WO2015190462A1 - Film de revêtement contenant du fluor ainsi qu'élément extérieur - Google Patents

Film de revêtement contenant du fluor ainsi qu'élément extérieur Download PDF

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Publication number
WO2015190462A1
WO2015190462A1 PCT/JP2015/066568 JP2015066568W WO2015190462A1 WO 2015190462 A1 WO2015190462 A1 WO 2015190462A1 JP 2015066568 W JP2015066568 W JP 2015066568W WO 2015190462 A1 WO2015190462 A1 WO 2015190462A1
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WIPO (PCT)
Prior art keywords
fluorine
coating film
containing coating
titanium oxide
powder
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PCT/JP2015/066568
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English (en)
Japanese (ja)
Inventor
俊 齋藤
将崇 相川
修平 尾知
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旭硝子株式会社
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Publication of WO2015190462A1 publication Critical patent/WO2015190462A1/fr

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    • 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
    • C09D5/03—Powdery paints
    • 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
    • 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
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • the present invention relates to a fluorine-containing coating film and an exterior member provided with the fluorine-containing coating film.
  • acrylic resin powder coating As the powder coating, acrylic resin powder coating, polyester resin powder coating, or epoxy resin powder coating is mainly used. However, cured films formed using these powder paints have the disadvantage of poor weather resistance.
  • Patent Document 1 describes a powder paint comprising a composition containing a hydroxyl group-containing fluororesin and a polyuretdione curing agent or a block isocyanate curing agent as a powder coating containing a fluororesin.
  • Patent Document 2 describes a powder coating containing a fluororesin, a polyester resin, a curing agent, and an ultraviolet absorber.
  • An object of the present invention is to provide a fluorine-containing coating film excellent in weather resistance even for a coating film formed of a powder paint, and an exterior member provided with the fluorine-containing coating film.
  • the present invention has the following configurations [1] to [8].
  • [1] A fluorine-containing coating film formed from a powder paint containing a fluororesin (A) and a titanium oxide pigment (B), A fluorine-containing coating film having a gloss retention (%) of 50% or more as measured in a fluorine-containing coating film having undergone the following accelerated weather resistance test ( ⁇ ).
  • ⁇ accelerated weather resistance test
  • the relative humidity in the test is 70% RH
  • the black panel temperature is 50 ° C.
  • the irradiation intensity of the xenon light source is 80 W / m 2 in the wavelength range of 300 to 400 nm
  • the spraying time of hydrogen peroxide water is 3 minutes
  • the drying time is repeated for 2 minutes.
  • the powder coating material further includes at least one curing agent selected from the group consisting of a ⁇ -hydroxyalkylamide curing agent, a triglycidyl isocyanurate curing agent, and a blocked isocyanate curing agent (D).
  • the fluorine-containing coating film according to any one of [1] to [6].
  • the powder coating further includes at least one non-fluorine resin (C) selected from the group consisting of an acrylic resin, a polyester resin, and an epoxy resin.
  • C non-fluorine resin
  • the fluorine-containing coating film of the present invention is excellent in weather resistance even if it is a coating film formed of a powder coating containing titanium oxide as a pigment.
  • the exterior member of the present invention includes a fluorine-containing coating film having excellent weather resistance.
  • Glass transition temperature means the midpoint glass transition temperature measured by the differential scanning calorimetry (DSC) method.
  • (Meth) acrylate” is a general term for acrylate and methacrylate, and “(meth) acryl” is a general term for “acrylic” and “methacrylic”.
  • the “unit” means a polymer unit derived from a monomer that exists in the polymer and constitutes the polymer. The unit derived from the monomer resulting from addition polymerization of a monomer having a carbon-carbon unsaturated double bond is a divalent unit generated by cleavage of the unsaturated double bond.
  • the unit derived from a polyvalent carboxylic acid compound constituting the polyester resin is a unit derived from a polyhydric alcohol compound, which is a monovalent or higher unit obtained by removing a hydroxyl group from at least one carboxy group of the polyvalent carboxylic acid compound. Is a monovalent or higher unit obtained by removing a hydrogen atom from at least one hydroxyl group of a polyhydric alcohol compound. Moreover, what unitally converted the structure of a unit after polymer formation is also called a unit. Hereinafter, in some cases, a unit derived from an individual monomer is referred to as a name obtained by adding “unit” to the monomer name.
  • the fluorine-containing coating film of the present invention is a fluorine-containing coating film formed from a powder paint containing a fluororesin (A) and a titanium oxide pigment (B), and the following accelerated weather resistance test ( ⁇ ) is performed.
  • the gloss retention measured in the passed fluorine-containing coating film is 50% or more, and the weather resistance is excellent.
  • the coating film having a gloss retention of 50% or more according to the accelerated weather resistance test ( ⁇ ) is particularly Excellent weather resistance in hot and humid areas.
  • the fluorine-containing coating film preferably has a gloss retention of 60% or more after the accelerated weathering test ( ⁇ ) described below, more preferably 70% or more, and particularly preferably 75% or more.
  • the xenon arc radiation 40 hours is the total radiation time. In the present invention, 2 hours of radiation is repeated 20 times for a total of 40 hours. After each irradiation, a cleaning process for 30 minutes is performed to clean the surface of the fluorine-containing coating film with water such as ion exchange water. Xenon arc radiation stops during cleaning. And after each washing
  • the glossiness is calculated according to JIS K 5600-4-7: 1999 (ISO 2813: 1994), and after 40 hours of xenon arc radiation with respect to the 60 ° gloss value of the fluorine-containing coating film immediately before xenon arc radiation.
  • the ratio of the 60 ° gloss value of the fluorine-containing coating film is defined as the gloss retention (unit:%).
  • the fluorine-containing coating film of the present invention has a color difference ( ⁇ E) between just before the xenon arc radiation and after 40 hours of the xenon arc radiation being excellent in weather resistance, so 5.0 or less is preferable, and 3.0 The following is more preferable, and 2.0 or less is particularly preferable.
  • the color measurement of the fluorine-containing coating film is performed using a color difference meter in accordance with JIS K 5600-4-5: 1999, and the color difference is calculated in accordance with JIS K 5600-4-6: 1999.
  • the fluorine-containing coating film has good surface smoothness, irregular reflection due to unevenness on the surface can be suppressed, so that there is less variation in glossiness and higher glossiness. Also, if the surface has large irregularities, the fluorine-containing coating tends to deteriorate from the convex part, the outermost resin is peeled off, and the internal titanium oxide pigment is exposed to promote the deterioration of the entire fluorine-containing coating. It will be. Therefore, if the surface smoothness of the fluorine-containing coating film is good, the gloss retention is also excellent.
  • the surface smoothness of the fluorine-containing coating film can be determined using a standard plate (1 to 10) for visually determining the smoothness of the powder coating film by a powder coating institute (PCI).
  • PCI powder coating institute
  • the numerical value of the standard version for visual judgment of smoothness indicates that the larger the numerical value, the better the surface smoothness.
  • the visual smoothness determination by PCI is preferably 6 or more, more preferably 7 or more, and particularly preferably 8 or more.
  • the water contact angle of the fluorine-containing coating film is preferably 1 to 55 degrees, particularly preferably 3 to 50 degrees. If the water contact angle is equal to or greater than the lower limit, the powder coating film (1) is less likely to be eroded by the organic acid component derived from bird droppings and insect carcasses, and to the surface of the powder coating film (1). Generation of mold is suppressed (generation of mold leads to poor appearance). If a water contact angle is below the said upper limit, it will be excellent in stain resistance.
