WO2024142549A1 - Procédé de production d'un film de revêtement multicouche - Google Patents

Procédé de production d'un film de revêtement multicouche Download PDF

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WO2024142549A1
WO2024142549A1 PCT/JP2023/037264 JP2023037264W WO2024142549A1 WO 2024142549 A1 WO2024142549 A1 WO 2024142549A1 JP 2023037264 W JP2023037264 W JP 2023037264W WO 2024142549 A1 WO2024142549 A1 WO 2024142549A1
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Prior art keywords
coating film
aqueous
mass
undercoat
topcoat
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PCT/JP2023/037264
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English (en)
Japanese (ja)
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雄貴 須川
勇武 尾形
哲男 倉田
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日本ペイント・インダストリアルコーティングス株式会社
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Publication of WO2024142549A1 publication Critical patent/WO2024142549A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • This disclosure relates to a method for producing a multi-layer coating film.
  • Industrial and construction machinery are generally large and can withstand heavy loads, so they are characterized by having thicker constituent substrates (steel plates) than automobile bodies, etc. Therefore, when such industrial and construction machinery are used as substrates, there is a problem that the substrate has a large heat capacity and heat is not sufficiently transferred to the substrate in the heating furnace. For this reason, when painting such substrates, a room temperature film-forming paint composition is selected, which does not require a high-temperature heating process and can form a coating film at room temperature.
  • One method for forming a coating film that satisfies both corrosion resistance and weather resistance performance is to use a coating composition with excellent corrosion resistance as an undercoat paint composition, and then use a topcoat paint composition with excellent weather resistance to form a multi-layer coating film.
  • Patent Document 1 describes a method for forming a thick-film anticorrosive coating, which is characterized by undercoating a weak-solvent high-solid modified epoxy resin paint containing a binder resin component consisting of a modified epoxy resin having an epoxy equivalent of 400 to 2,000 g/eq based on the total mass of the binder resin component, an amine resin, and a reactive diluent, and then overcoating a weak-solvent high-solid polyurethane resin paint containing a binder resin component consisting of a polyol resin having a hydroxyl value of 10 to 100 mg KOH/g and a polyisocyanate compound.
  • wet-on-wet also called 2 coats, 1 bake
  • This painting method can shorten the painting process by applying an undercoat paint composition, then applying a topcoat paint composition without drying the undercoat paint composition, and then drying the two types of paint films simultaneously.
  • Patent Document 2 discusses a method for forming a multilayer coating film, which includes applying an undercoat paint composition containing an epoxy resin, an alicyclic hydrocarbon resin, and a polyisocyanate compound onto an object to be coated to form an uncured undercoat coating film, and then applying a topcoat paint base paint composition containing an acrylic resin and a polyisocyanate compound onto the uncured undercoat coating film.
  • Patent Document 3 studies adjusting the pigment content and the extender pigment content in the primer coating and topcoat coating for a laminate coating having a primer coating containing a reaction product of an epoxy resin and a pigment, and a topcoat coating formed on the primer coating and containing a reaction product of an acrylic resin, a blocked isocyanate compound, and a pigment.
  • Patent Document 4 describes the use of a composition containing an acrylic resin, an epoxy resin, an isocyanate compound, and a surface conditioner as an undercoat paint composition, and a composition containing an acrylic resin, an isocyanate compound, and a surface conditioner as a topcoat paint composition, with the difference in surface tension between the undercoat paint composition and the topcoat paint composition being 2 to 8 mN/m.
  • the topcoat coating composition is a coating composition containing a base agent (III) and a curing agent (IV),
  • the base component (III) contains a film-forming resin,
  • the film-forming resin has a hydroxyl group
  • the manufacturing method for multilayer coatings disclosed herein makes it possible to produce multilayer coatings with a smooth appearance, even when using an aqueous coating composition as the undercoat coating composition and applying wet-on-wet coating.
  • the inventors envisioned suppressing the cure shrinkage of the undercoat paint film in order to improve the appearance of the multi-layer paint film, and investigated using a certain amount of particulate material in the undercoat paint composition. As a result, they found that while the cure proceeds, cure shrinkage is suppressed, and furthermore, the miscibility of the undercoat paint film and the topcoat paint film is appropriately maintained, resulting in a multi-layer paint film with good appearance without compromising the properties of wet-on-wet painting.
