WO2024257716A1 - Composition de peinture aqueuse à un seul bloc - Google Patents

Composition de peinture aqueuse à un seul bloc Download PDF

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Publication number
WO2024257716A1
WO2024257716A1 PCT/JP2024/020999 JP2024020999W WO2024257716A1 WO 2024257716 A1 WO2024257716 A1 WO 2024257716A1 JP 2024020999 W JP2024020999 W JP 2024020999W WO 2024257716 A1 WO2024257716 A1 WO 2024257716A1
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meth
mass
aqueous
coating film
resin
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Japanese (ja)
Inventor
翔輝 浦野
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Chugoku Marine Paints Ltd
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Chugoku Marine Paints Ltd
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Priority to KR1020257038450A priority Critical patent/KR20250174087A/ko
Priority to CN202480037902.4A priority patent/CN121263491A/zh
Publication of WO2024257716A1 publication Critical patent/WO2024257716A1/fr
Anticipated expiration legal-status Critical
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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
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of 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
    • 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
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Definitions

  • This disclosure relates to a one-component water-based paint composition.
  • an anticorrosive coating made of an anticorrosive coating composition (e.g., an epoxy resin-based anticorrosive coating composition) is applied as an undercoat paint to the surface of a substrate such as a steel structure, and a topcoat coating made of a topcoat paint composition is applied on the anticorrosive coating to improve design or weather resistance.
  • Known topcoat paint compositions include, for example, two-component reactive curing compositions such as urethane resin-based paint compositions, and one-component compositions such as (meth)acrylic resin-based paint compositions.
  • JP 2016-222901 A JP 2022-157093 A International Publication No. 2020-022073
  • a coating composition such as an anticorrosive coating composition (e.g., an epoxy resin-based anticorrosive coating composition) to the surface of a substrate to form a resin coating film, and then apply an aqueous coating composition as a topcoat to the resin coating film to form a topcoat coating film.
  • an anticorrosive coating composition e.g., an epoxy resin-based anticorrosive coating composition
  • a topcoat paint composition is applied after a specified coating interval.
  • this interval tends to be long. Therefore, even if the interval is long, it is desirable for the topcoat paint film to have high adhesion (adhesion) to the resin coating film. It is also desirable for such a topcoat paint film to have excellent coating film condition.
  • the present disclosure aims to provide an aqueous paint composition that is capable of forming a topcoat paint film that has excellent adhesion to the resin coating film and excellent coating film condition, even when an interval is used.
  • the aqueous coating composition of the present disclosure is a one-component aqueous coating composition that contains an aqueous (meth)acrylic resin (A) having a constituent unit derived from a vinyl ester of versatic acid, an aqueous (meth)acrylic resin (B) not having a constituent unit derived from a vinyl ester of versatic acid, and water.
  • an aqueous paint composition that is capable of forming a topcoat film that has excellent adhesion to resin coating films and excellent coating film condition, even when an interval is provided (e.g., when the interval is long).
  • FIG. 1 is a schematic cross-sectional view of a multilayer coating film according to one embodiment.
  • FIG. 2 is a schematic cross-sectional view of a coated article according to one embodiment.
  • FIG. 3 is a table showing the evaluation criteria for the cross-cut tape peel test.
  • polymer is used to include homopolymers and copolymers, i.e., the term “polymer” may mean either a homopolymer or a copolymer.
  • (Meth)acrylate is a term that collectively refers to acrylate and methacrylate.
  • (Meth)acrylic is a term that collectively refers to acrylic and methacrylic.
  • (Meth)acrylic acid is a term that collectively refers to acrylic acid and methacrylic acid. The same applies to other examples.
  • n1 to n2 means n1 or more and n2 or less.
  • n1 and n2 are any numbers that satisfy n1 ⁇ n2.
  • a numerical range formed by combining a value arbitrarily selected from the listed lower limit value and a value arbitrarily selected from the listed upper limit value is also considered to be listed.
  • the one-pack water-based coating composition of the present disclosure (hereinafter also referred to as the "composition of the present disclosure") comprises a water-based (meth)acrylic resin (A) having a constituent unit derived from a vinyl ester of versatic acid, and a water-based (meth)acrylic resin (B) having a constituent unit derived from a vinyl ester of versatic acid.
  • the composition contains an aqueous (meth)acrylic resin (B) that does not have any of the structural units of the above formula (1) and water.
  • aqueous (meth)acrylic resin refers to a highly hydrophilic (meth)acrylic resin, meaning a “water-soluble” (meth)acrylic resin that can be dissolved in water, or a “water-dispersible” (meth)acrylic resin that can be dispersed in water.
  • water-soluble resins that have hydrophilic groups such as carboxy groups and hydroxy groups and can be dissolved uniformly in water
  • water-dispersible resins that can be dispersed uniformly in water in the form of fine particles.
  • a topcoat coating composition may be applied on an anticorrosive coating film formed from an anticorrosive coating composition for the purpose of improving design and weather resistance.
  • organic solvent-based topcoat coating compositions containing organic solvents as a solvent have been mainstream, but in recent years, the demand for water-based coating compositions has been increasing.
  • coating films formed from conventional water-based coating compositions tend to have lower adhesion (adhesion) to resin coating films compared to coating films formed from organic solvent-based coating compositions.
  • an aqueous coating composition is applied as a topcoat on a resin coating film formed from an organic solvent-based coating composition (e.g., an organic solvent-based epoxy resin coating composition)
  • an organic solvent-based coating composition e.g., an organic solvent-based epoxy resin coating composition
  • the aqueous coating composition does not contain organic solvent or contains only a small amount of organic solvent, so it cannot dissolve or swell the surface of the lower resin coating film, and if the surface of the lower resin coating film is hydrophobic, it is difficult to get wet with water.
  • the composition of the present disclosure contains an aqueous (meth)acrylic resin (A) in addition to an aqueous (meth)acrylic resin (B).
  • a topcoat coating film formed from the composition of the present disclosure has excellent adhesion and interval adhesion to a resin coating film, particularly a resin coating film formed from an organic solvent-based paint composition (e.g., an organic solvent-based epoxy resin paint composition).
  • an organic solvent-based paint composition e.g., an organic solvent-based epoxy resin paint composition.
  • the adhesion of a topcoat coating film to a resin coating film when a resin coating film is formed on the surface of a substrate and then a topcoat coating film is formed on the resin coating film after a predetermined period of time is also referred to as "interval adhesion" in this specification.
  • the topcoat coating film formed from the composition of the present disclosure has low adhesion and excellent coating film condition.
  • the topcoat coating film formed from the composition of the present disclosure can exhibit a gloss equal to or greater than that of topcoat coating films formed from conventional organic solvent-based (meth)acrylic resin-based topcoat paint compositions, and has excellent appearance.
  • the aqueous (meth)acrylic resin (A) has a constituent unit derived from a versatic acid vinyl ester (hereinafter also referred to as "Veova"). It is presumed that the constituent unit derived from a versatic acid vinyl ester can impart moderate hydrophobicity and moderate flexibility to the coating film.
  • the aqueous (meth)acrylic resin (A) is a versatic acid vinyl ester copolymer.
  • the versatic acid vinyl ester copolymer may be, for example, a random copolymer or a block copolymer.
