WO2012036297A1 - Acryl-fluorine composite polymer particles, and aqueous dispersant - Google Patents

Acryl-fluorine composite polymer particles, and aqueous dispersant Download PDF

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Publication number
WO2012036297A1
WO2012036297A1 PCT/JP2011/071394 JP2011071394W WO2012036297A1 WO 2012036297 A1 WO2012036297 A1 WO 2012036297A1 JP 2011071394 W JP2011071394 W JP 2011071394W WO 2012036297 A1 WO2012036297 A1 WO 2012036297A1
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Prior art keywords
acrylic
unit
mass
polymer particles
composite polymer
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PCT/JP2011/071394
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French (fr)
Japanese (ja)
Inventor
良成 福原
真由美 飯田
井本　克彦
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ダイキン工業株式会社
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Priority to CN201180030705.2A priority Critical patent/CN102959000B/en
Publication of WO2012036297A1 publication Critical patent/WO2012036297A1/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
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of 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
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate

Definitions

  • the present invention relates to acrylic-fluorine composite polymer particles comprising a vinylidene fluoride (VDF) -based polymer portion and an acrylic polymer portion that is stable against light (particularly ultraviolet rays), an aqueous dispersion comprising the same, and
  • VDF vinylidene fluoride
  • the present invention relates to an aqueous coating composition containing the aqueous dispersion.
  • Fluoropolymer-containing paints are used for exterior coatings of buildings and various vehicles in order to give a coating film excellent in weather resistance, water resistance, chemical resistance, heat resistance and the like.
  • the fluororesin is more expensive than the acrylic resin and the urethane resin, the situation where it is applied is limited at present.
  • Patent Document 1 a method of copolymerizing a fluorine-containing monomer and a reactive light stabilizer
  • Patent Document 2 a radically polymerizable unsaturated monomer in an aqueous dispersion of fluororesin particles
  • Patent Document 3 A method of copolymerizing a monomer having an ultraviolet absorption site or a monomer having a light stabilization site when seed polymerizing the monomer (Patent Document 3) can be mentioned.
  • Patent Document 1 has a drawback in that the reaction process is complicated because it is necessary to add a reactive double bond to the fluororesin having a hydroxyl group with a urethane bond.
  • the present invention is a fluororesin that can significantly reduce the fluorine content and can form a coating film excellent in weather resistance even if the cost is greatly reduced, and can suppress a decrease in gloss of the resulting coating film.
  • An object of the present invention is to provide acrylic-fluorine composite polymer particles suitable for water-based paints.
  • the present invention provides a vinylidene fluoride system comprising (A) at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit as a structural unit and a vinylidene fluoride unit.
  • the present invention relates to an acrylic-fluorine composite polymer particle containing an acrylic polymer part containing, wherein the vinylidene fluoride polymer part (A) content is 50% by mass or less.
  • the present invention also relates to vinylidene fluoride polymer particles comprising at least one fluoroolefin unit selected from the group consisting of tetrafluoroethylene units, hexafluoropropylene units and chlorotrifluoroethylene units as structural units and vinylidene fluoride units.
  • an aqueous dispersion containing 100 parts by mass, an (meth) acrylic monomer and an ethylenically unsaturated group-containing monomer having an ultraviolet absorption site or an ethylenically unsaturated group-containing monomer having a light stabilization site Aqueous dispersion of acrylic-fluorine composite polymer particles having a vinylidene fluoride polymer portion content of 50% by mass or less, wherein 100 parts by mass or more of the acrylic monomer mixture containing is subjected to emulsion polymerization It also relates to the manufacturing method.
  • the present invention also relates to an aqueous dispersion containing the acrylic-fluorine composite polymer particles of the present invention, and further to an aqueous coating composition containing the aqueous dispersion.
  • the cost can be reduced and a coating film having excellent weather resistance can be formed. It is possible to provide a fluororesin water-based paint capable of suppressing the decrease in the temperature.
  • the acrylic-fluorine composite polymer particle of the present invention includes a vinylidene fluoride (VDF) polymer part (A) and an acrylic polymer part (B), and the content of the VDF polymer part (A) Is 50 mass% or less. Since the acrylic-fluorine composite polymer particles of the present invention have a VDF polymer portion (A) content of 50% by mass or less, a coating film having excellent weather resistance can be formed. Further, when the acrylic-fluorine composite polymer particles are used as a clear paint, discoloration of the base paint can be prevented.
  • VDF vinylidene fluoride
  • the acrylic polymer portion (B) When the content of the VDF polymer portion (A) in the acrylic-fluorine composite polymer particles exceeds 50% by mass, the acrylic polymer portion (B) has an ethylenically unsaturated group having an ultraviolet absorption site or a light stabilization site. Even if it contains a containing monomer unit, a coating film showing excellent weather resistance cannot be formed. Further, when acrylic-fluorine composite polymer particles are used as a clear paint, discoloration of the base paint cannot be prevented.
  • the VDF polymer part (A) has at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene (TFE) unit, a hexafluoropropylene (HFP) unit and a chlorotrifluoroethylene (CTFE) unit as a structural unit. As well as VDF units.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • CTFE chlorotrifluoroethylene
  • fluoroolefin units such as vinyl fluoride, trifluoroethylene and perfluoro (alkyl vinyl ether); olefin units such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE) and cyclohexyl vinyl ether (CHVE) , Vinyl ether units such as hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; alkenyl units such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether Vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9 ( Manufactured by E Le Co.), VeoVa10 (manufactured by Shell Co.) vinyl ester units, such as;
  • the copolymer composition constituting the preferred VDF polymer portion includes, for example, a VDF / HFP copolymer, a VDF / TFE / HFP copolymer, a VDF / CTFE copolymer, a VDF / TFE / PAVE copolymer, Examples thereof include VDF / TFE / CTFE copolymers.
  • VDF is contained in the polymer in an amount of 50 mol% or more from the viewpoint of good affinity with the non-fluorine monomer constituting the acrylic polymer portion (B).
  • a VDF / TFE / CTFE copolymer is preferable from the viewpoint of good weather resistance and durability.
  • the molecular weight of the VDF polymer part (A) is 1,000,000 or less, more preferably 200,000 or less, especially 100,000 or less in terms of number average molecular weight, which constitutes the acrylic polymer part (B).
  • those having 1,000 or more, more preferably 4,000 or more, and particularly 5,000 or more are preferred in terms of excellent weather resistance and durability.
  • the acrylic polymer part (B) is an ethylenically unsaturated group-containing monomer unit having a (meth) acrylic monomer unit and an ethylenically unsaturated group-containing monomer unit having an ultraviolet absorption site or a light stabilizing site. Includes units.
  • the acrylic polymer part (B) may contain both an ethylenically unsaturated group-containing monomer unit and an ethylenically unsaturated group-containing monomer unit having a light stabilizing site.
  • Preferred examples of the (meth) acrylic monomer include acrylic acid, an alkyl acrylate ester having an alkyl group having 1 to 18 carbon atoms, and an alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms. .
  • alkyl acrylate ester having 1 to 18 carbon atoms in the alkyl group examples include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, Examples thereof include t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like.
  • alkyl methacrylate having 1 to 18 carbon atoms in the alkyl group examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, Examples thereof include t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butyl cyclohexyl methacrylate, stearyl methacrylate, and lauryl methacrylate.
  • acrylic acid or methacrylic acid hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate
  • Silanol group-containing monomers such as ⁇ -trimethoxysilane methacrylate and ⁇ -triethoxysilane methacrylate
  • Amide compounds such as N-methylmethacrylamide and N-butoxymethylmethacrylamide
  • aldehyde group-containing monomers such as acrolein
  • copolymerizing acrylonitrile and the like May be.
  • polyfunctional monomers such as ethylene glycol dimethacrylate and propylene glycol dimethacrylate can be copolymerized for the purpose of improving solvent resistance and water resistance.
  • methyl methacrylate and (meth) acrylic having an alkyl group having 4 to 10 carbon atoms are particularly preferred. Acid alkyl esters and acrylic acid are preferred, and methyl methacrylate, butyl acrylate and acrylic acid are more preferred.
  • the acrylic polymer part (B) contains a methyl methacrylate unit, a butyl acrylate unit, and an acrylic acid unit, a coating film excellent in adhesion can be formed, thickening, and film-forming properties. Is preferable from the viewpoint of good. If the acrylic polymer portion (B) does not contain a butyl acrylate unit, a coating film may not be formed.
  • the acrylic polymer part (B) contains 25 to 65% by mass of a methyl methacrylate unit, and even if the content of the vinylidene fluoride copolymer part (A) is 50% by mass or less, it has high film-forming properties. Is preferable.
  • the (meth) acrylic acid alkyl ester those having an alkyl group having 1 to 18 carbon atoms have a high structure even if the content of the vinylidene fluoride copolymer portion (A) is 50% by mass or less. It is preferable because film properties can be obtained.
  • the acrylic polymer portion (B) preferably contains an alkyl acrylate unit having 2 to 4 carbon atoms in the alkyl group.
  • the content of the (meth) acrylic monomer unit in the acrylic polymer part (B) is preferably 80 to 99% by mass in the acrylic polymer part (B).
  • the amount is less than 80% by mass, the gloss and hardness of the coating film tend to decrease.
  • the amount exceeds 99% by mass the adhesion to the base tends to decrease.
  • a more preferable content is 90% by mass or more, particularly 95% by mass or more, and 98% by mass or less.
  • a plurality of (meth) acrylic monomers may be used.
  • methyl methacrylate is used as one of a plurality of (meth) acrylic monomers, methyl methacrylate units are included in the acrylic polymer (B). Is preferably contained in an amount of 25 to 65% by mass from the viewpoint of good coating film hardness.
  • Examples of the ethylenically unsaturated group-containing monomer having an ultraviolet absorption site include RUVA93 (manufactured by Otsuka Chemical Co., Ltd.), a cyanoacrylate, which is a methacrylate having a benzotriazole type ultraviolet absorption site. it can.
  • methacrylic acid esters and acrylics of ultraviolet absorbers obtained by reaction of known ultraviolet absorbers containing hydroxyl groups such as benzophenone, benzotriazole, and triazine with acid halides such as methacrylic acid chloride and acrylic acid chloride. Acid esters can also be mentioned. These may be used alone or in combination of two or more.
  • the ultraviolet absorbing site is preferably a site having a benzotriazole-based hydroxyl group.
  • Examples of the ethylenically unsaturated group-containing monomer having a light stabilizing site include Adeka Stub LA82 (Asahi Denka Kogyo Co., Ltd.), Adeka Stub LA87 (Asahi Denka Kogyo Co., Ltd.), etc. Mention may also be made of esters of stabilizers with methacrylic acid and acrylic acid. These may be used alone or in combination of two or more.
  • the content of the ethylenically unsaturated group-containing monomer having an ultraviolet absorption site and a light stabilization site in the acrylic polymer portion (B) is preferably 0.1 to 30% by mass in the acrylic-fluorine composite polymer particles. . If the amount is less than 0.1% by mass, the ultraviolet absorption effect and the light stabilizing effect tend not to be sufficiently exhibited. If the amount exceeds 30% by mass, a paint to which the obtained fluororesin aqueous dispersion is applied is used. When a coating film is formed by using it, the transparency of the coating film is lost, and the gloss of the pigment-dispersed coating film tends to decrease. A more preferable content is 0.3% by mass or more, 10% by mass or less, and further 5% by mass or less.
  • the acrylic polymer part (B) includes other ethylenically unsaturated group-containing monomer units, for example, ⁇ -olefins such as ethylene, propylene, and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), vinyl ethers such as butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, Vinyl esters such as vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9, VEOVA10 (manufactured by Shell); maleic acid, Water itaconic acid, succinic anhydride, ethylenically unsaturated carboxy
  • the content of the VDF polymer portion (A) is 50% by mass or less.
  • the fluorine content of the entire composite polymer particle can be reduced to, for example, 25% by mass or less.
  • the content of the preferred VDF polymer part (A) is 40% by mass or less.
  • the advantage of the fluororesin is obtained even if an ethylenically unsaturated group-containing monomer unit having an ultraviolet absorption site or a light stabilization site is introduced. Since the weather resistance and chemical resistance are reduced, it is preferably 30% by mass or more, and more preferably 35% by mass or more.
  • components that may impair water resistance and gloss of the coating film are not included as structural units or modified components.
  • components that may impair the water resistance and gloss of the coating film include reactive emulsifiers used as an emulsifier during emulsion polymerization in Patent Document 3, for example.
  • the use of a reactive emulsifier is not necessarily prohibited, but when used, it should be an amount that does not significantly impair the water resistance and gloss of the coating film.
  • the acrylic-fluorine composite polymer particles of the present invention can reduce the fluorine content by reducing the content of the VDF polymer part (A), and can keep the production cost low.
  • a coating film excellent in weather resistance can be formed, and a decrease in gloss of the resulting coating film can be suppressed.
  • the reactive emulsifier residue is not included, a coating film exhibiting high water resistance can be formed even when the fluorine content is low, and a decrease in gloss of the obtained coating film can be suppressed.
  • the acrylic polymer part (B) preferably does not contain a reactive emulsifier unit.
  • the acrylic-fluorine composite polymer particles of the present invention can be produced, for example, in the form of an aqueous dispersion by the following method of the present invention.
  • the method for producing an aqueous dispersion of acrylic-fluorine composite polymer particles having a VDF polymer content of 50% by mass or less is selected from the group consisting of TFE units, HFP units and CTFE units as structural units.