  • the thickness of the fluorine-containing coating film is preferably 20 to 1,000 ⁇ m, more preferably 20 to 500 ⁇ m, and particularly preferably 20 to 300 ⁇ m. For applications requiring high weather resistance such as outdoor units of air conditioners, signal poles and signs installed along the coast, 100 to 200 ⁇ m is preferable. In addition, when the thickness of a fluorine-containing coating film is thick, the thickness can be achieved by selecting the below-mentioned fluidized immersion method.
  • the powder paint in the present invention contains a fluororesin (A) and titanium oxide (B).
  • the powder coating material may further contain one or more of a non-fluororesin (C), a curing agent (D), a curing catalyst (E), and other components (H) described later, if necessary.
  • fluororesin (A) As a fluororesin (A), the homopolymer or copolymer which has a unit based on a fluoro olefin is mentioned.
  • the fluoroolefin is a compound in which one or more hydrogen atoms of a hydrocarbon-based olefin (general formula C n H 2n ) are substituted with a fluorine atom.
  • the carbon number n of the fluoroolefin is preferably 2-8, and particularly preferably 2-6.
  • the number of fluorine atoms contained in the fluoroolefin is preferably 2 or more, particularly preferably 3 to 4. If the number of fluorine atoms is 2 or more, the cured film has excellent weather resistance.
  • one or more hydrogen atoms not substituted with fluorine atoms may be substituted with chlorine atoms.
  • the fluoroolefin has a chlorine atom, it is easy to disperse pigments (especially colored organic pigments such as cyanine blue and cyanine green) in the fluororesin (A).
  • the glass transition temperature of the fluororesin (A) can be preferably designed to be 30 ° C. or higher, and blocking of the cured film can be suppressed.
  • the fluoroolefin is preferably at least one selected from the group consisting of tetrafluoroethylene (hereinafter referred to as “TFE”), chlorotrifluoroethylene (hereinafter referred to as “CTFE”), hexafluoropropylene and vinyl fluoride. , TFE, or CTFE are particularly preferred.
  • a fluoroolefin may be used individually by 1 type, and may use 2 or more types together.
  • Examples of the homopolymer having a unit based on a fluoroolefin include polyvinylidene fluoride (hereinafter referred to as “PVDF”), polyvinyl fluoride, polychlorotrifluoride and the like. PVDF is particularly preferred from the viewpoints of excellent adhesion to a substrate (particularly an aluminum substrate) and easy fixing of an aluminum curtain wall with a sealing agent.
  • the fluororesin (A) is a copolymer
  • it is a copolymer containing units based on fluoroolefin and units having a reactive group from the viewpoint of excellent antifouling properties, water resistance, acid resistance, and alkali resistance. It is preferable.
  • the copolymer may have units other than the units based on fluoroolefin and the units having reactive groups.
  • the unit having a reactive group may be a unit obtained by polymerizing a monomer having a reactive group, and a compound that decomposes a part of the copolymer or gives a reactive group to a functional group of the copolymer May be a unit obtained by reacting.
  • the reactive group examples include a hydroxyl group, a carboxy group, and an amino group.
  • an isocyanate curing agent particularly a blocked isocyanate curing agent
  • the curing rate is excellent, the pigments are easily dispersed, and the gloss is high (60 ° gloss is 60% or more).
  • a hydroxyl group and a carboxy group are preferable.
  • Examples of the monomer having a hydroxyl group include allyl alcohol, hydroxyalkyl vinyl ether (2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, etc.), hydroxyalkyl allyl ether (2-hydroxyethyl allyl ether, etc.). And vinyl hydroxyalkanoate (such as vinyl hydroxypropionate) and hydroxyalkyl (meth) acrylate (such as hydroxyethyl (meth) acrylate).
  • Examples of the monomer having a carboxyl group include (meth) acrylic acid, carboxyl alkyl vinyl ether, carboxyl allyl ether, and the like. Further, when a carboxyl group can be brought into the functional group of the copolymer, for example, after obtaining a copolymer containing units based on the monomer having a hydroxyl group, the copolymer and an acid anhydride are reacted. Thus, an ester bond and a carboxyl group can be obtained.
  • the acid anhydride is preferably a compound having a molecular weight of 90 to 200, a compound having 4 to 15 carbon atoms, and a compound having a melting point of 20 to 180 ° C. from the viewpoint of excellent reactivity with a hydroxyl group.
  • dibasic acid anhydrides examples include succinic anhydride (molecular weight: 100.1, melting point: 120 ° C., carbon number: 4), glutaric anhydride (molecular weight: 114.1, melting point: 52 ° C., carbon number: 5) Itaconic anhydride (molecular weight: 112.1, melting point: 67 ° C., carbon number: 5), 1,2-cyclohexanedicarboxylic anhydride (hexahydrophthalic anhydride) (molecular weight: 154.0, melting point: 35 ° C., carbon number 8), cis-4-cyclohexene-1,2-dicarboxylic anhydride (molecular weight: 152.0, melting point: 66 ° C., carbon number: 8), phthalic anhydride (molecular weight: 148.1, melting point: 131 ° C., Carbon number: 8), 4-methylhexahydrophthalic anhydride (molecular weight: 100.1, melting point: 120 ° C.,
  • Examples of other units include units based on fluorine-containing monomers other than fluoroolefin, units based on monomers having no fluorine atom and reactive group, and the like.
  • fluorine-containing monomers other than fluoroolefins include fluoro (alkyl vinyl ether).
  • a vinyl monomer is preferable because it is excellent in alternating copolymerization with a fluoroolefin and can increase the polymerization yield.
  • the vinyl monomer is preferable because it has little influence on the cured film even if it remains unreacted and can be easily removed in the production process.
  • Examples of vinyl monomers include vinyl ether, allyl ether, carboxylic acid vinyl ester, carboxylic acid allyl ester, and olefin.
  • vinyl ether examples include cycloalkyl vinyl ether (cyclohexyl vinyl ether (hereinafter referred to as “CHVE”)), alkyl vinyl ether (nonyl vinyl ether, 2-ethylhexyl vinyl ether, hexyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether). Etc.).
  • alkyl ethers include alkyl allyl ethers (ethyl allyl ether, hexyl allyl ether, etc.).
  • carboxylic acid vinyl esters examples include vinyl esters of carboxylic acids (such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid). Further, Veova-9, Veova-10 (both manufactured by Shell Chemical Co., Ltd.) and the like that are commercially available as vinyl esters of carboxylic acids having a branched alkyl group may be used.
  • carboxylic acid allyl esters examples include allyl esters of carboxylic acids (such as acetic acid, butyric acid, pivalic acid, benzoic acid, and propionic acid).
  • the olefin examples include ethylene, propylene, isobutylene and the like.
  • a unit based on cycloalkyl vinyl ether is preferable and a unit based on CHVE is preferable in that the glass transition temperature of the fluororesin (A) can be designed to be 30 ° C. or higher and blocking of the cured film can be suppressed. Particularly preferred.
  • a unit having a linear or branched alkyl group having 3 or more carbon atoms is preferable from the viewpoint of excellent flexibility of the cured film.
  • Other units may be used alone or in combination of two or more.
  • fluororesin (A) examples include TFE-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as “PFA”), TFE-hexafluoropropylene copolymer, TFE-perfluoro (alkyl vinyl ether) -hexafluoropropylene. And a copolymer, an ethylene-TFE copolymer (hereinafter referred to as “ETFE”), an ethylene-CTFE copolymer, and the like.
