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WO2024202850A1 - Composition de revêtement à haute teneur en solides - Google Patents

Composition de revêtement à haute teneur en solides Download PDF

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Publication number
WO2024202850A1
WO2024202850A1 PCT/JP2024/007239 JP2024007239W WO2024202850A1 WO 2024202850 A1 WO2024202850 A1 WO 2024202850A1 JP 2024007239 W JP2024007239 W JP 2024007239W WO 2024202850 A1 WO2024202850 A1 WO 2024202850A1
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WIPO (PCT)
Prior art keywords
high solids
coating composition
polyol
composition according
polyisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/007239
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English (en)
Japanese (ja)
Inventor
千里 芦田
剛男 柳口
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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Filing date
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Publication of WO2024202850A1 publication Critical patent/WO2024202850A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a high solids paint composition that has excellent weather resistance and corrosion resistance and can be applied directly to metal materials.
  • acrylic lacquer, acrylic urethane paint, amino acrylic resin paint, etc. have been used when painting industrial machinery, buildings, automobiles, structures, furniture (including steel), etc.
  • acrylic urethane paints containing a hydroxyl group-containing acrylic resin and a polyisocyanate compound are mainly used from the viewpoints of room temperature drying property, durability, etc.
  • ESG Environmental, Social, and Corporate governance
  • paint compositions containing acrylic resins and isocyanate compounds have been used to ensure weather resistance and corrosion resistance, but the paint solids concentration is generally low, and there are limitations to VOC reduction.
  • paint compositions made of polyamine compounds and isocyanate compounds have excellent coating performance, such as high corrosion resistance and chemical resistance, but because they are highly reactive, they cure quickly and have a short pot life, making them difficult to handle, such as in terms of paint workability.
  • paint compositions made of acrylic resins and isocyanate compounds have low coating hardness from the time of painting until the day after painting. For this reason, they have not been put to practical use in painting construction machinery, etc.
  • Patent Document 1 discloses a high-solids coating composition that uses a base polyol containing a low molecular weight acrylic polyol or polyester polyol, an aliphatic diisocyanate, and an alicyclic diisocyanate as raw materials, and that is characterized by using a polyisocyanate composition that has a content of 20 to 60 mass% of components with a molecular weight of 700 or less, a ratio of weight average molecular weight to number average molecular weight of 1.2 to 5.0, and a ratio of the viscosity of the polyisocyanate composition at 25°C (unit: mPa.s) to the number average functionality of the isocyanate groups expressed by a specific formula.
  • Patent Document 2 discloses a polyaspartic acid ester-based coating composition with a significantly reduced dialkyl fumarate content as a paint composition for producing a gloss-stable colored top coat.
  • Patent Document 2 had insufficient corrosion resistance and weather resistance, and sometimes had insufficient adhesion to metal materials, which is required especially when applying paint directly to metal materials.
  • the problem that this invention aims to solve is to provide a high-solids paint composition that has excellent weather resistance, corrosion resistance, and coating hardness, and can be applied directly to metal materials.
  • a high solids paint composition containing a polyaspartic acid ester (A), a polyisocyanate compound (B), an epoxy group-containing silane coupling agent (C), and a polyol (D) having a weight average molecular weight and hydroxyl value within a specific range, and have completed the present invention.
  • a high solids coating composition comprising a polyaspartic acid ester (A), a polyisocyanate compound (B), an epoxy group-containing silane coupling agent (C), and a polyol (D) having a weight average molecular weight of 250 to 2,300 and a hydroxyl value in the range of 50 to 800.
  • a high solids coating composition according to item 1 in which the polyaspartic acid ester (A) contains a polyaspartic acid ester having a secondary amino group represented by the following formula (1):
  • X is an n-valent cyclic or chain aliphatic hydrocarbon group or a polyoxyalkylene polyamine residue having a number average molecular weight of 25 to 5,000, R 1 and R 2 are each independently an organic group inactive to an isocyanate group, and n is an integer of 2 or more.
  • a high solids coating composition according to item 1 or 2 in which the polyol (D) contains a polyester polyol and/or a polyether polyol.
  • silyl group-containing modified polyisocyanate is a reaction product of raw materials including an alkoxysilane (x1) having a primary amino group, an alkyl carboxylate (x2), and a polyisocyanate (x3).
  • the coating composition of the present invention is made up of polyaspartic acid ester, polyisocyanate compound, epoxy group-containing silane coupling agent, and low molecular weight, high hydroxyl value polyol as its constituents, and therefore has low viscosity, a high VOC reduction effect, excellent curing properties, and the resulting urea crosslinked coating film has excellent weather resistance and corrosion resistance.
  • the improved corrosion resistance of the epoxy group-containing silane coupling agent leads to improved metal adhesion, so the coating composition of the present invention can be applied directly to metal materials. It is presumed that the improved crosslink density of the low molecular weight polyol will dramatically improve the weather resistance, corrosion resistance, and coating hardness of the coating composition.
