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WO2020090749A1 - Matière aqueuse de revêtement et article revêtu - Google Patents

Matière aqueuse de revêtement et article revêtu Download PDF

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Publication number
WO2020090749A1
WO2020090749A1 PCT/JP2019/042187 JP2019042187W WO2020090749A1 WO 2020090749 A1 WO2020090749 A1 WO 2020090749A1 JP 2019042187 W JP2019042187 W JP 2019042187W WO 2020090749 A1 WO2020090749 A1 WO 2020090749A1
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WO
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Prior art keywords
meth
fluoropolymer
water
acrylic polymer
monomer
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/042187
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English (en)
Japanese (ja)
Inventor
俊 齋藤
チン ヤン シェン セドリック
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AGC Inc
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Asahi Glass Co Ltd
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Filing date
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Publication of WO2020090749A1 publication Critical patent/WO2020090749A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to water-based paints and painted articles.
  • Patent Document 1 discloses an aqueous coating material containing a fluoropolymer containing a unit based on chlorotrifluoroethylene and a monomer unit having an aliphatic hydrocarbon ring (for example, a unit based on cyclohexyl vinyl ether). There is.
  • an aqueous paint containing a (meth) acrylic polymer together with a fluoropolymer may be used.
  • the present inventors have proposed an aqueous paint containing a (meth) acrylic polymer and a fluoropolymer having a low content of monomer units having an aliphatic hydrocarbon ring as described in Example 3 of Patent Document 1. When used, it was found that the water resistance of the coating film may be insufficient depending on the type of (meth) acrylic polymer.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a water-based paint and a coated article that can form a coating film having excellent water resistance.
  • the present inventors have found that in a water-based paint containing a fluoropolymer and a (meth) acrylic polymer, the content of a monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring is equal to or less than a predetermined value.
  • a fluoropolymer which is, a unit based on an alkyl (meth) acrylate having a branched chain alkyl group is contained, and a monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring is substantially not included. It was found that a coating film excellent in water resistance can be formed by using a (meth) acrylic polymer, and the present invention has been completed.
  • [1] contains a fluoropolymer, a (meth) acrylic polymer, and water, or A water-based paint comprising a core-shell polymer having the fluoropolymer as a core part and the (meth) acrylic polymer as a shell part, and water, wherein the fluorine atom content of the fluoropolymer is 25% by mass or more,
  • the content of the monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring is 5 mol% or less based on all monomer units contained in the fluoropolymer, and the (meth) acrylic polymer has a branched chain alkyl group.
  • An aqueous coating material which comprises a unit based on an alkyl (meth) acrylate and is substantially free of a monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring.
  • the content of the unit based on the alkyl (meth) acrylate having a branched alkyl group is 30 mol% or more based on all the monomer units of the (meth) acrylic polymer,
  • Water-based paint [3] The water-based paint according to [1] or [2], wherein the (meth) acrylic polymer does not substantially contain a monomer unit having a hydroxy group.
  • the fluoropolymer particles and the (meth) acrylic polymer particles are independently dispersed, and the absolute difference in average particle diameter between the fluoropolymer particles and the (meth) acrylic polymer particles is absolute.
  • (Meth) acrylate is a general term for acrylate and methacrylate
  • (meth) acrylic is a general term for acrylic and methacrylic.
  • the monomer unit is a generic term for an atomic group based on one molecule of the monomer, which is directly formed by polymerization of a monomer, and an atomic group obtained by chemically converting a part of the atomic group.
  • the content (mol%) of each monomer unit with respect to all the monomer units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy.
  • the average particle diameter is a value of D50 obtained by the dynamic light scattering method.
  • D50 is the particle diameter value of the cumulative volume of 50% by volume calculated from the small particle side in the particle size distribution of the particles measured by the dynamic light scattering method.
  • ELS-8000 manufactured by Otsuka Electronics Co., Ltd.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography using polystyrene as a standard substance.
  • the glass transition temperature (Tg) is a midpoint glass transition temperature measured by a differential scanning calorimetry (DSC) method.
  • the minimum film forming temperature is the minimum temperature at which a uniform coating film without cracks is formed when the fluoropolymer is dried.
