion of the coating film can be further improved, and the occurrence of cracks during the coating film formation can be suppressed.
  • the fluoropolymer according to the present embodiment may have a repeating unit derived from (C) monomer other than (A) monomer and (B) monomer.
  • Examples of such a monomer (C) include (meth) acrylic acid ester monomers, vinyl ether monomers, allyl ether monomers and the like that do not contain silicon atoms.
  • the monomer (C) other than the monomer (A) and the monomer (B) is used in a content ratio of 15 mol% or less with respect to 100 mol% of the monomer constituting the fluoropolymer. It is preferable.
  • Examples of the (meth) acrylic acid ester monomer not containing a silicon atom include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate , Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) Acrylate 2-ethyl
  • vinyl ether monomers not containing silicon atoms examples include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-aminoethyl vinyl ether. Etc. These vinyl ether monomers may be used alone or in combination of two or more.
  • allyl ether monomers not containing silicon atoms include methyl allyl ether, ethyl allyl ether, propyl allyl ether, butyl allyl ether, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, allyl glycidyl ether. , Ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and the like. These allyl ether monomers may be used alone or in combination of two or more.
  • the above-mentioned fluoropolymer is a method in which the above (A) monomer, (B) monomer, and (C) monomer, if necessary, are emulsion polymerized in an aqueous medium.
  • the polymer solution can be produced by phase inversion to an aqueous dispersion, precipitation polymerization, or the like, but emulsion polymerization is preferred because the molecular weight and particle diameter of the fluoropolymer are easy to control.
  • a monomer having an ethylenically unsaturated group (hereinafter also referred to as “(D) monomer”) or (E), which will be described later as it is, is an aqueous dispersion of a fluoropolymer obtained by emulsion polymerization. You may make it react with alkoxysilane (henceforth "(E) monomer”). Further, when the obtained fluoropolymer is in a powder form, an aqueous fluoropolymer dispersion is prepared by dispersing (re-emulsifying) in an aqueous medium, and the monomer (D) described later (E) You may make it react with a monomer.
  • the fluoropolymer according to the present embodiment comprises (A) 10 to 99 mol% of a monomer having a fluorine atom, and (B) hydrolysis when the total amount of all monomers is 100 mol%. 1 to 90 mol% of a vinyl monomer containing a silyl group having a silicon atom bonded to a functional group and / or a hydroxyl group, and (C) the monomer 15 other than the component (A) and the component (B) It is obtained by going through step (a) of obtaining a fluoropolymer by emulsion polymerization in an aqueous medium.
  • an aqueous medium (A) monomer, (B) monomer, (C) monomer and emulsifier, if necessary, are mixed, and the aqueous medium is mixed therewith.
  • a soluble polymerization initiator By adding a soluble polymerization initiator and reacting it, a fluoropolymer aqueous dispersion can be easily produced.
  • emulsifiers include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphates, perfluoroalkoxyfluorocarboxylates, anionic surfactants, and nonionic surfactants.
  • Amphoteric surfactants and cationic surfactants can be used.
  • a water-soluble polymerization initiator such as lithium persulfate, potassium persulfate, sodium persulfate, or ammonium persulfate can be used.
  • the use ratio of the polymerization initiator is not particularly limited, but is appropriately set in consideration of the monomer composition, the pH of the polymerization reaction system, a combination of other additives, and the like.
  • sodium hydrogen phosphate, sodium hydroxide, sodium carbonate, etc. can be used as a polymerization pH adjuster, and ethyl malonate, etc. can be used as a chain transfer agent.
  • the aqueous medium is a medium containing water as a main component, but may contain an organic solvent such as alcohol or glycol other than water as long as the physical properties are not impaired.
  • the content ratio of these organic solvents is 0 to 10 parts by mass, preferably 0 to 5 parts by mass with respect to 100 parts by mass of water.
  • the melt viscosity of the fluoropolymer according to the present embodiment is preferably 230 ° C. and a shear rate of 100 (1 / sec) 200 to 3500.
  • the melt viscosity of the fluoropolymer can be measured by a method according to JIS K7199. That is, a capillary type flow characteristic tester is used to measure a viscosity characteristic of a molten polymer when a sample such as a polymer is melted in a barrel, pressurized with a piston, and discharged from a capillary.
  • the fluoropolymer according to the present embodiment can be used as a solution of an organic solvent
  • the fluoropolymer obtained by the above emulsion polymerization method is usually in the form of particles (hereinafter referred to as particles) dispersed in an aqueous medium.
  • particles Such a particulate fluoropolymer is referred to as “fluoropolymer particles”).
  • the average particle size of the fluoropolymer particles can be appropriately changed depending on the application, but is usually preferably in the range of 0.03 to 0.3 ⁇ m, and preferably 0.03 to 0.2 ⁇ m. More preferred. This average particle diameter can be measured using a particle size distribution measuring apparatus based on the dynamic light scattering method. Examples of such a particle size distribution measuring apparatus include model “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
  • Fluoropolymer aqueous dispersion The fluoropolymer aqueous dispersion according to the present embodiment is characterized in that the above-mentioned fluoropolymer is dispersed in an aqueous medium.
  • Such an aqueous dispersion of fluoropolymer can form a coating film excellent in substrate adhesion, transparency and water resistance in addition to heat resistance and weather resistance, and was used as a coating agent for various substrates. In that case, the effect is remarkable.
  • the aqueous fluoropolymer dispersion according to the present embodiment comprises (D) a monomer having an ethylenically unsaturated group using the fluoropolymer particles as seed particles in the presence of the fluoropolymer particles described above. Can be reacted (step (b)). In this step (b), since the above-mentioned fluoropolymer particles are used as seed particles, (D) the operation of dissolving the fluoropolymer particles in the monomer is not performed. Further, (E) alkoxysilane may be further reacted when (D) the monomer is reacted or after that (step (c)).
  • (D) monomer, (E) monomer, and other components will be described in detail.
  • a monomer having an ethylenically unsaturated group plays a role in adjusting the film-forming temperature of the polymer to an appropriate value, and improves the weather resistance and stain resistance of the coating film. Can be made.
  • the monomer (D) include alkyl esters of ethylenically unsaturated carboxylic acids, cycloalkyl esters of ethylenically unsaturated carboxylic acids, hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, and ethylenically unsaturated carboxylic acids.
  • Examples include polyhydric alcohol esters, other ethylenically unsaturated carboxylic acid esters, ethylenically unsaturated carboxylic acid amides, and ethylenically unsaturated carboxylic acids.
  • alkyl ester of the ethylenically unsaturated carboxylic acid examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic.
  • N-butyl acid i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) N-octyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc .;
  • examples of the cycloalkyl ester of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid
  • Examples of the hydroxyalkyl ester of the ethylenically unsaturated carboxylic acid include cyclohexyl and the like.
  • the ethylenically unsaturated carboxylic acid ester include ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -methacryloxypropyltriethoxysilane.
  • Examples of the ethylenically unsaturated carboxylic acid amide include N-methylol (meth) acrylamide and diacetone.
  • (Meth) acrylamide etc. can be mentioned, respectively, It can be 1 or more types selected from these.
  • ethylenically unsaturated carboxylic acid examples include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and one or more selected from these. be able to. In particular, at least one selected from acrylic acid, methacrylic acid and itaconic acid is preferable.
  • the above-exemplified compounds may be used alone or in combination of two or more.
  • the monomer (D) is preferably used in an amount of 20 to 2000 parts by mass with respect to 100 parts by mass of the fluoropolymer particles.
  • (D) When a monomer is made to react by the content rate of the said range, the base-material adhesiveness of the coating film obtained can be improved more, and the crack generation at the time of coating-film formation can be suppressed.
  • the alkoxysilane can further improve the weather resistance when the resulting polymer is used as a coating film.
  • the monomer is preferably at least one monomer selected from the group consisting of monomers represented by the following general formulas (2) and (3).
  • R 3 n Si (OR 4 ) 4-n (2) wherein R 3 and R 4 each independently represents an organic group having 1 to 8 carbon atoms, and n represents an integer of 0 to 3)
  • R 5 m SiO (4-m) / 2 (3) wherein R 5 represents an organic group having 1 to 8 carbon atoms, and m represents a number of 0 to 3)
  • R 3 and R 5 are preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group or an ethyl group. .
  • R 4 examples include alkyl groups, aryl groups, and acyl groups having 1 to 8 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pentyl group.
  • aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group.
  • the acyl group is preferably an acyl group having 1 to 6 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
  • a plurality of R 3 and R 4 present in the general formula (2) may be the same as or different from each other.
  • dialkoxysilane, trialkoxysilane, and tetraalkoxysilane can be preferably used.
  • dialkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, and dimethyl-di-sec- Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n- Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane,
  • trialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert- Butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert- Examples include butoxysilane and ethyltriphenoxysilane.
  • tetraalkoxysilane examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Examples include butoxysilane and tetraphenoxysilane.
  • the said fluoropolymer aqueous dispersion may have a repeating unit derived from monomers other than (D) monomer and (E) monomer.
  • monomers other than (D) monomer and (E) monomer for example, the monomers listed in “1.3. (C) Monomer” can be preferably used.
  • the fluoropolymer aqueous dispersion according to the present embodiment comprises the above-mentioned (D) monomer and (E) single monomer in the presence of the above-mentioned fluoropolymer particles. It can be produced by reacting in the presence of a monomer, other monomers, an emulsifier (surfactant), a polymerization initiator, a molecular weight regulator and the like.
  • the emulsifier examples include sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, naphthalene sulfonic acid / formalin condensates, Anionic surfactants such as sulfate ester salts of ionic surfactants; nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, alkyl ethers of polyethylene glycol; perfluorobutyl sulfonates; Fluorosurfactants such as perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing carboxylates, and perfluoroalkylethylene oxide adducts can be mentioned.
  • the use ratio of the emulsifier is based on 100 parts by mass of (D) monomer (in the case of using (E) monomer, 100 parts by mass in total of (D) monomer and (E) monomer). 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass.
  • polymerization initiator examples include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, Oil-soluble polymerization initiators such as diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), etc. are selected as appropriate Can be used.
  • water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate
  • cumene hydroperoxide benzoyl peroxide
  • t-butyl hydroperoxide acetyl peroxide
  • Oil-soluble polymerization initiators such as di
  • the proportion of the polymerization initiator used is (C) 100 parts by mass of monomer (when (E) monomer is used, (D) monomer and (E) monomer in total 100 parts by mass)). On the other hand, it is preferably 0.3 to 3 parts by mass.
  • the molecular weight regulator examples include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenol compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Halogenated hydrocarbon compounds such as dichloromethane, dibromomethane
  • the proportion of molecular weight regulator used is (D) 100 parts by mass of monomer (when (E) monomer is used, the total of (D) monomer and (E) monomer is 100 parts by mass)). On the other hand, it is preferably 5 parts by mass or less.
  • Emulsion polymerization can be performed in a suitable aqueous medium.
  • the aqueous medium may contain an organic solvent such as alcohol or glycol other than water as long as the physical properties are not impaired, but it is preferable that the aqueous medium does not substantially contain these organic solvents.
  • the total content of the (D) monomer and the (E) monomer in the aqueous medium can be 10 to 50% by mass, and preferably 20 to 40% by mass.
  • the conditions for emulsion polymerization are preferably a polymerization time of 2 to 24 hours at a polymerization temperature of 40 to 85 ° C., and more preferably a polymerization time of 3 to 20 hours at a polymerization temperature of 50 to 80 ° C.
  • the average particle size of the fluoropolymer particles obtained by reacting the above (D) monomer and (E) monomer can be changed depending on the application, Usually, it is preferably in the range of 0.05 to 0.6 ⁇ m, more preferably in the range of 0.05 to 0.4 ⁇ m.
  • This average particle diameter can be measured using a particle size distribution measuring apparatus based on the dynamic light scattering method. Examples of such a particle size distribution measuring apparatus include model “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
  • the fluoropolymer aqueous medium obtained above may be used as it is, but a hydrazine derivative or other additives may be added as necessary.
  • a hydrazine derivative By adding a hydrazine derivative to the fluoropolymer aqueous dispersion according to the present embodiment, when water in the aqueous medium is scattered by drying, the carbonyl group derived from the monomer (D) and the hydrazine derivative An action of forming a network-structured film by crosslinking hydrazino groups is exhibited. Therefore, the water resistance and solvent resistance of the formed coating film can be improved.
  • This crosslinking reaction usually does not require a catalyst, but in some cases, a catalyst such as a water-soluble metal salt such as zinc sulfate, manganese sulfate, and cobalt sulfate can be used.
  • the amount of the hydrazine derivative added is preferably 0.02 to 1 mol, more preferably 0.2 to 0.6 mol, per 1 mol of the carbonyl group derived from the monomer (D).
  • the hydrazine derivative is preferably a hydrazine derivative having at least two hydrazino groups such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, Dicarboxylic acid dihydrazides having 2 to 10 carbon atoms (preferably 4 to 6 carbon atoms) such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; ethylene-1,2-dihydrazine, propylene-1,3-di And water-soluble aliphatic dihydrazine having 2 to 4 carbon atoms such as hydrazine and butylene-1,4-dihydrazine.
  • a silicone-based antifoaming agent ethylene glycol, propylene glycol, etc.
  • an antifreezing agent ethylene glycol, propylene glycol, etc.
  • a dye ethylene glycol, propylene glycol, etc.
  • a dispersing agent ethylene glycol, propylene glycol, etc.
  • a pH adjuster ethanolamine
  • thickeners hydroxyethyl cellulose, polyether urethane, acrylic acid copolymer, etc.
  • wettability improvers butyl cellosolve, ethyl cellosolve, etc.
  • preservatives antifungal agents, water resistance agents, anti-aging agents, ultraviolet rays
  • organic additives such as an absorber, an ultraviolet stabilizer, a water-soluble solvent, and a film forming aid can be added.
  • the amount of these organic additives added can be 40 parts by mass or less with respect to 100 parts by mass in terms of solid content of the above fluoropolymer aqueous disper
  • the fluoropolymer aqueous dispersion according to the present embodiment can be used in clear coating, but if necessary, an inorganic or organic compound such as an inorganic pigment, an organic pigment, or a filler is added and blended, It can also be used as an enamel.
  • an inorganic or organic compound such as an inorganic pigment, an organic pigment, or a filler is added and blended, It can also be used as an enamel.
  • JR-1000 Taika
  • CR-97 Ishihara Sangyo
  • R-630 Ishihara Sangyo
  • the aqueous fluoropolymer dispersion according to the present embodiment is particularly useful as a highly durable protective coating material for various substrates such as cement, tile, metal, plastic, glass and the like.
  • it is suitable for use in buildings, building materials, automobiles, and other highly durable paints intended for outdoor use, thermal barrier paints and anticorrosion paints that require durability and contamination resistance, and porous materials such as felt, glass, and paper.
  • It can also be suitably used as a material for impregnating material, packing material, fiber / woven fabric and tatami mat.
  • fluoropolymer aqueous dispersion according to the present embodiment can be directly applied on a substrate, depending on the application, an undercoat (epoxy-based, urethane-based, melamine-based, alkyd-based, etc.)
  • a primer epoxy-based, urethane-based, melamine-based, alkyd-based, etc.
  • a primer epoxy-based, urethane-based, melamine-based, alkyd-based, etc.
  • an anticorrosion layer such as zinc rich paint can be provided and used.
  • surface treatment can be performed in advance for the purpose of adjusting the foundation, improving adhesion, sealing the porous substrate, smoothing, and patterning.
  • Examples of the surface treatment for the metal base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment, coupling treatment, and the like.
  • Examples of the surface treatment for the plastic base material include blast treatment, Chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and the like.
  • surface treatments for inorganic ceramic base materials include polishing, Examples of the surface treatment for the wood base material include, for example, polishing, sealing, and insect repellent treatment.
  • Examples of the surface treatment for the paper base material include, for example, sealing, Insect repellent treatment and the like, and as surface treatment for a deteriorated coating film, for example, keren can be mentioned. .
  • Coating methods include spray coating, roller coating, brush coating, brush coating, flow coating, bar coater, knife coater, doctor blade, screen printing, spin coater, applicator, roll coater, flow coater, centrifugal coater, ultrasonic wave Techniques such as a coater, (micro) gravure coater, dip coating, flexographic printing, and potting can be used.
  • a coating film having a thickness of about 0.05 to 50 ⁇ m by one coating and a thickness of about 0.1 to 100 ⁇ m by two coatings. Can be formed.
  • VDF vinylidene fluoride
  • TFE tetrafluoroethylene
  • HFP propylene
  • Dispersions containing fluoropolymer particles A-2 to A-8 were obtained in the same manner as in Example 1 except that each component shown in Table 1 was used. Using the obtained dispersions containing the fluoropolymer particles A-2 to A-8 as samples, the average particle size was determined using a particle size distribution measuring apparatus based on the dynamic light scattering method. The results are also shown in Table 1.
  • Comparative Example 4 200 parts by mass of X40-9220 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon oligomer) is added in advance to 700 parts by mass of the solid content of the fluoropolymer particle A-7 obtained above and forced with a homogenizer. The emulsified water dispersion was added and stirred at room temperature for 5 hours to obtain a blended solution.