  • PFA TFE-perfluoro (alkyl vinyl ether) copolymer
  • ETFE ethylene-TFE copolymer
  • CTFE ethylene-CTFE copolymer
  • the following combination (1) is preferable from the point of a weather resistance, adhesiveness, a softness
  • Fluoroolefin TFE or CTFE, Monomer having a hydroxyl group: hydroxyalkyl vinyl ether, Monomer having no fluorine atom and reactive group: one or more selected from cycloalkyl vinyl ether, alkyl vinyl ether and carboxylic acid vinyl ester.
  • Fluoroolefin TFE or CTFE, Monomer having a hydroxyl group: hydroxyalkyl vinyl ether, Monomer having no fluorine atom and reactive group: CHVE or tert-butyl vinyl ether.
  • the proportion of units based on fluoroolefin is preferably from 30 to 70 mol%, particularly preferably from 40 to 60 mol%, based on the total units (100 mol%) in the copolymer. If the unit based on a fluoroolefin is more than the said lower limit, a cured film will be excellent in a weather resistance. If the unit based on fluoroolefin is not more than the above upper limit, when the cured film has a single-layer structure, the adhesiveness between the layer and the substrate is excellent, and when the cured film has a two-layer structure, the fluororesin (A) It is excellent in adhesion between the formed layer and a layer formed of the non-fluororesin (C) described later.
  • the proportion of units having a reactive group is preferably from 0.5 to 20 mol%, particularly preferably from 1 to 15 mol%, based on the total units (100 mol%) in the copolymer.
  • the proportion of the unit having a reactive group is at least the lower limit, when the cured film has a single layer structure, the adhesiveness between the layer and the substrate is excellent, and when the cured film has a two-layer structure, a fluororesin ( The adhesion between the layer formed by A) and the layer formed by the non-fluororesin (C) described later is excellent. If the ratio of the unit having a reactive group is not more than the above upper limit value, the scratch resistance of the cured film is excellent.
  • the proportion of other units is preferably 20 to 60 mol%, particularly preferably 30 to 50 mol%, based on the total units (100 mol%) in the copolymer.
  • the glass transition temperature of the fluororesin (A) can be set in an appropriate range, and the powder coating can be easily manufactured. If the proportion of other units is less than or equal to the above upper limit, when the cured film has a single layer structure, the adhesion between the layer and the substrate is excellent, and when the cured film has a two-layer structure, the fluororesin (A) It is excellent in adhesion between the formed layer and a layer formed of the non-fluororesin (C) described later.
  • the melting point of the fluororesin (A) is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower.
  • the glass transition temperature of the fluororesin (A) is preferably 30 ° C. or higher, and particularly preferably 35 ° C. or higher, from the viewpoint that the powder coating is easy to produce and blocking is easily prevented.
  • the glass transition temperature of the fluororesin (A) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and particularly preferably 100 ° C. or lower from the viewpoint that the surface smoothness of the formed cured film can be further improved.
  • the number average molecular weight of the fluororesin (A) is preferably 3,000 to 50,000, particularly preferably 5,000 to 30,000.
  • the cured film is excellent in water resistance and salt water resistance.
  • the number average molecular weight is not more than the above upper limit, the surface smoothness of the cured film is further improved.
  • the hydroxyl value of the fluororesin (A) is preferably from 5 to 100 mgKOH / g, particularly preferably from 10 to 80 mgKOH / g.
  • the hydroxyl value is not less than the lower limit, when the cured film has a single-layer structure, the adhesiveness between the layer and the substrate is excellent, and when the cured film has a two-layer structure, it is formed of the fluororesin (A). Excellent adhesion between the layer and a layer formed of the non-fluororesin (C) described later.
  • the hydroxyl value is less than or equal to the above upper limit value, the crack resistance of the cured film is excellent under a temperature cycle at a high temperature of 100 ° C. or higher and a low temperature of 10 ° C.
  • the acid value of the fluororesin (A) is preferably from 0.1 to 50 mgKOH / g, more preferably from 1.0 to 4.0 mgKOH / g. If the acid value of a fluororesin (A) is more than the said lower limit, it will be effective in the dispersibility improvement of a pigment, and if it is below the said upper limit, a cured film will be excellent in moisture resistance.
  • the acid value is measured according to JIS K 5601-2-1 (2009).
  • any fluororesin that can be used as a powder coating can be used as appropriate.
  • Lumiflon 710, 710F (trade name, manufactured by Asahi Glass Co., Ltd.), Zeffle (trade name, manufactured by Daikin Industries, Ltd.), Kyner (trade name, manufactured by Arkema Co., Ltd.), ZB-F1000 (trade name, manufactured by Dalian Shinkoku Co., Ltd.) Product), Etaflon (trade name, manufactured by Eternal Co., Ltd.), and DS203 (trade name, manufactured by Todake Shinshu Co., Ltd.).
  • Titanium oxide pigment refers to a pigment containing titanium oxide. Titanium oxide pigment (B) tends to advance the photocatalytic reaction in a hot and humid region. The photocatalytic reaction is promoted by moisture and ultraviolet rays.
  • a coated titanium oxide pigment (B1) surface-treated with one or more of silica, alumina, zirconia, selenium, organic components (polyol, etc.) is preferable.
  • the coated titanium oxide pigment (B1) is a titanium oxide that has been surface-treated so that the photocatalytic reaction does not easily proceed, and has excellent weather resistance.
  • the photocatalytic reaction with titanium oxide hardly proceeds. Therefore, the obtained fluorine-containing coating film is excellent in weather resistance, and the above-mentioned gloss retention (%) by the accelerated weather resistance test ( ⁇ ) falls within the above range. Further, the above-described color difference tends to be in the above range.
  • the coated titanium oxide pigment (B1) is particularly preferably one whose titanium oxide content is adjusted to 80 to 92% by mass. If titanium oxide content is more than the said lower limit, it will be excellent in the whiteness of a fluorine-containing coating film. If the titanium oxide content is less than or equal to the above upper limit value, the photocatalytic reaction is further suppressed, and the above-described gloss retention (%) by the accelerated weather resistance test ( ⁇ ) tends to be in the above range. Further, the above-described color difference tends to be in the above range.
  • the coated titanium oxide pigment (B1) may be used alone or in combination of two or more.
  • coated titanium oxide pigments (B1) include “Taipaque (trade name) PFC105” (titanium oxide content: 87% by mass) and “Taipaque (trade name) CR95” (containing titanium oxide) manufactured by Ishihara Sangyo Co., Ltd. Amount: 90% by mass), “D918” (titanium oxide content: 85% by mass) manufactured by Sakai Chemical Co., Ltd., “Ti-Pure (trade name) R960” (titanium oxide content: 89% by mass) manufactured by DuPont "Ti-Select (trade name)” (titanium oxide content: 90% by mass).
  • the coated titanium oxide pigment (B1) when used as the titanium oxide pigment (B), the coating treatment is not performed or the coating treatment is not sufficient even if the coating treatment is performed.
  • the titanium pigment (B2) (hereinafter, also simply referred to as “titanium oxide pigment (B2)”) may be included, but it is preferably not included from the viewpoint of weather resistance.
  • the titanium oxide pigment (B2) is preferably 30 parts by mass or less and more preferably 20 parts by mass or less with respect to 100 parts by mass of the coated titanium oxide pigment (B1).
  • the titanium oxide pigment (B2) is a titanium oxide pigment having a titanium oxide content of more than 92 mass% and not more than 100 mass%.