  • a film forming temperature measuring device IMC-1535 manufactured by Imoto Machinery Co., Ltd. was used as a measuring device.
  • the acid value and the hydroxyl value are values measured according to the method of JIS K 0070-3 (1992), respectively.
  • the solubility parameter (Solubility Parameter. Also referred to as SP value) is a cohesive energy density, that is, a value obtained by multiplying the evaporation energy per unit volume of one molecule to the power of 1/2, and is an index indicating the magnitude of polarity per unit volume. Is.
  • the SP value is calculated by the Fedros method (see the literature: RF Fedros, Polym. Eng. Sci., 14 (2) 147 (1974)).
  • Fluorine atom content means the ratio (%) of the mass of fluorine atoms to the total mass of the fluoropolymer, and can be measured by nuclear magnetic resonance (NMR) analysis.
  • the water-based paint of the present invention contains a fluoropolymer, a (meth) acrylic polymer, and water, or has the fluoropolymer as a core part and the (meth) acrylic polymer as a shell part. It is a water-based paint containing a core-shell polymer as defined below and water.
  • the fluoropolymer has a fluorine atom content of 25% by mass or more, and the content of a monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring (hereinafter, also referred to as unit D) is the fluoropolymer.
  • the (meth) acrylic polymer contains a unit (hereinafter, also referred to as a unit M0) based on an alkyl (meth) acrylate having a branched alkyl group, and has at least one of an aliphatic hydrocarbon ring and an aromatic ring. It does not substantially contain the monomer unit that it has (hereinafter, also referred to as unit M1).
  • a coating film formed using a fluoropolymer having a high content of fluorine atoms As in the case of the present paint, the adhesion of the coating film and the base material is reduced by the action of fluorine atoms, and the water resistance of the coating film is reduced. It tends to decrease.
  • a coating film formed from the present coating material (hereinafter, also referred to as the present coating film) is excellent in water resistance despite using a fluoropolymer having a high fluorine atom content. The reason is not always clear, but it can be considered as follows.
  • the fluoropolymer contained in the paint has a low content of the unit D.
  • the (meth) acrylic polymer contained in the present coating material does not substantially contain the unit M1. Therefore, it is considered that both the fluoropolymer and the (meth) acrylic polymer contained in the present paint have relatively high polymer fluidity. In particular, since the (meth) acrylic polymer contained in the present coating material contains the unit M0, the fluidity of the polymer tends to be higher. As a result, it is considered that the fluoropolymer and the (meth) acrylic polymer are likely to spread on the substrate during the heat treatment for forming the coating film, and the coating film having a uniform composition is likely to be formed. As described above, since the composition of the coating film is uniform, the adhesion between the coating film and the substrate is improved, and it becomes difficult for water to enter between the coating film and the substrate. It is speculated that a film was obtained.
  • the fluoropolymer includes a monomer unit having a fluorine atom.
  • a monomer unit having a fluorine atom a unit based on a fluoroolefin (hereinafter, also referred to as a unit F) is preferable.
  • Fluoroolefins are olefins in which one or more hydrogen atoms have been replaced by fluorine atoms. In the fluoroolefin, one or more hydrogen atoms which are not substituted with fluorine atoms may be substituted with chlorine atoms.
  • the carbon number of the fluoroolefin is preferably 2-8, and particularly preferably 2-4.
  • CF 2 ⁇ CF 2 or CF 2 ⁇ CFCl is more preferable, and CF 2 ⁇ CFCl is particularly preferable.
  • the content of the unit F is preferably 20 to 100 mol%, more preferably 30 to 70 mol% based on all the monomer units contained in the fluoropolymer. , 40 to 60 mol% is particularly preferable.
  • the unit D is a monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring, and a unit based on a monomer having at least one of an aliphatic hydrocarbon ring and an aromatic ring (hereinafter, also referred to as a monomer D) is preferable. ..
  • the unit D preferably does not have a fluorine atom.
  • aliphatic hydrocarbon ring examples include cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, monocyclic aliphatic hydrocarbon ring such as cyclooctane ring, bicyclohexyl ring, decahydronaphthalene ring and the like.
