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WO2025100337A1 - Composition de revêtement durcissable à une composante et procédé de revêtement - Google Patents

Composition de revêtement durcissable à une composante et procédé de revêtement Download PDF

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Publication number
WO2025100337A1
WO2025100337A1 PCT/JP2024/038944 JP2024038944W WO2025100337A1 WO 2025100337 A1 WO2025100337 A1 WO 2025100337A1 JP 2024038944 W JP2024038944 W JP 2024038944W WO 2025100337 A1 WO2025100337 A1 WO 2025100337A1
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Prior art keywords
mass
hydroxyl
coating
meth
coating composition
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Japanese (ja)
Inventor
雄太 去川
幹太 渕山
亮哉 越後
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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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
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • fluororesin-based paint compositions When a high level of weather resistance is required for paints for exterior building materials, fluororesin-based paint compositions have been used up until now. However, due to legal restrictions such as PFAS regulations and concerns about the supply of fluororesin, it is expected that the use of fluororesin will become more difficult in the future. On the other hand, silicone resin-based paints are a highly weather-resistant alternative to fluororesin, and are attracting attention as a highly weather-resistant alternative to fluororesin.
  • Patent Document 2 discloses a weather-resistant coating composition that contains a hydrolyzable silyl group-containing fluororesin, a hydrolyzable silyl group-containing acrylic resin, and a hydrolyzable silyl group-containing silicone resin, as a weather-resistant coating composition that can form a coating film with excellent thick-film coating properties and long-term weather resistance.
  • Patent Documents 1 and 2 produce coating films with excellent weather resistance and corrosion resistance, so when applied to steel structures, etc., the beauty of the structure can be maintained for a long period of time.
  • the coating compositions described in Patent Documents 1 and 2 are essentially two-component curing coatings that dry at room temperature, and the one-component coatings required for exterior building material applications pose a problem with the weather resistance of the coatings. Furthermore, for exterior building material applications, coating film performance such as high levels of boiling water resistance that are not available for steel structures and other applications is required, and impact resistance is also required.
  • the problem that this invention aims to solve is to provide a one-component curing paint composition that has excellent coating film properties such as weather resistance, impact resistance, and boiling water resistance.
  • a one-component curing coating composition containing a hydroxyl-containing acrylic resin (A) having a hydroxyl value of 40 to 300 mg KOH/g, at least one crosslinking agent (B) selected from a blocked isocyanate compound and a melamine resin, a hydrolyzable silyl-containing silicone resin (C), a color pigment (D), and a curing catalyst (E), and have thus completed the present invention.
  • A hydroxyl-containing acrylic resin
  • B crosslinking agent selected from a blocked isocyanate compound and a melamine resin
  • C hydrolyzable silyl-containing silicone resin
  • D color pigment
  • E curing catalyst
  • a one-component curing coating composition comprising: (A) a hydroxyl-containing acrylic resin having a hydroxyl value of 40 to 300 mgKOH/g; (B) at least one crosslinking agent selected from a blocked isocyanate compound and a melamine resin; (C) a hydrolyzable silyl-group-containing silicone resin; (D) a coloring pigment; and (E) a curing catalyst.
  • hydroxyl-containing acrylic resin (A) is a hydroxyl-containing acrylic resin (AX) having both a hydroxyl group and a hydrolyzable silyl group.
  • the coating composition according to this embodiment is a crosslinked form in which a specific hydroxyl-containing acrylic resin is crosslinked with at least one crosslinking agent selected from a blocked isocyanate compound and a melamine resin, and further crosslinks between the hydroxyl groups of the hydroxyl-containing acrylic resin and the hydrolyzable silyl groups of the hydrolyzable silyl-group-containing silicone resin, and between the hydrolyzable silyl groups of the hydrolyzable silyl-group-containing silicone resin, thereby integrating the entire bulk, and achieving a one-component structure.
  • a specific hydroxyl-containing acrylic resin is crosslinked with at least one crosslinking agent selected from a blocked isocyanate compound and a melamine resin, and further crosslinks between the hydroxyl groups of the hydroxyl-containing acrylic resin and the hydrolyzable silyl groups of the hydrolyzable silyl-group-containing silicone resin, and between the hydrolyzable silyl groups of the hydrolyzable silyl-
  • the coating composition according to this embodiment has the effect of providing a one-component curing paint composition that has excellent coating film performance, such as weather resistance, impact resistance, and boiling water resistance.
  • the one-component curing coating composition according to this embodiment is a one-component curing coating composition containing a hydroxyl-containing acrylic resin (A) having a hydroxyl value of 40 to 300 mgKOH/g, at least one crosslinking agent (B) selected from a blocked isocyanate compound and a melamine resin, a hydrolyzable silyl group-containing silicone resin (C), a color pigment (D), and a curing catalyst (E).
  • A hydroxyl-containing acrylic resin
  • B crosslinking agent
  • C hydrolyzable silyl group-containing silicone resin
  • D color pigment
  • E curing catalyst
  • the hydroxyl-containing acrylic resin (A) in this embodiment preferably contains hydroxyl groups and has a hydroxyl value of 40 to 300 mgKOH/g.
  • the hydroxyl-containing acrylic resin (A) is usually a copolymer of a hydroxyl-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl-containing polymerizable unsaturated monomer.
  • the copolymer can be obtained by any known method, such as bulk polymerization, suspension polymerization, solution polymerization in an organic solvent, or emulsion polymerization in water.
  • the solution polymerization method in an organic solvent is preferably used.
  • the hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule.
  • Specific examples of the hydroxyl group-containing polymerizable unsaturated monomer include Monoesters of (meth)acrylic acid with dihydric alcohols having 2 to 8 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 7-hydroxyheptyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; an ⁇ -caprolactone modified product of the monoesterification product of said (meth)acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms; N-hydroxymethyl(meth)acrylamide; Examples
  • the dihydric alcohol having 2 to 8 carbon atoms more preferably has 2 to 4 carbon atoms.