  • the film formed after the coating composition is applied and before it is dried or cured is also referred to as the coating film, and the film formed after it is dried or cured is also referred to as the coating film.
  • the method of applying the undercoat paint composition is not particularly limited, but examples include commonly used application methods such as immersion, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, and die coater.
  • a two-liquid mixing gun may be used as necessary. These can be appropriately selected depending on the object to be coated.
  • the undercoat paint composition can be applied so that the dry film thickness of the undercoat paint film (hereinafter, the "dry film of the paint film” is also referred to as the "coat film”, and the “dry film thickness of the paint film” is also referred to as the "coat film thickness”) is 10 to 100 ⁇ m, preferably 15 to 70 ⁇ m. In one embodiment, the undercoat paint composition can be applied so that the film thickness of the undercoat paint film is 30 to 70 ⁇ m, further 40 to 60 ⁇ m. By using the undercoat paint composition described later, a smooth and defect-free multilayer paint film can be obtained even when a thick film is applied. In addition, by making the undercoat paint film 10 ⁇ m or more, it becomes easy to sufficiently protect the substrate, and by making it 100 ⁇ m or less, it becomes easy to suppress the occurrence of defects such as popping in the multilayer paint film.
  • the substrate examples include metal substrates such as iron, zinc, tin, copper, titanium, and tinplate. These metal substrates may be plated with zinc, copper, chromium, etc., or may be surface-treated using a surface treatment agent such as chromate, zinc phosphate, or zirconium salt.
  • metal substrates such as iron, zinc, tin, copper, titanium, and tinplate. These metal substrates may be plated with zinc, copper, chromium, etc., or may be surface-treated using a surface treatment agent such as chromate, zinc phosphate, or zirconium salt.
  • the method for producing a multilayer coating film disclosed herein can be suitably used for coating objects with large heat capacity, such as metal substrates, which are difficult to sufficiently transfer heat to in a heating furnace.
  • coating objects include construction machinery (e.g., bulldozers, scrapers, hydraulic excavators, excavators, transport machinery (trucks, trailers, etc.), cranes and loading and unloading machinery, foundation construction machinery (diesel hammers, hydraulic hammers, etc.), tunnel construction machinery (boring machines, etc.), road rollers, etc.); industrial machinery such as light and heavy electrical equipment, agricultural machinery, steel furniture, machine tools, and large vehicles, which are called general industrial use; and other coating objects that are difficult to heat up even when heated, etc.
  • the method for producing a multilayer coating film disclosed herein can be suitably used for painting construction machinery or industrial machinery, which are coating objects with large heat capacity and difficult to heat up even when heated.
  • topcoat coating film formation process In the topcoat coating film forming step, a topcoat coating composition is applied wet-on-wet on the undercoat coating film to form a topcoat coating film, resulting in a state in which a wet topcoat coating film is formed on the wet undercoat coating film.
  • wet-on-wet includes a coating method in which an undried topcoat coating film is formed on an undried undercoat coating film, and the undried undercoat coating film and the undried topcoat coating film are simultaneously dried to form a multi-layer coating film.
  • Wet-on-wet coating can shorten the coating process, and is energy efficient because there is no need to dry the undercoat coating film.
  • the method for producing a multi-layer coating film disclosed herein uses a basecoat paint composition described below, so that a multi-layer coating film with a smooth surface can be produced even when an aqueous paint composition is used as the basecoat paint composition and wet-on-wet coating is performed.
  • the interval between the formation of the undercoat paint film and the application of the topcoat paint composition (hereinafter also referred to as the "painting interval” or “interval") is, from the viewpoint of work efficiency, more than 0 minutes, and may be 1 to 60 minutes, 1 to 30 minutes, or 1 to 15 minutes.
  • the temperature during the interval may be, for example, from 0°C to less than 40°C, or from 5°C to 35°C.
  • the undercoat coating film after forming the undercoat coating film, it is possible to pre-dry the undercoat coating film for about 1 to 10 minutes at a temperature above normal room temperature (for example, 40 to 100°C, more preferably 40 to 80°C) before applying the topcoat coating composition, and then apply the topcoat coating when the undercoat coating film is in a semi-dried state.