  • the versatic acid vinyl ester copolymer may have a constituent unit derived from versatic acid vinyl ester and a constituent unit derived from a (meth)acrylic monomer, and may further have a constituent unit derived from other ethylenically unsaturated monomers copolymerizable with versatic acid vinyl ester and/or (meth)acrylic monomer.
  • the versatic acid vinyl ester copolymer may have two or more constituent units derived from versatic acid vinyl ester.
  • the versatic acid vinyl ester copolymer may have two or more constituent units derived from (meth)acrylic monomer.
  • the versatic acid vinyl ester copolymer may have two or more constituent units derived from other ethylenically unsaturated monomer.
  • Versatic acid vinyl ester is a compound represented by the following formula (1).
  • R 1 and R 2 are each independently an alkyl group having 1 to 7 carbon atoms, and R 1 and R 2 may be bonded to each other to form a ring.
  • the total number of carbon atoms in R 1 and R 2 is preferably 6 to 10, more preferably 6 to 8.
  • the total number of carbon atoms in the entire formula (1) is preferably 11 to 15, more preferably 11 to 13.
  • alkyl group examples include methyl, ethyl, propyl groups such as n-propyl and isopropyl, butyl groups such as n-butyl, tert-butyl, sec-butyl and isobutyl, pentyl groups such as n-pentyl, tert-pentyl, isopentyl and sec-pentyl, hexyl, heptyl, 1,1-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, and 1-methyl-1-ethylpropyl.
  • the alkyl group may be linear or branched. At least one of R 1 and R 2 is preferably a branched alkyl group, and both R 1 and R 2 may be branched alkyl groups.
  • R 1 is a propyl group and R 2 is a propyl, butyl or pentyl group, hi one embodiment, R 1 is an n-butyl group and R 2 is an isobutyl group.
  • Examples of (meth)acrylic monomers include (meth)acrylic acid esters, (meth)acrylic acid amides, and (meth)acrylic acid.
  • Examples of (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate;
  • hydroxyalkyl (meth)acrylates such as butyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate; aminoalkyl (meth)acrylates such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and butylaminoethyl (meth)acrylate; and alkoxysilyl group-containing (meth)acrylates such as trimethoxysilylpropyl (meth)acrylate, triethoxysilylpropyl (meth)acrylate, tributoxysilylpropyl (meth)acrylate, dimethoxymethylsilylpropyl (meth)acrylate, and methoxydimethylsilylpropyl (meth)acrylate.
  • epoxy group-containing (meth)acrylates such as gly
  • Examples of (meth)acrylic acid amides include (meth)acrylic acid aminoalkylamides such as aminoethyl (meth)acrylamide, dimethylaminomethyl (meth)acrylamide, and methylaminopropyl (meth)acrylamide; and other amide group-containing (meth)acrylic monomers such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-methylol (meth)acrylamide, methoxybutyl (meth)acrylamide, and diacetone (meth)acrylamide.
  • (meth)acrylic acid aminoalkylamides such as aminoethyl (meth)acrylamide, dimethylaminomethyl (meth)acrylamide, and methylaminopropyl (meth)acrylamide
  • other amide group-containing (meth)acrylic monomers such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide,
  • ethylenically unsaturated monomers copolymerizable with versatic acid vinyl ester and/or (meth)acrylic monomers include, for example, ⁇ -olefins such as ethylene, propylene, and 1-butene; conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; styrene monomers such as styrene, ⁇ -methylstyrene, and halogenated styrene; vinyl esters such as vinyl acetate and vinyl propionate (excluding versatic acid vinyl ester); cyanide vinyl compounds such as (meth)acrylonitrile; unsaturated monocarboxylic acids such as crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; monoesters of unsaturated dicarboxylic acids such as ethyl maleate and butyl maleate; diesters of unsaturated dicarboxylic
  • aqueous (meth)acrylic resin (A) examples include versatic acid vinyl ester-(meth)acrylic monomer copolymer, versatic acid vinyl ester-(meth)acrylic monomer-styrene monomer copolymer, and versatic acid vinyl ester-vinyl ester copolymer.
  • the aqueous (meth)acrylic resin (A) may be a silicone-modified (meth)acrylic resin having a structural unit derived from a vinyl ester of versatic acid.
  • silicon-modified (meth)acrylic resins include resins in which a (meth)acrylic resin skeleton and a polysiloxane resin skeleton are bonded by a covalent bond, such as a block copolymer in which the ends of a (meth)acrylic resin and a polysiloxane resin are bonded together, a copolymer having a polysiloxane resin as the main skeleton and a (meth)acrylic resin bonded to the main skeleton as a side chain, and a copolymer having a (meth)acrylic resin as the main skeleton and a polysiloxane resin bonded to the main skeleton as a side chain.
  • the (meth)acrylic resins in these examples have constituent units derived from versatic acid vinyl ester.
  • the mass ratio of the (meth)acrylic resin skeleton and the polysiloxane resin skeleton that make up the silicon-modified (meth)acrylic resin is, for example, 1/10 to 50/1.
  • the silicon-modified (meth)acrylic resin may also be a versatic acid vinyl ester copolymer having a constituent unit derived from a versatic acid vinyl ester, a constituent unit derived from a (meth)acrylic monomer (excluding a constituent unit derived from a silyl group-containing unsaturated monomer), and a constituent unit derived from a silyl group-containing unsaturated monomer.
  • the silyl group-containing unsaturated monomer include the alkoxysilyl group-containing (meth)acrylate and alkoxysilyl group-containing ethylenically unsaturated monomer described above.
  • the versatic acid vinyl ester copolymer may have two or more constituent units derived from a silyl group-containing unsaturated monomer.
  • aqueous (meth)acrylic resin (A) from the viewpoint of being able to form a coating film with excellent weather resistance, a versatic acid vinyl ester-(meth)acrylic monomer copolymer and a silicon-modified (meth)acrylic resin having a structural unit derived from versatic acid vinyl ester are preferred.
  • the content of the constituent units derived from the versatic acid vinyl ester in 100% by mass of all constituent units is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, even more preferably 35% by mass or more, particularly preferably 40% by mass or more, 45% by mass or more, 50% by mass or more, or 55% by mass or more.
  • a composition containing such an aqueous (meth)acrylic resin (A) can impart moderate hydrophobicity and moderate flexibility to a coating film, and therefore can form a coating film that is excellent in water resistance and adhesion to resin coating films, particularly interval adhesion.
  • the content of the constituent units derived from the versatic acid vinyl ester is 30% by mass or more, the interval adhesion tends to be more excellent.
  • the content of each constituent unit is measured by nuclear magnetic resonance spectroscopy (NMR).
  • the content of constituent units derived from versatic acid vinyl ester in 100% by mass of all constituent units is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less.
  • Such an aqueous (meth)acrylic resin (A) tends to have excellent compatibility with the aqueous (meth)acrylic resin (B).
  • the content of constituent units derived from versatic acid vinyl ester in 100% by mass of all constituent units is, for example, 20 to 90% by mass.
  • the content of constituent units derived from (meth)acrylic monomers in 100% by mass of all constituent units is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, particularly preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 65% by mass or less, particularly preferably 60% by mass or less, 55% by mass or less, 50% by mass or less, or 45% by mass or less, for example, 10 to 80% by mass.