  • “(meth)acrylate” means at least one of acrylate and methacrylate
  • “(meth)acrylic acid” means at least one of acrylic acid and methacrylic acid
  • “(meth)acrylamide” means at least one of acrylamide and methacrylamide
  • “(meth)acryloyl” means at least one of acryloyl and methacryloyl
  • “(meth)acrylonitrile” means at least one of acrylonitrile and methacrylonitrile.
  • 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. can be preferably used from the viewpoint of coating film performance such as weather resistance, coating film hardness, chemical resistance, boiling water resistance, and impact resistance.
  • examples of other polymerizable unsaturated monomers copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer include a hydrolyzable silyl group-containing polymerizable unsaturated monomer, which is a compound having one or more hydrolyzable silyl groups and one or more polymerizable unsaturated bonds in one molecule; Carboxy group-containing polymerizable unsaturated monomers which are compounds having one or more carboxy groups and one or more polymerizable unsaturated bonds in one molecule, such as (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, allyloxypropionic acid, 2-(meth)acryloylethylsuccinic acid, 3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 3-octenoic acid
  • the hydrolyzable silyl group-containing polymerizable unsaturated monomer can be preferably used.
  • a hydrolyzable silyl group is a group that generates a silanol group by hydrolysis, and the silanol group undergoes dehydration condensation to form a siloxane bond.
  • the silyl group There are no particular limitations on the silyl group, so long as it is a silyl group that has both or either a monovalent hydrolyzable atom (an atom that generates a silanol group by reacting with water) directly bonded to a silicon atom and a monovalent hydrolyzable group (a group that generates a silanol group by reacting with water) directly bonded to a silicon atom.
  • hydrolyzable silyl group examples include halogenated silyl groups such as chlorosilyl and bromosilyl groups, alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl and butoxysilyl groups, and any combinations thereof.
  • halogenated silyl groups such as chlorosilyl and bromosilyl groups
  • alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl and butoxysilyl groups, and any combinations thereof.
  • the examples are not limited to the above.
  • hydrolyzable silyl group-containing polymerizable unsaturated monomers include vinyltri(C1-C6 alkoxy)silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris(2-methoxyethoxy)silane; vinyltri(C2-C6 alkanoyloxy)silanes such as vinyltriacetoxysilane; and (meth)acryloyloxyalkyltri-C1-C8 alkoxysilanes such as 2-(meth)acryloyloxyethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane (KBM-503), 3-(meth)acryloyloxypropyltriethoxysilane (KBE-503), and 8-(meth)acryloyloxyoctyltrimethoxysilane.
  • vinyltri(C1-C6 alkoxy)silanes such as vinyltrimeth
  • a notation consisting of C and a number means the number of carbon atoms constituting an alkoxy group, an alkanoyloxy group, or an alkoxysilane. These may be used alone or in combination of two or more.
  • silane compounds such as vinyltri(C1-C6 alkoxy)silane and (meth)acryloyloxyalkyltri-C1-C8 alkoxysilane are preferred from the viewpoint of coating film performance such as weather resistance, coating film hardness, chemical resistance, and impact resistance, and in particular (meth)acryloyloxyalkyltri-C1-C8 alkoxysilane can be more preferably used.
  • a copolymer having at least a hydroxyl group-containing polymerizable monomer and a hydrolyzable silyl group-containing polymerizable unsaturated monomer as constituent components, it is possible to obtain a hydroxyl group-containing acrylic resin (AX) that has both a hydroxyl group and a hydrolyzable silyl group.
  • the hydroxyl group-containing acrylic resin (AX) preferably contains 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass, of hydrolyzable silyl group-containing polymerizable unsaturated monomer relative to the total amount of all polymerizable unsaturated monomers.
  • the above content is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less.
  • the weight average molecular weight of the hydroxyl group-containing acrylic resin (A) is preferably within the range of 3000 to 50,000, particularly 5000 to 40,000, and even more particularly 10,000 to 30,000.
  • the weight average molecular weight is preferably 3000 or more, more preferably 5000 or more, and even more preferably 10,000 or more, and is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less.
  • weight average molecular weight in this specification is a value calculated based on the molecular weight of standard polystyrene from a chromatogram measured by gel permeation chromatography in accordance with the method described in JIS K 0124-2011.
  • the gel permeation chromatograph used is "HLC8120GPC” (manufactured by Tosoh Corporation).
  • the four columns used are "TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” and “TSKgel G-2000HXL” (all of which are product names manufactured by Tosoh Corporation), and the measurement can be performed under the following conditions: mobile phase: tetrahydrofuran, measurement temperature: 40° C., flow rate: 1 ml/min, and detector: RI.
  • the hydroxyl value of the hydroxyl-containing acrylic resin (A) is preferably within the range of 40 to 300 mgKOH/g, particularly 60 to 250 mgKOH/g, and even more particularly 100 to 200 mgKOH/g.
  • the hydroxyl value is preferably 40 mgKOH/g or more, more preferably 60 mgKOH/g or more, and even more preferably 100 mgKOH/g or more, and is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
  • the glass transition temperature (Tg point) of the hydroxyl group-containing acrylic resin (A) is preferably -20°C to 120°C, particularly preferably 0°C to 100°C, and even more particularly preferably 40°C to 90°C.
  • the Tg point is preferably -20°C or higher, more preferably 0°C or higher, and even more preferably 40°C or higher, and is preferably 120°C or lower, more preferably 100°C or lower, and even more preferably 90°C or lower.
  • the glass transition temperature (absolute temperature) of the acrylic resin is a value calculated using the following formula.
  • T1, T2, ... Tn are the glass transition temperature (absolute temperature) of the homopolymer of each monomer.