  • X40-9220 manufactured by Shin-Etsu Chemical Co., Ltd., silicon oligomer
  • the inside of a 7-liter separable flask was put in a nitrogen atmosphere, and 100 parts by mass (solid content concentration) of the dispersion containing the fluoropolymer particles A-1 produced above and 0.3 parts by mass of sodium persulfate And heated up to 75 ° C. Thereafter, the above monomer dispersion was continuously added over 3 hours, and the reaction solution was further maintained at 85 ° C. to 95 ° C. for 2 hours, and then cooled to 25 ° C.
  • aqueous dispersion Using the obtained aqueous dispersion as a sample, the average particle size was measured using a particle size distribution measuring apparatus based on the dynamic light scattering method, and the average particle size was 104 nm.
  • the obtained coating film was subjected to an accelerated weather resistance test for 500 hours using a metal weather (Daipura Wintes), and the 60 ° gloss of the coating film was measured to obtain a gloss retention (gloss after test / gloss before test;%) Was calculated.
  • the test conditions were cycle conditions of irradiation (75 mW / cm 2 under 63 ° C. and 50% RH) for 4 hours and dark (30 ° C. and 98% RH) for 4 hours.
  • Clearly opaque and low-gloss or peeled from the substrate were excluded from the evaluation.
  • the evaluation criteria are as follows, and the results are shown in Table 2. When the gloss retention is 80% or more, it is judged that the weather resistance is good. When the gloss retention is 60% or more and less than 80%, the weather resistance is judged to be slightly good. When the gloss retention is less than 60%, the weather resistance is judged to be poor.
  • Contamination resistance 100 parts by mass (converted to solid content) of the fluorinated composite polymer particles obtained above and 10 parts by mass of texanol on a hard aluminum base material previously coated with an aqueous epoxy primer and fired at 120 ° C was applied using an applicator having a gap value (wet film thickness) of 200 ⁇ m, and was allowed to stand at room temperature (25 ° C.) for 1 week to form a film.
  • Black FLTR Conc manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black aqueous dispersion
  • the gloss retention was calculated by evaluating the coating film after the above-mentioned visual observation with a Murakami gloss meter GM-26PRO / Auto (60 °) and a ratio with the initial value.
  • the evaluation criteria are as follows, and the results are also shown in Table 2. -When the gloss retention is 80% or more, the gloss retention is determined to be good. When the gloss retention rate is 60% or more and less than 80%, the gloss retention rate is judged to be slightly good. When the gloss retention rate is less than 60%, it is determined that the gloss retention rate is poor.
  • Table 2 shows the types and amounts of (D) monomer and (E) monomer used for the synthesis of the aqueous dispersions of fluorine-containing composite polymer particles according to Examples 6 to 18, and the evaluation results. .
  • Example 7 in which the (E) monomer is not used when the fluorine-containing composite polymer particles are synthesized, the weather resistance is reduced as compared to Example 6 in which the (E) monomer is used.
  • Example 7 In the water resistance evaluation, a decrease in gloss retention and swelling were observed.
  • Example 15 and Example 16 From these facts, it was shown that weather resistance and water resistance were improved by using the monomer (E) when synthesizing the fluorine-containing composite polymer particles.
  • the aqueous dispersions of the fluorine-containing composite polymer particles according to the present invention shown in Examples 6 to 18 are excellent in substrate adhesion, and have weather resistance, stain resistance and water resistance.
  • it can be suitably used for electrodeposition coating, fiber treatment material, paper processing material, floor coating material, and the like.
  • the present invention is not limited to the above embodiment, and various modifications can be made.
  • the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects).
  • the present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration.
  • the present invention includes a configuration that achieves the same effect as the configuration described in the above embodiment or a configuration that can achieve the same object.
  • the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

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Abstract

A fluorinated polymer according to the present invention is characterized by being produced by polymerizing (A) 10 to 99 mol% of a monomer having a fluorine atom, (B) 1 to 90 mol% of a vinyl monomer having a silyl group that has a silicon atom bond to a hydrolysable group and/or a hydroxy group and (C) 15 mol% or less of a monomer that is different from the component (A) or (B), wherein the total amount of the monomers is 100 mol%.

Description

含フッ素重合体、含フッ素重合体水性分散体およびその製造方法Fluoropolymer, fluoropolymer aqueous dispersion and production method thereof
　本発明は、含フッ素重合体、含フッ素重合体水性分散体およびその製造方法に関する。 The present invention relates to a fluoropolymer, a fluoropolymer aqueous dispersion, and a method for producing the same.
　含フッ素系重合体は、耐熱性、耐候性、電気絶縁性等に優れ、ガラス、金属、樹脂、木材、スレート等の各種基材に対して防汚性、耐薬品性を付与するコーティング剤として用いられている。含フッ素系重合体を実用的に用いるためには基材への密着性が特に重要であるが、非フッ素の有機系樹脂に比べ本質的に基材への密着性に劣り、各種添加剤の配合により密着性を向上させようとした場合は塗膜の耐候性が低下するという課題があった。 Fluorine-containing polymers have excellent heat resistance, weather resistance, electrical insulation, etc., and are coating agents that impart antifouling and chemical resistance to various substrates such as glass, metal, resin, wood, and slate. It is used. Adhesion to the base material is particularly important for practical use of the fluorinated polymer, but it is essentially inferior to the base material compared to non-fluorine organic resins. When it was going to improve adhesiveness by mix | blending, there existed a subject that the weather resistance of a coating film fell.
　例えば、特開平１０－１２０８５８号公報には、フッ化ビニリデン、ヘキサフルオロプロペン、及びクロロトリフルオロエチレンよりなる共重合体を水性媒体中に分散せしめた水性分散体が開示されており、水性分散体の機械的安定性を改善したとしている。また、特開２００９－２２７７５４号公報には、フッ化ビニリデン、テトラフルオロエチレン及びヘキサフルオロプロピレンを特定の含フッ素界面活性剤の存在下で水性媒体中で共重合させる製造方法が開示されており、同じく水性分散体の機械的安定性を向上させたとしている。しかしながら、これらの系をガラスや硬質アルミ等の各種基材上に塗布した場合の密着性についてはいずれも言及されておらず、十分な密着性を有する塗膜が得られるとは言い難い。 For example, JP-A-10-120858 discloses an aqueous dispersion in which a copolymer of vinylidene fluoride, hexafluoropropene, and chlorotrifluoroethylene is dispersed in an aqueous medium. It is said that the mechanical stability of has been improved. JP 2009-227754 A discloses a production method in which vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene are copolymerized in an aqueous medium in the presence of a specific fluorine-containing surfactant, Similarly, the mechanical stability of the aqueous dispersion is improved. However, no mention is made of the adhesion when these systems are applied on various substrates such as glass and hard aluminum, and it is difficult to say that a coating film having sufficient adhesion can be obtained.
　また、特開平０８－１２０２１１号公報では、フルオロオレフィン類等を重合して得られる含フッ素重合体水性分散体に対し、有機ケイ素系オリゴマーを配合する技術を開示している。国際公開第９８／２３６８０号では、同じくフルオロオレフィンとビニル系単量体の共重合体の水性分散体と有機ケイ素オリゴマーを配合する技術を開示している。また、特開２００３－２８６４４０号公報では、含フッ素系重合体とメタアクリル系重合体との複合重合体粒子の水性分散体と、有機ケイ素化合物とメタアクリル系重合体との複合重合体粒子の水性分散体との配合を開示している。さらに、特開平０５－１７０９０９号公報では、含フッ素重合体粒子の水性分散体の存在下でアルコキシシラン単量体を縮合反応させる水性分散体の製造方法が開示されている。しかしながら、これらの技術では、塗膜の密着性や耐候性は十分なものではなく、また塗膜の透明性についても何ら言及されていない。 Japanese Patent Application Laid-Open No. 08-120221 discloses a technique of blending an organosilicon oligomer with an aqueous dispersion of a fluoropolymer obtained by polymerizing fluoroolefins and the like. WO 98/23680 discloses a technique for blending an aqueous dispersion of a copolymer of a fluoroolefin and a vinyl monomer and an organosilicon oligomer. Japanese Patent Application Laid-Open No. 2003-286440 discloses an aqueous dispersion of a composite polymer particle of a fluorine-containing polymer and a methacrylic polymer, and a composite polymer particle of an organosilicon compound and a methacrylic polymer. Formulation with an aqueous dispersion is disclosed. Furthermore, Japanese Patent Application Laid-Open No. 05-170909 discloses a method for producing an aqueous dispersion in which an alkoxysilane monomer is subjected to a condensation reaction in the presence of an aqueous dispersion of fluoropolymer particles. However, in these techniques, the adhesion and weather resistance of the coating film are not sufficient, and nothing is mentioned about the transparency of the coating film.
　一方、特開昭６１－１４１７１３号公報では、有機溶剤中で合成される、フルオロオレフィン類と、２０モル％以上のビニルエーテル類と、オレフィン性不飽和結合及び加水分解可能な基を有する有機ケイ素化合物を共重合させたフッ素系重合体が挙げられ、耐候性、耐水性等に優れた塗膜を形成できるとしており、有機スズを添加して形成した塗膜に対して密着評価を行っている。しかしながら、密着を維持するため、環境負荷の大きい化合物である有機スズを塗布直前に添加して評価を行っており、実用性が高いとは言えないものであった。 On the other hand, in Japanese Patent Application Laid-Open No. 61-141713, an organosilicon compound having an olefinically unsaturated bond and a hydrolyzable group, synthesized in an organic solvent, fluoroolefins, 20 mol% or more vinyl ethers, It is said that a coating film excellent in weather resistance, water resistance and the like can be formed, and adhesion evaluation is performed on a coating film formed by adding organotin. However, in order to maintain adhesion, organotin, which is a compound with a large environmental load, was added immediately before coating, and evaluation was not possible.
　特開平１０－１４７７３８号公報でも、有機溶剤中でのフルオロオレフィン単量体と、メタクリル酸エステル単量体と、加水分解性シリル基を有するオレフィン性単量体からなる重合体が述べられている。（メタ）アクリル酸エステルは２０モル％以上が好ましいと述べられており、密着性や耐候性は十分なものではなかった。 Japanese Patent Application Laid-Open No. 10-147738 also describes a polymer composed of a fluoroolefin monomer in an organic solvent, a methacrylic acid ester monomer, and an olefinic monomer having a hydrolyzable silyl group. . It is stated that the (meth) acrylic acid ester is preferably 20 mol% or more, and the adhesion and weather resistance are not sufficient.
　さらに特開平０９－１９４５３８号公報では、フルオロオレフィン類と、不飽和結合とアルコキシシリル基を含有する有機ケイ素化合物と、不飽和カルボン酸と、３０モル％以上の脂肪酸ビニルエステル及び／又はアルキルビニルエーテルとからなるフッ素樹脂水性分散体が述べられているが、基材密着性については評価しておらず、言及もされていない。 Further, in JP 09-194538 A, a fluoroolefin, an organosilicon compound containing an unsaturated bond and an alkoxysilyl group, an unsaturated carboxylic acid, 30 mol% or more of a fatty acid vinyl ester and / or an alkyl vinyl ether, Although an aqueous fluororesin dispersion made of is described, the adhesion to the substrate is not evaluated and is not mentioned.
　上述したように、基材の密着性に優れ、かつ、透明性、耐候性及び耐水性にも優れる塗膜を形成するための材料の開発が望まれているという実態がある。そこで、本発明に係る幾つかの態様は、前記課題を解決することで、基材の密着性に優れ、かつ、透明性、耐候性及び耐水性が良好な塗膜を形成し得る含フッ素重合体（水性分散体）、これらの特性に加えてさらに耐汚染性が良好な塗膜を形成し得る含フッ素重合体水性分散体及びその製造方法を提供するものである。 As described above, there is a demand for the development of a material for forming a coating film that has excellent adhesion to the substrate and that is excellent in transparency, weather resistance, and water resistance. Accordingly, some aspects of the present invention provide a fluorine-containing heavy metal that can form a coating film that has excellent adhesion to the substrate and that has excellent transparency, weather resistance, and water resistance by solving the above-described problems. It is intended to provide a combined polymer (aqueous dispersion), a fluoropolymer aqueous dispersion capable of forming a coating film having excellent stain resistance in addition to these characteristics, and a method for producing the same.
　本発明は上述の課題の少なくとも一部を解決するためになされたものであり、以下の態様又は適用例として実現することができる。 The present invention has been made to solve at least a part of the above-described problems, and can be realized as the following aspects or application examples.
　［適用例１］
　本発明に係る含フッ素重合体の一態様は、
　全単量体の合計量を１００モル％としたときに、
　（Ａ）フッ素原子を有する単量体１０～９９モル％、
　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体１～９０モル％、
　（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体１５モル％以下、
を重合してなることを特徴とする。 [Application Example 1]
One aspect of the fluoropolymer according to the present invention is:
When the total amount of all monomers is 100 mol%,
(A) 10 to 99 mol% of a monomer having a fluorine atom,
(B) 1 to 90 mol% of a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group,
(C) 15 mol% or less of monomers other than the component (A) and the component (B),
It is characterized by being polymerized.
　［適用例２］
　本発明に係る含フッ素重合体の一態様は、
　全繰り返し単位１００モル％中、
　（Ａ）フッ素原子を有する単量体に由来する繰り返し単位１０～９９モル％と、
　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体に由来する繰り返し単位１～９０モル％と、
　（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体に由来する繰り返し単位１５モル％以下と、
を含有することを特徴とする。 [Application Example 2]
One aspect of the fluoropolymer according to the present invention is:
In 100 mol% of all repeating units,
(A) 10 to 99 mol% of repeating units derived from a monomer having a fluorine atom;
(B) 1 to 90 mol% of repeating units derived from a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group;
(C) 15 mol% or less of repeating units derived from monomers other than the component (A) and the component (B);
It is characterized by containing.
　［適用例３］
　適用例１または適用例２の含フッ素重合体において、
　前記（Ａ）フッ素原子を有する単量体が、フッ化ビニリデン、テトラフルオロエチレンおよびヘキサフルオロプロピレンよりなる群から選択される少なくとも１種であることができる。 [Application Example 3]
In the fluoropolymer of Application Example 1 or Application Example 2,
The monomer (A) having a fluorine atom may be at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
　［適用例４］
　適用例１ないし適用例３のいずれか一例の含フッ素重合体において、
　前記（Ｃ）成分が、ケイ素を含まない、（メタ）アクリル酸エステル単量体、ビニルエーテル系単量体およびアリルエーテル系単量体よりなる群から選択される少なくとも１種であることができる。 [Application Example 4]
In the fluoropolymer of any one of Application Examples 1 to 3,
The component (C) may be at least one selected from the group consisting of (meth) acrylic acid ester monomers, vinyl ether monomers, and allyl ether monomers that do not contain silicon.
　［適用例５］
　本発明に係る含フッ素重合体水性分散体の一態様は、
　適用例１ないし適用例４のいずれか一例の含フッ素重合体が水性媒体に分散されていることを特徴とする。 [Application Example 5]
One aspect of the fluoropolymer aqueous dispersion according to the present invention is:
The fluorine-containing polymer of any one of Application Examples 1 to 4 is dispersed in an aqueous medium.
　［適用例６］
　本発明に係る含フッ素重合体水性分散体の一態様は、
　適用例１ないし適用例４のいずれか一例の含フッ素重合体の存在下で、
　さらに（Ｄ）エチレン性不飽和基を有する単量体を反応させて得られることを特徴とする。 [Application Example 6]
One aspect of the fluoropolymer aqueous dispersion according to the present invention is:
In the presence of the fluoropolymer of any one of Application Examples 1 to 4,
Furthermore, it is obtained by reacting (D) a monomer having an ethylenically unsaturated group.
　［適用例７］
　適用例６の含フッ素重合体水性分散体において、
　前記含フッ素重合体１００質量部に対して、前記（Ｄ）エチレン性不飽和基を有する単量体を２０～２０００質量部反応させることができる。 [Application Example 7]
In the fluoropolymer aqueous dispersion of Application Example 6,
20 to 2000 parts by mass of the monomer (D) having an ethylenically unsaturated group can be reacted with 100 parts by mass of the fluoropolymer.
　［適用例８］
　適用例６または適用例７の含フッ素重合体水性分散体において、
　適用例１ないし適用例４のいずれか一例の含フッ素重合体の存在下で、前記（Ｄ）エチレン性不飽和基を有する単量体を反応させる際もしくは反応させた後に、さらに（Ｅ）アルコキシシランを反応させることができる。 [Application Example 8]
In the fluoropolymer aqueous dispersion of Application Example 6 or Application Example 7,
In the presence of the fluorine-containing polymer of any one of Application Examples 1 to 4, when (D) the monomer having an ethylenically unsaturated group is reacted or after reacting, (E) alkoxy Silane can be reacted.
　［適用例９］
　本発明に係る含フッ素重合体水性分散体の製造方法の一態様は、
　全単量体の合計量を１００モル％としたときに、
　（Ａ）フッ素原子を有する単量体１０～９９モル％と、
　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体１～９０モル％と、
　（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体１５モル％以下と、
を水性媒体中で乳化重合させて含フッ素重合体を得る工程（ａ）を含むことを特徴とする。 [Application Example 9]
One aspect of the method for producing an aqueous fluoropolymer dispersion according to the present invention is as follows:
When the total amount of all monomers is 100 mol%,
(A) 10 to 99 mol% of a monomer having a fluorine atom;
(B) 1 to 90 mol% of a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group,
(C) 15 mol% or less of monomers other than the component (A) and the component (B),
Characterized in that it comprises a step (a) of emulsion polymerization in an aqueous medium to obtain a fluoropolymer.