  • examples include polycyclic aliphatic hydrocarbon rings, norbornane rings, adamantane rings, and other bridged ring-structured aliphatic hydrocarbon rings, and spiro [3.4] octane rings, and other spiro-ring-structured aliphatic hydrocarbon rings.
  • aromatic ring examples include aromatic hydrocarbon rings such as benzene ring and naphthalene ring, furan ring, thiophene ring, pyrrole ring, pyridine ring and other aromatic heterocycles.
  • the monomer D vinyl ether, vinyl carboxylate, allyl ether, allyl ester and (meth) acrylate having at least one of an aliphatic hydrocarbon ring and an aromatic ring are preferable.
  • the monomer D two or more kinds may be used in combination.
  • the content of the unit D is 5 mol% or less, preferably 0 to 5 mol%, more preferably 1 to 4 mol%, based on all the monomer units contained in the fluoropolymer. It is particularly preferable that the content is 1 to 3 mol% from the viewpoint that the fluidity is maintained high and the coating film hardness is improved.
  • the fluoropolymer may include a monomer unit having no aliphatic hydrocarbon ring or aromatic ring and having at least one of a hydroxy group and a carboxy group (hereinafter, also referred to as a unit H).
  • the unit H preferably has no fluorine atom.
  • the unit H is a unit based on a monomer having at least one of a hydroxy group and a carboxy group (hereinafter, also referred to as a monomer H).
  • the unit H may be a unit obtained by converting this group into at least one of a hydroxy group and a carboxy group in a fluoropolymer including a monomer unit having a group that can be converted into a hydroxy group or a carboxy group.
  • Such a unit examples include a unit obtained by reacting a fluoropolymer containing a monomer unit having a hydroxy group with a polycarboxylic acid or an acid anhydride thereof to convert at least a part of the hydroxy group into a carboxy group. Can be mentioned.
  • Examples of the monomer H having a hydroxy group include vinyl ether, vinyl carboxylate, allyl ether, allyl ester, (meth) acrylate, and allyl alcohol having a hydroxy group.
  • the monomer having a hydroxy group is preferably vinyl ether from the viewpoint of weather resistance of the coating film.
  • Examples of the monomer H having a carboxy group include unsaturated carboxylic acid, (meth) acrylic acid, and a monomer obtained by reacting a carboxylic acid anhydride with the hydroxy group of the above-mentioned monomer having a hydroxy group.
  • the monomer H having a carboxy group examples include CH 2 ⁇ CHCOOH, CH (CH 3 ) ⁇ CHCOOH, CH 2 ⁇ C (CH 3 ) COOH, HOOCCH ⁇ CHCOOH, CH 2 ⁇ CH (CH 2 ) n11 COOH ( However, n11 represents an integer of 1 to 10), CH 2 ⁇ CHO (CH 2 ) n12 OC (O) CH 2 CH 2 COOH (provided that n12 represents an integer of 1 to 10), and From the viewpoint of copolymerizability with a fluoroolefin, CH 2 ⁇ CH (CH 2 ) n11 COOH or CH 2 ⁇ CHO (CH 2 ) n12 OC (O) CH 2 CH 2 COOH is preferable.
  • the monomer H may be used in combination of two or more kinds.
  • the content of the unit H is preferably more than 0 mol% and 30 mol% or less, and preferably 1 to 15 mol% with respect to all the monomer units contained in the fluoropolymer. More preferably, it is particularly preferably from 1.5 to 5 mol%.
  • the fluoropolymer includes a unit (hereinafter, also referred to as unit G) based on a monomer (hereinafter, also referred to as monomer G) that does not have an aliphatic hydrocarbon ring and an aromatic ring and does not have a hydroxy group and a carboxy group. But it's okay.
  • the unit G preferably has no fluorine atom.
  • the unit G may have a crosslinkable group other than a hydroxy group and a carboxy group. Specific examples of such a group include an amino group, an epoxy group, an oxetanyl group, and a hydrolyzable silyl group.
  • the hydrolyzable silyl group is a group that hydrolyzes to a silanol group.
  • the monomer G includes at least one selected from the group consisting of alkenes, vinyl ethers, vinyl carboxylates, allyl ethers, allyl esters, and (meth) acrylates.