  • the glass transition temperature of the homopolymer of each monomer is a value according to Polymer Hand Book (4th Edition), and the glass transition temperature of the homopolymer of a monomer not described in the document is measured by synthesizing a homopolymer of the monomer so that the weight average molecular weight is about 50,000, and measuring the glass transition temperature of the homopolymer using a differential scanning thermal analyzer "DSC-50Q type" (trade name, manufactured by Shimadzu Corporation) by placing the sample in a measuring cup, removing the solvent by vacuum suction, and measuring the heat change in the range of -100°C to +100°C at a heating rate of 3°C/min, and using the change point of the first baseline on the low temperature side.
  • DSC-50Q type trade name, manufactured by Shimadzu Corporation
  • the hydroxyl group-containing acrylic resin (A) preferably has a solubility parameter (SP value) of 7.0 to 12.0, more preferably 7.0 to 11.0, even more preferably 7.0 to 10.0, and even more preferably 8.0 to 10.0.
  • the solubility parameter is preferably 7.0 or more, more preferably 8.0 or more, and is preferably 12.0 or less, more preferably 11.0 or less, and even more preferably 10.0 or less.
  • the solubility parameter of a resin is quantified numerically based on a turbidity measurement method known to those skilled in the art, and specifically, can be calculated according to the formula of K. W. SUH and J. M. CORBETT (Journal of Applied Polymer Science, 12, 2359, 1968).
  • the hydroxyl-containing acrylic resin (A) can be used alone or in combination of two or more types.
  • the content is preferably 1 to 100% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 50% by mass, based on the total solid content of the hydroxyl-containing acrylic resin (A).
  • the content is preferably 1% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more.
  • the content may be 100% by mass, i.e., the total amount of the hydroxyl-containing acrylic resin (A) may be the hydroxyl-containing acrylic resin (AX), or it may be 80% by mass or less, or 50% by mass or less.
  • the crosslinking agent (B) in the present embodiment is at least one selected from a blocked isocyanate compound and a melamine resin, and is a component that undergoes a crosslinking reaction with the hydroxyl group-containing acrylic resin (A).
  • a blocked isocyanate compound is a compound in which the free isocyanate groups of an isocyanate compound are blocked with a blocking agent.
  • isocyanate compounds include aliphatic isocyanate compounds, alicyclic isocyanate compounds, aromatic aliphatic isocyanate compounds, aromatic isocyanate compounds and crude products thereof, modified products of these isocyanate compounds, etc. However, they are not limited to the above.
  • aliphatic isocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.
  • HDI hexamethylene diisocyanate
  • dodecamethylene diisocyanate 1,6,11-undecane triisocyanate
  • 2,2,4-trimethylhexamethylene diisocyanate lysine diisocyanate
  • 2,6-diisocyanatomethyl caproate bis(2-is
  • alicyclic isocyanate compounds include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornane diisocyanate, etc.
  • IPDI isophorone diisocyanate
  • MDI dicyclohexylmethane-4,4'-diisocyanate
  • TDI methylcyclohexylene diisocyanate
  • bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate 2,5- and/or 2,6-norbornane diisocyanate
  • aromatic aliphatic isocyanate compounds include m- and/or p-xylylene diisocyanate (XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (TMXDI), etc. However, they are not limited to the above.
  • aromatic isocyanate compounds include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and/or 4,4'-biphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, etc.
  • TDI 1,3- and/or 1,4-phenylene diisocyanate
  • MDI 2,4- and/or 2,6-tolylene diisocyanate
  • modified products include biuret modified products, isocyanurate modified products, and mixtures of two or more of these.
  • hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) can be preferably used from the viewpoint of coating film performance such as weather resistance, coating film hardness, chemical resistance, and impact resistance.
  • blocking agents for blocking isocyanate groups include Phenolics such as phenol, cresol, and xylenol; Lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, and ⁇ -propiolactam; Alcohols such as methanol, ethanol, n- or i-propyl alcohol, n-, i- or t-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; Oximes such as formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, benzophenone oxime, and cyclohexane oxime; Pyrazoles such as 3,5-
  • oxime, lactam, pyrazole, and active methylene blocking agents are preferably used from the viewpoint of curing properties.
  • methyl ethyl ketoxime, dimethylpyrazole such as 3,5-dimethylpyrazole, 1,5-dimethylpyrazole, and 3,4-dimethylpyrazole, and diethyl malonate are preferably used.
  • the free isocyanate groups of the isocyanate compound can be easily blocked.
  • the hydrolyzable silyl group-containing blocked isocyanate compound (BX) can be preferably used as the blocked isocyanate compound from the viewpoint of imparting reactivity with the hydrolyzable silyl group-containing silicone resin (C), and integrating the entire bulk to form a stronger crosslinked structure by crosslinking through siloxane bonds through a condensation reaction.
  • the blocked isocyanate compound (BX) containing a hydrolyzable silyl group includes all blocked isocyanate compounds that further contain a hydrolyzable silyl group, which are the blocked isocyanate compounds described above.
  • hydrolyzable silyl group examples include halogenated silyl groups such as chlorosilyl and bromosilyl groups, alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl and butoxysilyl groups, and any combinations thereof.
  • halogenated silyl groups such as chlorosilyl and bromosilyl groups
  • alkoxysilyl groups such as methoxysilyl, ethoxysilyl, propoxysilyl and butoxysilyl groups, and any combinations thereof.
  • the examples are not limited to the above.
  • an alkoxysilyl group is preferred as the hydrolyzable silyl group.
  • blocking agent for the hydrolyzable silyl group-containing blocked isocyanate compound (BX) from the viewpoint of coating film performance such as weather resistance, coating film hardness, chemical resistance, and impact resistance, blocking agents such as ethanol, caprolactam, and dimethylpyrazole, particularly hydrolyzable silyl group-containing caprolactam blocked isocyanate compounds, can be preferably used.