  • the glass transition temperature (Tg) of the aqueous (meth)acrylic resin (A) is preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and is preferably 100°C or lower, more preferably 60°C or lower, even more preferably 50°C or lower, even more preferably 40°C or lower, and particularly preferably 30°C or lower, for example, 0 to 100°C.
  • Tg is the midpoint glass transition temperature obtained by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012.
  • a composition containing a resin (A) whose Tg is equal to or higher than the lower limit can form a coating film that is excellent in strength and water resistance, and can form a coating film that is suppressed from softening or blisters even when exposed to a high temperature environment.
  • a composition containing a resin (A) whose Tg is equal to or lower than the upper limit can form a coating film that is excellent in adhesion to the substrate, and can form a coating film that is excellent in film formation and suppresses cracking even when applied in a low temperature environment such as winter.
  • the aqueous (meth)acrylic resin (A) may have an acid value of more than 0 mgKOH/g.
  • the acid value (unit: mgKOH/g) of the aqueous (meth)acrylic resin (A) is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and is preferably 35 or less, more preferably 30 or less, even more preferably 25 or less, for example, 1 to 35.
  • An aqueous (meth)acrylic resin (A) having an acid value within this range has moderate hydrophilicity and can exist stably in an aqueous paint composition.
  • a resin (A) having an acid value equal to or greater than the lower limit has excellent stability in an aqueous paint composition.
  • a composition containing a resin (A) having an acid value equal to or less than the upper limit can form a coating film with excellent water resistance, and the coating film is less likely to develop coating film defects such as whitening or blisters when it comes into contact with water, for example, rainfall.
  • the acid value is the amount (mg) of potassium hydroxide required to neutralize acid groups such as carboxyl groups per gram of nonvolatile matter in the sample, and is measured in accordance with JIS K0070:1992.
  • the aqueous (meth)acrylic resin (A) may be present in the composition in the form of particles.
  • the average particle size of the aqueous (meth)acrylic resin (A) is not particularly limited, but is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and particularly preferably 50 nm or more, and is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 500 nm or less, even more preferably 300 nm or less, and particularly preferably 200 nm or less, for example, 10 nm to 2 ⁇ m.
  • the aqueous (meth)acrylic resin (A) having an average particle size within this range tends to be able to exist stably in the aqueous paint composition and tends to be able to form a coating film with uniform coating film properties.
  • the average particle size is the volume-based average particle size measured by a laser diffraction method at a temperature of 25°C.
  • aqueous dispersion in which the aqueous (meth)acrylic resin (A) is dispersed in a dispersion medium containing water (hereinafter also referred to as "aqueous medium"), and mix the aqueous dispersion with other components.
  • aqueous medium a dispersion medium containing water
  • the aqueous dispersion is preferably an emulsion.
  • the content of the aqueous (meth)acrylic resin (A) in the aqueous dispersion is, for example, 20 to 60 mass%.
  • the aqueous medium is not particularly limited as long as it contains water, but the content of water in the aqueous medium is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass.
  • the aqueous medium may contain a medium other than water, and examples of such a medium include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diacetone alcohol, dioxane, ethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monohexyl ether.
  • the aqueous (meth)acrylic resin (A) may be of a self-crosslinking type.
  • Examples of a method for synthesizing the aqueous (meth)acrylic resin (A) include known methods, such as a method of polymerizing a monomer in the presence of a radical polymerization initiator by a solution polymerization method, a suspension polymerization method, a bulk polymerization method, or an emulsion polymerization method.
  • the content of the aqueous (meth)acrylic resin (A) in 100 parts by mass of the total content of the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B), and the (meth)acrylic polyol (C) that is optionally included is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, even more preferably 38 parts by mass or more, and is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, still more preferably 65 parts by mass or less, and particularly preferably 60 parts by mass or less, for example, 30 to 80 parts by mass.
  • a coating film formed from a composition having a content of the aqueous (meth)acrylic resin (A) within this range has low adhesion, and is excellent in adhesion and interval adhesion to resin coating films such as organic solvent-based resin coating films, and is suitable as a topcoat coating film.
  • the aqueous (meth)acrylic resin (B) has a constituent unit derived from a (meth)acrylic monomer and does not have a constituent unit derived from a vinyl ester of versatic acid, provided that in the present disclosure, the aqueous (meth)acrylic resin (B) does not include the (meth)acrylic polyol (C) described below.
  • the aqueous (meth)acrylic resin (B) may be a homopolymer of a (meth)acrylic monomer, a copolymer of two or more kinds of (meth)acrylic monomers, or a copolymer of a (meth)acrylic monomer and another ethylenically unsaturated monomer copolymerizable with the (meth)acrylic monomer.
  • the copolymer may be, for example, a random copolymer or a block copolymer.
  • the aqueous (meth)acrylic resin (B) may have two or more kinds of constituent units derived from a (meth)acrylic monomer.
  • the aqueous (meth)acrylic resin (B) may have two or more kinds of constituent units derived from another ethylenically unsaturated monomer.
  • Examples of (meth)acrylic monomers include (meth)acrylic acid esters, (meth)acrylic acid amides, and (meth)acrylic acid. Specific examples of (meth)acrylic acid esters and (meth)acrylic acid amides are as described above. Specific examples of other ethylenically unsaturated monomers are as described above.
  • the content of constituent units derived from (meth)acrylic monomers in 100% by mass of all constituent units is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more.
  • Examples of the aqueous (meth)acrylic resin (B) include nonionic (meth)acrylic resin, anionic (meth)acrylic resin, and cationic (meth)acrylic resin.
  • Examples of the aqueous (meth)acrylic resin (B) include (meth)acrylic monomer polymers, which are homopolymers or copolymers of (meth)acrylic monomers, (meth)acrylic monomer-styrene monomer copolymers, (meth)acrylic monomer-vinyl ester copolymers, silicone-modified (meth)acrylic resins, and urethane-modified (meth)acrylic resins.
  • silicone-modified (meth)acrylic resins include resins in which a (meth)acrylic resin skeleton and a polysiloxane resin skeleton are bonded by a covalent bond, such as block copolymers in which the ends of a (meth)acrylic resin and a polysiloxane resin are bonded together, copolymers having a polysiloxane resin as the main skeleton and a (meth)acrylic resin bonded to the main skeleton as a side chain, and copolymers having a (meth)acrylic resin as the main skeleton and a polysiloxane resin bonded to the main skeleton as a side chain.
  • the content ratio of the (meth)acrylic resin skeleton and the polysiloxane resin skeleton that constitute the silicone-modified (meth)acrylic resin ((meth)acrylic resin skeleton/polysiloxane resin skeleton) on a mass basis is, for example, 1/10 to 50/1.
  • the silicon-modified (meth)acrylic resin may also be a copolymer having a constituent unit derived from a (meth)acrylic monomer (excluding a constituent unit derived from a silyl group-containing unsaturated monomer) and a constituent unit derived from a silyl group-containing unsaturated monomer.
  • the silyl group-containing unsaturated monomer include the alkoxysilyl group-containing (meth)acrylate and alkoxysilyl group-containing ethylenically unsaturated monomer described above.