  • a monomer containing an ethylenically unsaturated group having a (meth) acrylic monomer and an ultraviolet absorbing site 100 parts by mass or more of an acrylic monomer mixture containing a monomer or an ethylenically unsaturated group-containing monomer having a light stabilizing site is used for emulsion polymerization.
  • the method for producing an aqueous dispersion of acrylic-fluorine composite polymer particles in which the content of the VDF polymer of the present invention is 50% by mass or less is selected from the group consisting of TFE units, HFP units and CTFE units as structural units.
  • an aqueous dispersion containing VDF polymer particles containing at least one selected fluoroolefin unit and VDF unit 100 parts by mass or more of (meth) acrylic single unit with respect to 100 parts by mass of VDF polymer particles.
  • a monomer and an ethylenically unsaturated group-containing monomer having an ultraviolet absorption site or an acrylic monomer mixture containing an ethylenically unsaturated group-containing monomer having a light stabilization site is subjected to emulsion polymerization. To do.
  • VDF polymer used in the production method of the present invention (meth) acrylic monomer, ethylenically unsaturated group-containing monomer having an ultraviolet absorption site, ethylenically unsaturated group-containing monomer having a light stabilization site
  • acrylic monomer ethylenically unsaturated group-containing monomer having an ultraviolet absorption site
  • acrylic-fluorine composite polymer particles ethylenically unsaturated group-containing monomer having a light stabilization site
  • (Meth) acrylic monomers are preferably methyl methacrylate, butyl acrylate and acrylic acid. The reason is that an aqueous dispersion capable of forming a coating film with excellent adhesion was obtained, and there was little risk of thickening when preparing a coating composition from the obtained aqueous dispersion, and the coating was applied. In this case, an aqueous dispersion having excellent film forming properties can be obtained. Further, when acrylic-fluorine composite polymer particles are used as a clear paint, it is preferable from the viewpoint that discoloration of the base paint can be prevented.
  • the particle size of the VDF polymer particles is closely related to the average particle size of the acrylic-fluorine composite polymer particles.
  • the average particle size of the acrylic-fluorine composite polymer particles is preferably 100 to 200 nm.
  • An aqueous dispersion of VDF polymer particles can be obtained by an ordinary emulsion polymerization method. Specifically, for example, a known method described in Japanese Patent Application Laid-Open No. 08-67795 can be employed. After adjusting the solid content concentration of the resulting aqueous dispersion to usually 30 to 60% by mass, the acrylic monomer mixture is polymerized using an emulsifier. This polymerization mode is called seed polymerization using VDF polymer particles as seed particles.
  • the emulsifier a non-reactive emulsifier is preferable because a coating film having high glossiness and excellent weather resistance and water resistance can be obtained.
  • Seed polymerization of the acrylic monomer mixture is a known method, for example, a method in which the whole amount of the acrylic monomer mixture is charged into the reaction system in the presence of VDF polymer particles, and the acrylic monomer mixture. After charging and reacting a part of the mixture, the rest can be continuously or dividedly charged, or the entire amount of the acrylic monomer mixture can be continuously charged.
  • the polymerization method by continuous charging is preferable from the viewpoint of good water resistance.
  • the polymerization conditions for the seed polymerization are the same as those for normal emulsion polymerization.
  • a non-reactive emulsifier, a polymerization initiator, a chain transfer agent, in some cases a chelating agent, a pH adjuster, etc. are added to an aqueous medium containing VDF polymer particles, and the temperature is 0 to 10 ° C. Polymerization is possible by carrying out the reaction for 5 to 6 hours.
  • an anionic emulsifier and a nonionic emulsifier may be used alone or in combination.
  • an amphoteric emulsifier can be used.
  • anionic emulsifiers examples include hydrocarbon anionic emulsifiers such as higher alcohol sulfates, alkylsulfonic acid sodium salts, alkylbenzenesulfonic acid sodium salts, succinic acid dialkylester sulfonic acid sodium salts, and alkyldiphenyl ether disulfonic acid sodium salts; Fluorine-containing anionic emulsifiers such as carboxylates, fluoroalkyl sulfonates, and fluoroalkyl sulfates can be mentioned.
  • hydrocarbon anionic emulsifiers such as higher alcohol sulfates, alkylsulfonic acid sodium salts, alkylbenzenesulfonic acid sodium salts, succinic acid dialkylester sulfonic acid sodium salts, and alkyldiphenyl ether disulfonic acid sodium salts
  • Fluorine-containing anionic emulsifiers such as carboxylates, fluoroal
  • nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, glycerin esters, and derivatives thereof.
  • amphoteric emulsifiers include lauryl betaine.
  • the addition amount of the non-reactive emulsifier is 1.0% by mass or less, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and the lower limit is usually 0.05% by mass with respect to water. is there.
  • the emulsifier a so-called reactive emulsifier and a non-reactive emulsifier that can be copolymerized with a (meth) acrylic monomer or an ethylenically unsaturated group-containing monomer can be used in combination.
  • a reactive emulsifier is used alone, the water resistance and gloss of the coating film may be greatly impaired. Therefore, the reactive emulsifier is not used alone in the present invention. Even when used in combination with a non-reactive emulsifier, the amount should be such that the water resistance and gloss of the coating film are not significantly impaired.
  • the polymerization initiator used in the seed polymerization is not particularly limited as long as it can be used for a free radical reaction in an aqueous medium. In some cases, it can be used in combination with a reducing agent.
  • the water-soluble polymerization initiator that can be used include persulfate, hydrogen peroxide, and examples of the reducing agent include sodium pyrobisulfite, sodium hydrogensulfite, sodium L-ascorbate, and longgarit.
  • examples of the oil-soluble polymerization initiator include diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN), and the like.
  • the amount of the polymerization initiator used is usually 0.05 to 2.0 parts by mass per 100 parts by mass of the acrylic monomer mixture.
  • chain transfer agents examples include halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. Can do.
  • the amount of the chain transfer agent used is usually 0 to 5.0 parts by mass per 100 parts by mass of the acrylic monomer mixture.
  • the ratio of the VDF polymer particles and the acrylic monomer mixture is 100 parts by mass or more for the acrylic monomer mixture with respect to 100 parts by mass of the VDF polymer particles. Furthermore, from the viewpoint of good adhesion and gloss, the acrylic monomer mixture is preferably 150 parts by mass or more, particularly 240 parts by mass or more with respect to 100 parts by mass of the VDF polymer particles.
  • the particle diameter of the acrylic-fluorine composite polymer particles in the aqueous dispersion is preferably 150 to 250 nm. More preferably, it is 170 to 230 nm.
  • the particle size is less than 150 nm, the viscosity of the aqueous dispersion is remarkably increased when the concentration of the acrylic-fluorine composite polymer particles in the aqueous dispersion is 30% by mass or more, which is within the practical range, and this hinders the work of coating. May come.
  • it exceeds 250 nm the sedimentation stability of the resulting aqueous dispersion tends to decrease, and the minimum film-forming temperature of the acrylic-fluorine composite polymer particles may increase.
  • the solid content concentration of the aqueous dispersion of the acrylic-fluorine composite polymer particles of the present invention is preferably 30 to 65% by mass, more preferably 35 to 50% by mass from the viewpoint of coating application.
  • the aqueous dispersion of acrylic-fluorine composite polymer particles of the present invention can be used for various applications in various forms.
  • Examples include, but are not limited to, coating composition components of various coating compositions, molding materials for films and sheets, adhesive compositions, ink compositions, and the like.
  • the paint composition includes a weather-resistant paint composition, particularly a weather-resistant paint composition for construction and building materials, a paint composition for interior / exterior of automobiles, a composition for interior / exterior paint of electrical products, office equipment or kitchen appliances.
  • the coating composition can be advantageously applied to a weather-resistant coating composition for building materials from the viewpoint of good weather resistance and durability.
  • the weather resistant coating composition may be, for example, a clear coating composition or a coating composition in which various pigments are blended.
  • paint additives include, in addition to curing agents, surfactants, pigments, dispersants, thickeners, preservatives, ultraviolet absorbers, antifoaming agents, leveling agents, and the like.
  • Films and sheets can be produced by a conventionally known method such as a casting method of the aqueous dispersion of the present invention.
  • Production Example 1 (Production of aqueous dispersion of VDF polymer particles)
  • 500 g of ion exchange water formula: CH 2 ⁇ C (CH 3 ) —CH 2 CH 2 —O— (BO) 6 — (EO) 10 —SO 3 NH 4
  • BO is a butylene oxide unit
  • EO is a CH 2 CH 2 O or CH (CH 3 ) O unit
  • 0.10 g 200 ppm / water (water as a polymerization medium; water as follows) The same)
  • the system was sufficiently replaced with nitrogen gas, and then the pressure was reduced.
  • VDF VDF / TFE / CTFE
  • Example 1 Production of aqueous dispersion of acrylic-fluorine composite polymer particles
  • 90 g of the aqueous dispersion of VDF copolymer particles (seed particles) obtained in Production Example 1 was charged into a 2 L four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, and seed polymerization was performed on this.
  • 707SF manufactured by Nippon Emulsifier Co., Ltd.
  • 707SF manufactured by Nippon Emulsifier Co., Ltd.
  • MMA methyl methacrylate
  • BA butyl acrylate
  • AA acrylic acid
  • RUVA93 reactive ultraviolet absorber
  • a mixed emulsion was prepared and dropped into the flask over 2 hours to polymerize. 2.5 hours after the start of the polymerization, the temperature in the flask was raised to 80 ° C., kept for 2 hours, cooled, neutralized with ammonia water to adjust the pH to 7, filtered through a 300 mesh wire mesh, and blue An aqueous dispersion of white acrylic-fluorine composite polymer particles (average particle size 200 nm) of the present invention was produced.
  • aqueous dispersion of acrylic-fluorine composite polymer particles obtained above and the additive were mixed at the following blending ratio, and thoroughly mixed using a disper stirrer to prepare a white paint composition.
  • Aqueous dispersion of acrylic-fluorine composite polymer particles 65.00 parts by weight Water 9.12 parts by weight Titanium oxide 31.39 parts by weight Pigment dispersant 2.35 parts by weight Antifreezing agent 1.79 parts by weight pH adjuster 0. 04 parts by weight Defoamer 0.11 parts by weight Thickener 0.38 parts by weight Film-forming aid 2.35 parts by weight
  • each used component is the following. Titanium oxide: Ishihara Sangyo Co., Ltd. Taipaek CR-97 (trade name) Pigment dispersant: Nopco Spurs SN-5027 (trade name) manufactured by San Nopco Antifreezing agent: Ethylene glycol pH adjuster: Ammonia water defoaming agent: BYK028 (trade name) manufactured by Big Chemie Thickener: Adecanol UH-420 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd. Film-forming aid: Diethyl adipate
  • the obtained white paint composition was coated with an aluminum plate (in advance, acrylic paint (DM774 (trade name) manufactured by Nippon Synthetic Chemical Co., Ltd.)) at 100 g / m 2 and dried at room temperature for 1 day. ) To 150 g / m 2 and dried at room temperature for 7 days to prepare a test coated plate.
  • acrylic paint DM774 (trade name) manufactured by Nippon Synthetic Chemical Co., Ltd.
  • the test coated plate was dried at 23 ° C. for 7 days, and then subjected to a 1000 hour test using an accelerated weather resistance tester QUV (manufactured by Q-LAB, USA), and the 60 ° specular gloss retention after the test was measured.
  • QUV accelerated weather resistance tester
  • Example 2 (Production of aqueous dispersion of acrylic-fluorine composite polymer particles) Using the aqueous dispersion of VDF copolymer particles obtained in Production Example 1, JS-20 (Sanyo Kasei Co., Ltd.) is used as a reactive emulsifier instead of 707SF as a non-reactive emulsifier as an emulsifier for ensuring stability.
  • Acrylic-fluorine composite polymer particles (average particle size 205 nm) of the present invention were subjected to seed polymerization in the same manner as in Example 1 except that 1.5% by mass was added to the VDF copolymer solid content. An aqueous dispersion of was prepared.
  • a white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
  • Comparative Example 1 Seed polymerization was carried out in the same manner as in Example 1 except that no reactive ultraviolet absorber was copolymerized to produce an aqueous dispersion of comparative acrylic-fluorine composite polymer particles (average particle size 198 nm).
  • a white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
  • Comparative Example 2 Seed polymerization was carried out in the same manner as in Example 2 except that the reactive ultraviolet absorber was not copolymerized to produce an aqueous dispersion of comparative acrylic-fluorine composite polymer particles (average particle size 203 nm).
  • a white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
  • Comparative Example 3 (Production of Aqueous Dispersion of Acrylic-Fluorine Composite Polymer Particles for Comparison) An aqueous dispersion of 490 g of the VDF copolymer particles obtained in Production Example 1 was charged into a 2 L four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, and this was seeded during seed polymerization.
  • non-reactive emulsifier 707SF manufactured by Nippon Emulsifier Co., Ltd.
  • reactive emulsifier RMA-450M Japan
  • Emulsifier Co., Ltd. was added in an amount of 3% by mass based on the solid content of the VDF copolymer.
  • the mixture was heated in a water bath with stirring, and the temperature in the flask was raised to 75 ° C.
  • the temperature in the flask was raised to 80 ° C., kept for 2 hours, cooled, neutralized with ammonia water to adjust the pH to 7, filtered through a 300 mesh wire mesh, and blue An aqueous dispersion of white acrylic-fluorine composite polymer particles (average particle size 230 nm) for comparison was produced.