  • hydrolyzable silyl group-containing blocked isocyanate compounds include X-12-1195, X-12-1293, and X-12-1308ES (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.).
  • one coating composition according to this embodiment contains a hydrolyzable silyl group-containing blocked isocyanate compound (BX)
  • the solid content is preferably 1 to 100 mass % relative to the total solid content of the blocked isocyanate compound (B), more preferably 20 to 80 mass %, and even more preferably 30 to 60 mass %.
  • the above content is preferably 1 mass % or more, more preferably 20 mass % or more, and even more preferably 30 mass % or more.
  • the above content may be 100 mass %, i.e., the total amount of the blocked isocyanate compound (B) may be the hydrolyzable silyl group-containing blocked isocyanate compound (BX), or may be 80 mass % or less, or 60 mass % or less.
  • the number average molecular weight of the blocked isocyanate compound is preferably 100 to 10,000 from the viewpoint of curability, and is particularly preferably within the range of 100 to 5,000.
  • the number average molecular weight is preferably 100 or more, and is preferably 10,000 or less, and more preferably 5,000 or less.
  • the blocked isocyanate compounds can be used alone or in combination of two or more.
  • An example of a melamine resin is methylol melamine resin obtained by reacting melamine with an aldehyde.
  • Aldehydes used in the above reaction include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, etc. However, they are not limited to the above.
  • methylol melamine resin can also be etherified with alcohol and used as the melamine resin.
  • Alcohols used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol, etc. However, they are not limited to the above.
  • melamine resins containing methyl ether groups etherified with methyl alcohol from the viewpoints of compatibility and coating hardness, it is preferable to use melamine resins containing methyl ether groups etherified with methyl alcohol, and melamine resins containing methyl ether groups and butyl ether groups etherified with methyl alcohol and butyl alcohol.
  • the weight average molecular weight of the melamine resin is preferably 400 to 4000, more preferably 500 to 3000, and even more preferably 600 to 2000.
  • the weight average molecular weight is preferably 400 or more, more preferably 500 or more, and even more preferably 600 or more, and is preferably 4000 or less, more preferably 3000 or less, and even more preferably 2000 or less.
  • the melamine resin include methyl etherified melamine resins such as Cymel (registered trademark) 300, 303, 325, 327, 350, 730, 736, and 738 (all manufactured by Mitsui Cytec Co., Ltd., trade names), Melan 522 and 523 (all manufactured by Hitachi Chemical Co., Ltd., trade names), Nikalac MS001, MX430, and MX650 (all manufactured by Sanwa Chemical Co., Ltd., trade names), Sumimar M-55, M-100, and M-40S (all manufactured by Sumitomo Chemical Co., Ltd., trade names), and Resimin 740 and 747 (all manufactured by Monsanto Co., Ltd., trade names); Butyl etherified melamine resins such as U-BAN (registered trademark) 20SE and 225 (all of which are trade names manufactured by Mitsui Toatsu Co., Ltd.), Super Beckamin J820-60, Super Beckamin L-117-60, Super Beckamin L
  • Melamine resins can be used alone or in combination of two or more types.
  • the solid content concentration of the blocked isocyanate compound is preferably more than 0% by mass and less than 100% by mass, more preferably 1 to 99% by mass, even more preferably 30 to 80% by mass, and even more preferably 50 to 70% by mass, based on the total solid content of both.
  • the solid content concentration of the melamine resin is preferably more than 0% by mass and less than 100% by mass, more preferably 1 to 99% by mass, even more preferably 20 to 70% by mass, and even more preferably 30 to 50% by mass.
  • the solid content concentration of the blocked isocyanate compound is preferably more than 0% by mass, more preferably 1% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, and also preferably less than 100% by mass, more preferably 99% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the hydrolyzable silyl group-containing silicone resin (C) is a resin that contains a hydrolyzable silyl group and has a polysiloxane skeleton.
  • the hydrolyzable silyl group-containing silicone resin (C) is, for example, a silicone resin represented by the following formula (1): SiX n Y 4-n formula (1) (In the formula, X represents a hydroxyl group or an alkoxy group, Y represents a monovalent hydrocarbon group which may have a substituent, and n represents an integer of 1 to 4.)
  • the organosilane compound is a resin, for example an oligomer, produced by chemically bonding two or more identical or different organosilanes, represented by the formula:
  • the organosilane represented by formula (1) can be bonded in a linear or branched chain.
  • the hydrolyzable silyl group-containing silicone resin (C) has a hydrocarbon group that is directly bonded to a silicon atom.
  • the organosilanes represented by formula (1) include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, ⁇ -(meth)acryloxypropyltriethoxy ...
  • the hydrolyzable silyl group-containing silicone resin (C) preferably has a methyl group and/or a phenyl group directly bonded to a silicon atom, from the viewpoints of compatibility with the hydroxyl group-containing acrylic resin (A) and the weather resistance of the coating film formed.
  • hydrolyzable silyl group-containing silicone resins include, for example, "DOWSIL(TM) SR2406", “DOWSIL(TM) SR2410", “DOWSIL(TM) SR2420", “DOWSIL(TM) SR2416", “DOWSIL(TM) SR2402", “DOWSIL(TM) AY42-161", “DOWSIL(TM) 3074” and “DOWSIL(TM) 3037” (all of which are product names manufactured by Dow Corning Toray Silicone Co., Ltd.), "FZ-3704" and “FZ-3511” (all of which are product names manufactured by Nippon Unicar Co., Ltd.), “KC-89S”, “KR-500”, “X-40-9225”, “X-40-9246", and “X-40-9250”.
  • the color pigment (D) is contained in order to give a coating film obtained from the coating composition according to this embodiment a desired color.