  • the coating composition of the present invention has the effect of being able to be applied directly to metal materials due to its excellent weather resistance, corrosion resistance, and coating hardness, as well as its high metal adhesion.
  • one-coat specification refers to paint that can be finished with one coat, and can also be written as one-coat specification.
  • the high solids paint composition disclosed herein (hereinafter sometimes simply referred to as the paint) is a composition containing a polyaspartic acid ester (A), a polyisocyanate compound (B), an epoxy group-containing silane coupling agent (C), and a polyol (D). It will be described in detail below.
  • Polyaspartic acid ester (A)> As the polyaspartic acid ester, from the viewpoints of reactivity and coating workability, a polyaspartic acid ester having a secondary amino group is preferred.
  • X is an n-valent cyclic or chain aliphatic hydrocarbon group or a polyoxyalkylene polyamine residue having a number average molecular weight of 25 to 5,000
  • R 1 and R 2 each independently represent an organic group that is inactive toward an isocyanate group
  • n is an integer of 2 or more
  • X is an n-valent cyclic or chain aliphatic hydrocarbon group or a polyoxyalkylene polyamine residue having a number average molecular weight of 25 to 5,000.
  • X is an n-valent group having a number average molecular weight of 25 to 5000, but the number average molecular weight is preferably 50 to 3000, and more preferably 100 to 2000.
  • X is an aliphatic hydrocarbon group or a polyoxyalkylene polyamine residue.
  • the aliphatic hydrocarbon group may be an alicyclic hydrocarbon group, a chain hydrocarbon group, or a group having both an alicyclic portion and a chain portion.
  • the alicyclic hydrocarbon group may have a side chain.
  • the chain hydrocarbon group may be a straight chain hydrocarbon group or a branched hydrocarbon group.
  • X is preferably a divalent aliphatic hydrocarbon group.
  • divalent aliphatic hydrocarbon groups include alkylene, cycloalkylene, cycloalkylalkylene, alkylcycloalkylene, alkylenebiscycloalkylene, alkylenebis(alkylcycloalkylene), cycloalkylenebisalkylene, etc.
  • alkylene is preferably an alkylene having 1 to 8 carbon atoms
  • cycloalkylene is preferably a cycloalkylene having 5 to 6 carbon atoms
  • alkyl is preferably an alkyl having 1 to 8 carbon atoms
  • cycloalkyl is preferably a cycloalkyl having 5 to 6 carbon atoms.
  • the polyoxyalkylene polyamine residue refers to a group obtained by removing primary amino groups from two or more terminals, preferably from both terminals, of a polyoxyalkylene polyamine.
  • the polyoxyalkylene polyamine residue may have a side chain.
  • the polyoxyalkylene polyamine residue is preferably a polyoxyethylene polyamine residue, a polyoxypropylene polyamine residue, a polyoxybutylene polyamine residue, or a polyoxyethylene polyoxypropylene polyamine residue.
  • the polyoxyalkylene polyamine residue is more preferably -(CH(CH 3 )-CH 2 -O)x-CH 2 -CH(CH 3 )- (wherein x is an integer of 3 to 6).
  • R 1 and R 2 are each independently an organic group inactive to an isocyanate group.
  • R 1 and R 2 are preferably alkyl having 1 to 15 carbon atoms, more preferably alkyl having 1 to 8 carbon atoms, further preferably methyl or ethyl, and most preferably ethyl.
  • n is an integer of 2 or more. n is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and most preferably 2.
  • the compound represented by formula (1) can be synthesized, for example, by reacting an optionally substituted maleic acid ester or fumaric acid ester with a polyamine.
  • the compound represented by formula (1) include, but are not limited to, tetraethyl N,N'-[methylenebis(cyclohexane-4,1-diyl)]bisaspartate, tetraethyl N,N'-(hexane-1,6-diyl)bisaspartate, tetrabutyl N,N'-(2-methylpentane-1,5-diyl)bisaspartate, tetraethyl N,N'-[methylenebis(3-methylcyclohexane-4,1-diyl)]bisaspartate, tetraethyl N, At least one selected from the group consisting of N'-(bis-2-propyl)polypropylene glycol 300-O,O'-diylbisaspartate tetraethyl, N,N'-(butane-1,4-diyl)bisaspartate t
  • N,N'-[methylenebis(cyclohexane-4,1-diyl)]bisaspartate tetraethyl, N,N'-(2-methylpentane-1,5-diyl)bisaspartate tetrabutyl, and N,N'-[methylenebis(3-methylcyclohexane-4,1-diyl)]bisaspartate tetraethyl are preferred.
  • polyaspartic acid esters include “Desmophen NH1420”, “Desmophen NH1423LF”, “Desmophen NH 1520”, and “Desmophen NH 1220” (all trade names, manufactured by Sumika Bayer Co., Ltd.), “FEISOARTIC F420”, “FEISOARTIC F220”, and “FEISOARTIC F520” (all trade names, manufactured by Feiyang Co., Ltd.), etc.