  • a white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
  • Comparative Example 4 (Production of Aqueous Dispersion of Acrylic-Fluorine Composite Polymer Particles for Comparison) An aqueous dispersion of 490 g of the VDF copolymer particles obtained in Production Example 1 was charged into a 2 L four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, and this was seeded during seed polymerization. In order to ensure the stability of the particles, JS-20 (manufactured by Sanyo Kasei Co., Ltd.), which is a reactive emulsifier, was added in an amount of 1.5% by mass relative to the solid content of the VDF copolymer.
  • JS-20 manufactured by Sanyo Kasei Co., Ltd.
  • MMA and AA 97.0 / 3.0 (mass ratio) mixed monomer (98 g) and dodecyl mercaptan 0.5 g (an amount corresponding to 0.5 mass% of the mixed monomer), APS
  • a mixed emulsion of 16 ml of a 1% aqueous solution (an amount corresponding to 0.158% by mass of the mixed monomer) was prepared, and this was dropped into the flask over 2 hours to initiate polymerization.

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Abstract

Provided are acryl-fluorine composite polymer particles suitable for aqueous fluororesin coatings, which significantly reduce the amount of fluorine, are capable of forming coatings with excellent weather resistance, while significantly reducing costs, and are capable of minimizing reductions in the sheen of obtained coatings. Acryl-fluorine composite polymer particles containing (A) a vinylidene fluoride polymer component containing at least one type of fluoroolefin unit selected from a group comprising a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit as structural units, and a vinylidene fluoride unit, and (B) an acrylic polymer component containing an monomer unit containing an ethylenically unsaturated group having a (meta) acrylic monomer unit and an ultraviolet absorption site, or a monomer unit containing an ethylenically unsaturated group having an optical stabilization site, wherein the content of said vinylidene fluoride polymer component (A) is not more than 50 mass %.

Description

アクリル－フッ素複合重合体粒子および水性分散体Acrylic-fluorine composite polymer particles and aqueous dispersion
　本発明は、フッ化ビニリデン（ＶＤＦ）系重合体部分と光（特に紫外線）に対して安定なアクリル重合体部分とを含むアクリル－フッ素複合重合体粒子、およびそれを含む水性分散体、さらには該水性分散体を含む水性塗料用組成物に関する。 The present invention relates to acrylic-fluorine composite polymer particles comprising a vinylidene fluoride (VDF) -based polymer portion and an acrylic polymer portion that is stable against light (particularly ultraviolet rays), an aqueous dispersion comprising the same, and The present invention relates to an aqueous coating composition containing the aqueous dispersion.
　フッ素樹脂を含む塗料は、耐候性、耐水性、耐薬品性、耐熱性などに優れた塗膜を与えるため、建造物や各種車輌などの外面塗装に用いられている。一方、フッ素樹脂はアクリル樹脂やウレタン樹脂に比較して高価であるため、その適用する場面が制限されているのが現状である。 Fluoropolymer-containing paints are used for exterior coatings of buildings and various vehicles in order to give a coating film excellent in weather resistance, water resistance, chemical resistance, heat resistance and the like. On the other hand, since the fluororesin is more expensive than the acrylic resin and the urethane resin, the situation where it is applied is limited at present.
　そこで、フッ素含有量を下げることによりコストダウンを図ることが考えられるが、その結果、フッ素樹脂の特徴である耐候性も低下してしまう。 Therefore, it is conceivable to reduce the cost by reducing the fluorine content, but as a result, the weather resistance characteristic of the fluororesin is also lowered.
　これまで知られている耐候性を向上させる方法としては、紫外線吸収剤や光安定化剤を添加剤として塗料組成物に配合する方法、含フッ素重合体に反応性光安定化剤などを溶剤中でグラフト重合する方法（特許文献１）、含フッ素単量体と反応性光安定化剤などを共重合する方法（特許文献２）、フッ素樹脂粒子の水性分散体中でラジカル重合性不飽和単量体をシード重合する際に紫外線吸収部位を有する単量体または光安定化部位を有する単量体を共重合する方法（特許文献３）があげられる。 Known methods for improving weather resistance include blending a UV light absorber and a light stabilizer into a coating composition as an additive, and adding a reactive light stabilizer to a fluoropolymer in a solvent. (Patent Document 1), a method of copolymerizing a fluorine-containing monomer and a reactive light stabilizer (Patent Document 2), a radically polymerizable unsaturated monomer in an aqueous dispersion of fluororesin particles A method of copolymerizing a monomer having an ultraviolet absorption site or a monomer having a light stabilization site when seed polymerizing the monomer (Patent Document 3) can be mentioned.
特開平０１－１４１９０３号公報Japanese Patent Laid-Open No. 01-141903 特開平０３－２１５５４４号公報Japanese Patent Laid-Open No. 03-215544 特開平１０－１２０８５７号公報Japanese Patent Laid-Open No. 10-120857
　特許文献１には、水酸基を有するフッ素樹脂にウレタン結合で反応性二重結合を付加する必要があるために、反応プロセスが複雑になるという欠点があった。 Patent Document 1 has a drawback in that the reaction process is complicated because it is necessary to add a reactive double bond to the fluororesin having a hydroxyl group with a urethane bond.
　特許文献２の方法では、塗膜全体のフッ素含有量の低減化を他の被膜形成樹脂とブレンドすることで行っており、フッ素樹脂自体のフッ素含有量の低減化には繋がらない。 In the method of Patent Document 2, reduction of the fluorine content of the entire coating film is performed by blending with other film forming resin, which does not lead to reduction of the fluorine content of the fluororesin itself.
　特許文献３の方法では、得られる粒子中のフッ素含有量が大きいので、得られる粒子が高価である。 In the method of Patent Document 3, since the fluorine content in the obtained particles is large, the obtained particles are expensive.
　本発明は、フッ素含有量を大幅に低下させ、大幅にコストを下げても、耐候性に優れた塗膜を形成させることができ、得られる塗膜の光沢の低下を抑えることができるフッ素樹脂水性塗料に好適なアクリル－フッ素複合重合体粒子を提供することを目的とする。 The present invention is a fluororesin that can significantly reduce the fluorine content and can form a coating film excellent in weather resistance even if the cost is greatly reduced, and can suppress a decrease in gloss of the resulting coating film. An object of the present invention is to provide acrylic-fluorine composite polymer particles suitable for water-based paints.
　すなわち本発明は、（Ａ）構造単位としてテトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびクロロトリフルオロエチレン単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにフッ化ビニリデン単位を含むフッ化ビニリデン系重合体部分と、（Ｂ）（メタ）アクリル系単量体単位および紫外線吸収部位を有するエチレン性不飽和基含有単量体単位または光安定化部位を有するエチレン性不飽和基含有単量体単位を含むアクリル重合体部分とを含むアクリル－フッ素複合重合体粒子であって、該フッ化ビニリデン系重合体部分（Ａ）の含有量が５０質量％以下であるアクリル－フッ素複合重合体粒子に関する。 That is, the present invention provides a vinylidene fluoride system comprising (A) at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit as a structural unit and a vinylidene fluoride unit. Polymer part, (B) (meth) acrylic monomer unit and ethylenically unsaturated group-containing monomer unit having ultraviolet absorption site or ethylenically unsaturated group-containing monomer unit having light stabilization site The present invention relates to an acrylic-fluorine composite polymer particle containing an acrylic polymer part containing, wherein the vinylidene fluoride polymer part (A) content is 50% by mass or less.
　また本発明は、構造単位としてテトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびクロロトリフルオロエチレン単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにフッ化ビニリデン単位を含むフッ化ビニリデン系重合体粒子１００質量部を含む水性分散体中において、（メタ）アクリル系単量体および紫外線吸収部位を有するエチレン性不飽和基含有単量体または光安定化部位を有するエチレン性不飽和基含有単量体を含むアクリル系単量体混合物１００質量部以上を乳化重合に供することを特徴とするフッ化ビニリデン系重合体部分の含有量が５０質量％以下であるアクリル－フッ素複合重合体粒子の水性分散体の製造方法にも関する。 The present invention also relates to vinylidene fluoride polymer particles comprising at least one fluoroolefin unit selected from the group consisting of tetrafluoroethylene units, hexafluoropropylene units and chlorotrifluoroethylene units as structural units and vinylidene fluoride units. In an aqueous dispersion containing 100 parts by mass, an (meth) acrylic monomer and an ethylenically unsaturated group-containing monomer having an ultraviolet absorption site or an ethylenically unsaturated group-containing monomer having a light stabilization site Aqueous dispersion of acrylic-fluorine composite polymer particles having a vinylidene fluoride polymer portion content of 50% by mass or less, wherein 100 parts by mass or more of the acrylic monomer mixture containing is subjected to emulsion polymerization It also relates to the manufacturing method.
　本発明はまた、本発明のアクリル－フッ素複合重合体粒子を含む水性分散体、さらには該水性分散体を含む水性塗料用組成物にも関する。 The present invention also relates to an aqueous dispersion containing the acrylic-fluorine composite polymer particles of the present invention, and further to an aqueous coating composition containing the aqueous dispersion.
　本発明のフッ素含有量が低減化されたアクリル－フッ素複合重合体粒子を用いることにより、コストの削減ができるうえ、耐候性に優れた塗膜を形成させることができ、得られる塗膜の光沢の低下を抑えることができるフッ素樹脂水性塗料を提供することができる。 By using the acrylic-fluorine composite polymer particles having a reduced fluorine content according to the present invention, the cost can be reduced and a coating film having excellent weather resistance can be formed. It is possible to provide a fluororesin water-based paint capable of suppressing the decrease in the temperature.
　本発明のアクリル－フッ素複合重合体粒子は、フッ化ビニリデン（ＶＤＦ）系重合体部分（Ａ）と、アクリル重合体部分（Ｂ）とを含み、該ＶＤＦ系重合体部分（Ａ）の含有量が５０質量％以下である。本発明のアクリル－フッ素複合重合体粒子は、ＶＤＦ系重合体部分（Ａ）の含有量が５０質量％以下であるので、耐候性に優れた塗膜を形成させることができる。また、アクリル－フッ素複合重合体粒子をクリア塗料として使用した場合に、下地塗料の変色を防止できる。 The acrylic-fluorine composite polymer particle of the present invention includes a vinylidene fluoride (VDF) polymer part (A) and an acrylic polymer part (B), and the content of the VDF polymer part (A) Is 50 mass% or less. Since the acrylic-fluorine composite polymer particles of the present invention have a VDF polymer portion (A) content of 50% by mass or less, a coating film having excellent weather resistance can be formed. Further, when the acrylic-fluorine composite polymer particles are used as a clear paint, discoloration of the base paint can be prevented.
　アクリル－フッ素複合重合粒子中のＶＤＦ系重合体部分（Ａ）の含有量が５０質量％を超えると、アクリル重合体部分（Ｂ）が紫外線吸収部位または光安定化部位を有するエチレン性不飽和基含有単量体単位を含むものであったとしても、優れた耐候性を示す塗膜を形成させることができない。また、アクリル－フッ素複合重合体粒子をクリア塗料として使用した場合に、下地塗料の変色を防止できない。 When the content of the VDF polymer portion (A) in the acrylic-fluorine composite polymer particles exceeds 50% by mass, the acrylic polymer portion (B) has an ethylenically unsaturated group having an ultraviolet absorption site or a light stabilization site. Even if it contains a containing monomer unit, a coating film showing excellent weather resistance cannot be formed. Further, when acrylic-fluorine composite polymer particles are used as a clear paint, discoloration of the base paint cannot be prevented.
　ＶＤＦ系重合体部分（Ａ）は、構造単位としてテトラフルオロエチレン（ＴＦＥ）単位、ヘキサフルオロプロピレン（ＨＦＰ）単位およびクロロトリフルオロエチレン（ＣＴＦＥ）単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにＶＤＦ単位を含む。 The VDF polymer part (A) has at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene (TFE) unit, a hexafluoropropylene (HFP) unit and a chlorotrifluoroethylene (CTFE) unit as a structural unit. As well as VDF units.
　これらの含フッ素構造単位のほか、フッ化ビニル、トリフルオロエチレン、パーフルオロ（アルキルビニルエーテル）などのフルオロオレフィン単位；エチレン、プロピレン、イソブチレンなどのオレフィン単位；エチルビニルエーテル（ＥＶＥ）、シクロヘキシルビニルエーテル（ＣＨＶＥ）、ヒドロキシブチルビニルエーテル（ＨＢＶＥ）、ブチルビニルエーテル、イソブチルビニルエーテル、メチルビニルエーテル、ポリオキシエチレンビニルエーテルなどのビニルエーテル単位；ポリオキシエチレンアリルエーテル、エチルアリルエーテル、ヒドロキシエチルアリルエーテル、アリルアルコール、アリルエーテルなどのアルケニル単位；酢酸ビニル、乳酸ビニル、酪酸ビニル、ピバリン酸ビニル、安息香酸ビニル、ＶＥＯＶＡ９（シェル社製）、ＶＥＯＶＡ１０（シェル社製）などのビニルエステル単位；無水イタコン酸、無水コハク酸、クロトン酸などのエチレン性不飽和カルボン酸単位；などを含んでいてもよい。 In addition to these fluorine-containing structural units, fluoroolefin units such as vinyl fluoride, trifluoroethylene and perfluoro (alkyl vinyl ether); olefin units such as ethylene, propylene and isobutylene; ethyl vinyl ether (EVE) and cyclohexyl vinyl ether (CHVE) , Vinyl ether units such as hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; alkenyl units such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether Vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9 ( Manufactured by E Le Co.), VeoVa10 (manufactured by Shell Co.) vinyl ester units, such as; the like may be contained; itaconic anhydride, succinic anhydride, ethylenically unsaturated carboxylic acid units, such as crotonic acid.