  • the silicon-modified (meth)acrylic resin may have two or more kinds of constituent units derived from a silyl group-containing unsaturated monomer.
  • aqueous (meth)acrylic resin (B) from the viewpoint of being able to form a coating film with excellent weather resistance, a (meth)acrylic monomer polymer, a (meth)acrylic monomer-vinyl ester copolymer, a silicon-modified (meth)acrylic resin, and a urethane-modified (meth)acrylic resin are preferred.
  • the glass transition temperature (Tg) of the aqueous (meth)acrylic resin (B) is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 8°C or higher, and is preferably 70°C or lower, more preferably 60°C or lower, and even more preferably 50°C or lower, for example, 0 to 70°C.
  • a composition containing a resin (B) with a Tg within this range can form a coating film that has a good appearance and is excellent in water resistance and adhesion to the substrate.
  • a composition containing a resin (B) with a Tg equal to or higher than the lower limit can form a coating film that is suppressed from softening or blisters even when exposed to a high temperature environment.
  • a composition containing a resin (B) with a Tg equal to or lower than the upper limit can form a coating film that has excellent film forming properties and is suppressed from cracking, even when applied in a low temperature environment such as winter.
  • the hydroxyl value (unit: mgKOH/g) of the aqueous (meth)acrylic resin (B) is preferably less than 30.
  • the hydroxyl value is the amount (mg) of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the nonvolatile content of the sample is acetylated, and is measured in accordance with JIS K0070:1992.
  • the aqueous (meth)acrylic resin (B) may be present in the composition in the form of particles.
  • the average particle size of the aqueous (meth)acrylic resin (B) is not particularly limited, but is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and particularly preferably 50 nm or more, and is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 500 nm or less, even more preferably 300 nm or less, and particularly preferably 200 nm or less, for example, 10 nm to 2 ⁇ m.
  • the aqueous (meth)acrylic resin (B) having an average particle size within this range tends to be able to exist stably in the aqueous coating composition and tends to be able to form a coating film with uniform coating film properties.
  • an aqueous dispersion in which the aqueous (meth)acrylic resin (B) is dispersed in an aqueous medium, and mix the aqueous dispersion with other components.
  • the aqueous dispersion is preferably an emulsion.
  • the content of the aqueous (meth)acrylic resin (B) in the aqueous dispersion is, for example, 20 to 60 mass%.
  • the aqueous (meth)acrylic resin (B) may be of the self-crosslinking type.
  • Examples of a method for synthesizing the aqueous (meth)acrylic resin (B) include known methods, such as a method of polymerizing a monomer in the presence of a radical polymerization initiator by a solution polymerization method, a suspension polymerization method, a bulk polymerization method, or an emulsion polymerization method.
  • the content of the aqueous (meth)acrylic resin (B) in a total of 100 parts by mass of the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B), and the optionally contained (meth)acrylic polyol (C) is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, for example, 20 to 65 parts by mass.
  • a composition with a content of the aqueous (meth)acrylic resin (B) within this range can form a coating film that has a good appearance and is excellent in water resistance, adhesion to the substrate, and interval adhesion.
  • composition of the present disclosure may further contain (meth)acrylic polyol (C).
  • (Meth)acrylic polyol (C) is a relatively low molecular weight aqueous (meth)acrylic resin having multiple hydroxyl groups.
  • the coating film formed from such a composition tends to have excellent initial gloss and leveling properties in addition to the above-mentioned adhesion and long-term interval adhesion.
  • (Meth)acrylic polyol (C) may be, for example, a copolymer of an ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer copolymerizable therewith.
  • (Meth)acrylic polyol (C) may have two or more types of structural units derived from an ethylenically unsaturated monomer having a hydroxyl group.
  • (Meth)acrylic polyol (C) may have two or more types of structural units derived from another ethylenically unsaturated monomer.
  • Ethylenically unsaturated monomers having a hydroxy group include, for example, the above-mentioned hydroxyalkyl (meth)acrylates.
  • Other ethylenically unsaturated monomers include, for example, the above-mentioned (meth)acrylic monomers (excluding the above-mentioned hydroxyalkyl (meth)acrylates) and the above-mentioned other ethylenically unsaturated monomers other than (meth)acrylic monomers.
  • the hydroxyl value (unit: mgKOH/g) of the (meth)acrylic polyol (C) is preferably 30 or more, more preferably 50 or more, even more preferably 70 or more, and is preferably 300 or less, more preferably 250 or less, even more preferably 200 or less, for example, 30 to 300.
  • the hydroxyl value of the (meth)acrylic polyol (C) is within this range, the compatibility between the aqueous (meth)acrylic resin (A) and the aqueous (meth)acrylic resin (B) can be improved, and the storage stability of the composition of the present disclosure can be further improved.
  • the (meth)acrylic polyol (C) may have an acid value of more than 0 mgKOH/g.
  • the acid value (unit: mgKOH/g) of the (meth)acrylic polyol (C) is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and is preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, for example, 1 to 30.
  • the weight average molecular weight (Mw) of the (meth)acrylic polyol (C) is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 5,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, for example, 1,000 to 100,000.
  • a composition containing such a relatively low molecular weight (meth)acrylic polyol (C) can form a coating film with excellent initial gloss and leveling properties.
  • Mw is a value calculated in terms of polystyrene measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC measurement conditions Apparatus: "HLC-8320GPC” (manufactured by Tosoh Corporation) Column: "TSKgel guardcolumn SuperMP(HZ)-M + TSKgel SuperMultiporeHZ-M + TSKgel SuperMultiporeHZ-M” (both manufactured by Tosoh Corporation)
  • Eluent tetrahydrofuran (THF)
  • Flow rate 0.35ml/min
  • Detector Differential refractive index (RI) detector
  • Calibration curve Standard polystyrene Sample preparation method: The polymer solution was diluted with THF, and then filtered through a membrane filter to obtain a filtrate, which was used as a GPC measurement sample.
  • the (meth)acrylic polyol (C) may be present in the composition in the form of particles.
  • the average particle size of the (meth)acrylic polyol (C) is not particularly limited, but is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and particularly preferably 50 nm or more, and is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 500 nm or less, even more preferably 300 nm or less, and particularly preferably 200 nm or less, for example, 10 nm to 2 ⁇ m.
  • the (meth)acrylic polyol (C) having an average particle size within this range tends to be able to exist stably in the aqueous coating composition and tends to be able to form a coating film with uniform coating film properties.
  • an aqueous dispersion in which the (meth)acrylic polyol (C) is dispersed in an aqueous medium, and mix the aqueous dispersion with other components.
  • the aqueous dispersion is preferably an emulsion.
  • the content of the (meth)acrylic polyol (C) in the aqueous dispersion is, for example, 20 to 60 mass%.
  • the content of (meth)acrylic polyol (C) is, in 100 parts by mass of the total content of the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B), and the (meth)acrylic polyol (C), preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, for example, 5 to 40 parts by mass.
  • a composition having a content of (meth)acrylic polyol (C) within this range can form a coating film with excellent gloss and leveling properties. Also, a composition having a content of (meth)acrylic polyol (C) equal to or less than the upper limit can form a coating film that is less susceptible to cracking and has excellent adhesion.