  • the monomer G at least one of vinyl ether and vinyl carboxylate is preferable, and vinyl ether is particularly preferable, from the viewpoint of copolymerizability with fluoroolefin and weather resistance of fluoropolymer.
  • a monomer having an alkyl group having 3 or less carbon atoms is preferable, and a vinyl ether having an alkyl group having 3 or less carbon atoms is particularly preferable.
  • the monomer G examples include ethylene, propylene, 1-butene, ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl acetate, vinyl pivalate, vinyl neononanoate (Hexion, trade name "Veova 9"), Examples thereof include vinyl neodecanoate (trade name “Veova 10” manufactured by HEXION) and tert-butyl (meth) acrylate.
  • the monomer G may use 2 or more types together.
  • the content of the unit G is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 40 to 50 mol% based on all the monomer units contained in the fluoropolymer. Particularly preferred.
  • the Tg of the fluoropolymer is preferably 0 to 80 ° C., and particularly preferably 10 to 30 ° C., from the viewpoint of fluidity of the fluoropolymer.
  • the MFT of the fluoropolymer is preferably 0 to 100 ° C., and particularly preferably 10 to 35 ° C. from the viewpoint of fluidity of the fluoropolymer. From the viewpoint of fluidity of the fluoropolymer, Mn of the fluoropolymer is preferably 1,000 to 1,000,000.
  • the hydroxyl value of the fluoropolymer is preferably 1 to 80 mgKOH / g, and particularly preferably 10 to 30 mgKOH / g.
  • the acid value of the fluoropolymer is preferably 1 to 80 mgKOH / g, and particularly preferably 10 to 30 mgKOH / g.
  • the fluoropolymer may have either an acid value or a hydroxyl value, or may have both.
  • the fluorine atom content of the fluoropolymer is 25% by mass or more, preferably 26% by mass or more, and particularly preferably 27% by mass or more. When the fluorine atom content is 25% by mass or more, the weather resistance of the coating film is excellent.
  • the fluorine atom content of the fluoropolymer is preferably 80% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. When the fluorine atom content is 80% by mass or less, the flexibility of the present coating film is excellent.
  • the unit M0 in the (meth) acrylic polymer is a unit based on an alkyl (meth) acrylate having a branched alkyl group (hereinafter, also referred to as a monomer M0).
  • the number of carbon atoms of the branched chain alkyl group is preferably from 3 to 12, and particularly preferably from 4 to 10 from the viewpoint that the water resistance of the present coating film is more excellent.
  • the monomer M0 examples include isopropyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, isopentyl (meth) acrylate, 3-pentyl (meth) acrylate, tert- Examples thereof include pentyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.
  • the monomers M0 may be used in combination of two or more kinds.
  • the content of the unit M0 is preferably 30 mol% or more, and is 35 mol% or more, based on all the monomer units contained in the (meth) acrylic polymer, from the viewpoint that the water resistance of the present coating film is more excellent. Is more preferable and 45 mol% or more is particularly preferable. From the viewpoint of weather resistance and transparency, the content of the unit M0 is preferably 60 mol% or less, and particularly preferably 55 mol% or less, based on all the monomer units contained in the (meth) acrylic polymer. ..
  • the (meth) acrylic polymer is substantially free of the unit M1.
  • the unit M1 is a monomer unit having at least one of an aliphatic hydrocarbon ring and an aromatic ring, and its specific example is the same as the unit D in the fluoropolymer, and therefore its description is omitted.
  • the content of the unit M1 with respect to all the monomer units included in the (meth) acrylic polymer is It means less than 0.1 mol%.
  • the content of the unit M1 is preferably 0.01 mol% or less, and particularly preferably 0 mol%.
  • the (meth) acrylic polymer is a unit (hereinafter, also referred to as unit M2) based on an alkyl (meth) acrylate having a linear alkyl group (hereinafter, also referred to as monomer M2) from the viewpoint of weather resistance and transparency. May be included.
  • the linear alkyl group preferably has 1 to 4 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
  • Specific examples of the monomer M2 include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and n-butyl (meth) acrylate, with methyl (meth) acrylate being preferred.
  • the monomer M2 may be used in combination of two or more kinds.
  • the content of the unit M2 is preferably 1 to 70 mol%, and particularly preferably 35 to 55 mol% based on all the monomer units contained in the (meth) acrylic polymer.