  • Polyisocyanate Compound (B) As the polyisocyanate compound, those which have been conventionally used in the production of polyurethanes can be used.
  • polyisocyanate compounds include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic aliphatic polyisocyanate compounds, aromatic polyisocyanate compounds, crude products thereof, and modified products of these polyisocyanate compounds.
  • modified products include biuret modified products, isocyanurate modified products, and mixtures of two or more of these.
  • aliphatic polyisocyanate compounds are preferably used from the viewpoint of high solids content.
  • Aliphatic polyisocyanate compounds are compounds that have a linear or branched chain carbon skeleton and have two or more free isocyanate groups per molecule.
  • aliphatic polyisocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.
  • HDI hexamethylene diisocyanate
  • dodecamethylene diisocyanate 1,6,11-undecane triisocyanate
  • 2,2,4-trimethylhexamethylene diisocyanate lysine diisocyanate
  • 2,6-diisocyanatomethyl caproate bis(2-
  • modified aliphatic polyisocyanate compounds include biuret-modified HDI and isocyanurate-modified HDI.
  • Hexamethylene diisocyanate (HDI) and modified HDI are suitable aliphatic polyisocyanate compounds from the standpoint of curing properties and finished appearance.
  • aliphatic polyisocyanate compounds (B) include, for example, TUL-100 (manufactured by Asahi Kasei Chemicals Corporation), Desmodur N3900 (manufactured by Sumika Covestro Urethanes), Desmodur N3600 (manufactured by Sumika Covestro Urethanes), Desmodur N3200 (manufactured by Sumika Covestro Urethanes), TOLONATE XF-800 (manufactured by Vencolex), and TOLONATE XF-450 (manufactured by Vencolex).
  • TUL-100 manufactured by Asahi Kasei Chemicals Corporation
  • Desmodur N3900 manufactured by Sumika Covestro Urethanes
  • Desmodur N3600 manufactured by Sumika Covestro Urethanes
  • Desmodur N3200 manufactured by Sumika Covestro Urethanes
  • TOLONATE XF-800 manufactured by Vencolex
  • alicyclic polyisocyanate compounds include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornane diisocyanate, etc.
  • IPDI isophorone diisocyanate
  • MDI dicyclohexylmethane-4,4'-diisocyanate
  • TDI methylcyclohexylene diisocyanate
  • bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate 2,5- and/or 2,6-norbornane diisocyanate, etc.
  • aromatic aliphatic polyisocyanate compounds include m- and/or p-xylylene diisocyanate (XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate (TMXDI), etc.
  • aromatic polyisocyanate compounds include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and/or 4,4'-biphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, etc.
  • TDI 1,3- and/or 1,4-phenylene diisocyanate
  • 2,4- and/or 2,6-tolylene diisocyanate crude
  • modified polyisocyanate compounds other than the above aliphatic polyisocyanate compounds include modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, isocyanurate-modified IPDI, and other modified polyisocyanate compounds; and mixtures of two or more of these [for example, a mixture of modified MDI and urethane-modified TDI].
  • a silyl group-containing modified polyisocyanate can be used to improve corrosion resistance.
  • silyl-group-containing modified polyisocyanates can further improve the corrosion resistance of the resulting coating film without reducing its gloss.
  • the silyl group-containing modified polyisocyanate is not particularly limited, and any modified polyisocyanate containing a silyl group can be used without restriction.
  • the silyl group-containing modified polyisocyanate (X) which is a reaction product of raw materials containing an alkoxysilane (x1) having a primary amino group, an alkyl carboxylate (x2), and a polyisocyanate (x3), can be preferably used.
  • Silyl group-containing modified polyisocyanate (X) is a modified polyisocyanate synthesized using a carboxylic acid alkyl ester (X2) as a modifier, which can be stably diluted in organic solvents and has excellent storage stability.
  • compound (x1) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl-methyldiethoxysilane, 3-aminopropyl-methyldimethoxysilane, 3-aminopropyl-ethyleneglycoloxymethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltriethoxysilane, and combinations thereof.
  • 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are particularly preferred.
  • the carboxylic acid alkyl ester (x2) is preferably a saturated carboxylic acid alkyl ester.
  • saturated carboxylic acid alkyl esters include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, cyclohexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 1-methylpentyl acetate (also known as sec-hexyl acetate), 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, n-p
  • polyisocyanate (x3) examples include the polyisocyanate compounds described in the above polyisocyanate compound (B).
  • the method for producing the silyl group-containing modified polyisocyanate (X) may be a method in which an alkoxysilane (x1) having a primary amino group, an alkyl carboxylate (x2), and a polyisocyanate (x3) are reacted simultaneously, but a preferred method is to react the alkoxysilane (x1) with an alkyl carboxylate (x2) in advance to obtain an N-position modified alkoxysilane having a secondary amino group or a secondary amide group, and then to react this with a polyisocyanate (x3).