  • the total ratio of the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B) and the (meth)acrylic polyol (C) to the total amount of solids in the composition is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, for example 40 to 90% by mass.
  • composition of the present disclosure may contain other components such as pigments, rust inhibitors, and additives, within the scope that does not impair the effects of the present invention.
  • additives include, for example, dispersants, wetting agents, anti-sagging agents (anti-settling agents, thixotropic agents, rheology control agents), defoamers, film-forming assistants, leveling agents, surfactants, thickeners, anti-mold agents, preservatives, UV absorbers, pH adjusters, antioxidants, and flash rust inhibitors. These may be used alone or in combination of two or more.
  • Pigments can be used to impart strength, corrosion resistance, hue, etc. to the coating film.
  • pigments include extender pigments, color pigments, and anti-rust pigments, and may be either organic or inorganic pigments.
  • the composition of the present disclosure contains a pigment, the pigment may be used alone or in combination of two or more types.
  • extender pigments examples include talc, mica, (precipitated) barium sulfate, (potash) feldspar, kaolin, alumina white, bentonite, wollastonite, clay, glass flakes, aluminum flakes, magnesium carbonate, barium carbonate, calcium carbonate, dolomite and silica.
  • the content of the extender pigment is preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, for example 1 to 50% by mass, based on 100% by mass of the total solid content in the composition.
  • the color pigment may be any color pigment known in the art, including, for example, inorganic pigments such as titanium oxide, yellow iron oxide, red iron oxide, and carbon black, organic pigments such as naphthol red, cyanine blue, and cyanine green, and gloss pigments such as aluminum flakes, scaly iron oxide, and stainless steel flakes.
  • inorganic pigments such as titanium oxide, yellow iron oxide, red iron oxide, and carbon black
  • organic pigments such as naphthol red, cyanine blue, and cyanine green
  • gloss pigments such as aluminum flakes, scaly iron oxide, and stainless steel flakes.
  • the content of the coloring pigment is, relative to the total solid content of the composition (100% by mass), preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, for example, 1 to 50% by mass.
  • anti-rust pigments examples include zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdate compounds, zinc cyanamide compounds, borate compounds, nitro compounds, and complex oxides.
  • the content of the anti-rust pigment is preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass, for example 1 to 20% by mass, based on 100% by mass of the total solid content in the composition.
  • the rust inhibitor is a compound that has rust-preventing properties, other than anti-rust pigments. Conventionally known compounds can be used as the rust inhibitor. There is no particular limit to the content of the rust inhibitor in the composition of the present disclosure.
  • the composition of the present disclosure preferably contains a dispersant from the viewpoints of improving the dispersibility of the pigments and the like in the composition, facilitating the formation of a coating film with a good appearance and excellent crack resistance.
  • dispersants include polymers having a pigment-adsorbing group (pigment-affinity group) and a compatible chain such as fatty acid, polyamino, polyether, polyester, polyurethane, and polyacrylate.
  • pigment-adsorbing groups include carboxy groups, phosphate groups, amino groups, salt groups of these, and ammonium bases.
  • the content of the dispersant is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, for example, 0.1 to 3% by mass, based on 100% by mass of the total solid content in the composition.
  • the composition of the present disclosure preferably contains an anti-dripping agent from the viewpoints of improving the thick coating property and anti-dripping property during application and suppressing the settling of insoluble matters such as pigments in water.
  • the anti-dripping agent include organic thixotropic agents such as hydrogenated castor oil-based thixotropic agents, amide wax-based thixotropic agents, polyethylene oxide-based thixotropic agents, and urethane-based thixotropic agents; and inorganic thixotropic agents such as clay minerals (e.g., bentonite, smectite, and hectorite) and synthetic fine silica powder.
  • the content of the drip-preventing agent is, based on 100% by mass of the total solid content in the composition, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, for example, 0.01 to 3% by mass.
  • the defoaming agent is preferably a material capable of suppressing the generation of bubbles during the production and application of the coating composition, or a material capable of breaking down bubbles generated in the coating composition.
  • a defoaming agent for example, the generation of bubble marks or pinholes in the coating film can be suppressed, and therefore the film-forming properties and crack resistance of the coating film can be improved.
  • defoaming agents include silicone-based defoaming agents, polymer-based (non-silicone-based) defoaming agents, and mineral oil-based defoaming agents.
  • the content of the antifoaming agent is, based on 100% by mass of the total solid content in the composition, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, for example, 0.05 to 5% by mass.
  • the composition of the present disclosure preferably contains a film-forming aid because the composition may freeze in winter due to the inclusion of water, and also from the viewpoint of improving film-forming properties at low temperatures and the finished appearance of the resulting coating film.
  • film-forming aids include alcohols, glycol ethers, and esters, and specific examples include alcohols having 1 to 3 carbon atoms such as isopropyl alcohol, 2,2,4-trimethylpentanediol, benzyl alcohol, and other alcohols; glycol ethers such as ethylene glycol monobutyl ether, ethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-butyl ether, ethylene glycol monobenzyl ether, and ethylene glycol monophenyl ether; and esters such as 2,2,4-trimethyl-1,3-p
  • the content of the film-forming aid is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and preferably 30 parts by mass or less, more preferably 25 parts by mass or less, for example, 0.5 to 30 parts by mass, relative to 100 parts by mass of the total content of the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B), and the (meth)acrylic polyol (C) that is optionally contained in the composition.
  • the composition of the present disclosure preferably contains a leveling agent from the viewpoints of improving repelling of the coating film when the composition is applied, improving wettability to the surface of the object to be coated, and making it easier to obtain a coating film of uniform thickness.
  • leveling agents include various leveling agents such as fluorine-based, acrylic-based, and silicone-based leveling agents.
  • the content of the leveling agent is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, for example, 0.005 to 2% by mass, based on 100% by mass of the total solid content in the composition.
  • the thickener for example, a commercially available product that is generally sold as a thickener can be used.
  • the thickener include alkali thickeners, nonionic association types, acrylic types, urethane types, water-soluble polymer types, polyamide types, and hydroxyethyl cellulose.
  • the content of the thickener is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and is preferably 5% by mass or less, more preferably 1% by mass or less, for example, 0.01 to 5% by mass, based on 100% by mass of the total solid content in the composition.
  • the composition of the present disclosure preferably contains a flash rust inhibitor.
  • Flash rust inhibitors include, for example, nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite and ammonium nitrite; benzoates such as sodium benzoate, potassium benzoate, calcium benzoate and ammonium benzoate; phytates such as sodium phytate and potassium phytate; organic carboxylates such as sebacic acid and dodecanoic acid; phosphoric acid derivatives such as alkyl phosphates and polyphosphoric acids; tannates; metal sulfonates; N-(2-hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid.
  • nitrites such as sodium nitrite, potassium nitrite, calcium nitrite, strontium nitrite, barium nitrite and ammonium nitrite
  • amine-based chelating agents such as dimethylaminopropylamine (DTPA), propylenediaminetetraacetic acid (PDTA), iminodiacetic acid, nitrilotriacetic acid (NTA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and alkali metal salts thereof; an addition reaction product of 4-methyl- ⁇ -oxo-benzenebutanoic acid and N-ethylmorpholine; intercalation compounds obtained by intercalating monoalkylamines, polyamines, quaternary ammonium ions, etc., into layered phosphates such as aluminum dihydrogen tripolyphosphate; hydrazine derivatives such as hydrazide compounds, semicarbazide compounds, and hydrazone compounds; and azole compounds such as benzotriazole, its derivatives, and its salts.