  • the (meth) acrylic polymer preferably does not substantially contain a monomer unit having a hydroxy group (hereinafter, also referred to as unit M3).
  • the unit M3 include units based on hydroxyalkyl (meth) acrylate (hereinafter, also referred to as monomer M3).
  • Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
  • Examples include hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the term "does not substantially include the unit M3" means that the unit M3 is not included, or when the unit M3 is included, the content of the unit M3 is based on all monomer units included in the (meth) acrylic polymer. It means less than 0.1 mol%.
  • the content of the unit M3 is preferably 0.01 mol% or less, and particularly preferably 0 mol%.
  • the (meth) acrylic polymer may contain monomer units other than the above.
  • the monomer unit include units based on monomers such as unsaturated carboxylic acid, hydrolyzable silyl group-containing monomer, vinyl carboxylate and ⁇ -olefin.
  • the content of the monomer unit is preferably 0 to 30 mol% and particularly preferably 0 to 10 mol% based on all the monomer units contained in the (meth) acrylic polymer.
  • the Tg of the (meth) acrylic polymer is preferably lower than the Tg of the fluoropolymer.
  • the Tg of the (meth) acrylic polymer is preferably ⁇ 30 to 10 ° C., particularly preferably ⁇ 20 to 0 ° C., from the viewpoint of fluidity of the (meth) acrylic polymer.
  • the MFT of the (meth) acrylic polymer is preferably lower than the MFT of the fluoropolymer. From the viewpoint of fluidity of the (meth) acrylic polymer, the MFT of the (meth) acrylic polymer is preferably ⁇ 20 to 30 ° C., particularly preferably ⁇ 10 to 20 ° C.
  • the Mn of the (meth) acrylic polymer is preferably 1,000 to 1,000,000 from the viewpoint of fluidity of the (meth) acrylic polymer.
  • the absolute value of the difference in SP value between the fluoropolymer and the (meth) acrylic polymer is preferably 20.0 (J / cm 3 ) 1/2 or less, more preferably 15 (J / cm 3 ) 1/2 or less. It is particularly preferably 10 (J / cm 3 ) 1/2 or less.
  • the absolute value of the difference in SP value between the fluoropolymer and the (meth) acrylic polymer is preferably 1.0 (J / cm 3 ) 1/2 or more, and 2.0 (J / cm 3 ) 1/2 or more. More preferably, 5.0 (J / cm 3 ) 1/2 or more is particularly preferable. Within the above range, the compatibility of both polymers is improved and a coating film having excellent composition uniformity can be formed.
  • the SP value of the fluoropolymer is preferably 15.0 to 20.0 (J / cm 3 ) 1/2, more preferably 16.0 to 19.0 (J / cm 3 ) 1/2 , and 16.5. ⁇ 17.5 (J / cm 3 ) 1/2 is particularly preferable.
  • the SP value of the (meth) acrylic polymer is preferably 15.0 to 30.0 (J / cm 3 ) 1/2, more preferably 18.0 to 29.0 (J / cm 3 ) 1/2 , 22.0 to 27.0 (J / cm 3 ) 1/2 is particularly preferable.
  • the fluoropolymer and the (meth) acrylic polymer may be dispersed independently in the dispersion medium.
  • the fluoropolymer is dispersed in the paint as particles of the fluoropolymer and the (meth) acrylic polymer is particles of the (meth) acrylic polymer.
  • the fluoropolymer and (meth) acrylic polymer in the present coating composition may be a core-shell polymer having a fluoropolymer as a core part and a (meth) acrylic polymer as a shell part.
  • the core-shell polymer is dispersed in the paint as particles (core-shell particles).
  • the core-shell particles are particles having a so-called core-shell structure having a core part of fluoropolymer and a shell part of (meth) acrylic polymer located on the surface of the core part.
  • the shell part may cover a part of the surface of the core part, or may cover the entire core part.
  • the polymer of the core part and the polymer of the shell part may have a chemical bond.
  • the average particle size of the fluoropolymer particles, the (meth) acrylic polymer particles, and the core-shell particles is preferably 30 to 300 nm, respectively, from the viewpoint that the particles are densely packed and the water resistance of the present coating film is more excellent. , 50 to 200 nm is more preferable.