  • a temperature above normal room temperature for example, 40 to 100°C, more preferably 40 to 80°C
  • the method for applying the topcoat paint composition is not particularly limited, but examples include commonly used application methods such as immersion, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, and die coater.
  • a two-liquid mixing gun may be used as necessary. These can be appropriately selected depending on the object to be coated.
  • the topcoat paint composition can be applied so that the dry film thickness of the topcoat paint film (hereinafter also referred to as the "topcoat paint film thickness") is 10 to 100 ⁇ m, preferably 20 to 80 ⁇ m. In one embodiment, the topcoat paint composition can be applied so that the film thickness of the topcoat paint film is 30 to 70 ⁇ m, further 40 to 60 ⁇ m.
  • the topcoat paint film thicker than 10 ⁇ m, it becomes easy to improve the hiding power of the undercoat paint film, and by making it thinner than 100 ⁇ m, it becomes easy to suppress the occurrence of defects such as popping in the multi-layer paint film.
  • the drying temperature may be preferably 5 to 100°C, or more preferably 15 to 80°C. In one embodiment, the drying temperature may be 5 to 35°C, and the drying time may be 1 to 10 days. In another embodiment, the drying temperature may be, for example, 50 to 100°C, or more preferably 60 to 80°C, and the drying time in this case may be 15 to 60 minutes. In yet another embodiment, the drying may be performed at 5 to 35°C for 15 to 60 minutes (room temperature drying), followed by drying at 50 to 100°C (preferably 60 to 80°C) for 15 to 60 minutes (forced drying).
  • the manufacturing method of the multilayer coating film of the present disclosure may further include a step of applying an intermediate coating composition wet-on-wet on an undried undercoat coating film to form an undried intermediate coating film, or may further include a step of applying an intermediate coating composition wet-on-wet on the undried intermediate coating film to form an undried intermediate coating film.
  • the method for applying the intermediate coating composition can be any of the methods described above for applying the topcoat coating composition.
  • the dry film thickness of the intermediate coating film (hereinafter also referred to as the "film thickness of the intermediate coating film”) may be applied so that the dry film thickness of the topcoat coating film falls within the range described above.
  • the undercoat paint composition is a two-component curing type aqueous paint composition containing an aqueous base agent (I) and an aqueous hardener (II).
  • the aqueous base agent (I) and the aqueous hardener (II) are stored separately, and are mixed immediately before painting, and the mixture is used for painting.
  • Aqueous paint compositions use water as a dispersion medium, and the drying rate of the dispersion medium is slower than that of solvent-based paint compositions that use a solvent as a dispersion medium.
  • the undercoat paint composition is an aqueous paint composition
  • the manufacturing method for multilayer paint films disclosed herein uses a specific undercoat paint composition, which suppresses such mixing and allows the formation of a multilayer paint film with a smooth surface.
  • the epoxy resin preferably has at least two epoxy groups per molecule on average.
  • the epoxy equivalent of the epoxy resin may be 100g/eq or more and 5,000g/eq or less, 100g/eq or more and 3,000g/eq or less, or 150g/eq or more and 1,000g/eq or less.By having the epoxy equivalent within such a range, there is an advantage that the water dispersion stability of the epoxy resin, the coating workability of the obtained coating composition, the film forming property of the obtained multi-layer coating film, and the good coating film appearance can be ensured.
  • the epoxy equivalent in the present disclosure represents the solid epoxy equivalent and can be measured by a method in accordance with JIS K 7236.
  • polyhydric phenols examples include resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), a mixture of isomers of dihydroxydiphenylmethane (bisphenol F), tetrabromobisphenol A, 4,4'-dihydroxydiphenylcyclohexane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis[4-(2'-hydroxypropoxy)phenyl]propane, 1,1-bis(4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, bis(2-hydroxynaphthyl)methane, 1,5-dihydroxynaphthalene, tris(4-hydroxyphenyl)methane,
  • the epoxy resin for example, a polyglycidyl ester obtained by reacting a polycarboxylic acid with epichlorohydrin or a derivative thereof can also be used.
  • the polycarboxylic acid is not particularly limited, and examples thereof include aliphatic, alicyclic or aromatic polycarboxylic acids such as oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized linoleic acid.