　好ましいＶＤＦ系重合体部分を構成する共重合組成としては、たとえばＶＤＦ／ＨＦＰ共重合体、ＶＤＦ／ＴＦＥ／ＨＦＰ共重合体、ＶＤＦ／ＣＴＦＥ系共重合体、ＶＤＦ／ＴＦＥ／ＰＡＶＥ系共重合体、ＶＤＦ／ＴＦＥ／ＣＴＦＥ系共重合体などがあげられる。これらのうち、アクリル重合体部分（Ｂ）を構成する非フッ素系の単量体との親和性が良好な点から、ＶＤＦが重合体中に５０モル％以上含有されていることが好ましい。これらのなかでも、耐侯性、耐久性が良好な点から、ＶＤＦ／ＴＦＥ／ＣＴＦＥ共重合体が好ましい。 The copolymer composition constituting the preferred VDF polymer portion includes, for example, a VDF / HFP copolymer, a VDF / TFE / HFP copolymer, a VDF / CTFE copolymer, a VDF / TFE / PAVE copolymer, Examples thereof include VDF / TFE / CTFE copolymers. Among these, it is preferable that VDF is contained in the polymer in an amount of 50 mol% or more from the viewpoint of good affinity with the non-fluorine monomer constituting the acrylic polymer portion (B). Among these, a VDF / TFE / CTFE copolymer is preferable from the viewpoint of good weather resistance and durability.
　ＶＤＦ系重合体部分（Ａ）の分子量は数平均分子量で１，０００，０００以下、さらには２００，０００以下、特に１００，０００以下のものがアクリル重合体部分（Ｂ）を構成する非フッ素系の単量体との親和性が良好な点で好ましく、１，０００以上、さらには４，０００以上、特に５，０００以上のものが耐候性、耐久性に優れる点で好ましい。 The molecular weight of the VDF polymer part (A) is 1,000,000 or less, more preferably 200,000 or less, especially 100,000 or less in terms of number average molecular weight, which constitutes the acrylic polymer part (B). In view of good affinity with the above monomer, those having 1,000 or more, more preferably 4,000 or more, and particularly 5,000 or more are preferred in terms of excellent weather resistance and durability.
　アクリル重合体部分（Ｂ）は、（メタ）アクリル系単量体単位および紫外線吸収部位を有するエチレン性不飽和基含有単量体単位または光安定化部位を有するエチレン性不飽和基含有単量体単位を含む。アクリル重合体部分（Ｂ）は、エチレン性不飽和基含有単量体単位及び光安定化部位を有するエチレン性不飽和基含有単量体単位の両方を含むものであってもよい。 The acrylic polymer part (B) is an ethylenically unsaturated group-containing monomer unit having a (meth) acrylic monomer unit and an ethylenically unsaturated group-containing monomer unit having an ultraviolet absorption site or a light stabilizing site. Includes units. The acrylic polymer part (B) may contain both an ethylenically unsaturated group-containing monomer unit and an ethylenically unsaturated group-containing monomer unit having a light stabilizing site.
　（メタ）アクリル系単量体としては、たとえば、アクリル酸、アルキル基の炭素数が１～１８のアクリル酸アルキルエステル、アルキル基の炭素数が１～１８のメタクリル酸アルキルエステルなどが好ましくあげられる。 Preferred examples of the (meth) acrylic monomer include acrylic acid, an alkyl acrylate ester having an alkyl group having 1 to 18 carbon atoms, and an alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms. .
　アルキル基の炭素数が１～１８のアクリル酸アルキルエステルとしては、たとえばアクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－プロピル、アクリル酸ｉ－プロピル、アクリル酸ｎ－ブチル、アクリル酸ｉ－ブチル、アクリル酸ｔ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸ラウリルなどをあげることができる。 Examples of the alkyl acrylate ester having 1 to 18 carbon atoms in the alkyl group include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, Examples thereof include t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like.
　アルキル基の炭素数が１～１８のメタクリル酸アルキルエステルとしては、たとえばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－プロピル、メタクリル酸ｉ－プロピル、メタクリル酸ｎ－ブチル、メタクリル酸ｉ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸２－エチルヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ｎ－ヘキシル、メタクリル酸ｔ－ブチルシクロヘキシル、メタクリル酸ステアリル、メタクリル酸ラウリルなどをあげることができる。 Examples of the alkyl methacrylate having 1 to 18 carbon atoms in the alkyl group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, Examples thereof include t-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butyl cyclohexyl methacrylate, stearyl methacrylate, and lauryl methacrylate.
　さらに、アクリル酸またはメタクリル酸；アクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシプロピルなどの水酸基含有単量体；アクリル酸グリシジル、メタクリル酸グリシジルなどのエポキシ基含有単量体；γ－トリメトキシシランメタクリレート、γ－トリエトキシシランメタクリレートなどのシラノール基含有単量体；アクリルアミド、メタクリルアミド、Ｎ－メチルアクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－ブトキシメチルアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ－ブトキシメチルメタクリルアミドなどのアミド化合物；アクロレインなどのアルデヒド基含有単量体；アクリロニトリルなどを共重合してもよい。 Furthermore, acrylic acid or methacrylic acid; hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate Silanol group-containing monomers such as γ-trimethoxysilane methacrylate and γ-triethoxysilane methacrylate; acrylamide, methacrylamide, N-methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methylolmethacrylamide, Amide compounds such as N-methylmethacrylamide and N-butoxymethylmethacrylamide; aldehyde group-containing monomers such as acrolein; copolymerizing acrylonitrile and the like May be.
　さらにまた、耐溶剤性、耐水性向上の目的で、エチレングリコールジメタクリレート、プロピレングリコールジメタクリレートなどの多官能性単量体を共重合することもできる。 Furthermore, polyfunctional monomers such as ethylene glycol dimethacrylate and propylene glycol dimethacrylate can be copolymerized for the purpose of improving solvent resistance and water resistance.
　（メタ）アクリル系単量体としては、なかでも、耐候性、耐薬品性、密着性、光沢などを向上させるために、メタクリル酸メチル、炭素数４～１０のアルキル基を有する（メタ）アクリル酸アルキルエステル、及び、アクリル酸が好ましく、メタクリル酸メチル、アクリル酸ブチル及びアクリル酸がより好ましい。特に、アクリル重合体部分（Ｂ）が、メタクリル酸メチル単位、アクリル酸ブチル単位およびアクリル酸単位を含むことが、密着性に優れた塗膜を形成することでき、増粘性、及び、造膜性が良好な点から好ましい。アクリル重合体部分（Ｂ）がアクリル酸ブチル単位を含まないと、塗膜を形成させることができないおそれがある。 Among the (meth) acrylic monomers, in order to improve weather resistance, chemical resistance, adhesion, gloss, etc., methyl methacrylate and (meth) acrylic having an alkyl group having 4 to 10 carbon atoms are particularly preferred. Acid alkyl esters and acrylic acid are preferred, and methyl methacrylate, butyl acrylate and acrylic acid are more preferred. In particular, when the acrylic polymer part (B) contains a methyl methacrylate unit, a butyl acrylate unit, and an acrylic acid unit, a coating film excellent in adhesion can be formed, thickening, and film-forming properties. Is preferable from the viewpoint of good. If the acrylic polymer portion (B) does not contain a butyl acrylate unit, a coating film may not be formed.
　アクリル－フッ素複合重合粒子中のフッ化ビニリデン系共重合体部分の含有量が５０質量％を超える場合、アクリル重合体部分がメタクリル酸メチル単位のみからなるものであっても、造膜性に問題はない。フッ化ビニリデン系共重合体部分の比率が５０質量％以下である場合、アクリル重合体部分がメタクリル酸メチル単位のみからなると、造膜性が低下するおそれがある。これは、フッ化ビニリデン系共重合体はガラス転移温度（Ｔｇ）が低く、メタクリル酸メチル単位のみからなるアクリル重合体はＴｇが高いからであると推測される。
　アクリル重合体部分（Ｂ）はメタクリル酸メチル単位を２５～６５質量％含むことが、フッ化ビニリデン系共重合体部分（Ａ）の含有量が５０質量％以下であっても、高い造膜性を得ることができることから好ましい。
　（メタ）アクリル酸アルキルエステルとしては、炭素数が１～１８のアルキル基を有するものが、フッ化ビニリデン系共重合体部分（Ａ）の含有量が５０質量％以下であっても、高い造膜性を得ることができることから好ましい。
　アクリル－フッ素複合重合粒子中の相溶性を維持するために、アクリル重合体部分（Ｂ）はアルキル基の炭素数が２～４のアクリル酸アルキルエステル単位を含むことが好ましい。 When the content of the vinylidene fluoride copolymer part in the acrylic-fluorine composite polymer particles exceeds 50% by mass, even if the acrylic polymer part consists only of methyl methacrylate units, there is a problem in film forming properties. There is no. When the ratio of the vinylidene fluoride copolymer portion is 50% by mass or less, if the acrylic polymer portion is composed only of methyl methacrylate units, the film forming property may be lowered. This is presumably because the vinylidene fluoride copolymer has a low glass transition temperature (Tg), and the acrylic polymer consisting only of methyl methacrylate units has a high Tg.
The acrylic polymer part (B) contains 25 to 65% by mass of a methyl methacrylate unit, and even if the content of the vinylidene fluoride copolymer part (A) is 50% by mass or less, it has high film-forming properties. Is preferable.
As the (meth) acrylic acid alkyl ester, those having an alkyl group having 1 to 18 carbon atoms have a high structure even if the content of the vinylidene fluoride copolymer portion (A) is 50% by mass or less. It is preferable because film properties can be obtained.
In order to maintain compatibility in the acrylic-fluorine composite polymer particles, the acrylic polymer portion (B) preferably contains an alkyl acrylate unit having 2 to 4 carbon atoms in the alkyl group.
　アクリル重合体部分（Ｂ）における（メタ）アクリル系単量体単位の含有量は、アクリル重合体部分（Ｂ）中の８０～９９質量％が好ましい。８０質量％未満の場合、塗膜の光沢、硬度が低下する傾向にあり、９９質量％を超える場合は、下地との密着性が低下する傾向にある。さらに好ましい含有量は９０質量％以上、特に９５質量％以上であり、また９８質量％以下である。（メタ）アクリル系単量体は複数用いても良く、複数の（メタ）アクリル系単量体の１つとしてメタクリル酸メチルを用いた場合は、アクリル重合体（Ｂ）中にメタクリル酸メチル単位が２５～６５質量％含まれることが、塗膜硬度が良好な点から好ましい。 The content of the (meth) acrylic monomer unit in the acrylic polymer part (B) is preferably 80 to 99% by mass in the acrylic polymer part (B). When the amount is less than 80% by mass, the gloss and hardness of the coating film tend to decrease. When the amount exceeds 99% by mass, the adhesion to the base tends to decrease. A more preferable content is 90% by mass or more, particularly 95% by mass or more, and 98% by mass or less. A plurality of (meth) acrylic monomers may be used. When methyl methacrylate is used as one of a plurality of (meth) acrylic monomers, methyl methacrylate units are included in the acrylic polymer (B). Is preferably contained in an amount of 25 to 65% by mass from the viewpoint of good coating film hardness.
　紫外線吸収部位を有するエチレン性不飽和基含有単量体としては、たとえばべンゾトリアゾール型の紫外線吸収部位を有するメタクリレートであるＲＵＶＡ９３（大塚化学（株）製）、シアノアクリレート系などをあげることができる。そのほか、ベンゾフェノン系、ベンゾトリアゾール系、トリアジン系などの水酸基を含有する公知の紫外線吸収剤とメタクリル酸クロリド、アクリル酸クロリドなどの酸ハロゲン化物との反応により得られる紫外線吸収剤のメタクリル酸エステル、アクリル酸エステルなどもあげることができる。これらは、単独で用いても、２種以上を併用してもよい。
　紫外線吸収部位は、ベンゾトリアゾール系の水酸基を有する部位であることが好ましい。 Examples of the ethylenically unsaturated group-containing monomer having an ultraviolet absorption site include RUVA93 (manufactured by Otsuka Chemical Co., Ltd.), a cyanoacrylate, which is a methacrylate having a benzotriazole type ultraviolet absorption site. it can. In addition, methacrylic acid esters and acrylics of ultraviolet absorbers obtained by reaction of known ultraviolet absorbers containing hydroxyl groups such as benzophenone, benzotriazole, and triazine with acid halides such as methacrylic acid chloride and acrylic acid chloride. Acid esters can also be mentioned. These may be used alone or in combination of two or more.
The ultraviolet absorbing site is preferably a site having a benzotriazole-based hydroxyl group.
　光安定化部位を有するエチレン性不飽和基含有単量体としては、たとえばアデカスタブＬＡ８２（旭電化工業（株）製）、アデカスタブＬＡ８７（旭電化工業（株）製）などのほか、水酸基を有する光安定化剤とメタクル酸、アクリル酸とのエステルなどもあげることができる。これらは、単独で用いても、２種以上を併用してもよい。 Examples of the ethylenically unsaturated group-containing monomer having a light stabilizing site include Adeka Stub LA82 (Asahi Denka Kogyo Co., Ltd.), Adeka Stub LA87 (Asahi Denka Kogyo Co., Ltd.), etc. Mention may also be made of esters of stabilizers with methacrylic acid and acrylic acid. These may be used alone or in combination of two or more.