  • the fluoropolymer and the (meth) acrylic polymer are independently dispersed in the dispersion medium from the viewpoint that the fluoropolymer and the (meth) acrylic polymer are easily wet and spread on the surface of the substrate when the coating film is formed.
  • the average particle size of the fluoropolymer particles is preferably 100 to 200 nm, particularly preferably 130 to 180 nm.
  • the average particle diameter of the particles of the (meth) acrylic polymer is preferably 50 to 180 nm, particularly preferably 80 to 130 nm.
  • the absolute value of the difference in average particle size between the fluoropolymer particles and the (meth) acrylic polymer particles makes the flow properties of the fluoropolymer and the (meth) acrylic polymer close to each other, which facilitates the formation of a coating film having a uniform composition. From the viewpoint, it is preferably less than 100 nm, more preferably 10 to 80 nm, particularly preferably 20 to 60 nm.
  • the average particle size of the particles of the (meth) acrylic polymer is preferably smaller than the average particle size of the particles of the fluoropolymer from the viewpoint that the fluoropolymer and the (meth) acrylic polymer are uniformly compatible with each other.
  • the content of the fluoropolymer with respect to the total mass of the fluoropolymer and the (meth) acrylic polymer is preferably 5 to 95% by mass, and 30 to 90% by mass from the viewpoint of achieving a good balance between weather resistance and water resistance. Is more preferable, 40 to 85% by mass is further preferable, and 60 to 85% by mass is particularly preferable.
  • the total content of the fluoropolymer particles and (meth) acrylic polymer particles is 10 to 10% with respect to the total mass of the coating composition. 80 mass% is preferable, and 10 to 50 mass% is particularly preferable.
  • the content of the core-shell particles is preferably 10 to 70% by mass with respect to the total mass of the coating composition.
  • the amount of water used may be appropriately determined so that it is preferably 20 to 90 mass% with respect to the total mass of the present coating composition.
  • the fluoropolymer and (meth) acrylic polymer may be obtained by copolymerizing each monomer in the presence of a solvent or a dispersion medium and a radical polymerization initiator.
  • Specific examples of the polymerization method include an emulsion polymerization method, a suspension polymerization method and a solution polymerization method, and the emulsion polymerization method is preferable.
  • the solution may be polymerized to obtain a polymer, and then the solvent may be replaced and dispersed in water.
  • the polymerization temperature and the polymerization time are appropriately selected.
  • a surfactant, a radical polymerization initiator, a chain transfer agent, a chelating agent, a pH adjusting agent and the like may be added.
  • the paint preferably contains a film-forming aid.
  • a film-forming aid having a boiling point of 100 to 400 ° C. is preferable, a film-forming auxiliary having a boiling point of 130 to 300 ° C. is more preferable, and a film-forming auxiliary having a boiling point of 150 to 250 ° C. is particularly preferable.
  • the film forming aid include glycol ether, glycol ether acetate, ester and the like.
  • a film-forming aid having a boiling point in the above range is less likely to evaporate as compared with water when a coating film is formed, and therefore it is possible to prevent the aqueous coating material applied on the substrate from rapidly becoming a coating film.
  • the fluoropolymer and the (meth) acrylic polymer are formed into a coating film while maintaining the uniformity of the composition, and it is presumed that the water resistance of the present coating film is more excellent.
  • it is difficult for the formed coating film to remain in the formed coating film it is difficult for water to be drawn into the coating film, and the water resistance of the present coating film is considered to be more excellent.
  • the film forming aid examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monobenzyl ether, dipropylene glycol mono n-butyl ether, ethylene glycol.
  • glycol ether such as ethylene glycol monoallyl ether
  • glycol ether acetate such as ethylene glycol mono n-butyl ether acetate and diethylene glycol n-monobutyl ether acetate
  • Te SANOL 2,2,4-trimethylpentane-1,3-diol Monoisobutyrate
  • triacetin diethyl adipate, diisodecyl adipate, (2-butoxyethyl), esters such as dibutyl sebacate.
  • the content of the film-forming auxiliary is preferably 1 to 30% by mass, and more preferably 4 to 20% by mass, based on the total mass of the water-based paint, from the viewpoint that the effect of the present invention is exhibited more. More preferably, it is particularly preferably 8 to 18% by mass.