  • diglycidyl adipate, diglycidyl phthalate and diglycidyl hexahydrophthalate are preferred.
  • bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred.
  • the epoxy resin may be a polyol-modified epoxy resin obtained by reacting an aliphatic polyol compound with an epoxy resin as required.
  • the polyol-modified epoxy resin can be prepared by subjecting the epoxy resin and the aliphatic polyol compound to a condensation reaction. In the condensation reaction, the mass ratio of the epoxy resin to the aliphatic polyol compound (mass of the epoxy resin: mass of the aliphatic polyol compound) is preferably within a range of 95:5 to 5:95.
  • the polyol-modified epoxy resin has the advantage of having good water dispersion performance.
  • an aliphatic polyol compound means a polyol compound that does not contain an aromatic hydrocarbon group in the molecule.
  • the epoxy equivalent of the modified epoxy resin is preferably 100 g/eq or more and 10,000 g/eq or less, more preferably 150 g/eq or more and 5,000 g/eq or less, and even more preferably 200 g/eq or more and 2,000 g/eq or less.
  • the above epoxy resin aqueous dispersions may be used alone or in combination of two or more types.
  • the aqueous base agent (I) may contain other resin components as necessary in addition to the epoxy resin water dispersion (A).
  • other resin components include polyurethane resin water dispersion, polyester resin water dispersion, acrylic resin water dispersion, etc.
  • polyurethane resin water dispersion is preferred from the viewpoint of compatibility with epoxy resin water dispersion (A).
  • the preferred amount when the aqueous base agent (I) further contains other resin components such as polyurethane resin water dispersion is provided that the amount does not impair the performance of the aqueous coating composition and the performance of the multi-layer coating film obtained.
  • the "resin solids" of the undercoat paint composition means the total amount of solids of the resin components that may be contained in the water-based base agent (I) and the water-based curing agent (II), and more specifically, means the total amount of solids of the resin that may be contained in the film-forming resins, such as polyurethane resin water dispersion, polyester water dispersion, and acrylic resin water dispersion, that are added as desired, in addition to the solids of the epoxy resin (A), and the solids of the polyamine compound (B) described below.
  • the film-forming resins such as polyurethane resin water dispersion, polyester water dispersion, and acrylic resin water dispersion
  • the amount of resin solids in the undercoat coating composition may be preferably 10 parts by mass or more and 80 parts by mass or less, more preferably 15 parts by mass or more and 70 parts by mass or less, per 100 parts by mass of the total solids contained in the undercoat coating composition.
  • solids content means the residue after drying at 105° C. for 1 hour.
  • the polyamine compound (B) may be any compound having two or more amino groups in one molecule.
  • polyamine compound (B) examples include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyoxyalkylene group-containing polyamines, polyoxyalkylene group-containing aromatic polyamines, and polyamidoamine compounds.
  • polyalkylene polyamines examples include diethylenetriamine, bis(3-aminopropylamine), triethylenetetramine, N,N-bis(3-aminopropyl)ethylenediamine, tetraethylenepentamine, pentaethylenehexamine, and hexamethylenetetramine.
  • aliphatic amines include, for example, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethyl)amine, bishexamethylenetriamine, etc.
  • alicyclic polyamines examples include 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebiscyclohexylamine, norbornadiamine, bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthenediamine (MDA), 1,4-bis(3-aminopropyl)piperazine, and the like.
  • aromatic polyamines include bis(aminoalkyl)benzenes, bis(aminoalkyl)naphthalenes, aromatic polyamine compounds having two or more primary amino groups bonded to a benzene ring, and other aromatic polyamine compounds.
  • polyoxyalkylene group-containing polyamines examples include polyoxyalkylene diamines such as polyoxyethylene diamine, polyoxypropylene diamine, and poly(oxyethylene-oxypropylene) diamine. These are compounds in which polyoxyalkylene groups have been introduced into aliphatic polyamines, and can also be called polyoxyalkylene group-containing aliphatic polyamines.
  • the total content of the anti-rust pigment (D1), the extender pigment (D2), the coloring pigment (D3) and the filler (D4) may be preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, based on a total of 100 parts by mass of the particulate material (D).