  • color pigments include titanium oxide, carbon black, yellow lead, yellow ochre, yellow iron oxide, Hansa yellow, pigment yellow, chrome orange, chrome vermilion, permanent orange, amber, permanent red, brilliant carmine, fast violet, methyl violet lake, ultramarine, Prussian blue, cobalt blue, phthalocyanine blue, pigment green, naphthol green, aluminum paste, etc.
  • they are not limited to the above.
  • titanium oxide when used as a coloring pigment, from the viewpoint of weather resistance of the coating film, titanium oxide that has been surface-treated with silica, alumina, zirconia, selenium, an organic component (polyol, etc.), etc. can be preferably used.
  • the amount of surface treatment is preferably such that the titanium oxide content falls within the range of 83 to 95% by mass.
  • TIPAQUE registered trademark
  • TIPAQUE CR95 all trade names, manufactured by Ishihara Sangyo Kaisha
  • D918 trade name, manufactured by Sakai Chemical Industry Co., Ltd.
  • TITANIX WP0038 all trade names, manufactured by Teika Corporation
  • Ti-Pure R960 all trade names, manufactured by Teika Corporation
  • Ti-Select TS-6200 all trade names, manufactured by DuPont
  • the coating composition according to this embodiment contains a curing catalyst from the viewpoints of curability and weather resistance of the resulting coating film.
  • the curing catalyst (E) is blended to promote the reaction between the hydroxyl group-containing acrylic resin (A) and the crosslinking agent (B) and to promote the hydrolysis and condensation of the hydrolyzable silyl group-containing silicone resin (C).
  • sulfonic acid compounds or amine neutralized products of sulfonic acid compounds, alkyl phosphate compounds or amine neutralized products of alkyl phosphate compounds can be suitably used.
  • Typical examples of sulfonic acid compounds include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalenedisulfonic acid.
  • alkyl phosphate compounds include dodecyl phosphate, tetradecyl phosphate, and stearyl phosphate.
  • the amine in the neutralized product may be any of primary, secondary, and tertiary amines.
  • amine neutralized products of p-toluenesulfonic acid and/or dodecylbenzenesulfonic acid, and amine neutralized products of alkyl phosphoric acid compounds are preferably used in terms of paint stability, reaction promotion effect, and the performance of the resulting coating film.
  • organometallic compounds include tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin trioctate, lead 2-ethylhexanoate, and zinc octylate.
  • organometallic compounds include tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin trioctate, lead 2-ethylhexanoate, and zinc octylate.
  • they are not limited to the above.
  • the coating composition according to this embodiment preferably contains castor oil (F) from the viewpoint of recoat adhesion of the coating film formed.
  • Castor oil (F) is a vegetable oil made from castor seeds, and is a glyceride of unsaturated fatty acids such as ricinoleic acid and oleic acid, and saturated fatty acids such as palmitic acid.
  • castor oil (F) includes natural castor oil, synthetic castor oil, and castor oil derivatives.
  • castor oil-based polyol (F') can be preferably used as the synthetic castor oil.
  • the castor oil-based polyol (F') is not particularly limited, but examples thereof include castor oil, alkylene oxide adducts of castor oil, and esters of castor oil fatty acids and hydroxyl group-containing compounds.
  • the castor oil-based polyol (F') may be a commercially available product.
  • the commercial product names include "URIC H-30”, “URIC H-31", “URIC H-52”, “URIC H-57”, “URIC H-62", “URIC H-73X”, “URIC H-81”, “URIC H-102", “URIC H-420", “URIC H-854”, “URIC H-870", “URIC H-1823”, “URIC H-1824", “URIC H-1830”, “URIC HF-1300”, “URIC POLYCASTOR #10", “URIC POLYCASTOR #30” (all of which are product names manufactured by Ito Oil Mills), "TLM”, LM-R”, “ELA-DR”, "HS CM”, “HS 2G-120”, “HS 2G-160R”, “HS 2G-270B”, “HS KA-001", “HS CM-025P”, “HS CM-075P”, “HS 3G-500B” (all trade names manufactured by Toy
  • the above castor oil-based polyols (F') can be used alone or in combination of two or more.
  • the hydroxyl value of the castor oil (F) is preferably within the range of 80 to 230 mgKOH/g, more preferably within the range of 90 to 215 mgKOH/g, and even more preferably within the range of 100 to 200 mgKOH/g, from the viewpoint of recoat adhesion, curing property, and finished appearance of the coating film formed.
  • the hydroxyl value is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, and even more preferably 100 mgKOH/g or more, and is preferably 230 mgKOH/g or less, more preferably 215 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
  • the coating composition according to the present embodiment is, based on the total solid content of the hydroxyl group-containing acrylic resin (A), the crosslinking agent (B), and the hydrolyzable silyl group-containing silicone resin (C),
  • the total solid content of the hydroxyl group-containing acrylic resin (A) is preferably 20 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 40 to 70% by mass.
  • the total solid content is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the total solid content of the crosslinking agent (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass.
  • the total solid content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the total solid content of the hydrolyzable silyl group-containing silicone resin (C) is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, and even more preferably 20 to 40 mass%, where the total solid content is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 20 mass% or more, and is preferably 60 mass% or less, more preferably 50 mass% or less, and even more preferably 40 mass% or less.
  • the total solid content of the color pigment (D) is preferably 10 to 200% by mass, more preferably 30 to 150% by mass, and even more preferably 40 to 100% by mass.
  • the total solid content is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, and is preferably 200% by mass or less, more preferably 150% by mass or less, and even more preferably 100% by mass or less.
  • the total solid content of the curing catalyst (E) is preferably 0.1 to 5.0 mass%, more preferably 0.1 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, where the total solid content is preferably 0.1 mass% or more, and is preferably 5.0 mass% or less, more preferably 2.0 mass% or less, and even more preferably 1.0 mass% or less.