  • the amount of isocyanate groups in the silyl group-containing modified polyisocyanate is preferably within a range of, for example, 1.0 mmol or more, 2.0 mmol or more, 5.5 mmol or less, and 5.0 mmol or less per 1 g of the nonvolatile content of the modified polyisocyanate, from the viewpoints of corrosion resistance, drying property, etc.
  • the amount of isocyanate groups in a modified polyisocyanate can be determined, for example, by adding 10 ml of 0.1 mol/L dibutylamine solution to 0.1 g of a sample to react with the NCO groups, and then titrating the remaining dibutylamine with an aqueous hydrochloric acid solution using bromophenol blue as a titration indicator.
  • the polyisocyanate compound (B) can be used alone or in combination of two or more types.
  • the ratio of the amino groups of the polyaspartic acid ester (A) to the isocyanate groups of the polyisocyanate compound (B) is within the range of 0.5 to 2.0 equivalents, particularly 0.8 to 1.5 equivalents, and more particularly 1.0 to 1.3 equivalents of isocyanate groups per equivalent of amino groups.
  • the polyaspartic acid ester (A) is within the range of 20 to 70 mass%, particularly 30 to 50 mass%, and the polyisocyanate compound (B) is within the range of 30 to 80 mass%, particularly 50 to 70 mass%, based on the total solid content of the polyaspartic acid ester (A) and the polyisocyanate compound (B).
  • the solid content of the silyl group-containing modified polyisocyanate is preferably within the range of 1 to 100% by mass, particularly 5 to 70% by mass, and more particularly 5 to 50% by mass, based on the total solid content of the polyisocyanate compound (B).
  • the epoxy group-containing silane coupling agent (C) is a component that contributes to improving the adhesion to metal materials, and thereby to improving the corrosion resistance, in particular, of the coating composition of the present disclosure.
  • the epoxy group-containing silane coupling agent (C) is a compound having both an alkoxysilyl group and an epoxy group in the molecule, and specific examples include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyl(methyl)dimethoxysilane, ⁇ -glycidoxypropyl(dimethyl)methoxysilane, ⁇ -glycidoxypropyl(ethyl)dimethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.
  • epoxy group-containing silane coupling agent (C) from the viewpoints of corrosion resistance and finished appearance, gamma-glycidoxypropyltrimethoxysilane and gamma-glycidoxypropylmethyldiethoxysilane can be preferably used.
  • the epoxy equivalent of the epoxy group-containing silane coupling agent (C) is preferably within the range of 100 to 1000 g/eq, particularly 100 to 500 g/eq, from the viewpoint of the appearance of the coating film.
  • the epoxy group-containing silane coupling agent (C) can be used alone or in combination of two or more types.
  • the amount of the epoxy group-containing silane coupling agent (C) is preferably 0.1 to 50 mass%, particularly 0.5 to 30 mass%, and more particularly 0.5 to 15 mass%, based on the total solid content of the polyaspartic acid ester (A) and the polyisocyanate compound (B).
  • Polyol (D) Specific examples include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, fluorine polyols, polycarbonate polyols, polyurethane polyols, etc.
  • the polyol (D) may contain one type alone or two or more types in combination.
  • polyether polyols and polyether polyols are preferred as polyol (D) from the viewpoints of dryness to the touch and weather resistance.
  • Polyester Polyol can be obtained, for example, by subjecting a dibasic acid and a polyhydric alcohol to a condensation reaction.
  • dibasic acid examples include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane, etc.
  • polyester polyols that can be used include polycaprolactones obtained by ring-opening polymerization of lactones such as ⁇ -caprolactone with polyhydric alcohols.
  • Alcohol components other than the above polyhydric alcohols can also be used.
  • monoalcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, and 2-phenoxyethanol
  • alcohol compounds obtained by reacting monoepoxy compounds such as propylene oxide, butylene oxide, and neodecanoic acid glycidyl ester (commercially available product is Cardura E 10P (trade name, manufactured by HEXION, glycidyl ester of synthetic highly branched saturated fatty acid)) with acids
  • esters of glycols and monobasic acids include
  • polyether polyols are not particularly limited, but include, for example, the following (1) to (3).
  • Polyether polyols obtained by random or block addition of an alkylene oxide or a mixture of alkylene oxides to a polyhydric hydroxy compound or a mixture of polyhydric hydroxy compounds using a catalyst.
  • the catalyst examples include hydroxides (lithium, sodium, potassium, etc.), strong base catalysts (alcoholates, alkylamines, etc.), and composite metal cyanide complexes (metal porphyrins, zinc hexacyanocobaltate complexes, etc.).
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.
  • polyamine compounds examples include ethylenediamines.
  • the alkylene oxide may be the same as those exemplified in (1).
  • polyhydric hydroxy compound examples include those shown in (i) to (vi) below.
  • Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and melibiose.
  • Acrylic Polyol is not particularly limited, but examples thereof include those obtained by copolymerizing a single or mixture of an ethylenically unsaturated bond-containing monomer having a hydroxyl group with a single or mixture of other ethylenically unsaturated bond-containing monomer copolymerizable therewith.