  • the topcoat paint composition may be a water-based paint composition that uses water as a dispersion medium, or a solvent-based paint composition that uses a solvent as a dispersion medium.
  • hydroxyl group-containing monomer examples include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-dihydroxybutyl (meth)acrylate; (meth)acrylic acid polyalkylene glycol monoesters such as polyethylene glycol mono(meth)acrylate; and ⁇ -caprolactone-modified (meth)acrylic acid hydroxyalkyl esters and (meth)acrylic acid polyalkylene glycol monoesters (also referred to as " ⁇ -caprolactone-modified (meth)acrylates").
  • (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-dihydroxybutyl (meth)acrylate
  • ⁇ -caprolactone-modified (meth)acrylates include PLACCEL FA-1, PLACCEL FA-2, PLACCEL FA-3, PLACCEL FA-4, PLACCEL FA-5, PLACCEL FM-1, PLACCEL FM-2, PLACCEL FM-3, PLACCEL FM-4, and PLACCEL FM-5 manufactured by Daicel Chemical Industries, Ltd.
  • (meth)acrylic acid means acrylic acid and methacrylic acid.
  • Carboxyl group-containing monomers include, for example, monocarboxylic acids such as (meth)acrylic acid, 2-ethylpropenoic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and dicarboxylic acid monoesters such as ethyl maleate, butyl maleate, ethyl itaconate, and butyl itaconate.
  • Carboxyl group-containing ethylenically unsaturated monomers are preferably acrylic acid, methacrylic acid, and the like.
  • a commercially available acrylic resin aqueous dispersion may be used.
  • commercially available products include the MACRYNAL series (manufactured by Surface Specialties) such as MACRYNAL VSM6299/42WA, the BAYHYDROL series (manufactured by Bayer AG) such as BARNOCK WD-551, the NeoCryl series (manufactured by DIC), and the NeoCryl series (manufactured by DSM) such as NeoCryl XK-555.
  • the polyisocyanate groups may be modified, and a crosslinked structure due to multiple isocyanate groups may exist between multiple polyisocyanate compounds or within a single polyisocyanate compound. Since the polymeric polyisocyanate compound is trifunctional or higher, at least one of the multiple isocyanate groups may be modified, and at least two isocyanate groups may contribute to the formation of a crosslinked structure.
  • the aqueous base agent (IIIa) and the aqueous hardener (IVa) contain water as a dispersion medium. Ion-exchanged water, distilled water, etc. may be used as the water.
  • the aqueous base agent (IIIa) and/or the aqueous curing agent (IVa) may contain an organic solvent as necessary.
  • organic solvents include butyl acetate, xylene, toluene, methyl isobutyl ketone, propylene glycol, dipropylene glycol dimethyl ether, methyl ether acetate, tetrahydrofuran, ethanol, methanol, propanol, isopropanol, 2-butanol, t-butyl alcohol, dioxane, methyl ethyl ketone, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate (butyl cellosolve acetate), propylene glycol monomethyl ether acetate, 2-methoxypropanol, 2-butoxypropanol, diethylene glycol monobutyl ether, butyl diglycol, N-
  • the water-based topcoat paint composition may contain other components such as pigments, resin particles, resin components, dispersants, curing catalysts, viscosity agents, film-forming assistants, and additives commonly used in paint compositions (e.g., ultraviolet absorbers, light stabilizers, antioxidants, defoamers, surface conditioners, pinhole inhibitors, rust inhibitors, etc.) depending on the purpose and use.
  • additives commonly used in paint compositions e.g., ultraviolet absorbers, light stabilizers, antioxidants, defoamers, surface conditioners, pinhole inhibitors, rust inhibitors, etc.
  • These components may be contained in either the water-based main agent (IIIa) or the water-based curing agent (IVa).
  • the ethylenically unsaturated monomers include hydroxyl group-containing monomers and other monomers.
  • Hydroxyl group-containing monomers include the (meth)acrylic acid hydroxyalkyl ester, the (meth)acrylic acid polyalkylene glycol monoester, and the ⁇ -caprolactone-modified (meth)acrylate.