  • the total solid content of the hydroxyl-containing acrylic resin (A), the crosslinking agent (B), and the hydrolyzable silyl-group-containing silicone resin (C) is 20 to 90 mass%, the total solid content of the crosslinking agent (B) is 5 to 50 mass%, the total solid content of the hydrolyzable silyl-group-containing silicone resin (C) is 5 to 60 mass%, the total solid content of the color pigment (D) is 10 to 200 mass%, and the total solid content of the curing catalyst (E) is 0.1 to 5.0 mass%.
  • the content of castor oil (F) is preferably within the range of 1 to 10 parts by mass, more preferably within the range of 2 to 8 parts by mass, and even more preferably within the range of 3 to 7 parts by mass, based on 100 parts by mass of the total solid content of the hydroxyl group-containing acrylic resin (A), the crosslinking agent (B), and the hydrolyzable silyl group-containing silicone resin (C).
  • the above content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less, from the viewpoint of recoat adhesion of the coating film formed.
  • the solid content means the residue remaining after removing the volatile components, and the residue may be in a solid form or in a liquid form having flowability at room temperature.
  • the solid content mass can be calculated by multiplying the sample mass before drying by the solid content percentage, which is the ratio of the amount of material remaining after drying to the mass before drying.
  • the drying conditions include heating 3 grams of the sample at 105°C for 3 hours.
  • the coating composition according to this embodiment may contain, as optional components, dehydrating agents; pigments (excluding color pigments (D)); modifying resins such as acrylic resins, fluororesins, alkyd resins, and urethane resins (excluding hydroxyl-containing acrylic resins (A), at least one crosslinking agent (B) selected from blocked isocyanate compounds and melamine resins, and hydrolyzable silyl-containing silicone resins (C)); organic solvents; reactive diluents; and coating additives such as adhesion promoters, antisettling agents, dispersants, wetting agents, UV absorbers, light stabilizers, antioxidants, surface conditioners, defoamers, surfactants, preservatives, and antifreeze agents.
  • dehydrating agents such as acrylic resins, fluororesins, alkyd resins, and urethane resins (excluding hydroxyl-containing acrylic resins (A), at least one crosslinking agent (B) selected from blocked isocyanate compounds and melamine
  • Dehydrating agents are used to improve storage stability and to prevent deterioration of paint caused by moisture present in the paint or air.
  • Specific examples include trimethyl orthoacetate and trimethyl orthoformate. However, they are not limited to the above.
  • the content of the dehydrating agent may be 0 to 20 mass%, 5 to 15 mass%, or 5 to 10 mass%, based on the total solid content of the hydroxyl group-containing acrylic resin (A), the crosslinking agent (B), and the hydrolyzable silyl group-containing silicone resin (C), from the viewpoint of the storage stability and curing property of the coating.
  • the content may be 0 mass% or more, may be more than 0 mass%, may be 5 mass% or more, may be 20 mass% or less, may be 15 mass% or less, or may be 10 mass% or less.
  • the above pigments include extender pigments such as talc, silica, calcium carbonate, mica, kaolin, barium sulfate, zinc oxide (zinc oxide), etc.; anti-rust pigments, etc. However, they are not limited to the above. These can be used alone or in combination of two or more kinds.
  • any known ultraviolet absorbent can be used, such as a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, or a benzophenone-based absorbent.
  • a benzotriazole-based absorbent such as a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, or a benzophenone-based absorbent.
  • the weather resistance of the coating film can be improved.
  • the above is not a limitation.
  • the content of the ultraviolet absorber in the coating composition may usually be 0 to 10 mass%, 0.2 to 5 mass%, or 0.3 to 2 mass% relative to the total amount of resin solids.
  • the content may be 0 mass% or more, more than 0 mass%, 0.2 mass% or more, 0.3 mass% or more, and 10 mass% or less, 5 mass% or less, or 2 mass% or less.
  • Any light stabilizer that has been known in the art can be used, such as, but not limited to, a hindered amine light stabilizer. By adding a light stabilizer, the weather resistance and yellowing resistance of the coating film can be improved.
  • the content of the light stabilizer in the coating composition may usually be 0 to 10 mass%, 0.2 to 5 mass%, or 0.3 to 2 mass% based on the total amount of resin solids.
  • the content may be 0 mass% or more, more than 0 mass%, 0.2 mass% or more, 0.3 mass% or more, 10 mass% or less, 5 mass% or less, or 2 mass% or less.
  • the coating composition according to this embodiment can be produced by mixing a hydroxyl group-containing acrylic resin (A), at least one crosslinking agent (B) selected from a blocked isocyanate compound and a melamine resin, a hydrolyzable silyl group-containing silicone resin (C), a coloring pigment (D), and a curing catalyst (E), as well as other optional components used as required, using a mixing device such as a disperser or homogenizer.
  • the coating composition according to this embodiment can be applied by a coating method such as dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, airless coating, electrostatic coating, die coating, etc.
  • a coating method such as dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, airless coating, electrostatic coating, die coating, etc.
  • a coating method such as dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, airless coating, electrostatic coating, die coating, etc.
  • a coating method such as dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, airless coating, electrostatic coating, die coating, etc.
  • the present invention also relates to a coating method for coating the above coating composition.
  • the one-component curing coating composition is applied to an object to be coated.
  • the coating thickness of the coating composition can be set arbitrarily depending on the substrate and the required coating performance, but is usually 10 to 100 ⁇ m, and preferably in the range of 20 to 60 ⁇ m.
  • the coating thickness may be 10 ⁇ m or more, 20 ⁇ m or more, or 100 ⁇ m or less, or 60 ⁇ m or less.
  • the coating film of the coating composition in this embodiment can be cured by heating at a temperature usually in the range of 100 to 200°C, particularly 130 to 180°C, for 5 to 40 minutes, particularly 10 to 30 minutes.
  • the temperature at which the coating film is cured may be 100°C or higher, or 130°C or higher, or 200°C or lower, or 180°C or lower.