　［適用例１０］
　適用例９の含フッ素重合体水性分散体の製造方法において、
　さらに、前記含フッ素重合体１００質量部の存在下で、（Ｄ）エチレン性不飽和基を有する単量体２０～２０００質量部を反応させる工程（ｂ）を含むことができる。 [Application Example 10]
In the method for producing an aqueous fluoropolymer dispersion of Application Example 9,
Further, (D) a step (b) of reacting 20 to 2000 parts by mass of a monomer having an ethylenically unsaturated group in the presence of 100 parts by mass of the fluoropolymer can be included.
　［適用例１１］
　適用例１０の含フッ素重合体水性分散体の製造方法において、
　前記工程（ｂ）と同時もしくはその後に、
　さらに（Ｅ）アルコキシシラン１～３００質量部を反応させる工程（ｃ）を含むことができる。 [Application Example 11]
In the method for producing a fluoropolymer aqueous dispersion of Application Example 10,
Simultaneously with or after the step (b),
Further, (E) a step (c) of reacting 1 to 300 parts by mass of alkoxysilane can be included.
　本発明に係る含フッ素重合体（水性分散体）を用いることにより、基材の密着性に優れ、かつ、透明性、耐候性及び耐水性が良好な塗膜を形成することができる。さらに、本発明に係る含フッ素重合体水性分散体を用いることにより、これらの特性に加えて耐汚染性が良好な塗膜を形成することもできる。本発明に係る含フッ素重合体水性分散体を各種基材へのコーティング剤として用いた場合、その効果が顕著に現れる。 By using the fluoropolymer (aqueous dispersion) according to the present invention, it is possible to form a coating film having excellent adhesion to the substrate and excellent transparency, weather resistance and water resistance. Furthermore, by using the fluoropolymer aqueous dispersion according to the present invention, a coating film having good stain resistance in addition to these characteristics can be formed. When the fluoropolymer aqueous dispersion according to the present invention is used as a coating agent for various substrates, the effect is remarkably exhibited.
　以下、本発明に係る好適な実施形態について詳細に説明する。なお、本発明は、以下に記載された実施形態のみに限定されるものではなく、本発明の要旨を変更しない範囲において実施される各種の変形例も含むものとして理解されるべきである。なお、本明細書における「～（メタ）アクリレート」とは、「～アクリレート」及び「～メタクリレート」の双方を包括する概念である。また、「（メタ）アクリル酸～」とは、「アクリル酸～」及び「メタクリル酸～」の双方を包括する概念である。 Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited to only the embodiments described below, and includes various modifications that are implemented without departing from the scope of the present invention. In the present specification, “˜ (meth) acrylate” is a concept encompassing both “˜acrylate” and “˜methacrylate”. The term “(meth) acrylic acid” is a concept encompassing both “acrylic acid” and “methacrylic acid”.
　１．含フッ素重合体
　本実施の形態に係る含フッ素重合体は、全単量体の合計量を１００モル％としたときに、（Ａ）フッ素原子を有する単量体（以下、「（Ａ）単量体」ともいう。）１０～９９モル％、（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体（以下、「（Ｂ）単量体」ともいう。）１～９０モル％、（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体１５モル％以下（以下、「（Ｃ）単量体」ともいう。）、を重合してなることを特徴とする。 1. Fluorine-containing polymer The fluorine-containing polymer according to the present embodiment comprises a monomer having (A) a fluorine atom (hereinafter referred to as “(A) single unit) when the total amount of all monomers is 100 mol%. 10-99 mol%, (B) a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group (hereinafter referred to as “(B) single monomer”) 1 to 90 mol%, (C) 15 mol% or less of monomer other than the component (A) and the component (B) (hereinafter also referred to as “(C) monomer”). And are polymerized.
　また、本実施の形態に係る含フッ素重合体を、構成される繰り返し単位の観点から捉えた場合には、全繰り返し単位１００モル％中、（Ａ）フッ素原子を有する単量体に由来する繰り返し単位１０～９９モル％と、（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体に由来する繰り返し単位１～９０モル％と、（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体に由来する繰り返し単位１５モル％以下と、を含有する、と言い換えることもできる。以下、各単量体について詳細に説明する。 Further, when the fluoropolymer according to the present embodiment is viewed from the viewpoint of the repeating unit to be configured, the repeating unit derived from a monomer having (A) a fluorine atom in 100 mol% of all repeating units. 10 to 99 mol% of units, (B) 1 to 90 mol% of repeating units derived from a vinyl monomer containing a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group, and (C In other words, it contains 15 mol% or less of repeating units derived from monomers other than the component (A) and the component (B). Hereinafter, each monomer will be described in detail.
　１．１．（Ａ）単量体
　（Ａ）フッ素原子を有する単量体は、主に得られる重合体を塗膜にした際に耐熱性及び耐候性の向上に寄与する。（Ａ）単量体としては、例えばフッ素原子を有するオレフィン化合物、フッ素原子を有する（メタ）アクリル酸エステル等が挙げられる。フッ素原子を有するオレフィン化合物としては、例えばフッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、テトラフルオロエチレン、クロロトリフルオロエチレン、ジクロロジフルオロエチレン、ヘキサフルオロプロピレン等が挙げられる。フッ素原子を有する（メタ）アクリル酸エステルとしては、例えば下記一般式（１）で表される化合物、（メタ）アクリル酸３［４〔１－トリフルオロメチル－２，２－ビス〔ビス（トリフルオロメチル）フルオロメチル〕エチニルオキシ〕ベンゾオキシ］２－ヒドロキシプロピル等が挙げられる。これらの（Ａ）単量体は、１種単独で用いてもよく、２種以上を併用してもよい。 1.1. (A) Monomer (A) The monomer having a fluorine atom contributes to the improvement of heat resistance and weather resistance when a polymer obtained is mainly used as a coating film. (A) As a monomer, the olefin compound which has a fluorine atom, the (meth) acrylic acid ester which has a fluorine atom, etc. are mentioned, for example. Examples of the olefin compound having a fluorine atom include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, dichlorodifluoroethylene, and hexafluoropropylene. Examples of the (meth) acrylic acid ester having a fluorine atom include a compound represented by the following general formula (1): (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (tri Fluoromethyl) fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl and the like. These (A) monomers may be used individually by 1 type, and may use 2 or more types together.
Figure JPOXMLDOC01-appb-C000001
 （上記一般式（１）中、Ｒ１は水素原子又はメチル基であり、Ｒ２はフッ素原子を有する炭素数１～１８の炭化水素基である。）
Figure JPOXMLDOC01-appb-C000001
 (In the general formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a C 1-18 hydrocarbon group having a fluorine atom.)
　上記一般式（１）中のＲ２としては、例えば炭素数１～１２のフッ化アルキル基、炭素数６～１６のフッ化アリール基、炭素数７～１８のフッ化アラルキル基などを挙げることができるが、炭素数１～１２のフッ化アルキル基であることが好ましい。上記一般式（１）中のＲ２の好ましい具体例としては、例えば２，２，２－トリフルオロエチル基、２，２，３，３，３－ペンタフルオロプロピル基、１，１，１，３，３，３－ヘキサフルオロプロパン－２－イル基、β－（パーフルオロオクチル）エチル基、２，２，３，３－テトラフルオロプロピル基、２，２，３，４，４，４－ヘキサフルオロブチル基、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル基、１Ｈ，１Ｈ，９Ｈ－パーフルオロ－１－ノニル基、１Ｈ，１Ｈ，１１Ｈ－パーフルオロウンデシル基、パーフルオロオクチル基などを挙げることができる。（Ａ）フッ素原子を有する単量体としては、これらのうち、フッ素原子を有するオレフィン化合物が好ましく、フッ化ビニリデン、テトラフルオロエチレン及びヘキサフルオロプロピレンよりなる群から選択される少なくとも１種であることがより好ましい。 Examples of R 2 in the general formula (1) include fluorinated alkyl groups having 1 to 12 carbon atoms, fluorinated aryl groups having 6 to 16 carbon atoms, and fluorinated aralkyl groups having 7 to 18 carbon atoms. However, it is preferably a fluorinated alkyl group having 1 to 12 carbon atoms. Preferable specific examples of R 2 in the general formula (1) include, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1, 3,3,3-hexafluoropropan-2-yl group, β- (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4- Hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H, 1H, 11H-perfluoroundecyl group, perfluorooctyl group, etc. Can do. (A) The monomer having a fluorine atom is preferably an olefin compound having a fluorine atom, and is at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene. Is more preferable.
　（Ａ）単量体は、含フッ素重合体を構成する単量体１００モル％に対して、１０～９９モル％使用することが好ましい。（Ａ）単量体の含有割合が前記範囲であると、塗膜の耐候性や耐熱性をより向上させ、基材への密着性をより向上させることができる。 (A) The monomer is preferably used in an amount of 10 to 99 mol% with respect to 100 mol% of the monomer constituting the fluoropolymer. (A) When the content rate of a monomer is the said range, the weather resistance and heat resistance of a coating film can be improved more, and the adhesiveness to a base material can be improved more.
　１．２．（Ｂ）単量体
　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体は、主に得られる重合体を塗膜にした際の基材密着性の向上に寄与する。前記加水分解性基の具体例としては、ハロゲン元素、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられるが、アルコキシ基であることが好ましい。 1.2. (B) Monomer (B) Vinyl-based monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group is a group obtained when a polymer obtained is mainly used as a coating film. Contributes to improved material adhesion. Specific examples of the hydrolyzable group include a halogen element, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group, and are alkoxy groups. It is preferable.
　加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体としては、例えば、ビニルトリメトキシシラン、ビニルジメトキシシラン、ビニルメトキシシラン、ビニルトリエトキシシラン、ビニルジエトキシシラン、ビニルエトキシシラン、ビニルトリプロポキシシラン、ビニルジプロポキシシラン、ビニルプロポキシシラン、ビニルトリブトキシシラン、ビニルジブトキシシラン、ビニルモノブトキシシラン、ビニルメチルジメトキシシラン、ビニルメチルジエトキシシラン、３－（メタ）アクリルオキシプロピルトリメトキシシラン、３－（メタ）アクリルオキシプロピルトリエトキシシラン、３－（メタ）アクリルオキシプロピルトリプロポキシシラン、３－（メタ）アクリルオキシプロピルトリブトキシシラン、３－（メタ）アクリルオキシエチルトリメトキシシラン、３－（メタ）アクリルオキシエチルトリエトキシシラン、３－（メタ）アクリルオキシエチルトリプロポキシシラン、３－（メタ）アクリルオキシエチルトリブトキシシラン、３－（メタ）アクリルオキシメチルトリメトキシシラン、３－（メタ）アクリルオキシメチルトリエトキシシラン、３－（メタ）アクリルオキシメチルトリプロポキシシラン、３－（メタ）アクリルオキシメチルトリブトキシシラン、３－（メタ）アクリルオキシブチルトリメトキシシラン、３－（メタ）アクリルオキシブチルトリエトキシシラン、３－（メタ）アクリルオキシブチルトリプロポキシシラン、３－（メタ）アクリルオキシブチルトリブトキシシラン、３－（メタ）アクリルオキシヘプチルトリメトキシシラン、３－（メタ）アクリルオキシヘプチルトリエトキシシラン、３－（メタ）アクリルオキシヘプチルトリプロポキシシラン、３－（メタ）アクリルオキシヘプチルトリブトキシシラン、３－（メタ）アクリルオキシヘキシルトリメトキシシラン、３－（メタ）アクリルオキシヘキシルトリエトキシシラン、３－（メタ）アクリルオキシヘキシルトリプロポキシシラン、３－（メタ）アクリルオキシヘキシルトリブトキシシラン、アリルトリメトキシシラン、アリルジメトキシシラン、アリルメトキシシラン、アリルトリエトキシシラン、アリルジエトキシシラン、アリルエトキシシラン、アリルトリプロポキシシラン、アリルジプロポキシシラン、アリルプロポキシシラン、アリルトリブトキシシラン、アリルジブトキシシラン、アリルブトキシシラン、パラスチリルトリメトキシシラン、パラスチリルトリエトキシシラン、パラスチリルトリプロポキシシラン、パラスチリルトリブトキシシラン等が挙げられる。これらの（Ｂ）単量体は、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of vinyl monomers containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group include vinyltrimethoxysilane, vinyldimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, and vinyldioxide. Ethoxysilane, vinylethoxysilane, vinyltripropoxysilane, vinyldipropoxysilane, vinylpropoxysilane, vinyltributoxysilane, vinyldibutoxysilane, vinylmonobutoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3- ( (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, 3- (meth) acryloxypropi Tributoxysilane, 3- (meth) acryloxyethyltrimethoxysilane, 3- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxyethyltripropoxysilane, 3- (meth) acryloxyethyltributoxy Silane, 3- (meth) acryloxymethyltrimethoxysilane, 3- (meth) acryloxymethyltriethoxysilane, 3- (meth) acryloxymethyltripropoxysilane, 3- (meth) acryloxymethyltributoxysilane, 3- (meth) acryloxybutyltrimethoxysilane, 3- (meth) acryloxybutyltriethoxysilane, 3- (meth) acryloxybutyltripropoxysilane, 3- (meth) acryloxybutyltributoxysilane, 3- (Meta) a Riloxyheptyltrimethoxysilane, 3- (meth) acryloxyheptyltriethoxysilane, 3- (meth) acryloxyheptyltripropoxysilane, 3- (meth) acryloxyheptylriboxysilane, 3- (meth) acryloxy Hexyltrimethoxysilane, 3- (meth) acryloxyhexyltriethoxysilane, 3- (meth) acryloxyhexyltripropoxysilane, 3- (meth) acryloxyhexyl riboxysilane, allyltrimethoxysilane, allyldimethoxysilane, Allylmethoxysilane, allyltriethoxysilane, allyldiethoxysilane, allylethoxysilane, allyltripropoxysilane, allyldipropoxysilane, allylpropoxysilane, allyltributoxysilane , Allyldibutoxysilane, allylbutoxysilane, parastyryltrimethoxysilane, parastyryltriethoxysilane, parastyryltripropoxysilane, parastyryltributoxysilane, and the like. These (B) monomers may be used individually by 1 type, and may use 2 or more types together.
　（Ｂ）単量体は、含フッ素重合体を構成する単量体１００モル％に対して、１～９０モル％使用することが好ましい。（Ｂ）単量体の含有割合が前記範囲であると、塗膜の基材密着性をより向上させることができ、塗膜形成時のクラックの発生を抑制することができる。 (B) The monomer is preferably used in an amount of 1 to 90 mol% with respect to 100 mol% of the monomer constituting the fluoropolymer. (B) If the content ratio of the monomer is within the above range, the substrate adhesion of the coating film can be further improved, and the occurrence of cracks during the coating film formation can be suppressed.
　１．３．（Ｃ）単量体
　本実施の形態に係る含フッ素重合体は、（Ａ）単量体および（Ｂ）単量体以外の（Ｃ）単量体に由来する繰り返し単位を有してもよい。このような（Ｃ）単量体としては、例えば、ケイ素原子を含有しない、（メタ）アクリル酸エステル系単量体、ビニルエーテル系単量体、アリルエーテル系単量体等が挙げられる。（Ａ）単量体および（Ｂ）単量体以外の（Ｃ）単量体は、含フッ素重合体を構成する単量体１００モル％に対して、１５モル％以下の含有割合で使用することが好ましい。 1.3. (C) Monomer The fluoropolymer according to the present embodiment may have a repeating unit derived from (C) monomer other than (A) monomer and (B) monomer. . Examples of such a monomer (C) include (meth) acrylic acid ester monomers, vinyl ether monomers, allyl ether monomers and the like that do not contain silicon atoms. The monomer (C) other than the monomer (A) and the monomer (B) is used in a content ratio of 15 mol% or less with respect to 100 mol% of the monomer constituting the fluoropolymer. It is preferable.
　ケイ素原子を含有しない（メタ）アクリル酸エステル系単量体としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－アミノエチル（メタ）アクリレート、２－アミノプロピル（メタ）アクリレート、３－アミノプロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、アミル（メタ）アクリレート、ｉ－アミル（メタ）アクリレート、へキシル（メタ）アクリレート、２－エチルへキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、アリル（メタ）アクリレート、メタクリル酸トリシクロ［５．２．１．０２．６］デカン－８－イル、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラプロピレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。これらの（メタ）アクリル酸エステル系単量体は、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of the (meth) acrylic acid ester monomer not containing a silicon atom include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, glycidyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate , Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) Acrylate 2-ethylhexyl (meth) acrylate, n- octyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, methacrylic acid tricyclo [5.2.1.0 2.6] decan-8-yl , Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylol group Examples include lopantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These (meth) acrylic acid ester monomers may be used alone or in combination of two or more.