  • the ethylenically unsaturated bond-containing monomer having a hydroxy group is not particularly limited, but examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc. These may be used alone or in combination of two or more. Of these, hydroxyethyl acrylate or hydroxyethyl methacrylate is preferred.
  • ethylenically unsaturated bond-containing monomers copolymerizable with the above monomers include, for example, the following (1) to (6). These may be used alone or in combination of two or more types.
  • Acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate.
  • Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, and phenyl methacrylate.
  • Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid.
  • Unsaturated amides such as acrylamide, methacrylamide, N,N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid amide, and maleimide.
  • Vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.
  • Vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and ⁇ -(meth)acryloxypropyltrimethoxysilane.
  • polyolefin polyol is not particularly limited, but examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.
  • the fluorine polyol means a polyol containing fluorine in the molecule.
  • Specific examples of the fluorine polyol include copolymers of fluoroolefin, cyclovinyl ether, hydroxyalkyl vinyl ether, monocarboxylic acid vinyl ester, etc., as disclosed in JP-A-57-34107 (Reference 1) and JP-A-61-275311 (Reference 2), etc.
  • Polycarbonate Polyol is not particularly limited, but examples thereof include the following (1) to (4).
  • Dialkyl carbonates such as dimethyl carbonate
  • Alkylene carbonates such as ethylene carbonate
  • Diaryl carbonates such as diphenyl carbonate
  • a product obtained by condensation polymerization of low molecular weight carbonate compounds such as those described in (1) to (3) above.
  • polyurethane Polyol is not particularly limited, but can be obtained, for example, by reacting a polyol with an isocyanate component by a conventional method.
  • polystyrene resin examples include low molecular weight ones such as ethylene glycol and propylene glycol.
  • high molecular weight ones include acrylic polyols, polyester polyols, polyether polyols, etc.
  • the hydroxyl value of polyol (D) is preferably in the range of 50 to 800, particularly 100 to 700, and more particularly 150 to 600, from the viewpoints of drying property, crosslink density, and weather resistance.
  • the hydroxyl value can be measured in accordance with JIS K1557.
  • the weight average molecular weight of polyol (D) is preferably 250 to 2300, particularly 250 to 1500, and more particularly 250 to 1000, from the viewpoints of drying property, crosslink density, weather resistance, corrosion resistance, and finished appearance. If the weight average molecular weight of polyol (D) exceeds 2300, corrosion resistance and finished appearance may be impaired.
  • weight average molecular weight is a value calculated based on the molecular weight of standard polystyrene from a chromatogram measured by gel permeation chromatography in accordance with the method described in JIS K 0124-2011.
  • the gel permeation chromatograph used was the "HLC8120GPC” (manufactured by Tosoh Corporation). Four columns were used: “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL”, and “TSKgel G-2000HXL” (all product names manufactured by Tosoh Corporation). Measurements were performed under the following conditions: mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 1 ml/min, detector: RI.
  • the amount of polyol (D) is preferably 1 to 20 mass %, particularly 1 to 10 mass %, and more particularly 3 to 10 mass %, based on the total solid content of the polyaspartic acid ester (A) and the polyisocyanate compound (B).
  • the molar ratio of the hydroxyl groups of the polyol (D) to the isocyanate groups of the polyisocyanate composition (B) is preferably within the range of 0.5 to 2.0 equivalents, particularly 0.8 to 1.5 equivalents, and more particularly 1.0 to 1.3 equivalents.
  • polyol (D) improves the crosslink density, and in particular the weather resistance of the coating film.
  • the coating composition of the present disclosure may contain a curing catalyst as necessary to promote the reaction between the polyisocyanate compound (B) and the polyol (D).
  • a curing catalyst include known urethane curing catalysts such as organometallic compounds, tertiary amines, and phosphoric acid compounds.
  • organometallic compounds include tin octoate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dibutyltin fatty acid salts, lead 2-ethylhexanoate, zinc octoate, zinc naphthenate, zinc fatty acids, cobalt naphthenate, calcium octoate, copper naphthenate, and tetra(2-ethylhexyl)titanate.
  • a coloring pigment can be used to achieve a desired color.
  • the coloring pigment include titanium white, zinc molybdate, calcium molybdate, carbon black, graphite, iron black, Prussian blue, ultramarine, cobalt blue, copper phthalocyanine blue, indanthrone blue, yellow lead, synthetic yellow iron oxide, red iron oxide, transparent red iron oxide, bismuth vanadate, titanium yellow, zinc yellow, monoazo yellow, ochre, disazo, isoindolinone yellow, metal complex azo yellow, and quinophthalone.
  • the amount used is preferably 5 to 100% by mass, and particularly 10 to 60% by mass, based on the total solid content of the polyaspartic acid ester (A) and the polyisocyanate compound (B), from the viewpoints of the coating film appearance, weather resistance, and base hiding ability.
  • the coating composition disclosed herein may contain extender pigments as needed.
  • the extender pigment examples include clay, silica, barium sulfate, talc, calcium carbonate, white carbon, diatomaceous earth, and magnesium carbonate.