  • DTPA dimethylaminopropylamine
  • PDTA propylenediaminetetraacetic acid
  • nitrites e.g., metal salts such as sodium, potassium, calcium, etc., and ammonium salts
  • benzoates e.g., metal salts such as sodium, potassium, calcium, etc., and ammonium salts
  • sodium nitrite being particularly preferred, from the viewpoints of easily obtaining a composition that exhibits high flash rust resistance even when used in small amounts.
  • the content of the flash rust inhibitor is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, for example 0.05 to 5% by mass, based on 100% by mass of the total solid content in the composition.
  • the composition of the present disclosure is an aqueous coating composition.
  • the term "aqueous" coating composition refers to a coating composition containing water.
  • the water is not particularly limited, and examples thereof include tap water, ion-exchanged water, and deionized water, with ion-exchanged water and deionized water being preferred.
  • the water includes water that is a dispersion medium when the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B), and the (meth)acrylic polyol (C) that is optionally included are dispersed in an aqueous medium, as well as water contained in additives.
  • the content of water in the composition of the present disclosure is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, and is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less, for example 20 to 70% by mass.
  • the total solid content in the composition of the present disclosure is preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 40% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, for example 30 to 80% by mass, from the viewpoint of providing a composition with excellent coating workability.
  • the content of volatile organic compounds (VOCs) in the composition of the present disclosure is preferably 150 g/L or less, more preferably 100 g/L or less, from the viewpoints of environmental conservation and safety of the working environment, etc.
  • VOCs include, for example, organic solvents.
  • organic solvents include aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and mesitylene; alcohol solvents such as ethanol, propanol, isopropyl alcohol, butanol, and isobutanol; ether solvents such as propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone; and ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.
  • VOC content (g/L) specific gravity of composition ⁇ 1000 ⁇ (100 ⁇ solids concentration ⁇ water concentration)/100 (1)
  • the specific gravity (g/mL) of the composition is a value calculated by filling a specific gravity cup having an internal volume of 100 mL with the composition at a temperature condition of 23° C. and measuring the mass of the composition.
  • the solid content concentration (mass%) is a value calculated by the method described in the Examples section below.
  • the solid content in the composition means the heating residue (non-volatile content) when the composition is dried in an incubator at 108°C for 3 hours as described in the Examples section below.
  • the solid content in each component e.g., aqueous dispersion
  • the water concentration (mass %) is the amount of water (mass %) contained in 100 mass % of the composition, and is measured using a water content measuring device (e.g., CA-310, manufactured by Nitto Seiko Analytech Co., Ltd.) according to the Karl Fischer method.
  • a water content measuring device e.g., CA-310, manufactured by Nitto Seiko Analytech Co., Ltd.
  • composition of the present disclosure can be produced by appropriately utilizing a known method.
  • the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B), and optionally the (meth)acrylic polyol (C), and optionally other components are added to a stirring vessel at once or in any order, and each component is mixed by a known stirring and mixing means to be dispersed or dissolved in water to produce the composition.
  • an aqueous dispersion in which the aqueous (meth)acrylic resin (A) is dispersed in an aqueous medium may be used, an aqueous dispersion in which the aqueous (meth)acrylic resin (B) is dispersed in an aqueous medium may be used, or an aqueous dispersion in which the (meth)acrylic polyol (C) is dispersed in an aqueous medium may be used.
  • mixing When mixing (kneading), conventionally known devices such as mixers, dispersers, and stirrers can be used. Examples of such devices include dispersers, mixing and dispersion mills, mortar mixers, rolls, paint shakers, and homogenizers. Mixing (kneading) may be performed while heating or cooling depending on the season and environment.
  • composition disclosed herein is an aqueous paint composition, and therefore has very little adverse effect on the environment and human body, and also has excellent storage stability. Even when the composition disclosed herein is applied in multiple coats, the coating film formed has excellent adhesion (tightness) to the base coating film, and is unlikely to crack or peel off, making the composition suitable for topcoat painting or repair painting.
  • the composition of the present disclosure is applied to, for example, a substrate.
  • the substrate refers to an article to which the composition of the present disclosure is applied.
  • the surface material of the substrate to which the composition is applied include resin coatings, metal materials, wood, plastics, rubber, stone, concrete, mortar, glass, porcelain, pottery, and composites thereof.
  • resin coatings include undercoat coatings, intermediate coatings, and resin coatings (old coatings) to be repaired.
  • metal materials include steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, zinc plating, zinc spraying, etc.), and stainless steel (SUS304, SUS410, etc.).
  • the object to be coated may have, for example, a substrate and a resin coating film provided on the surface of the substrate.
  • the material of the substrate at the location where the resin coating film is provided include metal materials, wood, plastic, rubber, stone, concrete, mortar, glass, porcelain, pottery, and composites of these, with metal materials being preferred.
  • Specific examples of substrates include ships, vehicles, aircraft, buildings, bridges, plants, tanks, containers, pipes, steel pipes, and cast iron pipes, such as structures such as steel structures.
  • the substrate may be a land structure or a marine structure.
  • the substrate surface may be treated as necessary (for example, blast treatment (ISO8501-1 Sa2 1/2), degreasing to remove oil and dust, etc.).
  • the substrate surface may be coated with a shop primer or the like for the purpose of primary rust prevention.
  • the coating film of the present disclosure is formed from the composition of the present disclosure.
  • the coating film of the present disclosure is suitable as a topcoat coating film to be laminated on a resin coating film because it is excellent in appearance, coating film condition, weather resistance, etc.
  • the thickness (dry film thickness) of the coating film of the present disclosure is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, even more preferably 30 ⁇ m or more, and preferably 1,000 ⁇ m or less, more preferably 500 ⁇ m or less, even more preferably 300 ⁇ m or less, for example, 10 to 1,000 ⁇ m.
  • the composition may be applied multiple times to form a coating film having a desired thickness.
  • a coating film having a desired thickness may be formed by one application (one application), or a coating film having a desired thickness may be formed by two or more applications (two or more applications).
  • the coating film of the present disclosure can be formed by applying the composition of the present disclosure to an object to be coated and drying it.
  • Coating methods include, for example, spray coating such as airless spray coating and air spray coating, brush coating, and roller coating.
  • the composition of the present disclosure can be dried by natural drying or by heat drying.
  • the drying time to obtain a dry coating film is preferably 1 hour or more, more preferably 1 day or more, and even more preferably 5 days or more.
  • a hot air dryer may be used.
  • the drying time to obtain a dry coating film is, for example, 5 minutes to 60 minutes, and the drying temperature is preferably 30°C or more and less than 100°C, more preferably 40 to 80°C.
  • the laminated coating film of the present disclosure has a resin coating film and a coating film of the present disclosure provided on the surface of the resin coating film.
  • FIG. 1 shows a schematic cross-sectional view of one embodiment of the laminated coating film of the present disclosure.