　ケイ素原子を含有しないビニルエーテル系単量体としては、例えば、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、シクロヘキシルビニルエーテル、２－ヒドロキシエチルビニルエーテル、３－ヒドロキシプロピルビニルエーテル、４－ヒドロキシブチルビニルエーテル、２－アミノエチルビニルエーテル等が挙げられる。これらのビニルエーテル系単量体は、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of vinyl ether monomers not containing silicon atoms include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-aminoethyl vinyl ether. Etc. These vinyl ether monomers may be used alone or in combination of two or more.
　ケイ素原子を含有しないアリルエーテル系単量体としては、例えば、メチルアリルエーテル、エチルアリルエーテル、プロピルアリルエーテル、ブチルアリルエーテル、ヒドロキシエチルアリルエーテル、ヒドロキシプロピルアリルエーテル、ヒドロキシブチルアリルエーテル、アリルグリシジルエーテル、エチレングリコールモノアリルエーテル、プロピレングリコールモノアリルエーテル等が挙げられる。これらのアリルエーテル系単量体は、１種単独で用いてもよく、２種以上を併用してもよい。 Examples of allyl ether monomers not containing silicon atoms include methyl allyl ether, ethyl allyl ether, propyl allyl ether, butyl allyl ether, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, allyl glycidyl ether. , Ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and the like. These allyl ether monomers may be used alone or in combination of two or more.
　１．４．含フッ素重合体の製造方法
　上記の含フッ素重合体は、上記の（Ａ）単量体、（Ｂ）単量体、必要に応じて（Ｃ）単量体を水性媒体中で乳化重合する方法、重合体溶液を水性分散体に転相する方法、沈殿重合等により製造することができるが、含フッ素重合体の分子量や粒子径の制御が容易であることから乳化重合する方法が好ましい。乳化重合により得られた含フッ素重合体の水性分散体をそのまま後述する（Ｄ）エチレン性不飽和基を有する単量体（以下、「（Ｄ）単量体」ともいう。）や（Ｅ）アルコキシシラン（以下、「（Ｅ）単量体」ともいう。）と反応させてもよい。また、得られた含フッ素重合体が粉末状である場合には、水性媒体中に分散（再乳化）させるなどして含フッ素重合体水性分散体を調製し、後述する（Ｄ）単量体や（Ｅ）単量体と反応させてもよい。 1.4. Method for Producing Fluoropolymer The above-mentioned fluoropolymer is a method in which the above (A) monomer, (B) monomer, and (C) monomer, if necessary, are emulsion polymerized in an aqueous medium. The polymer solution can be produced by phase inversion to an aqueous dispersion, precipitation polymerization, or the like, but emulsion polymerization is preferred because the molecular weight and particle diameter of the fluoropolymer are easy to control. (D) A monomer having an ethylenically unsaturated group (hereinafter also referred to as “(D) monomer”) or (E), which will be described later as it is, is an aqueous dispersion of a fluoropolymer obtained by emulsion polymerization. You may make it react with alkoxysilane (henceforth "(E) monomer"). Further, when the obtained fluoropolymer is in a powder form, an aqueous fluoropolymer dispersion is prepared by dispersing (re-emulsifying) in an aqueous medium, and the monomer (D) described later (E) You may make it react with a monomer.
　本実施の形態に係る含フッ素重合体は、全単量体の合計量を１００モル％としたときに、（Ａ）フッ素原子を有する単量体１０～９９モル％と、（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体１～９０モル％と、（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体１５モル％以下と、を水性媒体中で乳化重合させて含フッ素重合体を得る工程（ａ）を経ることにより得られる。この乳化重合法によれば、水性媒体と、（Ａ）単量体、（Ｂ）単量体、必要に応じて（Ｃ）単量体と、乳化剤と、を混合し、そこに水性媒体に溶解可能な重合開始剤を加えて反応させることにより、容易に含フッ素重合体水性分散体を製造することができる。 The fluoropolymer according to the present embodiment comprises (A) 10 to 99 mol% of a monomer having a fluorine atom, and (B) hydrolysis when the total amount of all monomers is 100 mol%. 1 to 90 mol% of a vinyl monomer containing a silyl group having a silicon atom bonded to a functional group and / or a hydroxyl group, and (C) the monomer 15 other than the component (A) and the component (B) It is obtained by going through step (a) of obtaining a fluoropolymer by emulsion polymerization in an aqueous medium. According to this emulsion polymerization method, an aqueous medium, (A) monomer, (B) monomer, (C) monomer and emulsifier, if necessary, are mixed, and the aqueous medium is mixed therewith. By adding a soluble polymerization initiator and reacting it, a fluoropolymer aqueous dispersion can be easily produced.
　乳化剤としては、例えば、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルリン酸エステル、パーフルオロアルコキシフルオロカルボン酸塩等や、陰イオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤、陽イオン性界面活性剤を用いることができる。 Examples of emulsifiers include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphates, perfluoroalkoxyfluorocarboxylates, anionic surfactants, and nonionic surfactants. , Amphoteric surfactants and cationic surfactants can be used.
　重合開始剤としては、例えば、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤を用いることができる。重合開始剤の使用割合は特に制限されないが、単量体組成、重合反応系のｐＨ、他の添加剤などの組み合わせなどを考慮して適宜設定される。 As the polymerization initiator, for example, a water-soluble polymerization initiator such as lithium persulfate, potassium persulfate, sodium persulfate, or ammonium persulfate can be used. The use ratio of the polymerization initiator is not particularly limited, but is appropriately set in consideration of the monomer composition, the pH of the polymerization reaction system, a combination of other additives, and the like.
　また、重合系のｐＨ調節剤として、リン酸水素ナトリウム、水酸化ナトリウム、炭酸ナトリウム等、連鎖移動剤としてマロン酸エチル等を適宜用いることができる。 Also, sodium hydrogen phosphate, sodium hydroxide, sodium carbonate, etc. can be used as a polymerization pH adjuster, and ethyl malonate, etc. can be used as a chain transfer agent.
　また、水性媒体は、水を主成分とする媒体であるが、物性を損なわない範囲において、水以外のアルコール系、グリコール系等の有機溶剤を含んでもよい。これらの有機溶剤の含有割合は、水１００質量部に対して０～１０質量部、好ましくは０～５質量部である。 The aqueous medium is a medium containing water as a main component, but may contain an organic solvent such as alcohol or glycol other than water as long as the physical properties are not impaired. The content ratio of these organic solvents is 0 to 10 parts by mass, preferably 0 to 5 parts by mass with respect to 100 parts by mass of water.
　１．５．含フッ素重合体の特性
　本実施の形態に係る含フッ素重合体の溶融粘度は、２３０℃、剪断速度１００（１／ｓｅｃ）２００～３５００であることが好ましい。含フッ素重合体の溶融粘度は、ＪＩＳ　Ｋ７１９９に準じた方法により測定することができる。すなわち、毛管式流れ特性試験機で、ポリマー等の試料をバレルの中で溶融させ、ピストンで加圧しキャピラリーから流出する時の溶融ポリマーの粘度特性を測定する。 1.5. Characteristics of Fluoropolymer The melt viscosity of the fluoropolymer according to the present embodiment is preferably 230 ° C. and a shear rate of 100 (1 / sec) 200 to 3500. The melt viscosity of the fluoropolymer can be measured by a method according to JIS K7199. That is, a capillary type flow characteristic tester is used to measure a viscosity characteristic of a molten polymer when a sample such as a polymer is melted in a barrel, pressurized with a piston, and discharged from a capillary.
　本実施の形態に係る含フッ素重合体は、有機溶剤の溶液として使用することもできるが、上記の乳化重合法によって得られる含フッ素重合体は、通常水性媒体中に分散された粒子状（以下、このような粒子状の含フッ素重合体を「含フッ素重合体粒子」という。）となる。この含フッ素重合体粒子の平均粒子径については、用途に応じて適宜変更できるが、通常は０．０３～０．３μｍの範囲にあることが好ましく、０．０３～０．２μｍであることがより好ましい。この平均粒子径は、動的光散乱法を測定原理とする粒度分布測定装置を用いて測定することができる。このような粒度分布測定装置としては、大塚電子株式会社製の型式「ＦＰＡＲ－１０００」等が挙げられる。 Although the fluoropolymer according to the present embodiment can be used as a solution of an organic solvent, the fluoropolymer obtained by the above emulsion polymerization method is usually in the form of particles (hereinafter referred to as particles) dispersed in an aqueous medium. Such a particulate fluoropolymer is referred to as “fluoropolymer particles”). The average particle size of the fluoropolymer particles can be appropriately changed depending on the application, but is usually preferably in the range of 0.03 to 0.3 μm, and preferably 0.03 to 0.2 μm. More preferred. This average particle diameter can be measured using a particle size distribution measuring apparatus based on the dynamic light scattering method. Examples of such a particle size distribution measuring apparatus include model “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
　２．含フッ素重合体水性分散体
　本実施の形態に係る含フッ素重合体水性分散体は、上記の含フッ素重合体が水性媒体に分散されていることを特徴とする。かかる含フッ素重合体水性分散体は、耐熱性、耐候性に加え、基材密着性、透明性、耐水性に優れた塗膜を形成することができ、各種基材へのコーティング剤として用いた場合、その効果が顕著である。 2. Fluoropolymer aqueous dispersion The fluoropolymer aqueous dispersion according to the present embodiment is characterized in that the above-mentioned fluoropolymer is dispersed in an aqueous medium. Such an aqueous dispersion of fluoropolymer can form a coating film excellent in substrate adhesion, transparency and water resistance in addition to heat resistance and weather resistance, and was used as a coating agent for various substrates. In that case, the effect is remarkable.
　本実施の形態に係る含フッ素重合体水性分散体は、上述の含フッ素重合体粒子の存在下で、該含フッ素重合体粒子をシード粒子として（Ｄ）エチレン性不飽和基を有する単量体を反応させることができる（工程（ｂ））。この工程（ｂ）では、上述の含フッ素重合体粒子をシード粒子として使用するため、（Ｄ）単量体中に含フッ素重合体粒子を溶解させる操作は行わない。また、（Ｄ）単量体を反応させる際もしくはその後に、さらに（Ｅ）アルコキシシランを反応させてもよい（工程（ｃ））。以下、（Ｄ）単量体、（Ｅ）単量体、その他の成分について詳細に説明する。 The aqueous fluoropolymer dispersion according to the present embodiment comprises (D) a monomer having an ethylenically unsaturated group using the fluoropolymer particles as seed particles in the presence of the fluoropolymer particles described above. Can be reacted (step (b)). In this step (b), since the above-mentioned fluoropolymer particles are used as seed particles, (D) the operation of dissolving the fluoropolymer particles in the monomer is not performed. Further, (E) alkoxysilane may be further reacted when (D) the monomer is reacted or after that (step (c)). Hereinafter, (D) monomer, (E) monomer, and other components will be described in detail.
　２．１．（Ｄ）単量体
　（Ｄ）エチレン性不飽和基を有する単量体は、重合体の造膜温度を適切な値に調節する役割を担うほか、塗膜の耐候性、耐汚染性を向上させることができる。（Ｄ）単量体としては、例えば、エチレン性不飽和カルボン酸のアルキルエステル、エチレン性不飽和カルボン酸のシクロアルキルエステル、エチレン性不飽和カルボン酸のヒドロキシアルキルエステル、エチレン性不飽和カルボン酸の多価アルコールエステル、その他のエチレン性不飽和カルボン酸エステル、エチレン性不飽和カルボン酸アミド、エチレン性不飽和カルボン酸等が挙げられる。 2.1. (D) Monomer (D) A monomer having an ethylenically unsaturated group plays a role in adjusting the film-forming temperature of the polymer to an appropriate value, and improves the weather resistance and stain resistance of the coating film. Can be made. Examples of the monomer (D) include alkyl esters of ethylenically unsaturated carboxylic acids, cycloalkyl esters of ethylenically unsaturated carboxylic acids, hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, and ethylenically unsaturated carboxylic acids. Examples include polyhydric alcohol esters, other ethylenically unsaturated carboxylic acid esters, ethylenically unsaturated carboxylic acid amides, and ethylenically unsaturated carboxylic acids.
　上記エチレン性不飽和カルボン酸のアルキルエステルとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸ｉ－プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｉ－ブチル、（メタ）アクリル酸ｎ－アミル、（メタ）アクリル酸ｉ－アミル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ラウリル等を；上記エチレン性不飽和カルボン酸のシクロアルキルエステルとしては、例えば（メタ）アクリル酸シクロヘキシル等を；上記エチレン性不飽和カルボン酸のヒドロキシアルキルエステルとしては、例えば（メタ）アクリル酸２－ヒドロキシメチル、（メタ）アクリル酸２－ヒドロキシエチル等を；上記エチレン性不飽和カルボン酸の多価アルコールエステルとしては、例えば（メタ）アクリル酸エチレングリコール等を、上記その他のエチレン性不飽和カルボン酸エステルとしては、γ－メタクリルオキシプロピルトリメトキシシラン、γ－メタクリルオキシプロピルトリエトキシシラン等を、上記エチレン性不飽和カルボン酸アミドとしては、Ｎ－メチロール（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド等を、それぞれ挙げることができ、これらのうちから選択される１種以上であることができる。これらのうち、（メタ）アクリル酸シクロヘキシル等のエチレン性不飽和カルボン酸のシクロアルキルエステルを（Ｄ）単量体の一成分とすることにより、得られる塗膜の耐候性を大幅に向上させることができる。 Examples of the alkyl ester of the ethylenically unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic. N-butyl acid, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) N-octyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc .; examples of the cycloalkyl ester of the ethylenically unsaturated carboxylic acid include (meth) acrylic acid Examples of the hydroxyalkyl ester of the ethylenically unsaturated carboxylic acid include cyclohexyl and the like. (Meth) acrylic acid 2-hydroxymethyl, (meth) acrylic acid 2-hydroxyethyl, etc .; as the above polyhydric alcohol ester of ethylenically unsaturated carboxylic acid, for example, (meth) acrylic acid ethylene glycol, etc. Examples of the ethylenically unsaturated carboxylic acid ester include γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane. Examples of the ethylenically unsaturated carboxylic acid amide include N-methylol (meth) acrylamide and diacetone. (Meth) acrylamide etc. can be mentioned, respectively, It can be 1 or more types selected from these. Among these, by using cycloalkyl ester of ethylenically unsaturated carboxylic acid such as cyclohexyl (meth) acrylate as one component of (D) monomer, the weather resistance of the resulting coating film is greatly improved. Can do.
　上記エチレン性不飽和カルボン酸としては、例えばアクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸等のモノ又はジカルボン酸を挙げることができ、これらから選択される１種以上であることができる。特に、アクリル酸、メタクリル酸及びイタコン酸から選択される１種以上であることが好ましい。 Examples of the ethylenically unsaturated carboxylic acid include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and one or more selected from these. be able to. In particular, at least one selected from acrylic acid, methacrylic acid and itaconic acid is preferable.
　（Ｄ）単量体は、上記例示した化合物を１種単独で使用してもよく、２種以上を混合して使用してもよい。（Ｄ）単量体は、含フッ素重合体粒子１００質量部に対して、２０～２０００質量部用いることが好ましい。（Ｄ）単量体を前記範囲の含有割合で反応させると、得られる塗膜の基材密着性をより向上させることができ、塗膜形成時のクラック発生を抑制することができる。 (D) As the monomer, the above-exemplified compounds may be used alone or in combination of two or more. The monomer (D) is preferably used in an amount of 20 to 2000 parts by mass with respect to 100 parts by mass of the fluoropolymer particles. (D) When a monomer is made to react by the content rate of the said range, the base-material adhesiveness of the coating film obtained can be improved more, and the crack generation at the time of coating-film formation can be suppressed.
　２．２．（Ｅ）単量体
　（Ｅ）アルコキシシランは、得られる重合体を塗膜にした際の耐候性をより向上させることができる。（Ｅ）単量体は、下記一般式（２）及び（３）で表される単量体よりなる群から選択される少なくとも１種の単量体であることが好ましい。
　Ｒ３ ｎＳｉ（ＯＲ４）４－ｎ　・・・・・（２）
（式中、Ｒ３及びＲ４はそれぞれ独立に炭素数１～８の有機基を表し、ｎは０～３の整数を表す。）
　Ｒ５ ｍＳｉＯ（４－ｍ）／２　・・・・・（３）
（式中、Ｒ５は炭素数１～８の有機基を表し、ｍは０～３の数を表す。） 2.2. (E) Monomer (E) The alkoxysilane can further improve the weather resistance when the resulting polymer is used as a coating film. (E) The monomer is preferably at least one monomer selected from the group consisting of monomers represented by the following general formulas (2) and (3).
R 3 n Si (OR 4 ) 4-n (2)
(Wherein R 3 and R 4 each independently represents an organic group having 1 to 8 carbon atoms, and n represents an integer of 0 to 3)
R 5 m SiO (4-m) / 2 (3)
(Wherein R 5 represents an organic group having 1 to 8 carbon atoms, and m represents a number of 0 to 3)
　上記一般式（２）及び（３）で表される単量体において、Ｒ３及びＲ５は炭素数１～８のアルキル基であることが好ましく、メチル基又はエチル基であることがより好ましい。 In the monomers represented by the general formulas (2) and (3), R 3 and R 5 are preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group or an ethyl group. .