  • Non-fluorine resin (C) examples include at least one selected from the group consisting of acrylic resins, polyester resins, polyurethane resins, epoxy resins, and silicone resins. Among them, the point of excellent adhesion to the substrate, the fluororesin (A) and the non-fluororesin (C) can be easily separated when formed into a coating film, and the surface layer is formed with a layer of the fluororesin (A). From the viewpoint of excellent weather resistance, an acrylic resin or a polyester resin is preferable, and a polyester resin is particularly preferable.
  • the acrylic resin is a polymer having units based on (meth) acrylate.
  • an acrylic resin what has reactive groups, such as a carboxy group, a hydroxyl group, and a sulfo group, is mentioned.
  • the acrylic resin can improve the dispersibility of the pigment.
  • the glass transition temperature of the acrylic resin is preferably 30 to 60 ° C, more preferably 32 to 58 ° C. If the glass transition temperature is equal to or higher than the lower limit, blocking is difficult. If the glass transition temperature of the acrylic resin is not more than the above upper limit value, the surface smoothness of the cured film is further improved.
  • the number average molecular weight of the acrylic resin is preferably 5,000 to 100,000, particularly preferably 30,000 to 100,000. If the number average molecular weight of the acrylic resin is not less than the lower limit, blocking is difficult. If the number average molecular weight of the acrylic resin is not more than the upper limit, the surface smoothness of the cured film can be further improved.
  • the mass average molecular weight of the acrylic resin is preferably 6,000 to 150,000, more preferably 40,000 to 150,000, and particularly preferably 60,000 to 150,000. If the mass average molecular weight of the acrylic resin is not less than the lower limit, blocking is difficult. If the mass average molecular weight of the acrylic resin is not more than the above upper limit value, the surface smoothness of the cured film can be further improved.
  • the acid value of the acrylic resin is preferably 30 to 400 mgKOH / g, more preferably 35 to 300 mgKOH / g. If the acid value of the acrylic resin is not less than the lower limit, there is an effect of improving the dispersibility of the pigment. If the acid value of an acrylic resin is below the said upper limit, a cured film will be excellent in moisture resistance.
  • acrylic resins include “Fine Dick (trade name) A-249”, “Fine Dick (trade name) A-251”, “Fine Dick (trade name) A-266” manufactured by DIC, Mitsui Chemicals, Inc. “Almatex (trade name) PD6200” manufactured by the company, “Almatex (trade name) PD7310”, “Sanpex PA-55” manufactured by Sanyo Chemical Industries, Ltd., and the like.
  • the polyester resin has a unit based on a polyvalent carboxylic acid compound and a unit based on a polyhydric alcohol compound, and if necessary, a unit other than these two types of units (for example, a unit based on a hydroxycarboxylic acid compound). You may have.
  • the polyester resin has at least either a carboxy group or a hydroxyl group at the end of the polymer chain.
  • the polyvalent carboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, trimellitic acid, pyromellitic acid, phthalic anhydride, and the like. From the point that the cured film has excellent weather resistance, isophthalic acid Is preferred.
  • polyhydric alcohol compound an aliphatic polyhydric alcohol or an alicyclic polyhydric alcohol is preferable, and an aliphatic polyhydric alcohol is more preferable from the viewpoint of excellent adhesion to the substrate and flexibility of the cured film.
  • polyhydric alcohol compounds include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • the polyhydric alcohol neopentyl glycol, 1,2-pentanediol, 1,5-pentanediol, trimethylolpropane and the like are preferable, and neopentylglycol or trimethylolpropane is particularly preferable from the viewpoint of easy availability.
  • polyester resins include “CRYLCOAT (trade name) 4642-3” and “CRYLCOAT (trade name) 4890-0” manufactured by Daicel Ornex Corporation, “GV-250” and “GV- 740 ",” GV-175 “and the like.
  • the curing agent (D) refers to a compound having two or more reactive groups, and at least one of the reactive groups is a reactive group that can react with the reactive group of the fluororesin (A).
  • the curing agent (D) is preferably contained in the powder coating material when the fluororesin (A) has a reactive group (hydroxyl group, carboxy group, etc.).
  • the curing agent (D) cures the fluororesin (A) by reacting with the reactive group to crosslink the fluororesin (A) or to increase the molecular weight.
  • the reactive group of the curing agent (D) does not react with the reactive group of the fluororesin (A) at room temperature, it is a reactive group that can react when the powder coating is heated and melted.
  • a blocked isocyanate group is preferable to an isocyanate group having a highly reactive group at room temperature. The blocked isocyanate group is released from the blocking agent when the powder coating is heated and melted to form an isocyanate group, and the isocyanate group acts as a reactive group.
  • the curing agent (D) known compounds can be used.
  • blocked isocyanate curing agents amine curing agents (melamine resin, guanamine resin, sulfoamide resin, urea resin, aniline resin, etc.), ⁇ -Hydroxyalkylamide type curing agents and triglycidyl isocyanurate type curing agents.
  • a blocked isocyanate curing agent is particularly preferred from the viewpoint of excellent adhesion to the substrate, workability of the product after coating, and water resistance of the fluorine-containing coating film.
  • the curing agent is preferably a ⁇ -hydroxyalkylamide curing agent or a triglycidyl isocyanurate curing agent.
  • curing agent (D) may be used individually by 1 type, and may use 2 or more types together.
  • the softening temperature of the curing agent (D) is preferably 10 to 120 ° C, particularly preferably 40 to 100 ° C.
  • the softening temperature is equal to or higher than the lower limit, the powder coating is difficult to cure at room temperature, and it is difficult to form a granular lump. If the softening temperature is not more than the above upper limit value, when the composition is melt-kneaded to produce a powder, the curing agent (D) can be easily dispersed homogeneously in the powder, and the surface of the resulting fluorine-containing coating film can be smoothed. Excellent in properties, strength, moisture resistance, etc.
  • the blocked isocyanate curing agent is preferably a solid at room temperature.
  • a polyisocyanate obtained by reacting an aliphatic, aromatic or araliphatic diisocyanate with a low molecular weight compound having active hydrogen is reacted with a blocking agent, Those produced by masking are preferred.
  • Diisocyanates include tolylene diisocyanate, 4,4′-diphenylmethane isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis (Isocyanate methyl) cyclohexane isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate and the like.
  • Low molecular weight compounds having active hydrogen include water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, ethanolamine, diethanolamine, hexamethylenediamine, isocyanurate, uretidione, a low molecular weight polyester containing a hydroxyl group, Examples include polycaprolactone.
  • the blocking agent examples include alcohols (methanol, ethanol, benzyl alcohol, etc.), phenols (phenol, crezone, etc.), lactams (caprolactam, butyrolactam, etc.), and oximes (cyclohexanone, oxime, methyl ethyl ketoxime, etc.).
  • the curing catalyst (E) accelerates the curing reaction and imparts good chemical performance and physical performance to the fluorine-containing coating film.
  • the curing catalyst (E) is preferably a tin catalyst (such as tin octylate, tributyltin laurate, dibutyltin dilaurate).
  • a hardening catalyst (E) may be used individually by 1 type, and may use 2 or more types together.
  • the surface conditioner (F) can be appropriately used as long as it improves the surface smoothness of the fluorine-containing coating film.
  • the glass transition temperature of the fluororesin (A) tends to be high in order to suppress blocking.
  • the coating film which consists of a melt of a powder coating material it is easy to contain air and it is difficult to fully obtain the surface smoothness of a fluorine-containing film.
  • a leveling agent that is unevenly distributed on the surface of the fluorine-containing coating a plasticizer that lowers the melt viscosity of the fluororesin (A), and an inorganic that fills the gaps in the fluorine-containing coating Examples include fine particles.