  • the time for curing the coating film may be 5 minutes or higher, 10 minutes or higher, or 40 minutes or lower, or 30 minutes or lower.
  • the surface to be coated with the coating composition in this embodiment is not particularly limited, and examples include metal materials that have been primed as desired, such as steel sheets such as cold-rolled steel sheets, black-skinned steel sheets, alloyed galvanized steel sheets, and electrolytic galvanized steel sheets, zinc plating, stainless steel, aluminum, and the like; alkaline substrates such as concrete, mortar, slate, slate roofing tiles, and the like; ceramic building materials; plastics, and the like.
  • metal materials that have been primed as desired such as steel sheets such as cold-rolled steel sheets, black-skinned steel sheets, alloyed galvanized steel sheets, and electrolytic galvanized steel sheets, zinc plating, stainless steel, aluminum, and the like; alkaline substrates such as concrete, mortar, slate, slate roofing tiles, and the like; ceramic building materials; plastics, and the like.
  • steel sheets such as cold-rolled steel sheets, black-skinned steel sheets, alloyed galvanized steel sheets, and electrolytic galvanized steel sheets, zinc plating, stainless steel
  • the application of the coating composition according to this embodiment is not particularly limited, but it can be particularly suitable for use as a topcoat coating for exterior building materials such as building exterior walls, civil engineering and construction materials, vehicles, and aircraft materials, and is particularly suitable for use as an exterior building material topcoat coating for building materials and materials.
  • the above-mentioned coating surfaces and objects may be subjected to shot blasting, surface conditioning, surface treatment, etc., or may even be subjected to a primer coating, as required.
  • the primer paint may be a water-based or solvent-based primer paint known in the art.
  • primer paint examples include epoxy resin paint, modified epoxy resin paint, epoxy resin-based glass flake paint, epoxy resin coating material, phthalic acid resin-based paint, epoxy ester resin paint, etc.
  • epoxy resin paint modified epoxy resin paint, epoxy resin-based glass flake paint, epoxy resin coating material, phthalic acid resin-based paint, epoxy ester resin paint, etc.
  • the above are not limited to these.
  • the coating composition according to this embodiment is a non-fluororesin type one-component curing coating composition that has excellent coating film performance such as weather resistance, impact resistance, and boiling water resistance, and is also easy to handle. Therefore, it can be particularly suitably used as a topcoat coating that complies with PFAS regulations for the above-mentioned coating applications.
  • Example 1 Preparation of coating composition No. 1 50 parts (solids) of hydroxyl-containing acrylic resin (A-1), 20 parts (solids) of blocked isocyanate compound (B-1), 30 parts (solids) of hydrolyzable silyl-containing silicone resin (C-1), 90 parts (solids) of color pigment (D-1) (PFC-105, titanium oxide, manufactured by Ishihara Sangyo Kaisha), 0.2 parts (solids) of curing catalyst (E-1) (TOS-TK1, organotin compound, manufactured by Osaka Shinyaku Co., Ltd.), 1.5 parts (solids) of ultraviolet absorber (Ti400, Note 2) and 1 part (solids) of light stabilizer (Ti123, Note 3) were mixed and stirred, and the solids concentration was adjusted with a solvent to obtain a coating composition No. 1 having a solids content of 60% by mass.
  • the color pigment (D-1) was added and mixed as a pigment dispersion paste prepared using 20 parts (solids) of the 50 parts (solids) of the hydroxyl-containing acrylic resin (A-1).
  • Examples 2 to 53 and Comparative Examples 1 to 6 Production of Coating Compositions No. 2 to 59 Coating compositions No. 2 to No. 59 each having a solid content of 60 mass% were obtained in the same manner as in Example 1, except that the raw materials were blended as shown in Tables 1 to 6.
  • the raw material compositions (values) in Tables 1 to 6 are solid masses. Also, blank spaces in the tables mean that no ingredients have been added.
  • Blocked isocyanate compound (B-1) "Desmodur (registered trademark) BL-3175", product name, manufactured by COVESTRO, methyl ethyl ketoxime blocked HDI isocyanurate, NCO content 11.2%.
  • Blocked isocyanate compound (B-2) "DURANATE SBN-70D", product name, manufactured by Asahi Kasei Corporation, dimethylpyrazole blocked HDI isocyanurate, NCO content 10.0%.
  • Melamine resin (B-3) "CYMEL (registered trademark) 325", product name, manufactured by Allnex, imino group-containing methyl etherified melamine resin. Weight average molecular weight: 650.
  • Melamine resin (B-4) Methyl/butyl etherified melamine resin containing imino groups. Weight average molecular weight: 750.
  • Hydrolyzable silyl group-containing silicone resin (C-1): "DOWSIL 3074": trade name, manufactured by Toray Dow Coating Co., Ltd., an alkoxysilyl group-containing silicone resin containing a methyl group and a phenyl group.
  • Hydrolyzable silyl group-containing silicone resin (C-2): “TSR-165": trade name, manufactured by Momentive Corporation, an alkoxysilyl group-containing silicone resin containing methyl groups and phenyl groups.
  • Silicone resin (C-4) "KF-96": Product name, manufactured by Shin-Etsu Chemical Co., Ltd., dimethyl silicone resin. Contains no alkoxysilyl groups. For comparison purposes.
  • Color pigment (D-1) "Tipake (registered trademark) PFC105", titanium oxide, product name, manufactured by Ishihara Sangyo Kaisha, Ltd., Al, Si, Zr organically treated titanium oxide, titanium oxide content 87%.
  • Color pigment (D-2) "MA-100", carbon black, product name, manufactured by Mitsubishi Chemical Corporation
  • Linseed oil natural oil, “linseed oil”, product name, manufactured by Summit Essential Oils Co., Ltd.
  • Ti400 ultraviolet absorber, "TINUVIN400", product name, manufactured by BASF.
  • Ti123 light stabilizer, "TINUVIN123”, trade name, manufactured by BASF.