  • This coating contains pigments (inorganic pigments, organic pigments, etc.), surfactants, curing agents, curing aids, thickeners, dispersants, defoamers, light stabilizers, UV absorbers, surface conditioners, etc.
  • the agent may be further included.
  • the dispersion medium of the present coating material mainly contains water.
  • "Mainly containing water” means containing 70% by mass or more of water with respect to the total mass of the dispersion medium, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the dispersion medium may contain components other than water. Examples of components other than water include water-soluble organic solvents. Examples of the water-soluble organic solvent include methanol, ethanol, propanol, butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol and the like.
  • a dispersion liquid in which polymer particles are dispersed in a dispersion medium mainly containing water is also referred to as an aqueous dispersion liquid.
  • one embodiment of the method for producing the present coating material includes a first aqueous dispersion containing a fluoropolymer and a (meth) acrylic polymer.
  • a method of mixing with the second aqueous dispersion to obtain an aqueous coating material containing a fluoropolymer and a (meth) acrylic polymer can be mentioned.
  • the present coating composition contains a core-shell polymer
  • the above-mentioned alkyl (meth) acrylate is polymerized in the presence of an aqueous dispersion of the fluoropolymer to form the fluoropolymer as a core part (meta )
  • a method of obtaining an aqueous paint in which a core-shell polymer having an acrylic polymer as a shell portion is dispersed in a dispersion medium mainly containing water can be mentioned.
  • a known surfactant may be used in the production of the present coating composition.
  • the coated article of the present invention has a base material and a coating film (main coating film) formed on the base material by using the water-based coating material (main coating material).
  • the base material include organic materials such as resin, rubber and wood, inorganic materials such as concrete, glass, ceramics and stone, iron, iron alloys, aluminum and aluminum alloys.
  • the thickness of the coating film is preferably 5 to 300 ⁇ m, particularly preferably 10 to 100 ⁇ m. When the thickness of the main coating film is at least the lower limit value, the durability of the main coating film will be improved, and when it is at most the upper limit value, the weather resistance of the main coating film will be improved.
  • a coated article can be manufactured by applying the present coating material on the surface of a base material and drying it to form the present coating film.
  • the present coating composition may be applied directly to the surface of the base material, or may be applied to the surface of the base material after subjecting the surface of the base material to a known surface treatment (such as base treatment). Further, after the undercoat layer is formed on the substrate, it may be applied on the undercoat layer.
  • Specific examples of the method for applying the present coating material include a method using a coating device such as a brush, roller, dipping, spray, roll coater, die coater, applicator, and spin coater. It is preferable that the present coating film is formed by applying a water-based paint to form a coating layer and drying the obtained coating layer.
  • the drying temperature after coating is preferably 0 to 50 ° C.
  • the present coating film may be formed by forming a coating layer and drying it, and then, if necessary, curing by heating.
  • the heat curing temperature is preferably 50 to 200 ° C.
  • the drying time is usually 30 minutes to 2 weeks, and the heat curing time is usually 1 minute to 24 hours.
  • Examples 1 to 9 and 21 to 29 are Examples, and Examples 10 to 11 and 30 to 31 are Comparative Examples.
  • Dispersion F1 50 mol% of units based on CTFE, 0.5 mol% of units based on CHVE, 47 mol% of units based on EVE and 1.50% of units based on CHMVE with respect to all monomer units contained in the polymer.
  • Dispersion F2 50 mol% of CTFE-based units and CHVE-based units of all monomer units contained in the polymer.