  • Leveling agent Commercially available leveling agents include trade names “BYK (trade name) -361N”, “BYK (trade name) -360P”, “BYK (trade name) -364P”, “BYK (trade name)” manufactured by Big Chemie. -368P ",” BYK (product name) -3900P ",” BYK (product name) -3931P “,” BYK (product name) -3933P “,” BYK (product name) -3950P “,” BYK (product name) " -3951P “,” BYK (trade name) -3955P ", and the like.
  • a plasticizer having a cyclic hydrocarbon group in the molecule is preferable.
  • the cyclic hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
  • compatibility with the resin component is improved, and the plasticizer is less likely to bleed out on the surface of the coating film. Therefore, blocking of the coating film can be suppressed, and a coating film having excellent coating film appearance and surface smoothness can be obtained.
  • the melting point of the plasticizer is preferably 60 to 200 ° C., more preferably 60 to 180 ° C., and particularly preferably 70 to 160 ° C. If melting
  • the molecular weight of the plasticizer is preferably 200 to 1,000, more preferably 220 to 980, and particularly preferably 240 to 960. If the molecular weight of the plasticizer is at least the lower limit of the above range, the volatility is low, the effect of reducing the melt viscosity of the molten film is sufficiently exerted, and a coating film with excellent coating film appearance and surface smoothness is obtained. Cheap. If the molecular weight of the plasticizer is not more than the upper limit of the above range, the plastic effect is suppressed from being excessively exhibited, and the coating film is prevented from being blocked.
  • plasticizer examples include the following. Dicyclohexyl phthalate (melting point: 68 ° C., molecular weight: 330), hexabromocyclododecane (melting point: 180 ° C., molecular weight: 641), tribenzoic acid glyceride (melting point: 68 ° C., molecular weight: 404), tetrabenzoic acid pentaerythritol (melting point) : 108 ° C., molecular weight: 552), 1,4-cyclohexanedimethanol dibenzoate (melting point: 118 ° C., molecular weight: 352).
  • inorganic fine particles examples include fine particles of silica, alumina, zirconia, and talc.
  • the average particle diameter of the inorganic fine particles is preferably 0.01 to 500 nm, more preferably 0.05 to 400 nm, and particularly preferably 0.1 to 300 nm.
  • examples of the inorganic fine particles include the following.
  • Silica Product name “AEROSIL (trade name) R972” (manufactured by Evonik), Alumina: Product name “A-42” (manufactured by Showa Denko KK), Zirconia: Product name “ELCOM V-9” (manufactured by JGC Catalysts and Chemicals) ), Talc: Product name "NANO-ACE” (Matsuo Sangyo Co., Ltd.)
  • the other components (H) of the powder coating in the present invention are fluororesin (A), titanium oxide (B), non-fluororesin (C), curing agent (D), curing catalyst (E), surface conditioner ( Components other than F).
  • Other components (H) include ultraviolet absorbers, light stabilizers, matting agents, surfactants (nonionic, cationic, or anionic), degassing agents (air entrained in powders, curing agents (C1) ) To remove the blocking agent, moisture, etc. coming out of the coating film from staying inside the powder coating film, although it is usually a solid, it becomes very low viscosity when melted. , Fillers, heat stabilizers, dispersants, antistatic agents, rust preventives, silane coupling agents, antifouling agents, antifouling treatment agents, and other pigments other than the titanium oxide pigment (B). .
  • UV absorber As the ultraviolet absorber, either an organic ultraviolet absorber or an inorganic ultraviolet absorber can be used.
  • An ultraviolet absorber may be used individually by 1 type, or may be used in combination of 2 or more type.
  • organic ultraviolet absorbers include salicylic acid ester ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.
  • the organic ultraviolet absorber a compound having a molecular weight of 200 to 1,000 is preferable. If the molecular weight is 200 or more, it is difficult to volatilize in the process of forming the fluorine-containing coating film and can remain in the fluorine-containing coating film. If the molecular weight is 1,000 or less, it is easy to disperse in the fluorine-containing coating film.
  • the organic ultraviolet absorber a compound having a melting point of 50 to 150 ° C. is preferable.
  • the melting point is 50 ° C. or higher, it is difficult to volatilize in the process of forming the fluorine-containing coating film and can remain in the fluorine-containing coating film.
  • the melting point is 150 ° C. or lower, the film easily melts in the process of forming the fluorine-containing coating film and is easily dispersed in the fluorine-containing coating film.
  • a compound having a volatilization temperature of 180 to 450 ° C. is preferable, and a compound having a 220 to 400 ° C. is particularly preferable. Since a temperature condition of 150 to 220 ° C. is required in the process of forming the powder coating film (1), it is difficult to volatilize within the above range and can remain in the fluorine-containing coating film.
  • inorganic ultraviolet absorbers include filler-type inorganic ultraviolet absorbers containing ultraviolet absorbing oxides (such as zinc oxide and cerium oxide).
  • ultraviolet absorbing oxides such as zinc oxide and cerium oxide.
  • composite particles of zinc oxide and titanium oxide, composite particles of cerium oxide and titanium oxide, composite particles of zinc oxide and cerium oxide, composite particles of titanium oxide, zinc oxide and cerium oxide are preferable.
  • a hindered amine light stabilizer is preferable, and a hindered amine light stabilizer having a molecular weight of 300 to 5,000 and a melting point of 50 to 250 ° C. is more preferable.
  • a hindered amine light stabilizer having a molecular weight of 400 to 4,000 and a melting point of 60 to 200 ° C. is more preferable from the viewpoint of uniformly diffusing into the composition at the time of kneading.
  • a compound having a volatilization temperature of 180 to 450 ° C. is preferable, and a compound having a temperature of 220 to 400 ° C. is particularly preferable. Since a temperature condition of 150 to 220 ° C. is required in the process of forming the fluorine-containing coating film, it is difficult to volatilize and stay in the fluorine-containing coating film within the above range.
  • a light stabilizer may be used individually by 1 type and may use 2 or more types together.
  • hindered amine light stabilizers include “Tinuvin (trade name) 111FDL” (molecular weight: 2,000 to 4,000, melting point: 115 to 150 ° C.) and “Tinuvin (trade name) 144” manufactured by BASF.
  • the pigment other than the titanium oxide pigment (B) at least one selected from the group consisting of luster pigments, rust preventive pigments, colored pigments and extender pigments is preferable.
  • the bright pigment is a pigment for brightening the coating film. Examples of the bright pigment include aluminum powder, nickel powder, stainless steel powder, copper powder, bronze powder, gold powder, silver powder, mica powder, graphite powder, glass flake, and scale-like iron oxide powder.
  • the rust preventive pigment is a pigment for preventing the corrosion and alteration of the base material with respect to the base material that requires the antirust property.
  • a lead-free rust preventive pigment having a low environmental load is preferable.
  • lead-free rust preventive pigments include cyanamide zinc, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, and calcium cyanamide zinc.
  • the color pigment is a pigment for coloring the coating film.
  • examples of the color pigment include carbon black, iron oxide, phthalocyanine blue, phthalocyanine green, quinacridone, isoindolinone, benzimidazolone, dioxazine and the like.
  • the extender pigment is a pigment for improving the hardness of the fluorine-containing coating film and increasing the thickness of the fluorine-containing coating film. It is also preferable to add it because the cut surface of the fluorine-containing coating film can be cleaned when a coated article such as a building exterior member is cut.
  • extender pigments include talc, barium sulfate, mica, and calcium carbonate.
  • the content of each component contained in the powder coating in the present invention is preferably as follows.