　Ｒ４としては、例えば、炭素数１～８の、アルキル基、アリール基、アシル基等が挙げられる。アルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基等が挙げられる。アリール基としては、フェニル基、メチルフェニル基、エチルフェニル基、クロロフェニル基、ブロモフェニル基、フルオロフェニル基等が挙げられる。アシル基としては、好ましくは、炭素数１～６のアシル基であり、例えば、アセチル基、プロピオニル基、ブチリル基、バレリル基、カプロイル基等が挙げられる。上記一般式（２）中に複数個存在するＲ３やＲ４は、相互に同一でも異なってもよい。 Examples of R 4 include alkyl groups, aryl groups, and acyl groups having 1 to 8 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pentyl group. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. The acyl group is preferably an acyl group having 1 to 6 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. A plurality of R 3 and R 4 present in the general formula (2) may be the same as or different from each other.
　上記一般式（２）で表される単量体としては、ジアルコキシシラン、トリアルコキシシラン、テトラアルコキシシランを好適に使用することができる。 As the monomer represented by the general formula (2), dialkoxysilane, trialkoxysilane, and tetraalkoxysilane can be preferably used.
　ジアルコキシシランとしては、例えば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチル－ジ－ｎ－プロポキシシラン、ジメチル－ジ－ｉｓｏ－プロポキシシラン、ジメチル－ジ－ｎ－ブトキシシラン、ジメチル－ジ－ｓｅｃ－ブトキシシラン、ジメチル－ジ－ｔｅｒｔ－ブトキシシラン、ジメチルジフェノキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチル－ジ－ｎ－プロポキシシラン、ジエチル－ジ－ｉｓｏ－プロポキシシラン、ジエチル－ジ－ｎ－ブトキシシラン、ジエチル－ジ－ｓｅｃ－ブトキシシラン、ジエチル－ジ－ｔｅｒｔ－ブトキシシラン、ジエチルジフェノキシシラン、ジ－ｎ－プロピルジメトキシシラン、ジ－ｎ－プロピルジエトキシシラン、ジ－ｎ－プロピル－ジ－ｎ－プロポキシシラン、ジ－ｎ－プロピル－ジ－ｉｓｏ－プロポキシシラン、ジ－ｎ－プロピル－ジ－ｎ－ブトキシシラン、ジ－ｎ－プロピル－ジ－ｓｅｃ－ブトキシシラン、ジ－ｎ－プロピル－ジ－ｔｅｒｔ－ブトキシシラン、ジ－ｎ－プロピル－ジ－フェノキシシラン、ジ－ｉｓｏ－プロピルジメトキシシラン、ジ－ｉｓｏ－プロピルジエトキシシラン、ジ－ｉｓｏ－プロピル－ジ－ｎ－プロポキシシラン、ジ－ｉｓｏ－プロピル－ジ－ｉｓｏ－プロポキシシラン、ジ－ｉｓｏ－プロピル－ジ－ｎ－ブトキシシラン、ジ－ｉｓｏ－プロピル－ジ－ｓｅｃ－ブトキシシラン、ジ－ｉｓｏ－プロピル－ジ－ｔｅｒｔ－ブトキシシラン、ジ－ｉｓｏ－プロピル－ジ－フェノキシシラン、ジ－ｎ－ブチルジメトキシシラン、ジ－ｎ－ブチルジエトキシシラン、ジ－ｎ－ブチル－ジ－ｎ－プロポキシシラン、ジ－ｎ－ブチル－ジ－ｉｓｏ－プロポキシシラン、ジ－ｎ－ブチル－ジ－ｎ－ブトキシシラン、ジ－ｎ－ブチル－ジ－ｓｅｃ－ブトキシシラン、ジ－ｎ－ブチル－ジ－ｔｅｒｔ－ブトキシシラン、ジ－ｎ－ブチル－ジ－フェノキシシラン、ジ－ｓｅｃ－ブチルジメトキシシラン、ジ－ｓｅｃ－ブチルジエトキシシラン、ジ－ｓｅｃ－ブチル－ジ－ｎ－プロポキシシラン、ジ－ｓｅｃ－ブチル－ジ－ｉｓｏ－プロポキシシラン、ジ－ｓｅｃ－ブチル－ジ－ｎ－ブトキシシラン、ジ－ｓｅｃ－ブチル－ジ－ｓｅｃ－ブトキシシラン、ジ－ｓｅｃ－ブチル－ジ－ｔｅｒｔ－ブトキシシラン、ジ－ｓｅｃ－ブチル－ジ－フェノキシシラン、ジ－ｔｅｒｔ－ブチルジメトキシシラン、ジ－ｔｅｒｔ－ブチルジエトキシシラン、ジ－ｔｅｒｔ－ブチル－ジ－ｎ－プロポキシシラン、ジ－ｔｅｒｔ－ブチル－ジ－ｉｓｏ－プロポキシシラン、ジ－ｔｅｒｔ－ブチル－ジ－ｎ－ブトキシシラン、ジ－ｔｅｒｔ－ブチル－ジ－ｓｅｃ－ブトキシシラン、ジ－ｔｅｒｔ－ブチル－ジ－ｔｅｒｔ－ブトキシシラン、ジ－ｔｅｒｔ－ブチル－ジ－フェノキシシラン、ジフェニルジメトキシシラン、ジフェニル－ジ－エトキシシラン、ジフェニル－ジ－ｎ－プロポキシシラン、ジフェニル－ジ－ｉｓｏ－プロポキシシラン、ジフェニル－ジ－ｎ－ブトキシシラン、ジフェニル－ジ－ｓｅｃ－ブトキシシラン、ジフェニル－ジ－ｔｅｒｔ－ブトキシシラン、ジフェニルジフェノキシシランなどを挙げることができる。 Examples of dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyl-di-n-propoxysilane, dimethyl-di-iso-propoxysilane, dimethyl-di-n-butoxysilane, and dimethyl-di-sec- Butoxysilane, dimethyl-di-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyl-di-n-propoxysilane, diethyl-di-iso-propoxysilane, diethyl-di-n- Butoxysilane, diethyl-di-sec-butoxysilane, diethyl-di-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyl-di -N Propoxysilane, di-n-propyl-di-iso-propoxysilane, di-n-propyl-di-n-butoxysilane, di-n-propyl-di-sec-butoxysilane, di-n-propyl-di- tert-butoxysilane, di-n-propyl-di-phenoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyl-di-n-propoxysilane, di-iso- Propyl-di-iso-propoxysilane, di-iso-propyl-di-n-butoxysilane, di-iso-propyl-di-sec-butoxysilane, di-iso-propyl-di-tert-butoxysilane, di- iso-propyl-di-phenoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxy Silane, di-n-butyl-di-n-propoxysilane, di-n-butyl-di-iso-propoxysilane, di-n-butyl-di-n-butoxysilane, di-n-butyl-di-sec -Butoxysilane, di-n-butyl-di-tert-butoxysilane, di-n-butyl-di-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyl -Di-n-propoxysilane, di-sec-butyl-di-iso-propoxysilane, di-sec-butyl-di-n-butoxysilane, di-sec-butyl-di-sec-butoxysilane, di-sec -Butyl-di-tert-butoxysilane, di-sec-butyl-di-phenoxysilane, di-tert-butyldimethoxysilane, di-tert -Butyldiethoxysilane, di-tert-butyl-di-n-propoxysilane, di-tert-butyl-di-iso-propoxysilane, di-tert-butyl-di-n-butoxysilane, di-tert-butyl -Di-sec-butoxysilane, di-tert-butyl-di-tert-butoxysilane, di-tert-butyl-di-phenoxysilane, diphenyldimethoxysilane, diphenyl-di-ethoxysilane, diphenyl-di-n-propoxy Examples thereof include silane, diphenyl-di-iso-propoxysilane, diphenyl-di-n-butoxysilane, diphenyl-di-sec-butoxysilane, diphenyl-di-tert-butoxysilane, and diphenyldiphenoxysilane.
　トリアルコキシシランとしては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ－ｎ－プロポキシシラン、メチルトリ－ｉｓｏ－プロポキシシラン、メチルトリ－ｎ－ブトキシシラン、メチルトリ－ｓｅｃ－ブトキシシラン、メチルトリ－ｔｅｒｔ－ブトキシシラン、メチルトリフェノキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリ－ｎ－プロポキシシラン、エチルトリ－ｉｓｏ－プロポキシシラン、エチルトリ－ｎ－ブトキシシラン、エチルトリ－ｓｅｃ－ブトキシシラン、エチルトリ－ｔｅｒｔ－ブトキシシラン、エチルトリフェノキシシランなどを挙げることができる。 Examples of trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert- Butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, ethyltri-tert- Examples include butoxysilane and ethyltriphenoxysilane.
　テトラアルコキシシランとしては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラ－ｎ－プロポキシシラン、テトラ－ｉｓｏ－プロポキシシラン、テトラ－ｎ－ブトキシシシラン、テトラ－ｓｅｃ－ブトキシシシラン、テトラ－ｔｅｒｔ－ブトキシシシラン、テトラフェノキシシシランなどを挙げることができる。 Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert- Examples include butoxysilane and tetraphenoxysilane.
　これらの（Ｅ）アルコキシシランは、１種単独で使用してもよく、２種以上を併用してもよい。 These (E) alkoxysilanes may be used alone or in combination of two or more.
　２．３．その他の単量体
　上記含フッ素重合体水性分散体は、（Ｄ）単量体及び（Ｅ）単量体以外の単量体に由来する繰り返し単位を有してもよい。このような単量体としては、例えば、「１．３．（Ｃ）単量体」で挙げた単量体を好適に使用することができる。 2.3. Other monomer The said fluoropolymer aqueous dispersion may have a repeating unit derived from monomers other than (D) monomer and (E) monomer. As such a monomer, for example, the monomers listed in “1.3. (C) Monomer” can be preferably used.
　２．４．含フッ素重合体水性分散体の製造方法
　本実施の形態に係る含フッ素重合体水性分散体は、上述の含フッ素重合体粒子の存在下で、上述の（Ｄ）単量体、（Ｅ）単量体、その他の単量体、乳化剤（界面活性剤）、重合開始剤、分子量調節剤等の存在下で反応させることにより製造することができる。 2.4. Method for Producing Fluoropolymer Aqueous Dispersion The fluoropolymer aqueous dispersion according to the present embodiment comprises the above-mentioned (D) monomer and (E) single monomer in the presence of the above-mentioned fluoropolymer particles. It can be produced by reacting in the presence of a monomer, other monomers, an emulsifier (surfactant), a polymerization initiator, a molecular weight regulator and the like.
　乳化剤としては、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、デヒドロアビエチン酸塩、ナフタレンスルホン酸・ホルマリン縮合物、非イオン性界面活性剤の硫酸エステル塩などのアニオン性界面活性剤；ポリエチレングリコールのアルキルエステル、ポリエチレングリコールのアルキルフェニルエーテル、ポリエチレングリコールのアルキルエーテルなどのノニオン性界面活性剤；パーフルオロブチルスルホン酸塩、パーフルオロアルキル基含有リン酸エステル、パーフルオロアルキル基含有カルボン酸塩、パーフルオロアルキルエチレンオキシド付加物などのフッ素系界面活性剤などを挙げることができ、これらのうちから選択される一種以上を使用することができる。乳化剤の使用割合は、（Ｄ）単量体１００質量部（（Ｅ）単量体を使用する場合には（Ｄ）単量体及び（Ｅ）単量体の合計１００質量部）に対して、０．０１～１０質量部とすることが好ましく、０．０２～５質量部とすることがより好ましい。 Examples of the emulsifier include sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, naphthalene sulfonic acid / formalin condensates, Anionic surfactants such as sulfate ester salts of ionic surfactants; nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, alkyl ethers of polyethylene glycol; perfluorobutyl sulfonates; Fluorosurfactants such as perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing carboxylates, and perfluoroalkylethylene oxide adducts can be mentioned. It can be used one or more selected from among. The use ratio of the emulsifier is based on 100 parts by mass of (D) monomer (in the case of using (E) monomer, 100 parts by mass in total of (D) monomer and (E) monomer). 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass.
　重合開始剤としては、例えば、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムなどの水溶性重合開始剤；クメンハイドロパーオキサイド、過酸化ベンゾイル、ｔ－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド、アゾビスイソブチロニトリル、１，１’－アゾビス（シクロヘキサンカルボニトリル）などの油溶性重合開始剤などを適宜選択して用いることができる。これらのうち、特に過硫酸カリウム、過硫酸ナトリウム、クメンハイドロパーオキサイド又はｔ－ブチルハイドロパーオキサイドを使用することが好ましい。重合開始剤の使用割合は、（Ｃ）単量体１００質量部（（Ｅ）単量体を使用する場合には（Ｄ）単量体及び（Ｅ）単量体の合計１００質量部）に対して、０．３～３質量部とすることが好ましい。 Examples of the polymerization initiator include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, Oil-soluble polymerization initiators such as diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), etc. are selected as appropriate Can be used. Of these, potassium persulfate, sodium persulfate, cumene hydroperoxide or t-butyl hydroperoxide is particularly preferably used. The proportion of the polymerization initiator used is (C) 100 parts by mass of monomer (when (E) monomer is used, (D) monomer and (E) monomer in total 100 parts by mass)). On the other hand, it is preferably 0.3 to 3 parts by mass.
　分子量調節剤としては、例えば、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン；ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物；ターピノレン、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム化合物；２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール化合物；アリルアルコール等のアリル化合物；ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物；α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミドなどのビニルエーテル化合物などのほか、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、α－メチルスチレンダイマーなどを挙げることができ、これらのうちから選択される一種以上を使用することができる。分子量調節剤の使用割合は、（Ｄ）単量体１００質量部（（Ｅ）単量体を使用する場合には（Ｄ）単量体及び（Ｅ）単量体の合計１００質量部）に対して、５質量部以下とすることが好ましい。 Examples of the molecular weight regulator include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogendi Xanthogen compounds such as sulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenol compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; α-benzyloxystyrene , Vinyl ether compounds such as α-benzyloxyacrylonitrile and α-benzyloxyacrylamide, as well as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, α- A methyl styrene dimer etc. can be mentioned and 1 or more types selected from these can be used. The proportion of molecular weight regulator used is (D) 100 parts by mass of monomer (when (E) monomer is used, the total of (D) monomer and (E) monomer is 100 parts by mass)). On the other hand, it is preferably 5 parts by mass or less.
　乳化重合は適当な水性媒体中で行うことができる。水性媒体は、物性を損なわない範囲で水以外のアルコール系、グリコール系などの有機溶剤を含んでも構わないが、これらの有機溶剤を実質的に含まないことが好ましい。この水性媒体中における（Ｄ）単量体と（Ｅ）単量体の合計の含有割合は、１０～５０質量％とすることができ、２０～４０質量％とすることが好ましい。乳化重合の条件としては、重合温度４０～８５℃において重合時間２～２４時間とすることが好ましく、重合温度５０～８０℃において重合時間３～２０時間とすることがさらに好ましい。 Emulsion polymerization can be performed in a suitable aqueous medium. The aqueous medium may contain an organic solvent such as alcohol or glycol other than water as long as the physical properties are not impaired, but it is preferable that the aqueous medium does not substantially contain these organic solvents. The total content of the (D) monomer and the (E) monomer in the aqueous medium can be 10 to 50% by mass, and preferably 20 to 40% by mass. The conditions for emulsion polymerization are preferably a polymerization time of 2 to 24 hours at a polymerization temperature of 40 to 85 ° C., and more preferably a polymerization time of 3 to 20 hours at a polymerization temperature of 50 to 80 ° C.
　２．５．含フッ素重合体水性分散体の特性
　上記の（Ｄ）単量体や（Ｅ）単量体を反応させて得られた含フッ素重合体粒子の平均粒子径は、用途に応じて変更できるが、通常は０．０５～０．６μｍの範囲にあることが好ましく、０．０５～０．４μｍの範囲にあることがより好ましい。この平均粒子径は、動的光散乱法を測定原理とする粒度分布測定装置を用いて測定することができる。このような粒度分布測定装置としては、大塚電子株式会社製の型式「ＦＰＡＲ－１０００」等が挙げられる。 2.5. Characteristics of Fluoropolymer Aqueous Dispersion The average particle size of the fluoropolymer particles obtained by reacting the above (D) monomer and (E) monomer can be changed depending on the application, Usually, it is preferably in the range of 0.05 to 0.6 μm, more preferably in the range of 0.05 to 0.4 μm. This average particle diameter can be measured using a particle size distribution measuring apparatus based on the dynamic light scattering method. Examples of such a particle size distribution measuring apparatus include model “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.
　２．６．添加剤
　上記で得られた含フッ素重合体水性媒体をそのまま用いてもよいが、必要に応じてヒドラジン誘導体や、その他の添加剤を添加して用いてもよい。 2.6. Additives The fluoropolymer aqueous medium obtained above may be used as it is, but a hydrazine derivative or other additives may be added as necessary.