  • Examples of other monomers used in the acrylic resin (Fb) include the carboxyl group-containing monomers; the (meth)acrylic acid alkyl esters; alicyclic (meth)acrylic monomers such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and adamantyl (meth)acrylate; amino group-containing (meth)acrylic acid esters such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and butylaminoethyl (meth)acrylate; amide group-containing monomers such as (meth)acrylamide, N-methylol (meth)acrylamide, methoxybutyl (meth)acrylamide, and diacetone (meth)acrylamide; amino group-containing (meth)acrylamides such as aminoethyl (meth)
  • acrylic resin (Fb) is preferably the (meth)acrylic acid alkyl esters and the alicyclic (meth)acrylic monomers, and more preferably acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, etc.
  • the hydroxyl value of the acrylic resin (Fb) is preferably 40 to 200 mgKOH/g, more preferably 50 to 200 mgKOH/g.
  • the acid value of the acrylic resin (Fb) is preferably 2 to 150 mgKOH/g, more preferably 5 to 30 mgKOH/g. By having the acid value within the above range, the desired coating film properties can be obtained. It is more preferable that the solid content acid value of the acrylic resin (Fb) is 5 to 30 mgKOH/g.
  • the number average molecular weight of the acrylic resin (Fb) is preferably 3,000 to 20,000, more preferably 3,500 to 15,000, and even more preferably 3,500 to 12,000.
  • the number average molecular weight of the acrylic resin (Fb) 3,000 or more the drying properties of the coating composition can be improved, and the adhesion of dust due to the stickiness of the coating composition scattered in the coating booth can be prevented, thereby maintaining a good coating environment and improving the coating film properties of the resulting multilayer coating film.
  • the gloss of the multilayer coating film can be improved.
  • the acrylic resin (Fb) can be produced by polymerizing the monomer mixture without a solvent or in the presence of a suitable organic solvent.
  • the polymerization method include a radical polymerization method, which can be carried out using a radical polymerization initiator, and specifically may be a bulk polymerization method, a solution polymerization method, or a two-stage bulk-suspension polymerization method in which suspension polymerization is carried out after bulk polymerization.
  • the solution polymerization method is particularly preferred, and an example of this is a method in which the monomer mixture is heated with stirring in the presence of a radical polymerization initiator at a temperature of, for example, 80 to 200°C.
  • acrylic resin (Fb) commercially available products may be used.
  • commercially available products include the Acrydic series such as Acrydic A-428 (manufactured by DIC Corporation), the Dianale series such as Dianale LC-2657 (manufactured by Mitsubishi Chemical Corporation), and the Hitaleoid series (manufactured by Showa Denko Materials Co., Ltd.).
  • the film-forming resin may contain, in addition to the acrylic resin (Fb), polyester resin, epoxy resin, etc., as necessary.
  • the solid content of the acrylic resin (Fb) in the 100% by mass solid content of the coating film-forming resin is preferably 40% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, in one embodiment 50% by mass or more and 90% by mass or less, and in another embodiment 90% by mass or more and 100% by mass or less, from the viewpoint of the water resistance of the coating film and the finish.
  • the acrylic resin in such a range, a multilayer coating film with excellent drying properties can be formed on the substrate by wet-on-wet coating.
  • the "solid content of the film-forming resin” means the total amount of the solid content of the acrylic resin, the solid content of the epoxy resin, and the solid content of other resins that may be contained in the film-forming resin.
  • Polyisocyanate compound (Gb) The polyisocyanate compound (Gb) represents a compound having two or more isocyanate groups in one molecule.
  • the polyisocyanate compound (Gb) may be an aliphatic diisocyanate; an alicyclic diisocyanate; an aromatic diisocyanate; a polymer of an aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate.
  • a polyisocyanate compound (Gb) may be of the so-called asymmetric type.
  • the number of carbon atoms contained in the polyisocyanate compound (Gb) is preferably 5 to 24, more preferably 6 to 18.
  • aliphatic diisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexane diisocyanate, undecane diisocyanate-(1,11), lysine ester diisocyanate, diethylene glycol diisocyanate, dipropylene glycol diisocyanate, triethylene glycol diisocyanate, and thiodipropyl diisocyanate.
  • alicyclic diisocyanate examples include cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate.