　アクリル重合体部分（Ｂ）における紫外線吸収部位および光安定化部位を有するエチレン性不飽和基含有単量体の含有量は、アクリル－フッ素複合重合体粒子中の０．１～３０質量％が好ましい。０．１質量％未満の場合、紫外線吸収効果や光安定化効果を充分に発揮することができなくなる傾向にあり、３０質量％を超えると、得られる含フッ素樹脂水性分散体を適用した塗料を用いて塗膜を形成した際に、塗膜の透明性が失われ、また顔料分散塗膜の光沢が低下する傾向にある。より好ましい含有量は、０．３質量％以上であり、１０質量％以下、さらには５質量％以下である。 The content of the ethylenically unsaturated group-containing monomer having an ultraviolet absorption site and a light stabilization site in the acrylic polymer portion (B) is preferably 0.1 to 30% by mass in the acrylic-fluorine composite polymer particles. . If the amount is less than 0.1% by mass, the ultraviolet absorption effect and the light stabilizing effect tend not to be sufficiently exhibited. If the amount exceeds 30% by mass, a paint to which the obtained fluororesin aqueous dispersion is applied is used. When a coating film is formed by using it, the transparency of the coating film is lost, and the gloss of the pigment-dispersed coating film tends to decrease. A more preferable content is 0.3% by mass or more, 10% by mass or less, and further 5% by mass or less.
　アクリル重合体部分（Ｂ）には、他のエチレン性不飽和基含有単量体単位、たとえばエチレン、プロピレン、イソブチレンなどのαオレフィン類；エチルビニルエーテル（ＥＶＥ）、シクロヘキシルビニルエーテル（ＣＨＶＥ）、ヒドロキシブチルビニルエーテル（ＨＢＶＥ）、ブチルビニルエーテル、イソブチルビニルエーテル、メチルビニルエーテル、ポリオキシエチレンビニルエーテルなどのビニルエーテル類；ポリオキシエチレンアリルエーテル、エチルアリルエーテル、ヒドロキシエチルアリルエーテル、アリルアルコール、アリルエーテルなどのアルケニル類；酢酸ビニル、乳酸ビニル、酪酸ビニル、ピバリン酸ビニル、安息香酸ビニル、ＶＥＯＶＡ９、ＶＥＯＶＡ１０（シェル社製）などのビニルエステル類；マレイン酸、無水イタコン酸、無水コハク酸、クロトン酸などのエチレン性不飽和カルボン酸類；スチレン、αメチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレンなどの芳香族ビニル化合物類などがあげられる。 The acrylic polymer part (B) includes other ethylenically unsaturated group-containing monomer units, for example, α-olefins such as ethylene, propylene, and isobutylene; ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), vinyl ethers such as butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; alkenyls such as polyoxyethylene allyl ether, ethyl allyl ether, hydroxyethyl allyl ether, allyl alcohol, allyl ether; vinyl acetate, Vinyl esters such as vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, VEOVA9, VEOVA10 (manufactured by Shell); maleic acid, Water itaconic acid, succinic anhydride, ethylenically unsaturated carboxylic acids such as crotonic acid; styrene, alpha-methyl styrene, and aromatic vinyl compounds such as p-tert-butylstyrene and the like.
　本発明のアクリル－フッ素複合重合体粒子の特徴の１つは、ＶＤＦ系重合体部分（Ａ）の含有量が５０質量％以下である点にある。ＶＤＦ系重合体部分（Ａ）の含有量を５０質量％以下にすることにより複合重合体粒子全体のフッ素含有量をたとえば２５質量％以下に低減化できる。好ましいＶＤＦ系重合体部分（Ａ）の含有量は４０質量％以下である。ただ、ＶＤＦ系重合体部分（Ａ）の含有量が低くなりすぎると、たとえ紫外線吸収部位または光安定化部位を有するエチレン性不飽和基含有単量体単位が導入されていてもフッ素樹脂の利点である耐候性や耐薬品性が低下してしまうことから、好ましくは３０質量％以上、さらには３５質量％以上である。 One of the characteristics of the acrylic-fluorine composite polymer particles of the present invention is that the content of the VDF polymer portion (A) is 50% by mass or less. By setting the content of the VDF polymer part (A) to 50% by mass or less, the fluorine content of the entire composite polymer particle can be reduced to, for example, 25% by mass or less. The content of the preferred VDF polymer part (A) is 40% by mass or less. However, if the content of the VDF polymer part (A) is too low, the advantage of the fluororesin is obtained even if an ethylenically unsaturated group-containing monomer unit having an ultraviolet absorption site or a light stabilization site is introduced. Since the weather resistance and chemical resistance are reduced, it is preferably 30% by mass or more, and more preferably 35% by mass or more.
　本発明のアクリル－フッ素複合重合体粒子において、耐水性や塗膜の光沢を損ねる可能性がある成分は、構造単位としても、または変性成分としても含まないことが望ましい。そうした耐水性や塗膜の光沢を損ねる可能性がある成分としては、たとえば特許文献３などにおいて乳化重合時に乳化剤として使用される反応性乳化剤などがあげられる。反応性乳化剤の使用は必ずしも禁止されるものではないが、使用する場合は、耐水性や塗膜の光沢を大きく損なわない量とすべきである。 In the acrylic-fluorine composite polymer particles of the present invention, it is desirable that components that may impair water resistance and gloss of the coating film are not included as structural units or modified components. Examples of such components that may impair the water resistance and gloss of the coating film include reactive emulsifiers used as an emulsifier during emulsion polymerization in Patent Document 3, for example. The use of a reactive emulsifier is not necessarily prohibited, but when used, it should be an amount that does not significantly impair the water resistance and gloss of the coating film.
　本発明のアクリル－フッ素複合重合体粒子はＶＤＦ系重合体部分（Ａ）の含有量を小さくすることでフッ素含有量を低減化し、製造コストを低く抑えることができると共に、紫外線吸収部位または光安定化部位を有するエチレン性不飽和基含有単量体単位を導入することにより、耐候性に優れた塗膜を形成させることができ、得られる塗膜の光沢の低下を抑えることができる。さらに、反応性乳化剤残渣を含まない場合には、フッ素含有量が低い場合でも高い耐水性を示す塗膜を形成でき、得られた塗膜の光沢の低下を抑えることができる。
　アクリル重合体部分（Ｂ）は、反応性乳化剤単位を含まないことが好ましい。 The acrylic-fluorine composite polymer particles of the present invention can reduce the fluorine content by reducing the content of the VDF polymer part (A), and can keep the production cost low. By introducing an ethylenically unsaturated group-containing monomer unit having a modified site, a coating film excellent in weather resistance can be formed, and a decrease in gloss of the resulting coating film can be suppressed. Furthermore, when the reactive emulsifier residue is not included, a coating film exhibiting high water resistance can be formed even when the fluorine content is low, and a decrease in gloss of the obtained coating film can be suppressed.
The acrylic polymer part (B) preferably does not contain a reactive emulsifier unit.
　本発明のアクリル－フッ素複合重合体粒子は、たとえばつぎの本発明の方法により水性分散体の形態で製造できる。 The acrylic-fluorine composite polymer particles of the present invention can be produced, for example, in the form of an aqueous dispersion by the following method of the present invention.
　本発明のＶＤＦ系重合体の含有量が５０質量％以下であるアクリル－フッ素複合重合体粒子の水性分散体の製造方法は、構造単位としてＴＦＥ単位、ＨＦＰ単位およびＣＴＦＥ単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにＶＤＦ単位を含むＶＤＦ系重合体粒子１００質量部を含む水性分散体中において、（メタ）アクリル系単量体および紫外線吸収部位を有するエチレン性不飽和基含有単量体または光安定化部位を有するエチレン性不飽和基含有単量体を含むアクリル系単量体混合物１００質量部以上を乳化重合に供することを特徴とする。 The method for producing an aqueous dispersion of acrylic-fluorine composite polymer particles having a VDF polymer content of 50% by mass or less according to the present invention is selected from the group consisting of TFE units, HFP units and CTFE units as structural units. In an aqueous dispersion containing 100 parts by mass of VDF polymer particles containing at least one fluoroolefin unit and VDF unit, a monomer containing an ethylenically unsaturated group having a (meth) acrylic monomer and an ultraviolet absorbing site 100 parts by mass or more of an acrylic monomer mixture containing a monomer or an ethylenically unsaturated group-containing monomer having a light stabilizing site is used for emulsion polymerization.
　すなわち、本発明のＶＤＦ系重合体の含有量が５０質量％以下であるアクリル－フッ素複合重合体粒子の水性分散体の製造方法は、構造単位としてＴＦＥ単位、ＨＦＰ単位およびＣＴＦＥ単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにＶＤＦ単位を含むＶＤＦ系重合体粒子を含む水性分散体中において、ＶＤＦ系重合体粒子１００質量部に対して、１００質量部以上の（メタ）アクリル系単量体および紫外線吸収部位を有するエチレン性不飽和基含有単量体または光安定化部位を有するエチレン性不飽和基含有単量体を含むアクリル系単量体混合物を乳化重合に供することを特徴とする。 That is, the method for producing an aqueous dispersion of acrylic-fluorine composite polymer particles in which the content of the VDF polymer of the present invention is 50% by mass or less is selected from the group consisting of TFE units, HFP units and CTFE units as structural units. In an aqueous dispersion containing VDF polymer particles containing at least one selected fluoroolefin unit and VDF unit, 100 parts by mass or more of (meth) acrylic single unit with respect to 100 parts by mass of VDF polymer particles. A monomer and an ethylenically unsaturated group-containing monomer having an ultraviolet absorption site or an acrylic monomer mixture containing an ethylenically unsaturated group-containing monomer having a light stabilization site is subjected to emulsion polymerization. To do.
　本発明の製造方法で使用するＶＤＦ系重合体、（メタ）アクリル系単量体および紫外線吸収部位を有するエチレン性不飽和基含有単量体、光安定化部位を有するエチレン性不飽和基含有単量体としては、前記アクリル－フッ素複合重合体粒子で説明したものが使用できる。 VDF polymer used in the production method of the present invention, (meth) acrylic monomer, ethylenically unsaturated group-containing monomer having an ultraviolet absorption site, ethylenically unsaturated group-containing monomer having a light stabilization site As the monomer, those described for the acrylic-fluorine composite polymer particles can be used.
　（メタ）アクリル系単量体は、メタクリル酸メチル、アクリル酸ブチルおよびアクリル酸であることが好ましい。この理由は、密着性に優れた塗膜を形成させることができる水性分散体が得られ、得られた水性分散体から塗料用組成物を調製する際に増粘させるおそれが少なく、しかも塗布した場合に造膜性に優れた水性分散体が得られるからである。また、アクリル－フッ素複合重合体粒子をクリア塗料として使用した場合に、下地塗料の変色を防止できる点からも好ましい。 (Meth) acrylic monomers are preferably methyl methacrylate, butyl acrylate and acrylic acid. The reason is that an aqueous dispersion capable of forming a coating film with excellent adhesion was obtained, and there was little risk of thickening when preparing a coating composition from the obtained aqueous dispersion, and the coating was applied. In this case, an aqueous dispersion having excellent film forming properties can be obtained. Further, when acrylic-fluorine composite polymer particles are used as a clear paint, it is preferable from the viewpoint that discoloration of the base paint can be prevented.
　ＶＤＦ系重合体粒子の粒径は、アクリル－フッ素複合重合体粒子の平均粒子径と密接に関連する。たとえばアクリル－フッ素複合重合体粒子の平均粒子径を１５０～２５０ｎｍとするためには、１００～２００ｎｍとすることが好ましい。 The particle size of the VDF polymer particles is closely related to the average particle size of the acrylic-fluorine composite polymer particles. For example, in order to set the average particle size of the acrylic-fluorine composite polymer particles to 150 to 250 nm, it is preferably 100 to 200 nm.
　ＶＤＦ系重合体粒子の水性分散体は、通常の乳化重合法によって得ることができる。具体的には、たとえば特開平０８－６７７９５号公報などに記載された公知の方法が採用できる。得られる水性分散体の固形分濃度を通常３０～６０質量％の範囲に調整した後、乳化剤を用いて、アクリル系単量体混合物を重合する。この重合形式はＶＤＦ系重合体粒子をシード粒子とするシード重合と呼ばれる。乳化剤としては、光沢度が高く、耐候性および耐水性に優れた塗膜を得ることができることから、非反応性乳化剤が好ましい。 An aqueous dispersion of VDF polymer particles can be obtained by an ordinary emulsion polymerization method. Specifically, for example, a known method described in Japanese Patent Application Laid-Open No. 08-67795 can be employed. After adjusting the solid content concentration of the resulting aqueous dispersion to usually 30 to 60% by mass, the acrylic monomer mixture is polymerized using an emulsifier. This polymerization mode is called seed polymerization using VDF polymer particles as seed particles. As the emulsifier, a non-reactive emulsifier is preferable because a coating film having high glossiness and excellent weather resistance and water resistance can be obtained.