　本実施の形態に係る含フッ素重合体水性分散体にヒドラジン誘導体を添加することで、水性媒体中の水が乾燥により飛散する際、上記（Ｄ）単量体に由来するカルボニル基とヒドラジン誘導体のヒドラジノ基が架橋して網目構造の被膜を形成する作用が発現する。したがって、形成される塗膜の耐水性や耐溶剤性を向上できる。この架橋反応には、通常触媒を要しないが、場合によっては硫酸亜鉛、硫酸マンガン、硫酸コバルト等の水溶性金属塩等の触媒を使用することができる。ヒドラジン誘導体の添加量は、上記（Ｄ）単量体に由来するカルボニル基１モルに対して、好ましくは０．０２～１モル、より好ましくは０．２～０．６モルである。 By adding a hydrazine derivative to the fluoropolymer aqueous dispersion according to the present embodiment, when water in the aqueous medium is scattered by drying, the carbonyl group derived from the monomer (D) and the hydrazine derivative An action of forming a network-structured film by crosslinking hydrazino groups is exhibited. Therefore, the water resistance and solvent resistance of the formed coating film can be improved. This crosslinking reaction usually does not require a catalyst, but in some cases, a catalyst such as a water-soluble metal salt such as zinc sulfate, manganese sulfate, and cobalt sulfate can be used. The amount of the hydrazine derivative added is preferably 0.02 to 1 mol, more preferably 0.2 to 0.6 mol, per 1 mol of the carbonyl group derived from the monomer (D).
　ヒドラジン誘導体としては、少なくとも２個のヒドラジノ基を有するヒドラジン誘導体であることが好ましく、例えばシュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジド、セバシン酸ジヒドラジド、マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジド等の炭素数２～１０個（好ましくは炭素数４～６個）のジカルボン酸ジヒドラジド；エチレン－１，２－ジヒドラジン、プロピレン－１，３－ジヒドラジン、ブチレン－１，４－ジヒドラジン等の炭素数２～４個の水溶性脂肪族ジヒドラジン；が挙げられ、これらの中でも、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジド、セバシン酸ジヒドラジドが好ましい。 The hydrazine derivative is preferably a hydrazine derivative having at least two hydrazino groups such as oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, Dicarboxylic acid dihydrazides having 2 to 10 carbon atoms (preferably 4 to 6 carbon atoms) such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; ethylene-1,2-dihydrazine, propylene-1,3-di And water-soluble aliphatic dihydrazine having 2 to 4 carbon atoms such as hydrazine and butylene-1,4-dihydrazine. Among these, adipic acid dihydrazide, isophthalic acid dihydrazide, and sebacic acid dihydrazide are preferable. .
　本実施の形態に係る含フッ素重合体水性分散体には、必要に応じて、シリコーン系消泡剤、凍結防止剤（エチレングリコール、プロピレングリコール等）、染料、分散剤、ｐＨ調整剤（エタノールアミン等）、増粘剤（ヒドロキシエチルセルロース、ポリエーテルウレタン、アクリル酸共重合体等）、濡れ性改善剤（ブチルセロソルブ、エチルセロソルブ等）、防腐剤、防黴剤、耐水化剤、老化防止剤、紫外線吸収剤、紫外線安定剤、水溶性溶剤、成膜助剤等の各種有機添加剤を添加することができる。これらの有機添加剤の添加量は、上記の含フッ素重合体水性分散体の固形分換算１００質量部に対して、４０質量部以下とすることができる。 In the fluoropolymer aqueous dispersion according to the present embodiment, if necessary, a silicone-based antifoaming agent, an antifreezing agent (ethylene glycol, propylene glycol, etc.), a dye, a dispersing agent, a pH adjuster (ethanolamine) Etc.), thickeners (hydroxyethyl cellulose, polyether urethane, acrylic acid copolymer, etc.), wettability improvers (butyl cellosolve, ethyl cellosolve, etc.), preservatives, antifungal agents, water resistance agents, anti-aging agents, ultraviolet rays Various organic additives such as an absorber, an ultraviolet stabilizer, a water-soluble solvent, and a film forming aid can be added. The amount of these organic additives added can be 40 parts by mass or less with respect to 100 parts by mass in terms of solid content of the above fluoropolymer aqueous dispersion.
　また、本実施の形態に係る含フッ素重合体水性分散体はクリアー塗装で用いることができるが、必要に応じて、無機顔料、有機顔料、充填剤等の無機あるいは有機化合物を添加・配合し、エナメルとして使用することもできる。例えばＪＲ－１０００（テイカ）、ＣＲ－９７（石原産業）、Ｒ－６３０（石原産業）などの酸化チタン、酸化鉄、黄酸化鉄、酸化亜鉛、酸化セリウム、酸化インジウム、アンチモン・スズ酸化物、アルミフレーク、鱗片状アルミ、コバルトブルー、リトポン、硫化鉛、酸化ジルコニウム等、フタロシアニン系、アントラキノン系、キナクリドン系、アゾ系、ペリノン系、ペリレン系、インジゴ／チオインジゴ系、ジオキサジン系、メチン／アゾメチン系、イソインドリノン系、ジケトピロロピロール系、カーボンブラック、ダイヤモンドブラック、グラファイト、フラーレン、グラフェン、アニリンブラック、カーボンナノチューブ、カーボンナノホーン、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、ケイソウ土、消石灰、石膏、炭酸バリウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、ベントナイト、酸化マグネシウム、アルミナ、シリカ、アクリルビーズ、タルク、クレー、雲母、粘土鉱物、鉄、銅、ニッケル、金、銀、亜鉛、フェライト、ステンレス鋼、酸化クロム、酸化コバルト、亜鉛緑、クロム緑、コバルト緑、ビリジアン、ギネー緑、コバルトクロム緑、シェーレ緑、緑土、マンガン緑、ピグメントグリーン、群青、紺青、ピグメントグリーン、岩群青、コバルト青、セルリアンブルー、ホウ酸銅、モリブデン青、硫化銅、コバルト紫、マルス紫、マンガン紫、ピグメントバイオレット、亜酸化鉛、鉛酸カルシウム、ジンクエロー、クロム黄、黄土、カドミウム黄、ストロンチウム黄、チタン黄、リサージ、ピグメントエロー、亜酸化銅、カドミウム赤、セレン赤、クロムバーミリオン、ベンガラ、亜鉛白、アンチモン白、塩基性硫酸鉛、ケイ酸鉛、酸化ジルコン、タングステン白、鉛、亜鉛華、バンチソン白、フタル酸鉛、マンガン白、硫酸鉛、ボーン黒、サーマトミック黒、植物性黒、チタン酸カリウムウィスカー、二硫化モリブデン等が挙げられる。有機顔料に金属キレートを形成した系も使用することができ、銅フタロシアニン系等が挙げられる。これらは単独で使用してもよいし、複数併用することもできる。 Further, the fluoropolymer aqueous dispersion according to the present embodiment can be used in clear coating, but if necessary, an inorganic or organic compound such as an inorganic pigment, an organic pigment, or a filler is added and blended, It can also be used as an enamel. For example, JR-1000 (Taika), CR-97 (Ishihara Sangyo), R-630 (Ishihara Sangyo), etc. titanium oxide, iron oxide, yellow iron oxide, zinc oxide, cerium oxide, indium oxide, antimony tin oxide, Aluminum flakes, scaly aluminum, cobalt blue, lithopone, lead sulfide, zirconium oxide, etc., phthalocyanine, anthraquinone, quinacridone, azo, perinone, perylene, indigo / thioindigo, dioxazine, methine / azomethine, Isoindolinone, diketopyrrolopyrrole, carbon black, diamond black, graphite, fullerene, graphene, aniline black, carbon nanotube, carbon nanohorn, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, diatom , Slaked lime, gypsum, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, magnesium oxide, alumina, silica, acrylic beads, talc, clay, mica, clay mineral, iron, copper, nickel, gold, silver, zinc, Ferrite, Stainless steel, Chromium oxide, Cobalt oxide, Zinc green, Chromium green, Cobalt green, Viridian, Guinea green, Cobalt chrome green, Shere green, Green earth, Manganese green, Pigment green, Ultramarine, Bituminous, Pigment green, Rock ultramarine , Cobalt Blue, Cerulean Blue, Copper Borate, Molybdenum Blue, Copper Sulfide, Cobalt Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow Cuprous oxide, Cadmium red, Selenium red, Chromium vermillion, Bengala, Zinc white, Antimony white, Basic lead sulfate, Lead silicate, Zircon oxide, Tungsten white, Lead, Zinc white, Bunchison white, Lead phthalate, Manganese Examples include white, lead sulfate, bone black, thermatomic black, vegetable black, potassium titanate whisker, and molybdenum disulfide. A system in which a metal chelate is formed on an organic pigment can also be used, and examples thereof include a copper phthalocyanine system. These may be used alone or in combination.
　本実施の形態に係る含フッ素重合体水性分散体は、特に各種基材、例えばセメント、タイル、金属、プラスチック、ガラス等に対する高耐久保護コーティング材として有用である。また、建築、建材、自動車等、屋外使用を想定した高耐久塗料、耐久性及び耐汚染性が要求される遮熱塗料や防食塗料用途で好適に用いられる他、フェルトやガラス、紙等の多孔質物質への含浸加工材、パッキング材、繊維・織物や畳の処理剤としても好適に使用することができる。本実施の形態に係る含フッ素重合体水性分散体を直接基材上に塗布することもできるが、用途に応じては基材上にエポキシ系、ウレタン系、メラミン系、アルキド系等の下塗り（プライマー）層や中塗り層を予め形成して用いることができるほか、ジンクリッチペイント等の防食層を設けて使用することもできる。 The aqueous fluoropolymer dispersion according to the present embodiment is particularly useful as a highly durable protective coating material for various substrates such as cement, tile, metal, plastic, glass and the like. In addition, it is suitable for use in buildings, building materials, automobiles, and other highly durable paints intended for outdoor use, thermal barrier paints and anticorrosion paints that require durability and contamination resistance, and porous materials such as felt, glass, and paper. It can also be suitably used as a material for impregnating material, packing material, fiber / woven fabric and tatami mat. Although the fluoropolymer aqueous dispersion according to the present embodiment can be directly applied on a substrate, depending on the application, an undercoat (epoxy-based, urethane-based, melamine-based, alkyd-based, etc.) A primer) layer and an intermediate coating layer can be formed and used in advance, or an anticorrosion layer such as zinc rich paint can be provided and used.
　また、下地調整、密着性向上、多孔質基材の目止め、平滑化、模様付けなどを目的として、予め表面処理を施すこともできる。金属系基材に対する表面処理としては、例えば、研磨、脱脂、メッキ処理、クロメート処理、火炎処理、カップリング処理などを挙げることができ、プラスチック系基材に対する表面処理としては、例えば、ブラスト処理、薬品処理、脱脂、火炎処理、酸化処理、蒸気処理、コロナ放電処理、紫外線照射処理、プラズマ処理、イオン処理などを挙げることができ、無機窯業系基材に対する表面処理としては、例えば、研磨、目止め、模様付けなどを挙げることができ、木質基材に対する表面処理としては、例えば、研磨、目止め、防虫処理などを挙げることができ、紙質基材に対する表面処理としては、例えば、目止め、防虫処理などを挙げることができ、さらに劣化塗膜に対する表面処理としては、例えば、ケレンなどを挙げることができる。 Also, surface treatment can be performed in advance for the purpose of adjusting the foundation, improving adhesion, sealing the porous substrate, smoothing, and patterning. Examples of the surface treatment for the metal base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment, coupling treatment, and the like. Examples of the surface treatment for the plastic base material include blast treatment, Chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, and the like. Examples of surface treatments for inorganic ceramic base materials include polishing, Examples of the surface treatment for the wood base material include, for example, polishing, sealing, and insect repellent treatment. Examples of the surface treatment for the paper base material include, for example, sealing, Insect repellent treatment and the like, and as surface treatment for a deteriorated coating film, for example, keren can be mentioned. .
　各種基材に塗膜を形成する際には、本実施の形態に係る含フッ素重合体水性分散体を塗布した後、通常、室温～２００℃程度の温度で乾燥させればよい。塗装法としては、スプレー塗布、ローラー塗装、刷毛塗り、筆塗り、流し塗りの他、バーコーター、ナイフコーター、ドクターブレード、スクリーン印刷、スピンコーター、アプリケーター、ロールコーター、フローコーター、遠心コーター、超音波コーター、（マイクロ）グラビアコーター、ディップコート、フレキソ印刷、ポッティング等の手法を用いることができる。本実施の形態に係る含フッ素重合体水性分散体の場合、乾燥膜厚として、１回塗りで厚さ０．０５～５０μｍ程度、２回塗りでは厚さ０．１～１００μｍ程度の塗膜を形成することができる。 When forming a coating film on various base materials, after applying the fluoropolymer aqueous dispersion according to the present embodiment, it is usually dried at a temperature of about room temperature to about 200 ° C. Coating methods include spray coating, roller coating, brush coating, brush coating, flow coating, bar coater, knife coater, doctor blade, screen printing, spin coater, applicator, roll coater, flow coater, centrifugal coater, ultrasonic wave Techniques such as a coater, (micro) gravure coater, dip coating, flexographic printing, and potting can be used. In the case of the fluoropolymer aqueous dispersion according to the present embodiment, as a dry film thickness, a coating film having a thickness of about 0.05 to 50 μm by one coating and a thickness of about 0.1 to 100 μm by two coatings. Can be formed.
　３．実施例
　以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。実施例、比較例中の「部」および「％」は、特に断らない限り質量基準である。 3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.
　３．１．含フッ素重合体粒子の合成
　３．１．１．実施例１
　攪拌機を有する内容積２リットルのステンレス製反応器に、ビニルトリメトキシシラン１１７．５質量部、イオン交換水６００質量部、炭酸ナトリウム１０水和物を１質量部、ニューコール５０４（日本乳化剤株式会社製、ノニオン系乳化剤）１３質量部を仕込んだ。内部を窒素ガスで置換して加圧脱気を３回行い、溶存空気を除去した後、フッ化ビニリデン（ＶＤＦ）５８．５モル％、テトラフルオロエチレン（ＴＦＥ）２２．５モル％、ヘキサフルオロプロピレン（ＨＦＰ）９モル％の混合組成を有する混合ガスを導入し、８０℃に昇温した。内圧は２．５ＭＰａであった。その後、過硫酸アンモニウム３質量部をイオン交換水１５０質量部に溶解して反応容器内に圧入し、重合反応を開始させた。開始後は内圧２．５ＭＰａとなるようにＶＤＦ／ＴＦＥ／ＨＦＰ＝５８．５／２２．５／９（モル％）の混合ガスを追加添加した。１２ｈｒの反応後、反応容器を冷却し反応を終了し、含フッ素重合体粒子Ａ－１を得た。得られた含フッ素重合体粒子Ａ－１を含有する分散液の固形分濃度は４８％であり、水を加えて固形分濃度４０％とした。得られた含フッ素重合体粒子Ａ－１を含有する分散液を試料として、動的光散乱法を測定原理とする粒度分布測定装置を用いて平均粒子径を測定したところ、平均粒子径は８１ｎｍであった。 3.1. Synthesis of fluoropolymer particles 3.1.1. Example 1
In a stainless steel reactor having an internal volume of 2 liters having a stirrer, 117.5 parts by mass of vinyltrimethoxysilane, 600 parts by mass of ion-exchanged water, 1 part by mass of sodium carbonate decahydrate, New Coal 504 (Nippon Emulsifier Co., Ltd.) Manufactured, nonionic emulsifier) 13 parts by mass. After the inside was replaced with nitrogen gas and pressurized degassing was performed three times to remove dissolved air, vinylidene fluoride (VDF) 58.5 mol%, tetrafluoroethylene (TFE) 22.5 mol%, hexafluoro A mixed gas having a mixed composition of 9 mol% of propylene (HFP) was introduced, and the temperature was raised to 80 ° C. The internal pressure was 2.5 MPa. Thereafter, 3 parts by mass of ammonium persulfate was dissolved in 150 parts by mass of ion-exchanged water and pressed into the reaction vessel to initiate the polymerization reaction. After the start, a mixed gas of VDF / TFE / HFP = 58.5 / 22.5 / 9 (mol%) was additionally added so that the internal pressure became 2.5 MPa. After the reaction for 12 hours, the reaction vessel was cooled to complete the reaction, and fluoropolymer particles A-1 were obtained. The resulting dispersion containing the fluoropolymer particles A-1 had a solid content of 48%, and water was added to give a solid content of 40%. Using the resulting dispersion containing the fluoropolymer particles A-1 as a sample, the average particle size was measured using a particle size distribution measuring apparatus based on the dynamic light scattering method. The average particle size was 81 nm. Met.
　３．１．２．実施例２～５、比較例１～３
　表１に示す各成分を用いたほかは、上記実施例１と同様の方法で含フッ素重合体粒子Ａ－２～Ａ－８を含有する分散液を得た。得られた含フッ素重合体粒子Ａ－２～Ａ－８を含有する分散液をそれぞれ試料として、動的光散乱法を測定原理とする粒度分布測定装置を用いて平均粒子径を求めた。その結果を表１に併せて示す。 3.1.2. Examples 2 to 5 and Comparative Examples 1 to 3
Dispersions containing fluoropolymer particles A-2 to A-8 were obtained in the same manner as in Example 1 except that each component shown in Table 1 was used. Using the obtained dispersions containing the fluoropolymer particles A-2 to A-8 as samples, the average particle size was determined using a particle size distribution measuring apparatus based on the dynamic light scattering method. The results are also shown in Table 1.