  • body pigments from the viewpoints of reducing the paint viscosity, coating workability and finished appearance, barium sulfate or calcium carbonate having an average particle size of 0.01 to 5 ⁇ m, preferably 0.05 to 4 ⁇ m, and more preferably 0.05 to 3 ⁇ m, can be suitably used.
  • extender pigments include, for example, barium sulfate, Varifine BF-20 (manufactured by Sakai Chemical Industry Co., Ltd., trade name, barium sulfate having an average particle size of 0.03 ⁇ m), Variace B-33 (manufactured by Sakai Chemical Industry Co., Ltd., trade name, barium sulfate having an average particle size of 0.3 ⁇ m), SPARWITE W-5HB (manufactured by Sino-Can, trade name, barium sulfate powder, average particle size: 1.6 ⁇ m), and BLANC FIXE MICRO (manufactured by Venator Materials, trade name, barium sulfate having an average particle size of 0.7 ⁇ m);
  • Examples of calcium carbonate include Neolite SA-200 (trade name, manufactured by Takehara Chemical Industry Co., Ltd., calcium carbonate having an average particle size of 0.08 ⁇ m), Micro POWDER 3N (trade name, manufactured by Bihoku Funk
  • the average particle size is a value obtained by measuring the particle size distribution using dynamic light scattering.
  • the value is measured using, for example, UPA-EX250 (product name, manufactured by Nikkiso Co., Ltd., a particle size distribution measuring device using dynamic light scattering method).
  • UPA-EX250 product name, manufactured by Nikkiso Co., Ltd., a particle size distribution measuring device using dynamic light scattering method.
  • the amount of the extender pigment used is preferably 10 to 200 mass %, particularly preferably 15 to 150 mass %, based on the total amount of solids of the polyaspartic acid ester (A) and the polyisocyanate compound (B), from the viewpoints of finished appearance and coating workability.
  • the amount of pigments (coloring pigments, extender pigments, and other pigments) used is preferably within the range of 5 to 250% by mass, particularly 20 to 200% by mass, and more particularly 25 to 150% by mass, based on the total solid content of the polyaspartic acid ester (A) and the polyisocyanate compound (B), from the viewpoints of finished appearance and coating workability.
  • zeolite can further be used for the purpose of improving the pot life.
  • Zeolite is a general term for crystalline aluminosilicates, whose constituent elements are Al, Si, O, and cations (positive ions), and whose basic structure is a tetrahedral structure (a tetrahedron formed with Si4 + or Al3 + at the center) formed from SiO4 and AlO4 . These elements are connected in a complex and regular manner, forming pores with diameters of several ⁇ to several tens of ⁇ that are roughly the same size as small molecules, regularly formed in one, two, or three dimensions. This is the characteristic of zeolite.
  • Zeolites include natural zeolites whose main component is hydrous aluminosilicate, and synthetic zeolites whose main component is Na 2 O.Al 2 O 3.xSiO 2.yH 2 O. Synthetic zeolites are also called palmitite and are produced by a dry method in which sodium carbonate, silica, alumina or kaolin are eutectic, or by a wet method in which sodium silicate and sodium aluminate are mixed together and a gel is precipitated.
  • Both natural and synthetic zeolites have ion exchange capacity, their crystal structure does not change even when dehydrated, and they have molecular-sized pores after dehydration, and have large adsorption capacity.
  • Zeolites made by hydrothermal synthesis which are crystallized from sodium aluminosilicate gel and dehydrated to obtain pores of a certain size, are generally called molecular sieves.
  • Zeolites generally called molecular sieves can be preferably used from the viewpoints of pot life and corrosion resistance.
  • Zeolites molded into powder or pellet form are commercially available, and molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X, etc. are commercially available depending on the type of raw zeolite.
  • the numbers indicate the approximate diameter (angstroms) of the pores, and the capital letters indicate the type of zeolite, with A representing LTA zeolite and X representing FAU zeolite.
  • molecular sieve 3A molecular sieve 3A
  • molecular sieve 4A molecular sieve 5A
  • molecular sieve 5A is particularly suitable for use.
  • molecular sieve 5A is molecular sieve 4A in which the sodium ions have been replaced with calcium ions.
  • the pore size (effective diameter of the pores) of the zeolite is preferably in the range of 0.50 nm or less, particularly preferably in the range of 0.10 to 0.50 nm, and further particularly preferably in the range of 0.20 to 0.50 nm.
  • the pore size of the zeolite can be measured by a nitrogen gas adsorption method.
  • the amount used is preferably within the range of 0.1 to 30 mass%, particularly 3 to 30 mass%, and more particularly 5 to 20 mass%, based on the total solid content of the polyaspartic acid ester (A) and the polyisocyanate compound (B), from the viewpoints of pot life and finished appearance.
  • the paint composition of the present disclosure can contain a rheology control agent to control the fluidity of the paint and improve the finished appearance and ease of painting.