　アクリル系単量体混合物のシード重合は、公知の方法、たとえばＶＤＦ系重合体粒子の存在下に、反応系にアクリル系単量体混合物の全量を一括して仕込む方法、アクリル系単量体混合物の一部を仕込み反応させた後、残りを連続または分割して仕込む方法、アクリル系単量体混合物の全量を連続して仕込む方法などによって行うことができる。これらのうち耐水性が良好な点から連続仕込みによる重合法が好ましい。 Seed polymerization of the acrylic monomer mixture is a known method, for example, a method in which the whole amount of the acrylic monomer mixture is charged into the reaction system in the presence of VDF polymer particles, and the acrylic monomer mixture. After charging and reacting a part of the mixture, the rest can be continuously or dividedly charged, or the entire amount of the acrylic monomer mixture can be continuously charged. Among these, the polymerization method by continuous charging is preferable from the viewpoint of good water resistance.
　また、このシード重合の重合条件は、通常の乳化重合と同様である。たとえば、ＶＤＦ系重合体粒子を含む水性媒体中に、非反応性乳化剤、重合開始剤、連鎖移動剤、場合によってはキレート化剤、ｐＨ調整剤などを添加し、１０～９０℃の温度で０．５～６時間反応を行うことにより重合することができる。 Further, the polymerization conditions for the seed polymerization are the same as those for normal emulsion polymerization. For example, a non-reactive emulsifier, a polymerization initiator, a chain transfer agent, in some cases a chelating agent, a pH adjuster, etc. are added to an aqueous medium containing VDF polymer particles, and the temperature is 0 to 10 ° C. Polymerization is possible by carrying out the reaction for 5 to 6 hours.
　非反応性乳化剤としては、アニオン性乳化剤、非イオン性乳化剤を単独またはこれらの併用があげられる。場合によっては両性乳化剤を用いることもできる。 As the non-reactive emulsifier, an anionic emulsifier and a nonionic emulsifier may be used alone or in combination. In some cases, an amphoteric emulsifier can be used.
　アニオン性乳化剤としては、たとえば高級アルコール硫酸エステル、アルキルスルホン酸ナトリウム塩、アルキルベンゼンスルホン酸ナトリウム塩、コハク酸ジアルキルエステルスルホン酸ナトリウム塩、アルキルジフェニルエーテルジスルホン酸ナトリウム塩などの炭化水素系アニオン性乳化剤；フルオロアルキルカルボン酸塩、フルオロアルキルスルホン酸塩、フルオロアルキル硫酸エステルなどの含フッ素アニオン性乳化剤などをあげることができる。 Examples of anionic emulsifiers include hydrocarbon anionic emulsifiers such as higher alcohol sulfates, alkylsulfonic acid sodium salts, alkylbenzenesulfonic acid sodium salts, succinic acid dialkylester sulfonic acid sodium salts, and alkyldiphenyl ether disulfonic acid sodium salts; Fluorine-containing anionic emulsifiers such as carboxylates, fluoroalkyl sulfonates, and fluoroalkyl sulfates can be mentioned.
　非イオン性乳化剤としては、たとえばポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類、ポリオキシエチレンアルキルフェニルエステル類、ソルビタンアルキルエステル類、グリセリンエステル類、これらの誘導体などをあげることができる。両性乳化剤としては、たとえばラウリルベタインなどをあげることができる。 Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, glycerin esters, and derivatives thereof. Etc. Examples of amphoteric emulsifiers include lauryl betaine.
　これらのなかでも、耐水性が良好な点から、高級アルコール硫酸エステルなどが好ましく、特にポリオキシエチレン多環フェニルエーテル硫酸エステルが、耐温水性が良好な点から好ましい。 Of these, higher alcohol sulfates are preferred from the viewpoint of good water resistance, and polyoxyethylene polycyclic phenyl ether sulfates are particularly preferred from the viewpoint of good warm water resistance.
　非反応性乳化剤の添加量は、水に対して１．０質量％以下、好ましくは０．５質量％以下、より好ましくは０．２質量％以下であり、下限は通常０．０５質量％である。 The addition amount of the non-reactive emulsifier is 1.0% by mass or less, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and the lower limit is usually 0.05% by mass with respect to water. is there.
　また、乳化剤として、（メタ）アクリル系単量体やエチレン性不飽和基含有単量体と共重合可能な、いわゆる反応性乳化剤と非反応性乳化剤とを併用することもできる。ただし、反応性乳化剤を単独で使用すると耐水性や塗膜の光沢を大きく損なうことがあるため、本発明においては反応性乳化剤の単独使用はない。非反応性乳化剤と併用する場合であっても、耐水性や塗膜の光沢を大きく損なわない量とすべきである。 Further, as the emulsifier, a so-called reactive emulsifier and a non-reactive emulsifier that can be copolymerized with a (meth) acrylic monomer or an ethylenically unsaturated group-containing monomer can be used in combination. However, if a reactive emulsifier is used alone, the water resistance and gloss of the coating film may be greatly impaired. Therefore, the reactive emulsifier is not used alone in the present invention. Even when used in combination with a non-reactive emulsifier, the amount should be such that the water resistance and gloss of the coating film are not significantly impaired.
　シード重合の際に用いる重合開始剤としては、水性媒体中でフリーラジカル反応に供し得るものであれば特に限定されず、場合によっては、還元剤と組み合せて用いることも可能である。使用可能な水溶性の重合開始剤としては、たとえば過硫酸塩、過酸化水素、還元剤としては、ピロ重亜硫酸ナトリウム、亜硫酸水素ナトリウム、Ｌ－アスコルビン酸ナトリウム、ロンガリットなどをあげることができる。油溶性の重合開始剤としては、たとえばジイソプロピルパーオキシジカーボネート（ＩＰＰ）、過酸化ベンゾイル、過酸化ジブチル、アゾビスイソブチロニトリル（ＡＩＢＮ）などをあげることができる。重合開始剤の使用量は、通常、アクリル系単量体混合物１００質量部あたり、０．０５～２．０質量部である。 The polymerization initiator used in the seed polymerization is not particularly limited as long as it can be used for a free radical reaction in an aqueous medium. In some cases, it can be used in combination with a reducing agent. Examples of the water-soluble polymerization initiator that can be used include persulfate, hydrogen peroxide, and examples of the reducing agent include sodium pyrobisulfite, sodium hydrogensulfite, sodium L-ascorbate, and longgarit. Examples of the oil-soluble polymerization initiator include diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN), and the like. The amount of the polymerization initiator used is usually 0.05 to 2.0 parts by mass per 100 parts by mass of the acrylic monomer mixture.
　シード重合の際に用いてもよい連鎖移動剤としては、たとえばクロロホルム、四塩化炭素などのハロゲン化炭化水素；ｎ－ドデシルメルカプタン、ｔｅｒｔ－ドデシルメルカプタン、ｎ－オクチルメルカプタンなどのメルカプタン類などをあげることができる。連鎖移動剤の使用量は、通常、アクリル系単量体混合物１００質量部あたり、０～５．０質量部である。 Examples of chain transfer agents that may be used in seed polymerization include halogenated hydrocarbons such as chloroform and carbon tetrachloride; mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octyl mercaptan. Can do. The amount of the chain transfer agent used is usually 0 to 5.0 parts by mass per 100 parts by mass of the acrylic monomer mixture.
　本発明の製造方法において、ＶＤＦ系重合体粒子とアクリル系単量体混合物との比率は、ＶＤＦ系重合体粒子１００質量部に対してアクリル系単量体混合物は１００質量部以上である。さらには、密着性、光沢が良好な点から、ＶＤＦ系重合体粒子１００質量部に対してアクリル系単量体混合物は１５０質量部以上、特に２４０質量部以上が好ましい。 In the production method of the present invention, the ratio of the VDF polymer particles and the acrylic monomer mixture is 100 parts by mass or more for the acrylic monomer mixture with respect to 100 parts by mass of the VDF polymer particles. Furthermore, from the viewpoint of good adhesion and gloss, the acrylic monomer mixture is preferably 150 parts by mass or more, particularly 240 parts by mass or more with respect to 100 parts by mass of the VDF polymer particles.
　本発明において水性分散体中でのアクリル－フッ素複合重合体粒子の粒子径は、１５０～２５０ｎｍが好ましい。より好ましくは、１７０～２３０ｎｍである。粒子径が１５０ｎｍ未満であると、水性分散体のアクリル－フッ素複合重合体粒子の濃度が実用的範囲である３０質量％以上において水性分散体の粘度が著しく増大し、塗料化の作業に支障を来すことがある。一方２５０ｎｍを超えると、得られる水性分散体の沈降安定性が低下する傾向があり、また、アクリル－フッ素複合重合体粒子の最低成膜温度の上昇を招くことがある。 In the present invention, the particle diameter of the acrylic-fluorine composite polymer particles in the aqueous dispersion is preferably 150 to 250 nm. More preferably, it is 170 to 230 nm. When the particle size is less than 150 nm, the viscosity of the aqueous dispersion is remarkably increased when the concentration of the acrylic-fluorine composite polymer particles in the aqueous dispersion is 30% by mass or more, which is within the practical range, and this hinders the work of coating. May come. On the other hand, if it exceeds 250 nm, the sedimentation stability of the resulting aqueous dispersion tends to decrease, and the minimum film-forming temperature of the acrylic-fluorine composite polymer particles may increase.
　本発明のアクリル－フッ素複合重合体粒子の水性分散体の固形分濃度は、塗料用途の観点からは３０～６５質量％であることが好ましく、より好ましくは３５～５０質量％である。 The solid content concentration of the aqueous dispersion of the acrylic-fluorine composite polymer particles of the present invention is preferably 30 to 65% by mass, more preferably 35 to 50% by mass from the viewpoint of coating application.
　本発明のアクリル－フッ素複合重合体粒子の水性分散体は、種々の形態で各種の用途に利用できる。 The aqueous dispersion of acrylic-fluorine composite polymer particles of the present invention can be used for various applications in various forms.
　たとえば、各種の塗料組成物の塗膜形成成分、フィルムやシートの成形材料のほか、接着剤組成物、インキ用組成物などが例示できるが、これらに限定されるものではない。 Examples include, but are not limited to, coating composition components of various coating compositions, molding materials for films and sheets, adhesive compositions, ink compositions, and the like.
　塗料組成物としては、耐候性塗料組成物、特に建築・建材用の耐候性塗料組成物、自動車の内・外装用塗料組成物、電気製品の内・外装塗料用組成物、事務機器あるいは厨房器具類の塗料組成物などが例示でき、特に耐候性・耐久性が良好な点から建材用の耐候性塗料組成物に有利に適用できる。 The paint composition includes a weather-resistant paint composition, particularly a weather-resistant paint composition for construction and building materials, a paint composition for interior / exterior of automobiles, a composition for interior / exterior paint of electrical products, office equipment or kitchen appliances. The coating composition can be advantageously applied to a weather-resistant coating composition for building materials from the viewpoint of good weather resistance and durability.
　耐候性塗料組成物は、たとえばクリアー塗料組成物でも、各種顔料が配合された塗料組成物でもよい。配合してもよい塗料用添加剤としては、硬化剤のほか、たとえば界面活性剤、顔料、分散剤、増粘剤、防腐剤、紫外線吸収剤、消泡剤、レベリング剤などがあげられる。 The weather resistant coating composition may be, for example, a clear coating composition or a coating composition in which various pigments are blended. Examples of paint additives that may be blended include, in addition to curing agents, surfactants, pigments, dispersants, thickeners, preservatives, ultraviolet absorbers, antifoaming agents, leveling agents, and the like.
　フィルムやシートは、本発明の水性分散体をキャスティング法といった従来公知の方法で製造することができる。 Films and sheets can be produced by a conventionally known method such as a casting method of the aqueous dispersion of the present invention.
　つぎに本発明を実施例に基づいて説明するが、本発明はこれらの実施例のみに限定されるものではない。 Next, the present invention will be described based on examples, but the present invention is not limited only to these examples.
製造例１（ＶＤＦ系重合体粒子の水性分散体の製造）
　２Ｌのステンレススチール製のオートクレーブに、イオン交換水５００ｇ、式：
ＣＨ２＝Ｃ（ＣＨ３）－ＣＨ２ＣＨ２－Ｏ－（ＢＯ）６－（ＥＯ）１０－ＳＯ３ＮＨ４
（式中、ＢＯはブチレンオキサイド単位；ＥＯはＣＨ２ＣＨ２ＯまたはＣＨ（ＣＨ３）Ｏ単位）で示される化合物（１－１）０．１０ｇ（２００ｐｐｍ／水（重合媒体としての水。以下同様））を仕込み、系内を窒素ガスで充分に置換後、減圧にした。続いて重合槽内を系内圧力が０．７５～０．８０ＭＰａとなるようにＶＤＦ／ＴＦＥ／ＣＴＦＥ（＝７４／１４／１２モル％）混合単量体を圧入し、７０℃に昇温した。 Production Example 1 (Production of aqueous dispersion of VDF polymer particles)
In a 2 L stainless steel autoclave, 500 g of ion exchange water, formula:
CH 2 ═C (CH 3 ) —CH 2 CH 2 —O— (BO) 6 — (EO) 10 —SO 3 NH 4
(Wherein BO is a butylene oxide unit; EO is a CH 2 CH 2 O or CH (CH 3 ) O unit) 0.10 g (200 ppm / water (water as a polymerization medium; water as follows) The same)), and the system was sufficiently replaced with nitrogen gas, and then the pressure was reduced. Subsequently, a VDF / TFE / CTFE (= 74/14/12 mol%) mixed monomer was injected into the polymerization tank so that the internal pressure was 0.75 to 0.80 MPa, and the temperature was raised to 70 ° C. .