　３．１．３．比較例４
　上記で得られた含フッ素重合体粒子Ａ－７の固形分７００質量部に対し、Ｘ４０－９２２０（信越化学株式会社製、シリコンオリゴマー）２００質量部を予め等量の水を加えてホモジナイザーで強制乳化した水分散体を加え、室温で５時間撹拌し、配合液を得た。 3.1.3. Comparative Example 4
200 parts by mass of X40-9220 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon oligomer) is added in advance to 700 parts by mass of the solid content of the fluoropolymer particle A-7 obtained above and forced with a homogenizer. The emulsified water dispersion was added and stirred at room temperature for 5 hours to obtain a blended solution.
　３．２．含フッ素重合体粒子の評価方法及び結果
　３．２．１．機械的安定性
　得られた含フッ素重合体粒子の分散液を、ディスパー（プライミクス社製；ＴＫホモディスパー）で、１，０００ｒｐｍで５分間撹拌処理を行い、凝集物発生の有無を目視観察した。判定基準は、以下の通りである。その結果を表１に併せて示す。
「○」・・・凝集なし
「×」・・・凝集物発生 3.2. Evaluation method and result of fluoropolymer particles 3.2.1. Mechanical stability The dispersion of the obtained fluoropolymer particles was subjected to a stirring process at 1,000 rpm for 5 minutes with a disper (Primics Co., Ltd .; TK homodisper), and the presence or absence of aggregates was visually observed. Judgment criteria are as follows. The results are also shown in Table 1.
“○”: No aggregation “×”: Aggregate generation
　３．２．２．保存安定性
　得られた含フッ素重合体粒子の分散液を常温（２５℃）下で２ヶ月保管し、含フッ素重合体粒子の沈降又は分離を目視により判定した。判定基準は、以下の通りである。その結果を表１に併せて示す。
「○」・・・含フッ素重合体粒子の沈降および分離なし
「×」・・・含フッ素重合体粒子の沈降または分離またはゲル化発生 3.2.2. Storage stability The dispersion of the obtained fluoropolymer particles was stored at room temperature (25 ° C.) for 2 months, and sedimentation or separation of the fluoropolymer particles was visually determined. Judgment criteria are as follows. The results are also shown in Table 1.
“○”: No sedimentation and separation of fluoropolymer particles “×”: Sedimentation or separation or gelation of fluoropolymer particles
　３．２．３．基材密着性
　得られた含フッ素重合体粒子の分散液をガラス上に２００μｍのアプリケーターを用いて塗布し、常温（２５℃）で１週間乾燥させて得た塗膜に対し、１ｍｍ角のクロスカット（５×５の２５マス）を行い、ニチバン製セロテープ（登録商標）を用いた密着試験を行った。判定基準は、以下の通りである。その結果を表１に併せて示す。
「○」・・・剥離なし
「△」・・・剥離が半数未満
「×」・・・剥離が半数以上 3.2.3. Adhesiveness to substrate The obtained fluoropolymer particle dispersion was coated on glass using a 200 μm applicator and dried at room temperature (25 ° C.) for 1 week. Cut (25 squares of 5 × 5) was performed, and an adhesion test using Nichiban cello tape (registered trademark) was performed. Judgment criteria are as follows. The results are also shown in Table 1.
“○”: No peeling “△”: Less than half peeling “×”: More than half peeling
　３．２．４．透明性
　上記「３．２．３．基材密着性」の評価で得られた塗膜の透明性を目視で観察した。判定基準は、以下の通りである。その結果を表１に併せて示す。
「○」・・・白化無し
「△」白もやあり
「×」明らかな白化あり 3.2.4. Transparency The transparency of the coating film obtained in the evaluation of “3.2.3. Adhesiveness to base material” was visually observed. Judgment criteria are as follows. The results are also shown in Table 1.
“○”: no whitening “△” white haze “×” clear whitening
　３．２．５．耐水性
　上記「３．２．３．基材密着性」の評価で得られた塗膜につき５０℃×２４ｈｒ浸漬の耐水試験を行い、取り出して常温下で３０分放置後の白化の度合いを目視観察した。判定基準は、以下の通りである。その結果を表１に併せて示す。
「○」・・・白化無し
「△」・・・白もやあり
「×」・・・明らかな白化あり 3.2.5. Water resistance The coating film obtained in the above evaluation of “3.2.3. Adhesion to base material” is subjected to a water resistance test at 50 ° C. × 24 hours, taken out, and visually checked for the degree of whitening after standing at room temperature for 30 minutes. Observed. Judgment criteria are as follows. The results are also shown in Table 1.
“○”: No whitening “△”: White haze “×”: Clear whitening
　３．２．６．耐熱性
　上記「３．２．３．基材密着性」の評価で得られた塗膜につき５０℃×２ヶ月の耐熱試験を行い、目視観察で初期状態と比較した。判定基準は、以下の通りである。その結果を表１に併せて示す。
「○」・・・黄変無し
「△」・・・わずかな黄変あり
「×」・・・明らかな黄変あり 3.2.6. Heat resistance A heat resistance test at 50 ° C. for 2 months was performed on the coating film obtained in the evaluation of “3.2.3. Adhesiveness to base material”, and compared with the initial state by visual observation. Judgment criteria are as follows. The results are also shown in Table 1.
“○”: no yellowing “△”: slight yellowing “×”: clear yellowing
　３．２．７．耐候性
　得られた含フッ素重合体粒子の分散液１００質量部（有姿）に対しテキサノールを５部加えてよく撹拌し、予め水性エポキシ下塗り材を塗布し１２０℃で焼成しておいた硬質アルミ基材上に２００μｍのアプリケーターを用いて塗布し、常温（２５℃）下で１週間放置し成膜した。メタルウェザー（ダイプラ・ウィンテス製）により促進耐候性試験５００ｈｒを行い、塗膜の６０°光沢を測定し光沢保持率（試験後の光沢／試験前の光沢；％）を求めた。試験条件は、照射（６３℃５０％ＲＨ下で７５ｍＷ／ｃｍ２）４ｈｒ⇔暗黒（３０℃９８％ＲＨ）４ｈｒのサイクル条件とした。明らかに不透明で低光沢のものや、基材から剥離したものは評価対象外とした。
「○」・・・光沢保持率８０％以上
「△」・・・光沢保持率６０％以上８０％未満
「×」・・・光沢保持率６０％未満 3.2.7. Weather resistance Hard aluminum which 5 parts of texanol was added to 100 parts by mass (solid) of the obtained fluoropolymer particles (stirred), stirred well, pre-coated with an aqueous epoxy primer and fired at 120 ° C. The film was coated on a substrate using a 200 μm applicator and left at room temperature (25 ° C.) for 1 week to form a film. The accelerated weather resistance test was conducted for 500 hours with a metal weather (Daipura Wintes), and the 60 ° gloss of the coating film was measured to determine the gloss retention (gloss after test / gloss before test;%). The test conditions were cycle conditions of irradiation (75 mW / cm 2 at 63 ° C. and 50% RH) for 4 hours and darkness (30 ° C. and 98% RH) for 4 hours. Clearly opaque and low-gloss or peeled from the substrate were excluded from the evaluation.
“◯”: Gloss retention 80% or more “△”: Gloss retention 60% or more and less than 80% “X”: Gloss retention 60% or less
　３．２．８．耐汚染性
　上記「３．２．３．基材密着性」の評価で得られた塗膜につきＢｌａｃｋ　ＦＬＴＲ　Ｃｏｎｃ（大日精化工業株式会社製、カーボンブラック水分散液）を塗膜表面に均一に塗布し、すぐに３０℃オーブンにて３０分間乾燥した。その後水洗浄を行い、水分を乾燥により除去した後、目視で汚れの落ち具合を観察し、以下の３段階で評価した。なお、評価基準は以下の通りであり、その結果を表１に併せて示す。
「○」・・・塗膜の汚染が完全に除去できた。
「△」・・・塗膜の汚染が若干残留した。
「×」・・・塗膜の汚染が残留した。 3.2.8. Contamination resistance Black FLTR Conc (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black aqueous dispersion) is uniformly applied to the coating film surface with respect to the coating film obtained in the evaluation of “3.2.3. It was applied and immediately dried in a 30 ° C. oven for 30 minutes. After washing with water and removing moisture by drying, the degree of soiling was visually observed and evaluated in the following three stages. The evaluation criteria are as follows, and the results are also shown in Table 1.
“◯”: Contamination of the coating film was completely removed.
“B”: Some contamination of the coating film remained.
“×”: Contamination of the coating film remained.
　３．２．９．評価結果
　実施例１～５、比較例１～４に係る含フッ素重合体粒子の合成に使用した（Ａ）単量体、（Ｂ）単量体及び（Ｃ）単量体の種類、使用量、評価結果を表１に示す。 3.2.9. Evaluation Results (A) Monomer, (B) Monomer, and (C) Monomer Types and Amounts Used for Synthesis of Fluoropolymer Particles According to Examples 1 to 5 and Comparative Examples 1 to 4 The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　３．３．含フッ素複合重合体粒子の合成
　３．３．１．実施例６
　メタクリル酸メチル２０質量部、アクリル酸２－エチルヘキシル３５質量部、アクリル酸５質量部、ジアセトンアクリルアミド５質量部、メタクリル酸２－ヒドロキシエチル５質量部、メタクリル酸シクロヘキシル３０質量部、アルキルベンゼンスルホン酸ナトリウム１質量部及び水５０質量部を乳化混合した単量体分散液を準備した。容量７リットルのセパラブルフラスコの内部を窒素雰囲気にして、上記で製造した含フッ素重合体粒子Ａ－１を含有する分散液１００質量部（固形分濃度）と、過硫酸ナトリウム０．３質量部とを混合し、７５℃まで昇温させた。その後、上述の単量体分散液を３時間かけて連続的に添加した後、反応液をさらに８５℃～９５℃で２時間維持した後、２５℃まで冷却した。 3.3. Synthesis of fluorine-containing composite polymer particles 3.3.1. Example 6
20 parts by weight of methyl methacrylate, 35 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of acrylic acid, 5 parts by weight of diacetone acrylamide, 5 parts by weight of 2-hydroxyethyl methacrylate, 30 parts by weight of cyclohexyl methacrylate, sodium alkylbenzene sulfonate A monomer dispersion prepared by emulsifying 1 part by mass and 50 parts by mass of water was prepared. The inside of a 7-liter separable flask was put in a nitrogen atmosphere, and 100 parts by mass (solid content concentration) of the dispersion containing the fluoropolymer particles A-1 produced above and 0.3 parts by mass of sodium persulfate And heated up to 75 ° C. Thereafter, the above monomer dispersion was continuously added over 3 hours, and the reaction solution was further maintained at 85 ° C. to 95 ° C. for 2 hours, and then cooled to 25 ° C.
　次に、１０％アンモニア水を添加して反応液のｐＨを８．０に調整した後、さらにメチルトリエトキシシラン３０質量部を添加し、約３０分間激しく攪拌した。その後、反応液を７０℃に昇温し、３時間加熱することにより、含フッ素複合重合体粒子の水性分散体を得た。その後、回収した水性分散体にＳＮデフォーマー１１３（サンノプコ株式会社製、消泡剤）を０．１質量部、ロシマ５４１（ローム・アンド・ハース・ジャパン製、防腐剤）を０．１５質量部、アジピン酸ジヒドラジド３５質量％水溶液７質量部を添加し、さらに約３０分間撹拌を行った。この水性分散体においては凝固物の発生は観察されず、また、長時間放置したところ、分散粒子の分離もなく、安定した分散状態を維持し得ることが確認された。得られた水性分散体を試料として、動的光散乱法を測定原理とする粒度分布測定装置を用いて平均粒子径を測定したところ、平均粒子径は１０４ｎｍであった。 Next, 10% aqueous ammonia was added to adjust the pH of the reaction solution to 8.0, and 30 parts by mass of methyltriethoxysilane was further added and stirred vigorously for about 30 minutes. Then, the reaction liquid was heated to 70 ° C. and heated for 3 hours to obtain an aqueous dispersion of fluorine-containing composite polymer particles. Then, 0.1 mass part of SN deformer 113 (manufactured by Sannopco, defoaming agent), 0.15 mass part of roshima 541 (manufactured by Rohm and Haas Japan, antiseptic), 7 parts by mass of an adipic acid dihydrazide 35% by mass aqueous solution was added, and the mixture was further stirred for about 30 minutes. In this aqueous dispersion, no coagulated product was observed, and it was confirmed that a stable dispersion state could be maintained without separation of the dispersed particles when left for a long time. Using the obtained aqueous dispersion as a sample, the average particle size was measured using a particle size distribution measuring apparatus based on the dynamic light scattering method, and the average particle size was 104 nm.
　３．３．２．実施例７～１８
　上記実施例６と同様の方法で、表２に示した成分を用いて重合を行ない、実施例７～１８に係る含フッ素複合重合体粒子の水性分散体を作製した。また、実施例６と同様にして平均粒子径を測定した。その結果を表２に併せて示す。 3.3.2. Examples 7-18
Polymerization was carried out using the components shown in Table 2 in the same manner as in Example 6 to prepare aqueous dispersions of fluorine-containing composite polymer particles according to Examples 7 to 18. Further, the average particle size was measured in the same manner as in Example 6. The results are also shown in Table 2.
　３．４．含フッ素複合重合体粒子の評価方法及び結果
　３．４．１．耐候性
　予め水性エポキシ下塗り材を塗布し１２０℃で焼成しておいた硬質アルミ基材上に、上記で得られた含フッ素複合重合体粒子の水性分散体１００質量部（固形分換算）とテキサノール１０質量部の混合液をギャップ値２００μｍのアプリケーターを用いて塗布し、常温（２５℃）下で１週間放置し成膜した。 3.4. Evaluation method and results of fluorine-containing composite polymer particles 3.4.1. Weather resistance 100 parts by mass (in terms of solid content) of an aqueous dispersion of the fluorine-containing composite polymer particles obtained above on a hard aluminum base previously coated with an aqueous epoxy primer and fired at 120 ° C. and texanol 10 parts by mass of the mixed solution was applied using an applicator having a gap value of 200 μm, and was allowed to stand at room temperature (25 ° C.) for 1 week to form a film.
　得られた塗膜に対してメタルウェザー（ダイプラ・ウィンテス製）により促進耐候性試験５００ｈｒを行い、塗膜の６０°光沢を測定し光沢保持率（試験後の光沢／試験前の光沢；％）を算出した。試験条件は、照射（６３℃５０％ＲＨ下で７５ｍＷ／ｃｍ２）４ｈｒと暗黒（３０℃９８％ＲＨ）４ｈｒのサイクル条件とした。明らかに不透明で低光沢のものや、基材から剥離したものは評価対象外とした。なお、評価基準は以下の通りであり、その結果を表２に示した。
・光沢保持率が８０％以上のとき、耐候性は良好であると判断。
・光沢保持率が６０％以上８０％未満のとき、耐候性はやや良好であると判断。
・光沢保持率が６０％未満のとき、耐候性は不良であると判断。 The obtained coating film was subjected to an accelerated weather resistance test for 500 hours using a metal weather (Daipura Wintes), and the 60 ° gloss of the coating film was measured to obtain a gloss retention (gloss after test / gloss before test;%) Was calculated. The test conditions were cycle conditions of irradiation (75 mW / cm 2 under 63 ° C. and 50% RH) for 4 hours and dark (30 ° C. and 98% RH) for 4 hours. Clearly opaque and low-gloss or peeled from the substrate were excluded from the evaluation. The evaluation criteria are as follows, and the results are shown in Table 2.
When the gloss retention is 80% or more, it is judged that the weather resistance is good.
When the gloss retention is 60% or more and less than 80%, the weather resistance is judged to be slightly good.
When the gloss retention is less than 60%, the weather resistance is judged to be poor.
　３．４．２．密着性
　上記で得られた含フッ素複合重合体粒子の水性分散体をガラス上にギャップ値２００μｍのアプリケーターを用いて塗布し、常温（２５℃）で１週間放置し製膜した。得られた塗膜をカッターで１ｍｍ角にクロスカット（５×５の２５マス）し、ニチバン製セロテープ（登録商標）を用いた密着試験を行って下記基準で評価した。なお、評価基準は以下の通りであり、その結果を表２に示した。
・塗膜の剥離が無い場合には、密着性は良好であると判断して「○」
・塗膜の剥離が半数未満の場合には、密着性はやや良好であると判断して「△」
・塗膜の剥離が半数以上の場合には、密着性は不良であると判断して「×」 3.4.2. Adhesiveness The aqueous dispersion of the fluorine-containing composite polymer particles obtained above was applied onto glass using an applicator having a gap value of 200 μm, and allowed to stand at room temperature (25 ° C.) for 1 week to form a film. The obtained coating film was cut into 1 mm square with a cutter (5 × 5 25 squares), and an adhesion test using Nichiban cello tape (registered trademark) was performed and evaluated according to the following criteria. The evaluation criteria are as follows, and the results are shown in Table 2.