  • rheology control agents include clay minerals (e.g., metal silicates, montmorillonite), acrylic resins (e.g., those containing a structure consisting of a polymer or oligomer of an acrylic acid ester or methacrylic acid ester in the molecule), polyolefins (e.g., polyethylene, polypropylene, etc.), amides (higher fatty acid amides, polyamides, oligomers, etc.), polycarboxylic acids (including derivatives having at least two or more carboxyl groups in the molecule), cellulose (including various derivatives such as nitrocellulose, acetyl cellulose, cellulose ether, etc.), and urethanes (polymers, oligomers, etc.
  • clay minerals e.g., metal silicates, montmorillonite
  • acrylic resins e.g., those containing a structure consisting of a polymer or oligomer of an acrylic acid ester or methacrylic acid este
  • ureas polymers, oligomers, etc. containing a urea structure in the molecule
  • urethane ureas polymers, oligomers, etc. containing a urethane structure and a urea structure in the molecule
  • acrylic resin, urea and urethane urea are preferred from the perspective of the finished appearance.
  • the rheology control agent is a substance different from the crosslinked product of the polyaspartic acid ester (A) and the isocyanate compound (B) and from the polyol (D).
  • rheology control agents include, for example, amide waxes such as Disparlon 6900 (Kusumoto Chemicals Co., Ltd.), Disparlon A603 (Kusumoto Chemicals Co., Ltd.), and Thixol W300 (Kyoeisha Chemical Co., Ltd.); polyethylene waxes such as Disparlon 4200 (Kusumoto Chemicals Co., Ltd.); CAB (cellulose acetate butyrate, Eastman Chemical Products Co., Ltd.), HEC (hydroxyethyl cellulose), hydrophobized HEC, and CMC (carbo Examples of rheology control agents include cellulose-based rheology control agents such as BYK-410, BYK-411, BYK-420, and BYK-425 (all manufactured by BYK-Chemie Co., Ltd.); polyolefin-based rheology control agents such as Flonone SA-345HF (Kyoeisha Chemical Co., Ltd.); and higher fatty acids
  • the amount used is preferably within the range of 0.1 to 20 mass %, particularly 0.5 to 15 mass %, and more particularly 0.8 to 10 mass %, based on the total amount of solids of the polyaspartic acid ester (A) and the polyisocyanate compound (B), from the viewpoints of finished appearance and coating workability.
  • the coating composition of the present disclosure may further contain, as necessary, a pigment dispersant, a surface conditioner, a surfactant, an antifoaming agent, a resin other than the polyaspartic acid ester (A) (e.g., an epoxy resin, etc.), a curing agent (excluding the polyisocyanate compound (B)), a preservative, an antifreeze agent, etc.
  • a pigment dispersant e.g., a surface conditioner, a surfactant, an antifoaming agent, a resin other than the polyaspartic acid ester (A) (e.g., an epoxy resin, etc.), a curing agent (excluding the polyisocyanate compound (B)), a preservative, an antifreeze agent, etc.
  • the coating composition disclosed herein is a two-component coating composition consisting of a polyisocyanate compound (B) having free isocyanate groups, which undergoes a crosslinking reaction with the base resin polyaspartic acid ester (A) at room temperature, and therefore consists of a base agent containing polyaspartic acid ester (A) and a curing agent containing polyisocyanate compound (B).
  • the base agent and curing agent are mixed immediately before painting, and a solvent such as an organic solvent is added as necessary to adjust the viscosity, making it suitable for use.
  • Mixing can be carried out using a mixing device such as a disperser or homogenizer.
  • the coating composition disclosed herein is a high solids coating composition, which can reduce the amount of volatile substances such as VOCs emitted during coating.
  • the concentration of solids (non-volatile matter) in the coating can be 70% by mass or more, and particularly 80% by mass or more.
  • the paint solids (non-volatile content) concentration at the time of painting can be determined by weighing 1.0 g of a sample immediately before painting, which has been adjusted to a viscosity suitable for painting under conditions of a temperature of 20°C and a humidity of 60%, onto a tin plate, heating it at a temperature of 105°C for three hours to remove the volatile components, and calculating the remaining amount as a mass percentage.
  • the coating composition of the present disclosure can be applied by a coating method such as dip coating, brush coating, roll brush coating, spray coating, roll coating, spin coating, dip coating, bar coating, flow coating, electrostatic coating, airless coating, electrostatic coating, die coating, etc.
  • substrates include cold-rolled steel sheets, black-skinned steel sheets, alloyed galvanized steel sheets, electrolytic galvanized steel sheets, etc., as well as construction machinery or industrial machinery made from these materials, such as bulldozers, hydraulic excavators, and wheel loaders. These may be shot-blasted, surface-conditioned, surface-treated, or even primed, as required.
  • the coating composition disclosed herein is a high solids coating composition that has excellent weather resistance and corrosion resistance and can be applied directly to metal materials, so it can be suitably used as a topcoat coating that complies with VOC regulations from an ESG perspective for the above-mentioned coating applications, particularly as a one-coat topcoat coating that is applied directly to metal materials.