　ついで過硫酸アンモニウム（ＡＰＳ）１．０ｇ（２０００ｐｐｍ／水）を４ｍｌのイオン交換水に溶解した重合開始剤溶液および酢酸エチル０．７５ｇ（１５００ｐｐｍ／水）を窒素ガスで圧入し、６００ｒｐｍで攪拌しながら反応を開始した。 Next, a polymerization initiator solution in which 1.0 g (2000 ppm / water) of ammonium persulfate (APS) was dissolved in 4 ml of ion-exchanged water and 0.75 g (1500 ppm / water) of ethyl acetate were injected with nitrogen gas and stirred at 600 rpm. The reaction was started.
　重合の進行に伴い内圧が降下し始めた時点で、ＶＤＦ／ＴＦＥ／ＣＴＦＥ（＝７４／１４／１２モル％）混合単量体を内圧が０．７５～０．８０ＭＰａを維持するように供給した。重合開始から２時間５分後に未反応単量体を放出し、オートクレーブを冷却して、固形分濃度１０．６質量％のＶＤＦ系（ＶＤＦ／ＴＦＥ／ＣＴＦＥ）共重合体粒子の水性分散体を得た。 When the internal pressure began to decrease as the polymerization progressed, a VDF / TFE / CTFE (= 74/14/12 mol%) mixed monomer was supplied so that the internal pressure was maintained at 0.75 to 0.80 MPa. . After 2 hours and 5 minutes from the start of polymerization, the unreacted monomer is released, the autoclave is cooled, and an aqueous dispersion of VDF (VDF / TFE / CTFE) copolymer particles having a solid content concentration of 10.6% by mass is obtained. Obtained.
実施例１（アクリル－フッ素複合重合体粒子の水性分散体の製造）
　攪拌翼、冷却管、温度計を備えた内容量２Ｌの四つ口フラスコに、製造例１で得られたＶＤＦ系共重合体粒子（シード粒子）の水性分散液９０ｇを仕込み、これにシード重合の際のシード粒子の安定性確保のために非反応性乳化剤である７０７ＳＦ（日本乳化剤（株）製）をＶＤＦ系共重合体固形分に対して２．６質量％添加した。攪拌下に水浴中で加温し、該フラスコ内の温度を７５℃に上げた。別途、メタクリル酸メチル（以下、ＭＭＡと略す）とブチルアクリレート（以下、ＢＡと略す）とアクリル酸（以下、ＡＡと略す）と反応性紫外線吸収剤ＲＵＶＡ９３（大塚化学工業（株）製）の６２．３／３５．７／１．１／０．９（質量比）の混合単量体（９８ｇ）とＡＰＳの１％水溶液１６ｍｌ（混合単量体の０．１５８質量％に相当する量）の混合エマルジョンを調製し、これを２時間かけてフラスコ中に滴下し、重合した。重合開始２．５時間後に、前記フラスコ内の温度を８０℃に上げ、２時間保持したのち冷却し、アンモニア水で中和してｐＨを７に調整し、３００メッシュの金網で濾過して青白色の本発明のアクリル－フッ素複合重合体粒子（平均粒子径２００ｎｍ）の水性分散体を製造した。 Example 1 (Production of aqueous dispersion of acrylic-fluorine composite polymer particles)
90 g of the aqueous dispersion of VDF copolymer particles (seed particles) obtained in Production Example 1 was charged into a 2 L four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, and seed polymerization was performed on this. In order to ensure the stability of the seed particles at this time, 707SF (manufactured by Nippon Emulsifier Co., Ltd.), which is a non-reactive emulsifier, was added at 2.6% by mass with respect to the solid content of the VDF copolymer. The mixture was heated in a water bath with stirring, and the temperature in the flask was raised to 75 ° C. Separately, 62 of methyl methacrylate (hereinafter abbreviated as MMA), butyl acrylate (hereinafter abbreviated as BA), acrylic acid (hereinafter abbreviated as AA), and a reactive ultraviolet absorber RUVA93 (manufactured by Otsuka Chemical Co., Ltd.). .3 / 35.7 / 1.1 / 0.9 (mass ratio) of a mixed monomer (98 g) and 16 ml of a 1% aqueous solution of APS (an amount corresponding to 0.158 mass% of the mixed monomer) A mixed emulsion was prepared and dropped into the flask over 2 hours to polymerize. 2.5 hours after the start of the polymerization, the temperature in the flask was raised to 80 ° C., kept for 2 hours, cooled, neutralized with ammonia water to adjust the pH to 7, filtered through a 300 mesh wire mesh, and blue An aqueous dispersion of white acrylic-fluorine composite polymer particles (average particle size 200 nm) of the present invention was produced.
（白塗料組成物の調製）
　上記で得られたアクリル－フッ素複合重合体粒子の水性分散体と添加物を以下に示す配合比で混合し、ディスパー攪拌機を用いて充分混合して白塗料組成物を調製した。
　アクリル－フッ素複合重合体粒子の水性分散液　　　６５．００質量部
　水　　　　　　　　　　　　　　　　　　　　　　　　９．１２質量部
　酸化チタン　　　　　　　　　　　　　　　　　　　３１．３９質量部
　顔料分散剤　　　　　　　　　　　　　　　　　　　　２．３５質量部
　凍結防止剤　　　　　　　　　　　　　　　　　　　　１．７９質量部
　ｐＨ調整剤　　　　　　　　　　　　　　　　　　　　０．０４質量部
　消泡剤　　　　　　　　　　　　　　　　　　　　　　０．１１質量部
　増粘剤　　　　　　　　　　　　　　　　　　　　　　０．３８質量部
　造膜助剤　　　　　　　　　　　　　　　　　　　　　２．３５質量部 (Preparation of white paint composition)
The aqueous dispersion of acrylic-fluorine composite polymer particles obtained above and the additive were mixed at the following blending ratio, and thoroughly mixed using a disper stirrer to prepare a white paint composition.
Aqueous dispersion of acrylic-fluorine composite polymer particles 65.00 parts by weight Water 9.12 parts by weight Titanium oxide 31.39 parts by weight Pigment dispersant 2.35 parts by weight Antifreezing agent 1.79 parts by weight pH adjuster 0. 04 parts by weight Defoamer 0.11 parts by weight Thickener 0.38 parts by weight Film-forming aid 2.35 parts by weight
　なお、使用した各成分はつぎのものである。
酸化チタン：石原産業（株）製タイペークＣＲ－９７（商品名）
顔料分散剤：サンノプコ（株）製ノプコスパースＳＮ－５０２７（商品名）
凍結防止剤：エチレングリコール
ｐＨ調整剤：アンモニア水
消泡剤：ビックケミー製ＢＹＫ０２８（商品名）
増粘剤：旭電化工業（株）製アデカノールＵＨ－４２０（商品名）
造膜助剤：アジピン酸ジエチル In addition, each used component is the following.
Titanium oxide: Ishihara Sangyo Co., Ltd. Taipaek CR-97 (trade name)
Pigment dispersant: Nopco Spurs SN-5027 (trade name) manufactured by San Nopco
Antifreezing agent: Ethylene glycol pH adjuster: Ammonia water defoaming agent: BYK028 (trade name) manufactured by Big Chemie
Thickener: Adecanol UH-420 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.
Film-forming aid: Diethyl adipate
　得られた白塗料組成物について、つぎの試験を行なった。結果を表１に示す。 The following test was performed on the obtained white paint composition. The results are shown in Table 1.
（被験塗板の作製）
　得られた白塗料組成物をアルミ板（予めアクリル系塗料（日本合成化学（株）製のＤＭ７７４（商品名））を１００ｇ／ｍ２となるように塗装し、室温で１日間乾燥させたもの）に１５０ｇ／ｍ２となるように塗装し、室温で７日間乾燥させ、被験塗板を作製した。 (Preparation of test coated plate)
The obtained white paint composition was coated with an aluminum plate (in advance, acrylic paint (DM774 (trade name) manufactured by Nippon Synthetic Chemical Co., Ltd.)) at 100 g / m 2 and dried at room temperature for 1 day. ) To 150 g / m 2 and dried at room temperature for 7 days to prepare a test coated plate.
（光沢）
　被験塗板を２３℃で７日間乾燥した後、ＪＩＳ　Ｋ５６００－４－７に従って変角光沢計（日本電色工業（株）製ＶＧＳ－ＳＥＮＳＯＲ）を用いて６０°鏡面光沢度を測定した。 (Glossy)
The test coated plate was dried at 23 ° C. for 7 days, and then the 60 ° specular gloss was measured using a variable angle gloss meter (VGS-SENSOR manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K5600-4-7.
（耐侯性）
　被験塗板を２３℃で７日間乾燥した後、促進耐侯性試験機ＱＵＶ（米国Ｑ－ＬＡＢ社製）を用いて１０００時間試験を行い、試験後の６０°鏡面光沢度保持率を測定した。 (Wear resistance)
The test coated plate was dried at 23 ° C. for 7 days, and then subjected to a 1000 hour test using an accelerated weather resistance tester QUV (manufactured by Q-LAB, USA), and the 60 ° specular gloss retention after the test was measured.
（耐水性試験）
　被験塗板を２３℃で１日間乾燥した後、ＪＩＳ　Ｋ５６００－５－６に従って一次密着試験を行い、はがれ（ＪＩＳ　Ｋ５６００－８－５に準拠）の等級を評価した。その後ＪＩＳ　Ｋ５６００－６－２に従って２３℃の水中に６日間浸漬し、その後２３℃で１日間乾燥し、膨れ（ＪＩＳ　Ｋ５６００－８－２）、割れ（ＪＩＳ　Ｋ５６００－８－４）、はがれ（ＪＩＳ　Ｋ５６００－８－５）の等級を評価した。さらに被験塗板を２３℃で１日間乾燥した後、ＪＩＳ　Ｋ５６００－５－６に従って二次密着試験を行いはがれ（ＪＩＳ　Ｋ５６００－８－５に準拠）の等級を評価した。 (Water resistance test)
After the test coated plate was dried at 23 ° C. for 1 day, a primary adhesion test was performed according to JIS K5600-5-6, and the grade of peeling (according to JIS K5600-8-5) was evaluated. After that, it is immersed in water at 23 ° C. for 6 days according to JIS K5600-6-2, and then dried at 23 ° C. for 1 day, swelled (JIS K5600-8-2), cracked (JIS K5600-8-4), and peeled off (JIS The grade of K5600-8-5) was evaluated. Further, after the test coated plate was dried at 23 ° C. for 1 day, a secondary adhesion test was conducted according to JIS K5600-5-6, and the grade of peeling (conforming to JIS K5600-8-5) was evaluated.
膨れの等級（ＪＩＳ　Ｋ５６００－８－２）の評価基準
　密度を０～５の等級（小さい方が０）に、大きさをＳ１～Ｓ５の等級（Ｓ１の方が小さい）に分け、たとえば２（Ｓ１）のように記載する。 Evaluation criteria for blister grade (JIS K5600-8-2) Density is divided into 0-5 grades (smaller is 0), and sizes are divided into S1-S5 grades (S1 is smaller). It is described as S1).
割れの等級（ＪＩＳ　Ｋ５６００－８－４）の評価基準
　密度を０～５の等級（小さい方が０）に、大きさをＳ０～Ｓ５の等級（Ｓ０の方が小さい）に、深さをａ～ｃの等級（ａの方が浅い）に分け、たとえば２（Ｓ１）ｂのように記載する。 Evaluation criteria for cracking grade (JIS K5600-8-4) Density is graded from 0 to 5 (smaller is 0), size is from S0 to S5 (S0 is smaller), and depth is a It is divided into ˜c grades (a is shallower) and described as 2 (S1) b, for example.
はがれの等級（ＪＩＳ　Ｋ５６００－８－５）の評価基準
　密度を０～５の等級（小さい方が０）に、大きさをＳ１～Ｓ５の等級（Ｓ１の方が小さい）に、深さをａ～ｂの等級（ａの方が浅い）に分け、たとえば２（Ｓ１）ａのように記載する。 Evaluation standard for peeling grade (JIS K5600-8-5) Density is graded from 0 to 5 (smaller is 0), size is from S1 to S5 (S1 is smaller), and depth is a It is divided into ˜b grades (a is shallower) and is described as 2 (S1) a, for example.
実施例２（アクリル－フッ素複合重合体粒子の水性分散体の製造）
　製造例１で得られたＶＤＦ系共重合体粒子の水性分散体を用い、安定性確保のための乳化剤として非反応性乳化剤である７０７ＳＦに代えて反応性乳化剤であるＪＳ－２０（三洋化成社製）をＶＤＦ系共重合体固形分に対して１．５質量％添加したほかは実施例１と同様にしてシード重合を行い、本発明のアクリル－フッ素複合重合体粒子（平均粒子径２０５ｎｍ）の水性分散体を製造した。 Example 2 (Production of aqueous dispersion of acrylic-fluorine composite polymer particles)
Using the aqueous dispersion of VDF copolymer particles obtained in Production Example 1, JS-20 (Sanyo Kasei Co., Ltd.) is used as a reactive emulsifier instead of 707SF as a non-reactive emulsifier as an emulsifier for ensuring stability. Acrylic-fluorine composite polymer particles (average particle size 205 nm) of the present invention were subjected to seed polymerization in the same manner as in Example 1 except that 1.5% by mass was added to the VDF copolymer solid content. An aqueous dispersion of was prepared.