  • the laminated coating film 1 of FIG. 1 has a resin coating film 10 and a coating film 20 of the present disclosure provided on the surface of the resin coating film 10.
  • the resin coating film includes an epoxy resin coating film such as an epoxy resin-based corrosion protection coating film.
  • the resin coating film may be, for example, an undercoat coating film intended to improve adhesion to a substrate or corrosion resistance, or may have an undercoat coating film and an intermediate coating film provided on the undercoat coating film. That is, the resin coating film may have a laminated structure.
  • the laminated coating film of the present disclosure may have, for example, an undercoat coating film and a coating film of the present disclosure as a topcoat coating film, in that order in the thickness direction, or may have an undercoat coating film, an intermediate coating film, and a coating film of the present disclosure as a topcoat coating, in that order in the thickness direction.
  • the undercoat coating film may be, for example, a coating film formed from various anticorrosive coating compositions such as an epoxy resin-based anticorrosive coating composition.
  • the thickness of the undercoat coating film is preferably 20 to 300 ⁇ m, more preferably 20 to 250 ⁇ m.
  • the intermediate coating film may be, for example, a coating film formed from various intermediate coating compositions such as a (meth)acrylic resin-based coating composition, an epoxy resin-based coating composition, and a urethane resin-based coating composition.
  • the thickness of the intermediate coating film is preferably 10 to 300 ⁇ m, more preferably 10 to 250 ⁇ m.
  • the coating film of the present disclosure has excellent adhesion and interval adhesion to resin coating films such as epoxy resin coating films (e.g., epoxy resin-based corrosion protection coating films), particularly to resin coating films formed from organic solvent-based paint compositions (e.g., organic solvent-based epoxy resin paint compositions).
  • epoxy resin coating films e.g., epoxy resin-based corrosion protection coating films
  • organic solvent-based paint compositions e.g., organic solvent-based epoxy resin paint compositions
  • the coated article of the present disclosure has a substrate and a coating film of the present disclosure.
  • the coated article of the present disclosure preferably has a substrate and a laminate coating film of the present disclosure, specifically, a substrate, a resin coating film, and a coating film of the present disclosure, in that order in the thickness direction.
  • FIG. 2 shows a schematic cross-sectional view of one embodiment of the coated article of the present disclosure.
  • the coated article 2 of FIG. 2 has a substrate 30 and a laminate coating film 1 of the present disclosure provided on the substrate 30.
  • the details of the resin coating film are as described above.
  • the coated article of the present disclosure can be manufactured, for example, by a manufacturing method having a step of applying a composition of the present disclosure to an object to be coated and a step of drying the applied composition to form a coating film.
  • a one-component aqueous coating composition comprising an aqueous (meth)acrylic resin (A) having a structural unit derived from a vinyl ester of versatic acid, an aqueous (meth)acrylic resin (B) not having a structural unit derived from a vinyl ester of versatic acid, and water.
  • the one-component aqueous coating composition according to any one of [1] to [6], further comprising a (meth)acrylic polyol (C) as desired, wherein the content of the aqueous (meth)acrylic resin (A) is 30 to 80 parts by mass per 100 parts by mass of the total content of the aqueous (meth)acrylic resin (A), the aqueous (meth)acrylic resin (B) and the (meth)acrylic polyol (C).
  • the one-component aqueous coating composition according to any one of [1] to [7], wherein the content of the water in the one-component aqueous coating composition is 20 to 70 mass %.
  • the coated article according to [13] further comprising a resin coating film between the substrate and the coating film.
  • the coated article according to [14], wherein the resin coating film comprises an epoxy resin coating film.
  • the one-component water-based paint composition of the present disclosure will be explained in more detail below with reference to examples, but the one-component water-based paint composition of the present disclosure is in no way limited to the following examples.
  • “parts” refers to "parts by mass.”
  • Flash rust inhibitor sodium nitrite (molecular weight 69), Dispersant (wetting dispersant) manufactured by Kanto Chemical Co., Ltd.: DISPERBYK-190, Non-volatile content: 40% by weight
  • Defoamer A BYK-024, manufactured by Dow Chemical Company
  • non-volatile content 100% by weight
  • Defoamer B BYK-1770 manufactured by BYK-Chemie GmbH, non-volatile content: 100% by mass
  • Titanium oxide Tipaque R-930 manufactured by BYK-Chemie GmbH, film-forming agent: Dowanol DPnB manufactured by Ishihara Sangyo Kaisha, Ltd.
  • Non-volatile content 100% by mass
  • AV emulsion of versatic acid vinyl ester (Veova) modified acrylic resin (composition ratio (meth)acrylic: 40% by mass, Veova: 60% by mass), non-volatile content: 45% by mass, Tg: 19°C, acid value: 16 mgKOH/g, average particle size: 100 nm, non-self-crosslinking, manufactured by VANORA; resin emulsion (B-1): Polysol AP-3900, (meth)acrylic resin emulsion, non-volatile content: 50% by mass, Tg: 10°C, manufactured by Resonac Co., Ltd.; resin emulsion (B-2): Polysol AP-3720N, (meth)acrylic resin emulsion, non-volatile content: 50% by mass, Tg: 8°C, manufactured by Resonac Co., Ltd.; resin emulsion (B-3): Polysol AP-3770, styrene-(meth)acrylic resin emulsion, non-vola
  • Resin emulsion (B-4) U-DOUBLE E-135, (meth)acrylic resin emulsion, non-volatile content: 50% by mass, Tg: 10°C, manufactured by Nippon Shokubai Co., Ltd.
  • Resin emulsion (B-5) U-DOUBLE E-015, (meth)acrylic resin emulsion, non-volatile content: 50% by mass, Tg: 15°C, manufactured by Nippon Shokubai Co., Ltd.
  • the solid content or non-volatile content of the composition and each component means the heating residue when the composition and each component are dried in an incubator at 108° C. for 3 hours.
  • the heating residue is the residue of a sample obtained by weighing 1.0 g of the sample onto a flat-bottom dish, spreading it evenly using a wire of known mass, and drying it in an incubator at 1 atmosphere and 108° C. for 3 hours.
  • the solid content (solid content concentration) (mass%) of the composition and each component was calculated from the amount of the heating residue.
  • Example 1 A container was charged with 7 parts of ion-exchanged water, 0.1 parts of a flash rust inhibitor, 1 part of a dispersant, 0.4 parts of a sagging agent, 0.3 parts of an antifoaming agent A, and 24 parts of titanium oxide, and each component was dispersed in the ion-exchanged water using a paint shaker until the particle gauge reached 30 ⁇ m or less according to the method of JIS K5600-2-5:1999. In this manner, a pigment dispersion was prepared.
  • Examples 2 to 22 and Comparative Examples 1 to 12 Each coating composition was prepared in the same manner as in Example 1, except that the components shown in Tables 1 to 3 were used in the amounts shown in the respective tables.
  • a sandblasted steel plate of SS400 having dimensions of 150 mm in length, 70 mm in width, and 1.6 mm in thickness was prepared.
  • the arithmetic mean roughness (Ra, in accordance with JIS B0601:2013) of the surface of the sandblasted steel plate was in the range of 30 to 75 ⁇ m.