  • the content of the titanium oxide pigment (B) in the powder coating is preferably 20 to 250 parts by mass, particularly preferably 50 to 220 parts by mass with respect to 100 parts by mass of the fluororesin (A). If it exists in the said range, the above-mentioned gloss retention (%) of the fluorine-containing coating film by an accelerated weather resistance test ((alpha)) will become easily in the said range. Further, the above-described color difference tends to be in the above range.
  • the content of the non-fluororesin (C) is preferably 10 to 90 parts by mass, and 20 to 80 parts by mass with respect to 100 parts by mass of the fluororesin (A). Part is more preferable, and 30 to 70 parts by weight is particularly preferable.
  • the content of the curing agent (D) is preferably 1 to 50 parts by mass, preferably 3 to 30 parts by mass with respect to 100 parts by mass of the fluororesin (A). Particularly preferred.
  • the curing agent (D) is a blocked isocyanate curing agent
  • the fluororesin (A) preferably has a hydroxyl group.
  • the content of the blocked isocyanate curing agent is preferably such that the molar ratio of the isocyanate group to the hydroxyl group of the fluororesin (A) is 0.05 to 1.5, preferably 0.8 to 1.2. The amount is particularly preferred.
  • the molar ratio is not less than the lower limit, the degree of curing of the powder coating is increased, and the hardness and chemical resistance of the fluorine-containing coating film are excellent.
  • the molar ratio is not more than the above upper limit, the fluorine-containing coating film is not easily brittle, and the heat resistance, chemical resistance, moisture resistance and the like are excellent.
  • the content of the curing catalyst (E) is 0.0001 based on 100 parts by mass of the total solid content other than the titanium oxide pigment (B) of the powder coating. Up to 10.0 parts by mass is preferred. If content of a curing catalyst (E) is more than the said lower limit, a catalyst effect will be fully easy to be acquired. If the content of the curing catalyst (E) is not more than the above upper limit value, the gas such as air entrained in the powder coating during the melting and curing process of the powder coating is likely to escape, and the content of the curing catalyst (E) is caused by the remaining gas. Little decrease in heat resistance, weather resistance and water resistance of fluorine coating.
  • the content of the surface conditioner (F) is preferably 0.1 to 15.0 parts by mass with respect to 100 parts by mass of the fluororesin (A). 1.0 to 10.0 parts by mass is more preferable, and 1.5 to 8.0 parts by mass is particularly preferable.
  • the surface conditioner (F) is in the above range, the surface smoothness is excellent, and the above-described gloss retention (%) of the fluorine-containing coating film by the accelerated weather resistance test ( ⁇ ) tends to be in the above range.
  • the powder coating contains another component (H)
  • the total content of the other components (H) is preferably 45% by mass or less, and 30% by mass or less in the powder coating (100% by mass). Particularly preferred.
  • the powder coating can be produced by a known method. For example, the following method is mentioned.
  • Method I A method in which the fluororesin (A) and titanium oxide (B) as raw materials are each pulverized in advance and then mixed.
  • Method II A method in which these raw materials are mixed in a solid state and then pulverized into a powder.
  • Method III A method in which these raw materials are mixed in a solid state, then melt-kneaded, cooled to form a lump, and pulverized into a powder.
  • the method III is preferable because a cured film having excellent homogeneity can be obtained by uniformly distributing each component in the obtained powder.
  • the mixing of the raw materials may be liquid or dry blend, and can be performed using a known mixer.
  • the mixer include a high-speed mixer, a V-type mixer, an inverting mixer, a high-speed mixer, a double cone mixer, a kneader, a dumpler mixer, a mixing shaker, a drum shaker, and a rocking shaker.
  • the melt-kneading can be performed using various types of extruders such as a single shaft, a twin shaft, and a planetary gear.
  • the mixture of each component is kneaded in a heated and melted state, and each component is made uniform.
  • the extruded melt-kneaded product is preferably cooled to pellets.
  • the pellets can be pulverized using a known pulverizer. Examples of the type of pulverizer include a pin mill, a hammer mill, and a jet mill.
  • Classification is preferably performed after pulverization. When performing classification, it is preferable to remove at least one of particles having a particle diameter of less than 10 ⁇ m and particles having a particle diameter exceeding 100 ⁇ m.
  • Examples of the classification method include a screening method and an air classification method.
  • the particle size of the particles contained in the powder coating is preferably about 25 to 50 ⁇ m with a 50% average volume particle size distribution, for example.
  • the particle size of the particles is measured using a generally used particle size measuring instrument.
  • Examples of the format of the particle size measuring device include a format that captures a potential change when passing through a pore, a laser diffraction method, an image determination format, a sedimentation velocity measurement method, and the like.
  • the powder coating material in the present invention includes a non-fluororesin (C), a curing agent (D), a curing catalyst (E), and other components (F), mixing, melt-kneading, and pulverization are similarly performed. be able to.
  • a fluorine-containing coating film can be manufactured with the manufacturing method which has the following process (1) and process (2).
  • Step (1) A step of coating a base material with a powder coating material to form a coating film made of a melt of the powder coating material.
  • Step (2) A step of cooling the coating film to form a fluorine-containing coating film.
  • a powder coating is applied to the base material to form a coating film made of a melt of the powder coating on the base material.
  • a reactive component is contained in each layer, a curing reaction occurs.
  • the coating film consisting of the powder coating melt may be formed at the same time as the coating of the powder coating on the substrate. After the powder coating is adhered to the substrate, the powder coating is heated and melted on the substrate. May be formed. If the powder coating contains a reactive component, the curing reaction of the reactive component starts almost simultaneously with the powder coating being heated and melted. It is necessary to heat and melt the powder coating after the powder coating adheres to the substrate.
  • a heating temperature (hereinafter also referred to as “baking temperature”) and a heating maintenance time (hereinafter also referred to as “baking time”) for heating and melting the powder coating material and maintaining the molten state for a predetermined time are: It is appropriately set depending on the type and composition of the raw material components of the powder coating material, the desired thickness of the fluorine-containing coating film, and the like.
  • the baking temperature is preferably set according to the reaction temperature of the curing agent (D).
  • the baking temperature when a blocked polyisocyanate curing agent is used as the curing agent (D) is preferably 170 to 210 ° C.
  • the baking time is preferably 5 to 120 minutes, particularly preferably 10 to 60 minutes.
  • the heating temperature and the heating maintenance time are determined according to the melting point of the fluororesin (A) and the like.
  • Examples of coating methods include electrostatic coating, electrostatic spraying, electrostatic dipping, spraying, fluid dipping, spraying, spraying, thermal spraying, plasma spraying, and the like. Even when the coating film is made thin, an electrostatic coating method using a powder coating gun is preferable from the viewpoint of excellent surface smoothness of the coating film and excellent concealability of the fluorine-containing coating film.
  • Examples of the powder coating gun include a corona charging type coating gun and a friction charging type coating gun.
  • the corona electrification type coating gun sprays powder paint after corona discharge treatment.
  • the friction charging type coating gun sprays a powder coating after friction charging.
  • the discharge amount of the powder paint from the powder coating gun is preferably 50 to 200 g / min.
  • the distance from the tip of the gun portion of the powder coating gun to the substrate is preferably 150 to 400 mm from the viewpoint of coating efficiency.
  • the load voltage applied to the components constituting the powder coating by corona discharge treatment is preferably ⁇ 50 to ⁇ 100 kV, and the coating efficiency (the ratio at which the powder coating adheres to the substrate) From the viewpoint of excellent appearance of the coating film, ⁇ 60 to ⁇ 80 kV is preferable.