  • aromatic diisocyanate examples include 1,5-dimethyl-2,4-bis(isocyanatomethyl)benzene, 1,5-trimethyl-2,4-bis( ⁇ -isocyanatoethyl)-benzene, 1,3,5-trimethyl-2,4-bis(isocyanatomethyl)benzene, 1,3,5-triethyl-2,4-bis(isocyanatomethyl)benzene, 2,4- and/or 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 1,4-diisocyanatoisopropylbenzene.
  • polymer examples include biuret, isocyanurate, and trimethylolpropane (TMP) adduct.
  • TMP trimethylolpropane
  • the polyisocyanate compound (Gb) preferably contains at least an isocyanurate of the aliphatic diisocyanate, alicyclic diisocyanate, or aromatic diisocyanate, and preferably contains an isocyanurate of the aliphatic diisocyanate.
  • the content of the isocyanurate in the polyisocyanate compound (Gb) is preferably 60 mass% or more.
  • the molar ratio (NCO/OH) of the isocyanate groups in the polyisocyanate compound (Gb) to the hydroxyl groups in the film-forming resin is preferably within the range of 0.5 to 2.0, more preferably 0.8 to 1.6.
  • the solvent-based topcoat paint composition is sufficiently cured, and the desired film properties are obtained.
  • the extender pigment is selected from the group consisting of calcium carbonate, barium sulfate, and talc.
  • the extender pigment is selected from the group consisting of calcium carbonate, barium sulfate, and talc.
  • heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, and surface-treated talc can be used.
  • Such extender pigments may be used alone or in combination.
  • the base agent (IIIb) and the curing agent (IVb) contain an organic solvent as a dispersion medium.
  • the organic solvent may include those commonly used in solvent-based paints, such as methyl ethyl ketone, cyclohexanone, Solvesso 100 (manufactured by Exxon Chemical), methoxybutyl acetate, cellosolve acetate, butyl cellosolve acetate, methyl acetate, ethyl acetate, butyl acetate, petroleum ether, and petroleum naphtha.
  • paint design is possible without selecting organic solvents that are subject to specialized legal restrictions depending on the amount used, such as xylene.
  • ⁇ Production Example 2> Preparation example of water-based topcoat paint composition
  • ⁇ Preparation example of pigment dispersion paste for water-based topcoat paint composition> (Pigment Dispersion Paste for Water-Based Topcoat Paint Composition)
  • a dispersion vessel 23.4 parts by mass of ion-exchanged water, 0.5 parts by mass of BYK-420 as a viscosity modifier, 5.6 parts by mass of BYK-2015 as a dispersant, 2.0 parts by mass of Surfynol 440 as an antifoaming agent, and 70 parts by mass of TI-PURE R-960 as a pigment were premixed using a disperser.
  • Topcoat Aqueous Hardener 2 69.5 parts by weight of Vibidur 304 as a water-dispersible polyisocyanate and 35.3 parts by weight of 2-butoxyethyl acetate as an organic solvent were mixed and stirred using a disperser to obtain hardener 2 for water-based topcoat paint.
  • the undercoat (1) was formulated so that the ratio of the active hydrogen equivalent of the polyamine compound in the aqueous curing agent 1 for the undercoat coating composition to the epoxy equivalent of the epoxy resin, which is the film-forming resin in the aqueous main component 1 for the undercoat coating composition, (active hydrogen equivalent/epoxy equivalent) was 0.8.
  • Example 2 Undercoat paint compositions and topcoat paint compositions were produced in the same manner as in Production Example 1, except that the type and/or amount of each component was changed to the amount shown in Tables 1 to 4.
  • the aqueous topcoat paint composition was prepared by mixing with a disperser so that the molar ratio (NCO/OH) between the isocyanate group of the polyisocyanate compound in the curing agent 2 for the aqueous topcoat paint composition obtained in the above Production Example and the hydroxyl group of the acrylic resin, which is the film-forming resin in the base agent 2 for the aqueous topcoat paint composition, was 1.0 (topcoat (2)).
  • a test piece having a multi-layer coating film was obtained in the same manner as in Example 1, except that a coating film was formed under the conditions (combination of coating compositions) shown in Tables 1 to 4 using the undercoat coating composition and the topcoat coating composition.
  • the internal stress (S) of the undercoat coating film at 20°C according to the method of Inoue and Obata was calculated based on the following formula, by measuring the amount of distortion of the undercoat coating film and the PET film according to the bimetal method shown in Figure 1 (Sato Kozo; Polymer Processing, 42 (11), 557 (1993)).