　上記で得られたアクリル－フッ素複合重合体粒子の水性分散体を用いたほかは実施例１と同様にして白塗料組成物を調製し、各種の特性を調べた。結果を表１に示す。 A white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
比較例１（比較用のアクリル－フッ素複合重合体粒子の水性分散体の製造）
　反応性紫外線吸収剤を共重合しなかったほかは実施例１と同様にしてシード重合を行い、比較用のアクリル－フッ素複合重合体粒子（平均粒子径１９８ｎｍ）の水性分散体を製造した。 Comparative Example 1 (Production of Aqueous Dispersion of Acrylic-Fluorine Composite Polymer Particles for Comparison)
Seed polymerization was carried out in the same manner as in Example 1 except that no reactive ultraviolet absorber was copolymerized to produce an aqueous dispersion of comparative acrylic-fluorine composite polymer particles (average particle size 198 nm).
　上記で得られた比較用のアクリル－フッ素複合重合体粒子の水性分散体を用いたほかは実施例１と同様にして白塗料組成物を調製し、各種の特性を調べた。結果を表１に示す。 A white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
比較例２（比較用のアクリル－フッ素複合重合体粒子の水性分散体の製造）
　反応性紫外線吸収剤を共重合しなかったほかは実施例２と同様にしてシード重合を行い、比較用のアクリル－フッ素複合重合体粒子（平均粒子径２０３ｎｍ）の水性分散体を製造した。 Comparative Example 2 (Production of aqueous dispersion of acrylic-fluorine composite polymer particles for comparison)
Seed polymerization was carried out in the same manner as in Example 2 except that the reactive ultraviolet absorber was not copolymerized to produce an aqueous dispersion of comparative acrylic-fluorine composite polymer particles (average particle size 203 nm).
　上記で得られた比較用のアクリル－フッ素複合重合体粒子の水性分散体を用いたほかは実施例１と同様にして白塗料組成物を調製し、各種の特性を調べた。結果を表１に示す。 A white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
比較例３（比較用のアクリル－フッ素複合重合体粒子の水性分散体の製造）
　攪拌翼、冷却管、温度計を備えた内容量２Ｌの四つ口フラスコに、製造例１で得られたＶＤＦ系共重合体粒子の水性分散液４９０ｇを仕込み、これにシード重合の際のシード粒子の安定性確保のために非反応性乳化剤である７０７ＳＦ（日本乳化剤（株）製）をＶＤＦ系共重合体固形分に対して２．６質量％、反応性乳化剤であるＲＭＡ－４５０Ｍ（日本乳化剤（株）製）をＶＤＦ系共重合体固形分に対して３質量％添加した。攪拌下に水浴中で加温し、該フラスコ内の温度を７５℃に上げた。別途、ＭＭＡとＢＡとＡＡの６３．２／３５．７／１．１（質量比）の混合単量体（９８ｇ）とドデシルメルカプタン０．５ｇ（混合単量体の０．５質量％に相当する量）、ＡＰＳの１％水溶液１６ｍｌ（混合単量体の０．１５８質量％に相当する量）の混合エマルジョンを調製し、これを２時間かけてフラスコ中に滴下し、重合を開始した。重合開始２．５時間後に、前記フラスコ内の温度を８０℃に上げ、２時間保持したのち冷却し、アンモニア水で中和してｐＨを７に調整し、３００メッシュの金網で濾過して青白色の比較用のアクリル－フッ素複合重合体粒子（平均粒子径２３０ｎｍ）の水性分散体を製造した。 Comparative Example 3 (Production of Aqueous Dispersion of Acrylic-Fluorine Composite Polymer Particles for Comparison)
An aqueous dispersion of 490 g of the VDF copolymer particles obtained in Production Example 1 was charged into a 2 L four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, and this was seeded during seed polymerization. In order to ensure the stability of the particles, non-reactive emulsifier 707SF (manufactured by Nippon Emulsifier Co., Ltd.) is 2.6% by mass based on the solid content of VDF copolymer, and reactive emulsifier RMA-450M (Japan) (Emulsifier Co., Ltd.) was added in an amount of 3% by mass based on the solid content of the VDF copolymer. The mixture was heated in a water bath with stirring, and the temperature in the flask was raised to 75 ° C. Separately, MMA, BA and AA 63.2 / 35.7 / 1.1 (mass ratio) mixed monomer (98 g) and dodecyl mercaptan 0.5 g (corresponding to 0.5 mass% of mixed monomer) A mixed emulsion of 16 ml of 1% aqueous solution of APS (an amount corresponding to 0.158% by mass of the mixed monomer) was prepared, and this was added dropwise into the flask over 2 hours to initiate polymerization. 2.5 hours after the start of the polymerization, the temperature in the flask was raised to 80 ° C., kept for 2 hours, cooled, neutralized with ammonia water to adjust the pH to 7, filtered through a 300 mesh wire mesh, and blue An aqueous dispersion of white acrylic-fluorine composite polymer particles (average particle size 230 nm) for comparison was produced.
　上記で得られた比較用のアクリル－フッ素複合重合体粒子の水性分散体を用いたほかは実施例１と同様にして白塗料組成物を調製し、各種の特性を調べた。結果を表１に示す。 A white paint composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
比較例４（比較用のアクリル－フッ素複合重合体粒子の水性分散体の製造）
　攪拌翼、冷却管、温度計を備えた内容量２Ｌの四つ口フラスコに、製造例１で得られたＶＤＦ系共重合体粒子の水性分散液４９０ｇを仕込み、これにシード重合の際のシード粒子の安定性確保のために反応性乳化剤であるＪＳ－２０（三洋化成社製）をＶＤＦ系共重合体固形分に対して１．５質量％添加した。攪拌下に水浴中で加温し、該フラスコ内の温度を７５℃に上げた。別途、ＭＭＡとＡＡの９７．０／３．０（質量比）の混合単量体（９８ｇ）とドデシルメルカプタン０．５ｇ（混合単量体の０．５質量％に相当する量）、ＡＰＳの１％水溶液１６ｍｌ（混合単量体の０．１５８質量％に相当する量）の混合エマルジョンを調製し、これを２時間かけてフラスコ中に滴下し、重合を開始した。重合開始２．５時間後に、前記フラスコ内の温度を８０℃に上げ、２時間保持したのち冷却し、アンモニア水で中和してｐＨを７に調整し、３００メッシュの金網で濾過して青白色の比較用のアクリル－フッ素複合重合体粒子（平均粒子径２３０ｎｍ）の水性分散体を製造した。
　上記で得られた比較用のアクリル－フッ素複合重合体粒子の水性分散体を用いたほかは実施例１と同様にして白塗料組成物を調製し、各種の特性を調べた。結果を表１に示す。 Comparative Example 4 (Production of Aqueous Dispersion of Acrylic-Fluorine Composite Polymer Particles for Comparison)
An aqueous dispersion of 490 g of the VDF copolymer particles obtained in Production Example 1 was charged into a 2 L four-necked flask equipped with a stirring blade, a cooling tube, and a thermometer, and this was seeded during seed polymerization. In order to ensure the stability of the particles, JS-20 (manufactured by Sanyo Kasei Co., Ltd.), which is a reactive emulsifier, was added in an amount of 1.5% by mass relative to the solid content of the VDF copolymer. The mixture was heated in a water bath with stirring, and the temperature in the flask was raised to 75 ° C. Separately, MMA and AA 97.0 / 3.0 (mass ratio) mixed monomer (98 g) and dodecyl mercaptan 0.5 g (an amount corresponding to 0.5 mass% of the mixed monomer), APS A mixed emulsion of 16 ml of a 1% aqueous solution (an amount corresponding to 0.158% by mass of the mixed monomer) was prepared, and this was dropped into the flask over 2 hours to initiate polymerization. 2.5 hours after the start of the polymerization, the temperature in the flask was raised to 80 ° C., kept for 2 hours, cooled, neutralized with ammonia water to adjust the pH to 7, filtered through a 300 mesh wire mesh, and blue A white aqueous dispersion of comparative acrylic-fluorine composite polymer particles (average particle size 230 nm) was prepared.
A white coating composition was prepared in the same manner as in Example 1 except that the aqueous dispersion of comparative acrylic-fluorine composite polymer particles obtained above was used, and various characteristics were examined. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
表１から、反応性紫外線吸収剤を共重合した場合、ＶＤＦ系重合体部分が少なくても耐候性が維持できしかも塗膜光沢が向上することが分かる。特に、アクリル－フッ素複合重合体粒子の水性分散体の製造工程で非反応性乳化剤を用いた場合、耐水性がさらに向上することが分かる。 From Table 1, it can be seen that when a reactive ultraviolet absorber is copolymerized, the weather resistance can be maintained even when the VDF polymer portion is small and the gloss of the coating film is improved. In particular, it can be seen that the water resistance is further improved when a non-reactive emulsifier is used in the production process of the aqueous dispersion of acrylic-fluorine composite polymer particles.

Claims (9)

  1. （Ａ）構造単位としてテトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびクロロトリフルオロエチレン単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにフッ化ビニリデン単位を含むフッ化ビニリデン系重合体部分と、
    （Ｂ）（メタ）アクリル系単量体単位および紫外線吸収部位を有するエチレン性不飽和基含有単量体単位または光安定化部位を有するエチレン性不飽和基含有単量体単位を含むアクリル重合体部分とを含むアクリル－フッ素複合重合体粒子であって、該フッ化ビニリデン系重合体部分（Ａ）の含有量が５０質量％以下であるアクリル－フッ素複合重合体粒子。     (A) a vinylidene fluoride polymer part containing at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit and a chlorotrifluoroethylene unit as a structural unit, and a vinylidene fluoride unit;
    (B) Acrylic polymer containing (meth) acrylic monomer units and ethylenically unsaturated group-containing monomer units having an ultraviolet absorption site or ethylenically unsaturated group-containing monomer units having a light stabilization site Acrylic-fluorine composite polymer particles containing a portion, wherein the vinylidene fluoride polymer portion (A) content is 50% by mass or less.
  2. アクリル系重合体部分（Ｂ）が、メタクリル酸メチル単位、アクリル酸ブチル単位およびアクリル酸単位を含む請求項１記載のアクリル－フッ素複合重合体粒子。 The acrylic-fluorine composite polymer particle according to claim 1, wherein the acrylic polymer part (B) comprises a methyl methacrylate unit, a butyl acrylate unit and an acrylic acid unit.
  3. フッ化ビニリデン系重合体部分（Ａ）が、テトラフルオロエチレン単位およびクロロトリフルオロエチレン単位を含む請求項１または２記載のアクリル－フッ素複合重合体粒子。 The acrylic-fluorine composite polymer particle according to claim 1 or 2, wherein the vinylidene fluoride polymer portion (A) contains a tetrafluoroethylene unit and a chlorotrifluoroethylene unit.
  4. アクリル系重合体部分（Ｂ）が、メタクリル酸メチル単位を２５～６５質量％含む請求項１～３のいずれか１項に記載のアクリル－フッ素複合重合体粒子。 The acrylic-fluorine composite polymer particle according to any one of claims 1 to 3, wherein the acrylic polymer portion (B) contains 25 to 65 mass% of methyl methacrylate units.
  5. 構造単位としてテトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびクロロトリフルオロエチレン単位よりなる群から選ばれる少なくとも１種のフルオロオレフィン単位ならびにフッ化ビニリデン単位を含むフッ化ビニリデン系重合体粒子１００質量部を含む水性分散体中において、（メタ）アクリル系単量体および紫外線吸収部位を有するエチレン性不飽和基含有単量体または光安定化部位を有するエチレン性不飽和基含有単量体を含むアクリル系単量体混合物１００質量部以上を乳化重合に供することを特徴とするフッ化ビニリデン系重合体の含有量が５０質量％以下であるアクリル－フッ素複合重合体粒子の水性分散体の製造方法。 100 parts by mass of vinylidene fluoride polymer particles containing at least one fluoroolefin unit selected from the group consisting of tetrafluoroethylene units, hexafluoropropylene units and chlorotrifluoroethylene units as structural units and vinylidene fluoride units In an aqueous dispersion, an acrylic monomer containing a (meth) acrylic monomer and an ethylenically unsaturated group-containing monomer having an ultraviolet absorption site or an ethylenically unsaturated group-containing monomer having a light stabilization site. A method for producing an aqueous dispersion of acrylic-fluorine composite polymer particles having a vinylidene fluoride polymer content of 50% by mass or less, wherein 100 parts by mass or more of the monomer mixture is subjected to emulsion polymerization.
  6. （メタ）アクリル系単量体は、メタクリル酸メチル、アクリル酸ブチルおよびアクリル酸である請求項５記載のアクリル－フッ素複合重合体粒子の水性分散体の製造方法。 6. The method for producing an aqueous dispersion of acrylic-fluorine composite polymer particles according to claim 5, wherein the (meth) acrylic monomer is methyl methacrylate, butyl acrylate or acrylic acid.
  7. 請求項１～４のいずれか１項に記載のアクリル－フッ素複合重合体粒子を含む水性分散体。 An aqueous dispersion comprising the acrylic-fluorine composite polymer particles according to any one of claims 1 to 4.
  8. 請求項５または６記載の製造方法により得られるアクリル－フッ素複合重合体粒子の水性分散体。 An aqueous dispersion of acrylic-fluorine composite polymer particles obtained by the production method according to claim 5 or 6.
  9. 請求項７または８記載の水性分散体を含む水性塗料用組成物。 An aqueous coating composition comprising the aqueous dispersion according to claim 7 or 8.
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