  • the internally generated current value of the powder coating by the frictional charging treatment is preferably 1 to 8 ⁇ A from the viewpoint of excellent coating efficiency and appearance of the coating film.
  • an unpainted mirror (base material) and a grounded conductive horizontal belt conveyor for grounding are installed in the coating room.
  • a gun at the top of the painting chamber.
  • the coating pattern width is preferably 50 to 500 mm
  • the operation speed of the gun is preferably 1 to 30 m / min
  • the conveyor speed is preferably 1 to 50 m / min, and conditions suitable for the purpose may be selected from the above range.
  • the fluid immersion method is preferable from the viewpoint that a relatively thick fluorine-containing coating film can be formed.
  • a substrate whose coating surface is heated to a temperature equal to or higher than the melting temperature of the powder coating material in a fluid tank in which the powder coating material that is flowing and supported by a gas such as air is accommodated.
  • the coated base material is taken out of the fluid tank, and in some cases for a predetermined time. It is preferable to maintain the molten state of the coating and then cool.
  • the temperature in the fluidized tank is preferably 15 to 55 ° C, and the temperature of gas such as air blown into the fluidized tank in order to fluidize the powder is also preferably 15 to 55 ° C.
  • the temperature of at least the coated surface of the substrate when immersed in the fluidized tank is preferably 300 to 450 ° C., and the time for which the substrate is immersed in the fluidized tank is preferably 1 to 120 seconds.
  • the substrate taken out from the fluidized tank is preferably maintained at a temperature of 150 to 250 ° C. for 1 to 5 minutes.
  • the molten coating film is cooled to room temperature (20 to 25 ° C.) to form a fluorine-containing coating film.
  • the cooling after baking may be either rapid cooling or slow cooling.
  • the exterior member of the present invention is a member provided with the fluorine-containing coating film of the present invention on a substrate.
  • a base material what consists of metals, such as aluminum, iron, magnesium, for example, is preferable, and aluminum is especially preferable from the point which is excellent in corrosion resistance, is lightweight, and has the performance excellent in building material uses, such as an exterior member.
  • the shape, size, etc. of the substrate are not particularly limited.
  • an exterior member of the present invention it is only necessary to provide a base material with a fluorine-containing coating film.
  • aluminum composite panels, aluminum panels for curtain walls, aluminum frames for curtain walls, aluminum window frames, etc. Examples include exterior members such as exterior members, petroleum tanks, natural gas tanks, ceramic building materials, housing exterior materials, automobile members, aircraft members, railway vehicle members, solar cell BS members, wind power generation towers, wind power generation blades, and the like.
  • Examples 1, 3 to 6 are examples, and examples 2, 7, and 8 are comparative examples.
  • the gloss retention (%) and color difference ( ⁇ E) are calculated from the results before and after the accelerated weather resistance test ( ⁇ ).
  • the specific evaluation is as follows.
  • the gloss retention (%) was measured in accordance with JIS K 5600-4-7: 1999 (ISO 2813: 1994), and the 60 ° gloss value of the fluorine coating immediately before xenon arc radiation was defined as 100%.
  • the ratio of the 60 ° gloss value of the fluorine-containing coating film after 40 hours of xenon arc radiation is calculated. From the calculated gloss retention, weather resistance was evaluated according to the following criteria.
  • the gloss meter uses “PG-1M” manufactured by Nippon Denshoku Industries Co., Ltd.
  • the color difference ( ⁇ E) between immediately before xenon arc radiation and 40 hours after xenon arc radiation was also determined as follows. That is, a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the color measurement of the surface of the fluorine-containing coating film immediately before xenon arc radiation and to measure the color measurement of the surface of the fluorine-containing coating film 40 hours after xenon arc radiation. , SA4000). The measurement was based on JIS K 5600-4-5: 1999.
  • Fluorine resin (A-1) hydroxyl group-containing fluoropolymer (manufactured by Asahi Glass Co., Ltd., Lumiflon (trade name) LF710F, hydroxyl value: 51.3 mg KOH / g, glass transition temperature: 55 ° C., number average molecular weight: 10,000).
  • Fluororesin (A-2) PVDF (manufactured by SHENZHOU NEWMATERIAL (Tougaku), PVDF DS203, mass average molecular weight: 270,000, number average molecular weight: 160,000).
  • Titanium oxide pigment (B1) and titanium oxide pigment (B2) Titanium oxide pigment (B1-1): Taipure R960 (trade name, manufactured by DuPont, titanium oxide content: 89% by mass, coated metal: silica, alumina). Titanium oxide pigment (B1-2): Taipei PFC105 (trade name, manufactured by Ishihara Sangyo Co., Ltd., titanium oxide content: 87% by mass, coating metal: silica, alumina, zirconia). Titanium oxide pigment (B1-3): D918 (trade name, manufactured by Sakai Chemical Co., Ltd., titanium oxide content: 85% by mass, coating metal: silica, alumina, zirconia).
  • Polyester resin CRYLCOAT 4890-0 (trade name, manufactured by Daicel Ornex)
  • Curing agent (D) Blocked isocyanate curing agent (Evonik's Vestagon (trade name) B1530).
  • Examples 1, 2, 4 to 8 Each component shown in Table 1 was mixed for about 10 to 30 minutes using a high-speed mixer (manufactured by Amagasaki Co., Ltd.) in the parts by mass shown in Table 1 to obtain a powdery mixture. The mixture was melt kneaded at a barrel setting temperature of 120 ° C. using a twin-screw extruder (manufactured by Thermo Prism, 16 mm extruder) to obtain powder pellets.
  • the obtained pellets were pulverized at room temperature using a pulverizer (manufactured by FRITSCH, rotor speed mill P14), classified by a 150 mesh sieve, and the average particle size (50% average volume particle size distribution) was about A 40 ⁇ m powder coating was obtained.
  • the obtained powder coating material was electrostatically coated with an electrostatic coating machine (GX3600C, manufactured by Onoda Cement Co., Ltd.) on one side of the chromate-treated aluminum plate, and held in a 200 ° C. atmosphere for 20 minutes. It was allowed to cool to room temperature to obtain an aluminum plate having a fluorine-containing coating film having a thickness of 55 to 65 ⁇ m.
  • the accelerated weather resistance test ( ⁇ ) using the obtained fluorine-containing coated aluminum plate as a test piece the gloss retention and color difference described in Table 1 were obtained. The results are shown in Table 1.
  • Example 3 Manufacturing method of acrylic resin 2 g of 200 mL of deionized water and reactive emulsifier (manufactured by Sanyo Kasei Kogyo Co., Ltd., Eleminol (trade name) JS-2, succinic acid ester derivative) in a 1 L 4-neck flask equipped with a condenser and a thermometer 2 g of polyoxyethylene nonylphenyl ether (10 mol addition of ethylene oxide) were introduced. When the temperature reached 80 ° C. in a warm bath under a nitrogen stream, 20 mL of a 2 mass% aqueous solution of ammonium persulfate was added.
  • a mixture of 140.2 g of methyl methacrylate, 80.0 g of ethyl methacrylate, and 0.2 g of n-lauryl mercaptan as a chain transfer agent was added dropwise over 1 hour.
  • 2 mL of a 2 mass% aqueous solution of ammonium persulfate was added to initiate the reaction.
  • the temperature in the flask was raised to 85 ° C. and held for 1 hour, and then filtered through a 300-mesh wire mesh to obtain a blue-white aqueous dispersion.
  • the aqueous dispersion was frozen and coagulated at ⁇ 25 ° C., dehydrated and washed, and then vacuum dried at 80 ° C. to obtain 209.2 g of a white powdery acrylic resin.