  • Dispersion liquid A2 based on all monomer units contained in the polymer A (meth) acrylic polymer containing 51 mol% of MMA-based units, 39 mol% of IBA-based units, and 10 mol% of 2-EHA-based units (MFT: 3 ° C., SP value: 1.2 (J / cm 3) 1/2 , comprising particles of an average particle diameter of 135 nm), polymer concentration 54% by weight of the aqueous dispersion Dispersion A3: the total monomer units polymer comprises, units based on MMA 66 mol%, the units based on IBA 13 mol%, including the units based on 2-EHA 21 mole% (meth) acrylic polymer (MFT: 13 ° C., SP value: 20.4 (J / cm 3) 1
  • mol% including the units based on 2-EHA 21 mole% (meth) acrylic polymer (MFT:: 13 °C, SP value 20.4 (J / cm 3) 1/2 , average particle size 250 nm)
  • Film-forming aid 1 dipropylene glycol mono-n-butyl ether (boiling point: 230 ° C)
  • Film-forming aid 2 ethylene glycol mono-2-ethylhexyl ether (boiling point: 229 ° C)
  • Film-forming aid 3 ethylene glycol monoallyl ether (boiling point: 159 ° C)
  • Film-forming aid 4 Texanol (boiling point: 260 ° C)
  • Thickener Brand name Rheolate 288 by Elementis
  • the test piece A was immersed in water at 23 ° C. for 15 hours, and the appearance of the coating film on the test piece after immersion was evaluated according to the following criteria. 5: No blister was observed in 80% or more of the surface of the coating film. 4: No swelling was observed in the area of 70% or more and less than 80% of the coated surface. 3: No swelling was observed in the area of 60% or more and less than 70% of the coating film surface. 2: No blistering was observed in the area of 50% or more and less than 60% of the coating film surface. 1: Occurrence of blistering was observed in an area of more than 50% of the coating film surface.
  • the test piece B was measured using a haze meter (trade name “NDH-5000W” manufactured by Nippon Denshoku Co., Ltd.) according to JIS K7136.
  • the difference in particle size is the absolute value of the difference between the average particle size of fluoropolymer particles and the average particle size of (meth) acrylic polymer particles.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne : une matière aqueuse de revêtement permettant de former un film de revêtement ayant une excellente résistance à l'eau ; et un article revêtu. Cette matière aqueuse de revêtement contient un polymère fluoré, un polymère (méth)acrylique et de l'eau ou contient de l'eau et un polymère cœur-écorce dans lequel la partie cœur est un polymère fluoré et la partie écorce est un polymère (méth)acrylique. La teneur d'atomes de fluor dans le polymère fluoré est supérieure ou égale à 25 % en masse. La teneur de motifs monomères ayant un cycle hydrocarboné aliphatique et/ou un cycle aromatique est inférieure ou égale à 5 % en moles par rapport à tous les motifs monomères contenus dans le polymère fluoré. Le polymère (méth)acrylique contient des motifs dérivés d'un (méth)acrylate d'alkyle ayant un groupe alkyle à chaîne ramifiée et ne contient pratiquement pas de motifs monomères ayant un cycle hydrocarboné aliphatique et/ou un cycle aromatique.
PCT/JP2019/042187 2018-10-29 2019-10-28 Matière aqueuse de revêtement et article revêtu Ceased WO2020090749A1 (fr)

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JP2018202755A JP2022013956A (ja) 2018-10-29 2018-10-29 水性塗料および塗装物品

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024075612A1 (fr) * 2022-10-06 2024-04-11 Ａｇｃ株式会社 Composition de matériau de revêtement, et article revêtu

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005162994A (ja) * 2003-12-05 2005-06-23 Daikin Ind Ltd 含フッ素水性分散組成物
JP2012092316A (ja) * 2010-09-27 2012-05-17 Daikin Industries Ltd アクリル−フッ素複合重合体粒子
JP2015067829A (ja) * 2013-10-01 2015-04-13 Jsr株式会社 塗料用組成物、塗料及び塗装体
JP6274339B1 (ja) * 2017-03-29 2018-02-07 旭硝子株式会社 水性分散液

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005162994A (ja) * 2003-12-05 2005-06-23 Daikin Ind Ltd 含フッ素水性分散組成物
JP2012092316A (ja) * 2010-09-27 2012-05-17 Daikin Industries Ltd アクリル−フッ素複合重合体粒子
JP2015067829A (ja) * 2013-10-01 2015-04-13 Jsr株式会社 塗料用組成物、塗料及び塗装体
JP6274339B1 (ja) * 2017-03-29 2018-02-07 旭硝子株式会社 水性分散液

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024075612A1 (fr) * 2022-10-06 2024-04-11 Ａｇｃ株式会社 Composition de matériau de revêtement, et article revêtu

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