WO2012036297A1 - Particules polymères composites à base d'acrylique fluoré, et dispersant aqueux - Google Patents

Particules polymères composites à base d'acrylique fluoré, et dispersant aqueux 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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acrylic
unit
mass
polymer particles
composite polymer
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PCT/JP2011/071394
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English (en)
Japanese (ja)
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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/zh
Publication of WO2012036297A1 publication Critical patent/WO2012036297A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des particules polymères composites à base d'acrylique fluoré pouvant être utilisées dans des revêtements aqueux à base de fluororésine, lesdites particules polymères présentant une faible teneur en fluor, donnant des revêtements présentant une très bonne résistance aux intempéries, permettant une forte baisse des coûts et se révélant capables de minimiser les pertes de lustre susceptibles d'affecter les revêtements obtenus. L'invention concerne, plus précisément, des particules polymères composites à base d'acrylique fluoré contenant (A) un composant polymère de type fluorure de vinylidène contenant au moins un type de motif fluorooléfine, choisi dans le groupe constitué des motifs tétrafluoroéthylène, hexafluoropropylène et chlorotrifluoroéthylène, en tant que motifs structurels, ainsi qu'un motif de type fluorure de vinylidène, et (B) un composant polymère acrylique contenant un motif monomère comportant un groupe éthyléniquement insaturé possédant un motif monomère (méta)acrylique et un site d'absorption des UV, ou un motif monomère comportant un groupe éthyléniquement insaturé possédant un site de stabilisation optique, la teneur en composant polymère (A) de type fluorure de vinylidène ne dépassant pas 50 % en poids.
PCT/JP2011/071394 2010-09-17 2011-09-20 Particules polymères composites à base d'acrylique fluoré, et dispersant aqueux WO2012036297A1 (fr)

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WO2018190371A1 (fr) * 2017-04-14 2018-10-18 ダイキン工業株式会社 Composition de résine et corps moulé
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JP6260782B2 (ja) * 2014-01-15 2018-01-17 Jsr株式会社 塗料用組成物、塗料及び塗装体
WO2019065638A1 (fr) * 2017-09-28 2019-04-04 Ａｇｃ株式会社 Procédé de production de polytétrafluoroéthylène modifié, procédé de production de poudre de polytétrafluoroéthylène modifié et procédé de production de corps poreux étiré
WO2019124215A1 (fr) * 2017-12-20 2019-06-27 ダイキン工業株式会社 Particule, dispersion et poudre de type noyau-enveloppe
CN112839970B (zh) 2018-11-22 2022-08-30 东丽株式会社 含氟聚合物粒子
KR20200097533A (ko) * 2019-02-08 2020-08-19 (주)올리브그린 후면 투사형 빔 프로젝트 스크린에 이용되는 voc 프리 이미지 형성용 코팅액 조성물
WO2020263804A1 (fr) * 2019-06-25 2020-12-30 Arkema Inc. Séparateur revêtu comportant des fluoropolymères pour batterie au lithium-ion

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US10138712B2 (en) 2013-05-08 2018-11-27 Siemens Aktiengesellschaft Subsea electrical unit and system
CN108431147A (zh) * 2016-01-21 2018-08-21 罗门哈斯公司 用于耐久涂料的聚合物分散体和包含所述聚合物分散体的涂料
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WO2018190371A1 (fr) * 2017-04-14 2018-10-18 ダイキン工業株式会社 Composition de résine et corps moulé
JPWO2018190371A1 (ja) * 2017-04-14 2019-11-07 ダイキン工業株式会社 樹脂組成物及び成形体
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