  • the undercoat paint composition was first applied to a strip-shaped PET film having a thickness of 100 ⁇ m so that the dry thickness of the undercoat coating film was 40 ⁇ m (h 1 ), to obtain a PET film having a coating film.
  • knife edges shown by ⁇ marks in FIG. 1
  • the PET film having the coating film was placed on the knife edges.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'objectif de la présente divulgation est de fournir un procédé qui est destiné à la production d'un film de revêtement multicouche et par lequel un film de revêtement multicouche ayant un aspect lisse peut être obtenu même lorsqu'un revêtement humide sur humide est effectué à l'aide d'une composition de revêtement aqueuse en tant que composition de revêtement d'apprêt.　Le procédé de production d'un film de revêtement multicouche selon la présente divulgation comprend : une étape de formation de film de revêtement d'apprêt qui applique une composition de revêtement d'apprêt sur un objet à revêtir pour former un film de revêtement d'apprêt ; une étape de formation de film de revêtement de couche de finition qui applique une composition de revêtement de couche de finition sur le dessus du film de revêtement d'apprêt d'une manière humide sur humide pour former un film de revêtement de couche de finition ; et une étape de séchage qui sèche simultanément le film de revêtement d'apprêt et le film de revêtement de finition pour former un film de revêtement multicouche, la composition de revêtement d'apprêt étant une composition de revêtement aqueuse contenant un agent principal aqueux (I) et un agent de durcissement aqueux (II), l'agent principal aqueux (I) contenant une dispersion aqueuse d'une résine époxy (A), l'agent de durcissement aqueux (II) contenant un composé polyamine (B), au moins l'un de l'agent principal aqueux (I) et de l'agent de durcissement aqueux (II) contenant un matériau particulaire (D), et la teneur en matériau particulaire (D) étant de plus de 120 parties en masse à 380 parties en masse pour 100 parties en masse de solides de résine contenus dans la composition de revêtement aqueuse.
PCT/JP2023/037264 2022-12-26 2023-10-13 Procédé de production d'un film de revêtement multicouche WO2024142549A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09220516A (ja) * 1996-02-16 1997-08-26 Dainippon Ink & Chem Inc 自動車トップコート用複層塗膜の形成方法
JP2006501046A (ja) * 2002-02-13 2006-01-12 ピーピージー インダストリーズ オハイオ， インコーポレイテッド 基材上に多層複合コーティングを形成するためのコーティングラインおよびプロセス
JP2010253942A (ja) * 2009-03-30 2010-11-11 Nippon Steel Corp 複層皮膜被覆金属板及びその製造方法
CN112552777A (zh) * 2019-09-26 2021-03-26 雅图高新材料有限公司 一种湿碰湿工艺的水性环氧底漆及其制备方法
CN112876962A (zh) * 2021-01-15 2021-06-01 万华化学集团股份有限公司 一种应用于工程机械的水性环氧湿碰湿聚氨酯配套漆及其制备方法
CN115368805A (zh) * 2022-09-21 2022-11-22 擎天材料科技有限公司 一种水性双组分的配套漆及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09220516A (ja) * 1996-02-16 1997-08-26 Dainippon Ink & Chem Inc 自動車トップコート用複層塗膜の形成方法
JP2006501046A (ja) * 2002-02-13 2006-01-12 ピーピージー インダストリーズ オハイオ， インコーポレイテッド 基材上に多層複合コーティングを形成するためのコーティングラインおよびプロセス
JP2010253942A (ja) * 2009-03-30 2010-11-11 Nippon Steel Corp 複層皮膜被覆金属板及びその製造方法
CN112552777A (zh) * 2019-09-26 2021-03-26 雅图高新材料有限公司 一种湿碰湿工艺的水性环氧底漆及其制备方法
CN112876962A (zh) * 2021-01-15 2021-06-01 万华化学集团股份有限公司 一种应用于工程机械的水性环氧湿碰湿聚氨酯配套漆及其制备方法
CN115368805A (zh) * 2022-09-21 2022-11-22 擎天材料科技有限公司 一种水性双组分的配套漆及其制备方法和应用

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