  • MOA trimethyl orthoacetate
  • test panels were prepared and their performance evaluated according to the procedure below, and the results obtained from the tests are shown in Table 1.
  • a chromium phosphate-treated aluminum plate A-1050P (size 0.8 ⁇ 150 ⁇ 150 mm, degreased with acetone) was air-spray-coated with KAMPE Baked Plassaf 500A (product name, manufactured by Kansai Paint Co., Ltd.) to a dry film thickness of 10 ⁇ m (pressure 0.4 MPa), set at 20° C. for 10 minutes, and then heated at 130° C. for 10 minutes using an electric drying oven. Thereafter, each of the coating compositions No. 1 to 59 was air-spray-coated (pressure 0.4 MPa) to a dry film thickness of 40 ⁇ m, set at 20° C. for 10 minutes, and then heated and dried at 160° C. for 20 minutes using an electric hot air dryer, and further aged at 20° C. for 72 hours to obtain test plates on which coating films of each of the coating compositions No. 1 to 59 were formed.
  • KAMPE Baked Plassaf 500A product name, manufactured by Kansai Paint Co.
  • Performance evaluation Each of the coating compositions No. 1 to 59 and each of the test panels on which the coating film was formed were subjected to performance tests for the following test items, and performance evaluation was performed according to the following evaluation criteria. The performance evaluation results are also shown in Tables 1 to 6. Of the test items below, it is sufficient that all of weather resistance, impact resistance, and boiling water resistance are passed, and further, it is preferable that one or more of storage stability, pencil hardness, finished appearance, acid resistance, alkali resistance, and recoat adhesion are passed, more preferably two or more are passed. The more items that are passed, the better, and it is most preferable that all are passed.
  • ⁇ Weather resistance> The accelerated weather resistance of each test panel was evaluated using a xenon weather meter tester.
  • the gloss of the test panel coating film after 5000 hours was compared with the gloss of the initial test panel coating film that had not been subjected to the accelerated weather resistance test according to the following criteria. ⁇ or ⁇ indicates pass, and ⁇ or ⁇ indicates fail.
  • ⁇ or ⁇ indicates pass, and ⁇ or ⁇ indicates fail.
  • ⁇ The gloss was hardly reduced.
  • Good The gloss was slightly reduced, but this did not cause any problems in practical use.
  • ⁇ The gloss is reduced and is not at a practical level.
  • x The gloss was significantly reduced.
  • ⁇ Pencil hardness> According to JIS K 5600-5-4:1999, a pencil lead was placed at an angle of about 45° against the surface (test-coated panel surface) of each test panel on which a coating film was formed by each coating composition, and the pencil lead was pressed against the test-coated panel surface hard enough not to break, while being moved forward at a uniform speed of about 10 mm. The hardness symbol of the hardest pencil that did not break the coating film was taken as the pencil hardness. ⁇ or ⁇ indicates passing, and ⁇ or ⁇ indicates failing. ⁇ : 2H or more. ⁇ : H or F. ⁇ :HB. ⁇ : B or less.
  • the gloss value is a specular gloss value, and is a value obtained by measuring the specular gloss value at a measurement angle of 60 degrees using a specular gloss meter.
  • ⁇ or ⁇ is a pass, and ⁇ is a fail.
  • ⁇ Good smoothness and 60 degree gloss value of 70 or more.
  • ⁇ The smoothness is good, and the 60 degree gloss value is 60 or more and less than 70.
  • x At least one of the appearances selected from side cracks, wavy areas, dullness, and chipped skin is significantly deteriorated, or the 60 degree gloss value is less than 60.
  • the present invention provides a one-component curing paint composition that has excellent coating film performance, such as weather resistance, impact resistance, and boiling water resistance, and is compliant with fluororesin regulations such as PFAS regulations.

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Abstract

La présente invention concerne une composition de revêtement durcissable à une composante comprenant une résine acrylique hydroxylée (A) ayant un indice d'hydroxyle de 40 à 300 mg de KOH/g, au moins un agent de réticulation (B) choisi parmi des composés isocyanate séquencés et des résines de mélamine, une résine de silicone (C) contenant un groupe silyle hydrolysable, un pigment coloré (D) et un catalyseur de durcissement (E).
PCT/JP2024/038944 2023-11-08 2024-10-31 Composition de revêtement durcissable à une composante et procédé de revêtement Pending WO2025100337A1 (fr)

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JPH03172368A (ja) * 1989-11-30 1991-07-25 Nippon Paint Co Ltd 塗料組成物
JPH10503787A (ja) * 1994-04-19 1998-04-07 日本ペイント株式会社 硬化性樹脂組成物、塗料組成物、塗膜形成方法及び塗装物
JPH09143421A (ja) * 1995-11-20 1997-06-03 Kansai Paint Co Ltd 高固形分塗料組成物及びそれを用いる上塗り塗膜形成方法
WO2012128223A1 (fr) * 2011-03-18 2012-09-27 関西ペイント株式会社 Composition de revêtement résistant aux intempéries et procédé de fabrication d'un article revêtu ayant un film de revêtement résistant aux intempéries
JP2016180093A (ja) * 2015-03-24 2016-10-13 関西ペイント株式会社 常温乾燥型塗料組成物
WO2019131459A1 (fr) * 2017-12-28 2019-07-04 関西ペイント株式会社 Composition de matériau de revêtement
JP2021091744A (ja) * 2019-11-28 2021-06-17 関西ペイント株式会社 塗料組成物及び塗膜形成方法
WO2022244538A1 (fr) * 2021-05-18 2022-11-24 関西ペイント株式会社 Composition de matériau de revêtement à teneur élevée en solides et méthode de formation de film de revêtement multicouche
JP2023157445A (ja) * 2022-04-15 2023-10-26 関西ペイント株式会社 塗料組成物及び複層塗膜形成方法

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