  • the obtained acrylic resin had a glass transition temperature of 56.6 ° C., a mass average molecular weight of 92,000, and a number average molecular weight of 43,000.
  • Example 3 Each component shown in Table 1 was used in parts by mass shown in Table 1 to obtain a powder coating material of Example 3.
  • a powder paint was obtained in the same manner as in Examples 1, 2, 4 to 8, except that the barrel set temperature was 190 ° C. when obtaining the pellets.
  • the obtained powder coating material was electrostatically coated on one surface of an aluminum plate subjected to chromate treatment with an electrostatic coating machine (GX3600C, manufactured by Onoda Cement Co., Ltd.) and held in a 250 ° C. atmosphere for 20 minutes.
  • the plate was allowed to cool to room temperature to obtain an aluminum plate having a powder coating film having a thickness of 55 to 65 ⁇ m.
  • ⁇ accelerated weather resistance test
  • the fluorine-containing coating film of the present invention is useful as a coating film provided on articles (base materials) used outdoors, and in particular, exterior members (aluminum composite panels, aluminum panels for curtain walls, aluminum frames for curtain walls, This is useful as a fluorine-containing coating provided on an aluminum window frame.

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Abstract

　L'invention concerne un film de revêtement contenant du fluor, lequel film contient de l'oxyde de titane en tant que pigment, et lequel film est excellent en termes de résistance aux intempéries. L'invention concerne également un élément extérieur mettant en oeuvre ce film.　Plus spécifiquement, ce film de revêtement contenant du fluor est constitué d'un matériau de revêtement pulvérulent contenant (A) une fluororésine et (B) un pigment d'oxyde de titane. En outre, pour ce film de revêtement contenant du fluor, le taux (%) de rétention de brillance mesuré par un essai (α) accéléré de résistance aux agents intempériques est supérieur ou égal à 50%. L'essai (α) accéléré de résistance aux agents intempériques consiste, au moyen d'un weatheromètre au xénon, à émettre dans le film de revêtement contenant du fluor, un arc au xénon. En plus de la vaporisation d'une solution de peroxyde d'hydrogène à 1% en masse à la place de l'eau dans le film de revêtement contenant du fluor, l'essai est conforme à la procédure de la norme JIS K 5600-7-7.　Le taux de rétention de brillance correspond au pourcentage (%) de la valeur du degré de brillance à 60° du film de revêtement contenant du fluor après 40 minutes d'émission d'arc au xénon, par rapport à une valeur du degré de brillance à 60° de ce même film de revêtement juste avant l'émission de l'arc au xénon.
PCT/JP2015/066568 2014-06-09 2015-06-09 Film de revêtement contenant du fluor ainsi qu'élément extérieur WO2015190462A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2014-118759 2014-06-09
JP2014118759 2014-06-09
JP2014177541 2014-09-01
JP2014-177541 2014-09-01
JP2015-040534 2015-03-02
JP2015040534 2015-03-02

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WO2015190462A1 true WO2015190462A1 (fr) 2015-12-17

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WO2016139966A1 (fr) * 2015-03-02 2016-09-09 旭硝子株式会社 Composition de revêtement en poudre, revêtement en poudre, et article revêtu
CN106189709A (zh) * 2016-08-14 2016-12-07 安庆市沁之源电器有限公司 一种电风扇抗氧化涂料及其制备方法
WO2017119373A1 (fr) * 2016-01-04 2017-07-13 旭硝子株式会社 Composition de revêtement en poudre, procédé de production de composition de revêtement en poudre, et article revêtu
WO2017130841A1 (fr) * 2016-01-25 2017-08-03 旭硝子株式会社 Matériau de revêtement en poudre, procédé de production d'un matériau de base pourvu d'un film de revêtement et article revêtu
CN107036959A (zh) * 2017-04-14 2017-08-11 攀钢集团研究院有限公司 钛白粉耐候性快速检测方法
WO2019177170A1 (fr) * 2018-03-16 2019-09-19 ダイキン工業株式会社 Film de revêtement et article revêtu
WO2019240186A1 (fr) * 2018-06-12 2019-12-19 Ａｇｃ株式会社 Matériau de revêtement en poudre, son procédé de production, procédé de production d'un matériau de base pourvu d'un film de revêtement et article revêtu

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WO2001025346A1 (fr) * 1999-10-04 2001-04-12 Daikin Industries, Ltd. Composition de revetement pulverulent a resistance aux intemperies elevees
WO2014002964A1 (fr) * 2012-06-29 2014-01-03 旭硝子株式会社 Composition de revêtement en poudre, procédé de production d'un film durci, et article revêtu

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WO2001025346A1 (fr) * 1999-10-04 2001-04-12 Daikin Industries, Ltd. Composition de revetement pulverulent a resistance aux intemperies elevees
WO2014002964A1 (fr) * 2012-06-29 2014-01-03 旭硝子株式会社 Composition de revêtement en poudre, procédé de production d'un film durci, et article revêtu

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WO2016139966A1 (fr) * 2015-03-02 2016-09-09 旭硝子株式会社 Composition de revêtement en poudre, revêtement en poudre, et article revêtu
EP3266841A4 (fr) * 2015-03-02 2018-12-12 AGC Inc. Composition de revêtement en poudre, revêtement en poudre, et article revêtu
EP3401374A4 (fr) * 2016-01-04 2019-10-30 AGC Inc. Composition de revêtement en poudre, procédé de production de composition de revêtement en poudre, et article revêtu
WO2017119373A1 (fr) * 2016-01-04 2017-07-13 旭硝子株式会社 Composition de revêtement en poudre, procédé de production de composition de revêtement en poudre, et article revêtu
JPWO2017119373A1 (ja) * 2016-01-04 2018-10-18 Ａｇｃ株式会社 粉体塗料、粉体塗料の製造方法、および塗装物品
US10655022B2 (en) 2016-01-04 2020-05-19 AGC Inc. Powder coating material, method for producing powder coating material, and coated article
WO2017130841A1 (fr) * 2016-01-25 2017-08-03 旭硝子株式会社 Matériau de revêtement en poudre, procédé de production d'un matériau de base pourvu d'un film de revêtement et article revêtu
JPWO2017130841A1 (ja) * 2016-01-25 2018-12-06 Ａｇｃ株式会社 粉体塗料、塗膜付き基材の製造方法、および塗装物品
US10723825B2 (en) 2016-01-25 2020-07-28 AGC Inc. Powder coating material, method for producing substrate provided with coating film and coated article
CN106189709A (zh) * 2016-08-14 2016-12-07 安庆市沁之源电器有限公司 一种电风扇抗氧化涂料及其制备方法
CN107036959A (zh) * 2017-04-14 2017-08-11 攀钢集团研究院有限公司 钛白粉耐候性快速检测方法
JP2019163460A (ja) * 2018-03-16 2019-09-26 ダイキン工業株式会社 塗膜及び塗装物品
WO2019177170A1 (fr) * 2018-03-16 2019-09-19 ダイキン工業株式会社 Film de revêtement et article revêtu
EP3766942A4 (fr) * 2018-03-16 2021-12-01 Daikin Industries, Ltd. Film de revêtement et article revêtu
WO2019240186A1 (fr) * 2018-06-12 2019-12-19 Ａｇｃ株式会社 Matériau de revêtement en poudre, son procédé de production, procédé de production d'un matériau de base pourvu d'un film de revêtement et article revêtu
CN112262185A (zh) * 2018-06-12 2021-01-22 Ａｇｃ株式会社 粉体涂料、其制造方法、带涂膜的基材的制造方法及涂装物品

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