・ If there is no peeling of the coating film, it is judged that the adhesion is good, and
・ If less than half of the films are peeled off, it is judged that the adhesion is slightly good, and “△”
・ If peeling of the coating film is more than half, it is judged that the adhesion is poor and “×”
　３．４．３．耐汚染性
　予め水性エポキシ下塗り材を塗布し１２０℃で焼成しておいた硬質アルミ基材上に、上記で得られた含フッ素複合重合体粒子１００質量部（固形分換算）とテキサノール１０質量部の混合液をギャップ値（ウェット膜厚）２００μｍのアプリケーターを用いて塗布し、常温（２５℃）下で１週間放置し成膜した。 3.4.3. Contamination resistance 100 parts by mass (converted to solid content) of the fluorinated composite polymer particles obtained above and 10 parts by mass of texanol on a hard aluminum base material previously coated with an aqueous epoxy primer and fired at 120 ° C Was applied using an applicator having a gap value (wet film thickness) of 200 μm, and was allowed to stand at room temperature (25 ° C.) for 1 week to form a film.
　Ｂｌａｃｋ　ＦＬＴＲ　Ｃｏｎｃ（大日精化工業株式会社製、カーボンブラック水分散液）を塗膜表面に均一に塗布し、すぐに３０℃オーブンにて３０分間乾燥した。その後水洗浄を行い、水分を乾燥により除去した後、目視で汚れの落ち具合を観察し、以下の３段階で評価した。なお、評価基準は以下の通りであり、その結果を表２に示した。
・塗膜の汚染が完全に除去できた場合には、耐汚染性は良好であると判断して「○」
・塗膜の汚染が若干残留する場合には、耐汚染性はやや良好であると判断して「△」
・塗膜の汚染が残留する場合には、耐汚染性は不良であると判断して「×」 Black FLTR Conc (manufactured by Dainichi Seika Kogyo Co., Ltd., carbon black aqueous dispersion) was uniformly applied to the surface of the coating film, and immediately dried in an oven at 30 ° C. for 30 minutes. After washing with water and removing moisture by drying, the degree of soiling was visually observed and evaluated in the following three stages. The evaluation criteria are as follows, and the results are shown in Table 2.
・ If the contamination of the coating is completely removed, it is judged that the stain resistance is good, and “○”
・ If the coating film remains slightly contaminated, it is judged that the stain resistance is slightly good, and "△"
・ If the paint film remains contaminated, it is judged that the stain resistance is poor.
　３．４．４．耐水性
　ガラス基板上に、上記で得られた含フッ素複合重合体粒子の水性分散体１００質量部（固形分換算）とテキサノール１質量部の混合液をギャップ値２００μｍのアプリケーターを用いて塗布し、８０℃オーブンで２時間乾燥させた。作製した塗膜付のガラス板を５０℃温水中に２４時間浸漬した後の塗膜の膨れの程度を目視にて観察し、塗膜の膨れを評価した。なお、評価基準は以下の通りであり、その結果を表２に示した。
・塗膜の膨れが認められない場合には、耐水性は良好であると判断して「○」
・塗膜の膨れが僅かに認められる場合には、耐水性はやや良好であると判断して「△」
・塗膜の膨れが大幅に求められる場合には、耐水性は不良であると判断して「×」 3.4.4. On a water-resistant glass substrate, a mixture of 100 parts by mass (in terms of solid content) of the aqueous dispersion of fluorine-containing composite polymer particles obtained above and 1 part by mass of texanol was applied using an applicator having a gap value of 200 μm, It was dried in an 80 ° C. oven for 2 hours. The degree of swelling of the coated film after the produced coated glass plate was immersed in warm water at 50 ° C. for 24 hours was visually observed to evaluate the swelling of the coated film. The evaluation criteria are as follows, and the results are shown in Table 2.
・ If no swelling of the coating is observed, it is judged that the water resistance is good and “○”
・ If swelling of the coating is slightly observed, it is judged that the water resistance is slightly good and “△”.
・ If blistering of the coating is greatly required, it is judged that the water resistance is poor and “×”
　また、光沢保持率は、上述の目視観察後の塗膜を村上式光沢計ＧＭ－２６ＰＲＯ／Ａｕｔｏ（６０°）により評価し、初期値との比で算出した。なお、評価基準は以下の通りであり、その結果を表２に併せて示した。
・光沢保持率が８０％以上のとき、光沢保持率は良好であると判断。
・光沢保持率が６０％以上８０％未満のとき、光沢保持率はやや良好であると判断。
・光沢保持率が６０％未満のとき、光沢保持率は不良であると判断。 The gloss retention was calculated by evaluating the coating film after the above-mentioned visual observation with a Murakami gloss meter GM-26PRO / Auto (60 °) and a ratio with the initial value. The evaluation criteria are as follows, and the results are also shown in Table 2.
-When the gloss retention is 80% or more, the gloss retention is determined to be good.
When the gloss retention rate is 60% or more and less than 80%, the gloss retention rate is judged to be slightly good.
When the gloss retention rate is less than 60%, it is determined that the gloss retention rate is poor.
　３．４．５．評価結果
　実施例６～１８に係る含フッ素複合重合体粒子の水性分散体の合成に使用した（Ｄ）単量体及び（Ｅ）単量体の種類、使用量、評価結果を表２に示す。 3.4.5. Evaluation Results Table 2 shows the types and amounts of (D) monomer and (E) monomer used for the synthesis of the aqueous dispersions of fluorine-containing composite polymer particles according to Examples 6 to 18, and the evaluation results. .
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例６～１８によれば、基材密着性に優れ、かつ、耐候性、耐汚染性及び耐水性が良好な塗膜を形成できることが判明した。含フッ素複合重合体粒子を合成する際に（Ｅ）単量体を使用していない実施例７では、（Ｅ）単量体を使用している実施例６に比べて、耐候性の低下や耐水性評価において光沢保持率の低下や膨れが認められた。なお、実施例１５と実施例１６との間にも同様の傾向が認められた。これらのことから、含フッ素複合重合体粒子を合成する際に（Ｅ）単量体を使用することで、耐候性や耐水性が向上することが示された。 According to Examples 6 to 18, it was found that it was possible to form a coating film having excellent substrate adhesion and good weather resistance, stain resistance and water resistance. In Example 7 in which the (E) monomer is not used when the fluorine-containing composite polymer particles are synthesized, the weather resistance is reduced as compared to Example 6 in which the (E) monomer is used. In the water resistance evaluation, a decrease in gloss retention and swelling were observed. In addition, the same tendency was recognized between Example 15 and Example 16. From these facts, it was shown that weather resistance and water resistance were improved by using the monomer (E) when synthesizing the fluorine-containing composite polymer particles.
　以上の結果から明らかなように、実施例６～１８に示した本発明に係る含フッ素複合重合体粒子の水性分散体は、基材密着性に優れ、かつ、耐候性、耐汚染性及び耐水性が良好な塗膜を形成できることから、各種塗料のほか、電着塗装、繊維処理材、紙加工材、床塗布材等に好適に利用することができる。 As is clear from the above results, the aqueous dispersions of the fluorine-containing composite polymer particles according to the present invention shown in Examples 6 to 18 are excellent in substrate adhesion, and have weather resistance, stain resistance and water resistance. In addition to various paints, it can be suitably used for electrodeposition coating, fiber treatment material, paper processing material, floor coating material, and the like.
　本発明は、上記の実施形態に限定されるものではなく、種々の変形が可能である。本発明は、実施形態で説明した構成と実質的に同一の構成（例えば、機能、方法及び結果が同一の構成、あるいは目的及び効果が同一の構成）を包含する。また本発明は、上記の実施形態で説明した構成の本質的でない部分を他の構成に置き換えた構成を包含する。さらに本発明は、上記の実施形態で説明した構成と同一の作用効果を奏する構成又は同一の目的を達成することができる構成をも包含する。さらに本発明は、上記の実施形態で説明した構成に公知技術を付加した構成をも包含する。 The present invention is not limited to the above embodiment, and various modifications can be made. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention includes a configuration that achieves the same effect as the configuration described in the above embodiment or a configuration that can achieve the same object. Furthermore, the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

Claims (11)

  1. 　全単量体の合計量を１００モル％としたときに、
    　（Ａ）フッ素原子を有する単量体１０～９９モル％、
    　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体１～９０モル％、
    　（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体１５モル％以下、
    を重合してなることを特徴とする、含フッ素重合体。     When the total amount of all monomers is 100 mol%,
    (A) 10 to 99 mol% of a monomer having a fluorine atom,
    (B) 1 to 90 mol% of a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group,
    (C) 15 mol% or less of monomers other than the component (A) and the component (B),
    A fluoropolymer characterized by being polymerized.
  2. 　全繰り返し単位１００モル％中、
    　（Ａ）フッ素原子を有する単量体に由来する繰り返し単位１０～９９モル％と、
    　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体に由来する繰り返し単位１～９０モル％と、
    　（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体に由来する繰り返し単位１５モル％以下と、
    を含有することを特徴とする、含フッ素重合体。     In 100 mol% of all repeating units,
    (A) 10 to 99 mol% of repeating units derived from a monomer having a fluorine atom;
    (B) 1 to 90 mol% of repeating units derived from a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group;
    (C) 15 mol% or less of repeating units derived from monomers other than the component (A) and the component (B);
    A fluorine-containing polymer comprising:
  3. 　前記（Ａ）フッ素原子を有する単量体が、フッ化ビニリデン、テトラフルオロエチレンおよびヘキサフルオロプロピレンよりなる群から選択される少なくとも１種であることを特徴とする、請求項１または請求項２に記載の含フッ素重合体。 The monomer (A) having a fluorine atom is at least one selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene. The fluorine-containing polymer as described.
  4. 　前記（Ｃ）成分が、ケイ素を含まない、（メタ）アクリル酸エステル単量体、ビニルエーテル系単量体およびアリルエーテル系単量体よりなる群から選択される少なくとも１種であることを特徴とする、請求項１ないし請求項３のいずれか一項に記載の含フッ素重合体。 The component (C) is at least one selected from the group consisting of (meth) acrylic acid ester monomers, vinyl ether monomers and allyl ether monomers, which does not contain silicon. The fluorine-containing polymer according to any one of claims 1 to 3.
  5. 　請求項１ないし請求項４のいずれか一項に記載の含フッ素重合体が水性媒体に分散されていることを特徴とする、含フッ素重合体水性分散体。 A fluorine-containing polymer aqueous dispersion, wherein the fluorine-containing polymer according to any one of claims 1 to 4 is dispersed in an aqueous medium.
  6. 　請求項１ないし請求項４のいずれか一項に記載の含フッ素重合体の存在下で、
    　さらに（Ｄ）エチレン性不飽和基を有する単量体を反応させて得られることを特徴とする、含フッ素重合体水性分散体。     In the presence of the fluoropolymer according to any one of claims 1 to 4,
    Furthermore, (D) a fluoropolymer aqueous dispersion obtained by reacting a monomer having an ethylenically unsaturated group.
  7. 　前記含フッ素重合体１００質量部に対して、前記（Ｄ）エチレン性不飽和基を有する単量体を２０～２０００質量部反応させることを特徴とする、請求項６に記載の含フッ素重合体水性分散体。 The fluorine-containing polymer according to claim 6, wherein 20 to 2000 parts by mass of the monomer (D) having an ethylenically unsaturated group is reacted with 100 parts by mass of the fluorine-containing polymer. Aqueous dispersion.
  8. 　請求項１ないし請求項４のいずれか一項に記載の含フッ素重合体の存在下で、前記（Ｄ）エチレン性不飽和基を有する単量体を反応させる際もしくは反応させた後に、さらに（Ｅ）アルコキシシランを反応させて得られることを特徴とする、請求項６または請求項７に記載の含フッ素重合体水性分散体。 In the presence of the fluoropolymer according to any one of claims 1 to 4, when (D) the monomer having an ethylenically unsaturated group is reacted or after the reaction, E) The fluoropolymer aqueous dispersion according to claim 6 or 7, which is obtained by reacting an alkoxysilane.
  9. 　全単量体の合計量を１００モル％としたときに、
    　（Ａ）フッ素原子を有する単量体１０～９９モル％と、
    　（Ｂ）加水分解性基および／または水酸基と結合したケイ素原子を有するシリル基を含有するビニル系単量体１～９０モル％と、
    　（Ｃ）前記（Ａ）成分および前記（Ｂ）成分以外の単量体１５モル％以下と、
    を水性媒体中で乳化重合させて含フッ素重合体を得る工程（ａ）を含む、含フッ素重合体水性分散体の製造方法。     When the total amount of all monomers is 100 mol%,
    (A) 10 to 99 mol% of a monomer having a fluorine atom;
    (B) 1 to 90 mol% of a vinyl monomer containing a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group,
    (C) 15 mol% or less of monomers other than the component (A) and the component (B),
    A method for producing an aqueous fluoropolymer dispersion, comprising the step (a) of emulsion-polymerizing an aqueous solution in an aqueous medium to obtain a fluoropolymer.
  10. 　さらに、前記含フッ素重合体１００質量部の存在下で、（Ｄ）エチレン性不飽和基を有する単量体２０～２０００質量部を反応させる工程（ｂ）を含む、請求項９に記載の含フッ素重合体水性分散体の製造方法。 10. The method according to claim 9, further comprising the step (b) of reacting 20 to 2000 parts by mass of a monomer having an ethylenically unsaturated group (D) in the presence of 100 parts by mass of the fluoropolymer. A method for producing an aqueous fluoropolymer dispersion.
  11. 　前記工程（ｂ）と同時もしくはその後に、
    　さらに（Ｅ）アルコキシシラン１～３００質量部を反応させる工程（ｃ）を含む、請求項１０に記載の含フッ素重合体水性分散体の製造方法。     Simultaneously with or after the step (b),
    The method for producing an aqueous fluoropolymer dispersion according to claim 10, further comprising (E) a step (c) of reacting 1 to 300 parts by mass of alkoxysilane.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189390A1 (en) * 2018-03-30 2019-10-03 ダイキン工業株式会社 Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion
EP3990542A4 (en) * 2019-06-25 2023-07-19 Arkema, Inc. Hybrid functional fluoropolymers
EP3991239A4 (en) * 2019-06-25 2024-03-27 Arkema Inc Coated separator with fluoropolymers for lithium ion battery

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6284137A (en) * 1985-10-09 1987-04-17 Dainippon Ink & Chem Inc Ambient temperature-curable resin composition
JPH05170909A (en) * 1991-12-20 1993-07-09 Japan Synthetic Rubber Co Ltd Production of aqueous dispersion of polymer particle
JPH07331115A (en) * 1994-06-10 1995-12-19 Toyo Ink Mfg Co Ltd Composition for antireflection film
JPH08120210A (en) * 1994-10-24 1996-05-14 Daikin Ind Ltd Aqueous dispersion of fluoropolymer
JPH0977829A (en) * 1995-09-08 1997-03-25 Toagosei Co Ltd Perhaloolefin copolymer and production of crosslinked molded form made therefrom
JP2000313725A (en) * 1999-03-04 2000-11-14 Kanto Denka Kogyo Co Ltd Fluorine-containing copolymer and its production
JP2001163927A (en) * 1999-12-07 2001-06-19 Kanto Denka Kogyo Co Ltd Fluorine-containing copolymer and method for manufacturing same
JP2001217010A (en) * 2000-02-01 2001-08-10 Reiko Udagawa Polymer electrolyte and lithium ion secondary battery using the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6284137A (en) * 1985-10-09 1987-04-17 Dainippon Ink & Chem Inc Ambient temperature-curable resin composition
JPH05170909A (en) * 1991-12-20 1993-07-09 Japan Synthetic Rubber Co Ltd Production of aqueous dispersion of polymer particle
JPH07331115A (en) * 1994-06-10 1995-12-19 Toyo Ink Mfg Co Ltd Composition for antireflection film
JPH08120210A (en) * 1994-10-24 1996-05-14 Daikin Ind Ltd Aqueous dispersion of fluoropolymer
JPH0977829A (en) * 1995-09-08 1997-03-25 Toagosei Co Ltd Perhaloolefin copolymer and production of crosslinked molded form made therefrom
JP2000313725A (en) * 1999-03-04 2000-11-14 Kanto Denka Kogyo Co Ltd Fluorine-containing copolymer and its production
JP2001163927A (en) * 1999-12-07 2001-06-19 Kanto Denka Kogyo Co Ltd Fluorine-containing copolymer and method for manufacturing same
JP2001217010A (en) * 2000-02-01 2001-08-10 Reiko Udagawa Polymer electrolyte and lithium ion secondary battery using the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189390A1 (en) * 2018-03-30 2019-10-03 ダイキン工業株式会社 Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion
CN111989355A (en) * 2018-03-30 2020-11-24 大金工业株式会社 Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion
US20210070973A1 (en) * 2018-03-30 2021-03-11 Dai Kin Industries, Ltd. Aqueous dispersion, coating film, coated article, and method for producing aqueous dispersion
JP7046029B2 (en) 2018-03-30 2022-04-01 ダイキン工業株式会社 Aqueous dispersion, coating film and painted article, and method for producing aqueous dispersion
EP3990542A4 (en) * 2019-06-25 2023-07-19 Arkema, Inc. Hybrid functional fluoropolymers
EP3991239A4 (en) * 2019-06-25 2024-03-27 Arkema Inc Coated separator with fluoropolymers for lithium ion battery

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