  • An organic solvent-based epoxy resin paint (Banno 1500 light gray, manufactured by Chugoku Paint Co., Ltd.) was applied to the surface of the sandblasted steel plate using an air spray painter (W-77, manufactured by Anest Iwata Corporation) so that the dry film thickness was about 200 ⁇ m, and the paint was dried for one day under conditions of a temperature of 23 ° C. and a humidity of 50% to form an undercoat coating film.
  • Each of the coating compositions of the examples and comparative examples was applied to the surface of the undercoat coating film using an applicator so that the dry film thickness was about 60 ⁇ m, and the paint was dried for 7 days under conditions of a temperature of 23 ° C. and a humidity of 50% to form a topcoat coating film. In this manner, a test piece I having a sandblasted steel plate, an undercoat coating film and a topcoat coating film in this order was prepared.
  • the appearance and adhesion of the topcoat coating of test piece I were evaluated according to the following evaluation criteria.
  • the gloss value of the topcoat coating of test piece I was measured in accordance with JIS K5600-4-7:1999 using a surface gloss meter (model: Micro Trigloss 4446, manufactured by BYK-Gardner) to measure the reflectance of light incident at an angle of 60° from the normal to the coating surface (60° gloss).
  • the test piece I was placed in a QUV accelerated weathering tester (model: QUV/SE 200V, UVA-340 lamp, manufactured by Q-Lab) and weathering tests were carried out for 200 hours, 400 hours, 600 hours and 1,200 hours in accordance with ASTM G154 CYCLE1. Thereafter, the reflectance (60° gloss) of light incident at an angle of 60° from the perpendicular direction of the coating surface after the weathering test was measured using a surface gloss meter (model: Micro Trigloss 4446, manufactured by BYK-Gardner). The gloss retention (%) of the 60° gloss after the weathering test relative to the 60° gloss value of the coating film before the weathering test was calculated.
  • a sandblasted steel plate of SS400 having dimensions of 150 mm length, 70 mm width and 1.6 mm thickness was prepared.
  • the arithmetic mean roughness (Ra) of the surface of the sandblasted steel plate was in the range of 30 to 75 ⁇ m.
  • An organic solvent-based epoxy resin paint (Banno 1500 light gray, manufactured by Chugoku Paint Co., Ltd.) was applied to the surface of the sandblasted steel plate using an air spray painter (W-77, manufactured by Anest Iwata Co., Ltd.) so that the dry film thickness was about 200 ⁇ m, and the paint was dried for one day under conditions of a temperature of 23° C. and a humidity of 50%, to form an undercoat coating film.
  • a coated piece was obtained.
  • the coated piece was exposed outdoors for 1 day, 7 days, 14 days, 21 days, 30 days and 60 days.
  • the coated piece exposed outdoors was lightly washed with water and thoroughly dried.
  • the coating compositions of the Examples and Comparative Examples were applied to the surface of the undercoat film using an applicator so that the dry film thickness was about 60 ⁇ m, and the coating was dried for 7 days under conditions of a temperature of 23° C. and a humidity of 50% to form a topcoat film.
  • test pieces II for interval adhesion tests were prepared, each having a sandblasted steel plate, an undercoat film, and a topcoat film in this order, and having different outdoor exposure days.
  • test piece II was exposed outdoors for 30 days. After 30 days had passed, the coating surface was lightly washed with water and thoroughly dried, and then a test similar to the cross-cut tape peel test performed in the initial adhesion test was performed.
  • Multilayer coating film 2 Coated item 10: Resin coating film 20: Coating film 30: Substrate

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne une composition de peinture aqueuse à un seul bloc qui contient : une résine (méth) acrylique aqueuse (A) ayant des motifs structuraux dérivés d'un ester vinylique d'acide versatique ; une résine (méth) acrylique aqueuse (B) exempte d'unités structurales dérivées d'un ester vinylique d'acide versatique ; et de l'eau.
PCT/JP2024/020999 2023-06-12 2024-06-10 Composition de peinture aqueuse à un seul bloc Pending WO2024257716A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020257038450A KR20250174087A (ko) 2023-06-12 2024-06-10 1 액형 수성 도료 조성물
CN202480037902.4A CN121263491A (zh) 2023-06-12 2024-06-10 一液型水性涂料组合物

Applications Claiming Priority (2)

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JP2023096328A JP2024177918A (ja) 2023-06-12 2023-06-12 １液型水性塗料組成物
JP2023-096328 2023-06-12

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WO2024257716A1 true WO2024257716A1 (fr) 2024-12-19

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JP (1) JP2024177918A (fr)
KR (1) KR20250174087A (fr)
CN (1) CN121263491A (fr)
WO (1) WO2024257716A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04318083A (ja) * 1991-04-17 1992-11-09 Mitsubishi Motors Corp 塗料
EP0546640A1 (fr) * 1991-12-13 1993-06-16 Shell Internationale Researchmaatschappij B.V. Liants à base de copolymères
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
JP2000169784A (ja) * 1998-12-04 2000-06-20 Nippon Paint Co Ltd 自動車上塗り用クリヤー塗料、複層塗膜形成方法及び自動車車体
JP2001172548A (ja) * 1999-12-15 2001-06-26 Mitsubishi Rayon Co Ltd 防汚性塗料組成物
JP2004204205A (ja) * 2002-06-14 2004-07-22 Daikin Ind Ltd 含フッ素共重合体および塗料用組成物
JP2012224840A (ja) * 2011-04-18 2012-11-15 Rohm & Haas Co 水白化耐性コーティングのためのコポリマー分散物
JP2013209554A (ja) * 2012-03-30 2013-10-10 Nippon Bee Chemical Co Ltd 塗料組成物及び複層塗膜形成方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6106311B2 (ja) 2015-05-26 2017-03-29 日本ペイント株式会社 自然乾燥型水性塗料組成物
CN112424298A (zh) 2018-07-27 2021-02-26 关西涂料株式会社 水性涂料组合物
JP2022157093A (ja) 2021-03-31 2022-10-14 大日本塗料株式会社 塗料組成物、塗装方法および塗装体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04318083A (ja) * 1991-04-17 1992-11-09 Mitsubishi Motors Corp 塗料
EP0546640A1 (fr) * 1991-12-13 1993-06-16 Shell Internationale Researchmaatschappij B.V. Liants à base de copolymères
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
JP2000169784A (ja) * 1998-12-04 2000-06-20 Nippon Paint Co Ltd 自動車上塗り用クリヤー塗料、複層塗膜形成方法及び自動車車体
JP2001172548A (ja) * 1999-12-15 2001-06-26 Mitsubishi Rayon Co Ltd 防汚性塗料組成物
JP2004204205A (ja) * 2002-06-14 2004-07-22 Daikin Ind Ltd 含フッ素共重合体および塗料用組成物
JP2012224840A (ja) * 2011-04-18 2012-11-15 Rohm & Haas Co 水白化耐性コーティングのためのコポリマー分散物
JP2013209554A (ja) * 2012-03-30 2013-10-10 Nippon Bee Chemical Co Ltd 塗料組成物及び複層塗膜形成方法

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CN121263491A (zh) 2026-01-02
KR20250174087A (ko) 2025-12-11

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