  • Coating composition production example 1 Production of coating composition No. 1 Coating composition No. 1 was obtained by the following steps 1 and 2.
  • Step 1 Aspartic acid ester resin (A-1) 49.5 parts (solid content), polyol compound (D-1) 5.5 parts (solid content), Variace B-33 (Note 1) 18 parts, Typec CR-95 (Note 2) 8 parts, Carbon MA-100 (Note 3) 1 part, BYK-161 (Note 4) 3 parts, TINUVIN 400 (Note 5) 2 parts, TINUVIN 123 (Note 6) 2 parts, BYK-052N (Note 7) 0.01 parts, BYK-300 (Note 8) 0.05 parts were mixed and stirred, and the solid content concentration was adjusted with a solvent to obtain a base agent of coating composition No. 1 with a solid content of 80% by mass.
  • the extender pigment and color pigment were added and mixed as a pigment dispersion paste prepared using 20 parts of aspartic acid ester resin (A-1).
  • Step 2 45.1 parts of polyisocyanate compound (D-1) and 7.0 parts of epoxy group-containing silane coupling agent (C-1) were added to the base resin obtained in step 1 above, and the solids concentration was adjusted with a solvent to obtain coating composition No. 1 with a solids content of 80% by mass.
  • Examples 2 to 26 and Comparative Examples 1 to 4 Preparation of Coating Compositions No. 2 to 30 Coating compositions No. 2 to 30 were obtained in the same manner as in Example 1, except that the formulations were as shown in Table 1. Coating compositions No. 27 to 30 are comparative examples.
  • the raw material composition (values) in Table 1 are solid masses.
  • Polyaspartic acid ester compound (A) Polyaspartic acid ester (A-1): Desmophen NH-1420: Trade name, manufactured by Covestro, polyaspartic acid ester, amine value 201. Molecular weight 554.7 Viscosity 1000 mPa ⁇ s Polyaspartic acid ester (A-2): Desmophen NH-1423LF: trade name, manufactured by Covestro, polyaspartic acid ester, amine value 230, molecular weight 554.7, viscosity 1500 mPa ⁇ s Polyaspartic acid ester (A-3): Desmophen NH-1220: trade name, manufactured by Covestro, polyaspartic acid ester, amine value 206, molecular weight 460.6, viscosity 100 mPa ⁇ s
  • Polyisocyanate compound (B) Polyisocyanate compound (B-1): Desmodur N 3900: Trade name, manufactured by Covestro, low viscosity HDI isocyanurate, NCO group content 23.5%. Viscosity at 23°C: 700 mPa ⁇ s Polyisocyanate compound (B-2): Desmodur N 3600: trade name, manufactured by Covestro, HDI isocyanurate, NCO group content 23%. Viscosity at 23°C: 1200 mPa ⁇ s Polyisocyanate compound (B-3): Desmodur N 3200: trade name, manufactured by Covestro, HDI burette type isocyanate, NCO group content 23%.
  • Viscosity at 23°C 2500 mPa ⁇ s
  • Epoxy group-containing silane coupling agent (C) Epoxy group-containing silane coupling agent (C-1): "KBM-403": trade name, manufactured by Shin-Etsu Chemical Co., Ltd., ⁇ -glycidoxypropyltrimethoxysilane, epoxy equivalent 236, molecular weight 236.
  • Epoxy resin (1) "JER-828”: Product name, manufactured by Mitsubishi Chemical Corporation, bisphenol A type liquid epoxy resin, epoxy equivalent 188.
  • Polyol Compounds (D) Polyol compound (D-1): "Desmophen XP-2488”: trade name, manufactured by Covestro, polyester polyol, hydroxyl value 528, molecular weight 1400
  • Polyol compound (D-4) "TA22-981”: trade name, manufactured by Resonac Corporation, polyester polyol, hydroxyl value 55, molecular weight 2000.
  • Variace B-33 Product name, manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate, average particle size 0.3 ⁇ m
  • TYPAQUE CR-95 Product name, titanium dioxide, manufactured by Ishihara Sangyo Kaisha, Ltd.
  • CARBON MA-100 Product name, carbon black, manufactured by Mitsubishi Chemical Corporation
  • BYK-161 Product name, wetting and dispersing agent, manufactured by BYK-Chemie Co., Ltd.
  • TINUVIN 400 Product name, hydroxyphenyltriazine ultraviolet absorber, manufactured by B.A.S.F.
  • TINUVIN 123 Product name, hydroxyphenyltriazine ultraviolet absorber, manufactured by B.A.S.F.
  • BYK-052N BYK Corporation, product name, defoamer, alkyl vinyl ether copolymer
  • BYK-300 BYK Corporation, product name, silicone surface conditioner
  • Neostan U-100 Nitto Kasei Co., Ltd., product name, dibutyltin dilaurate, urethane curing catalyst (Note 10)
  • Silyl group-containing modified polyisocyanate X1 89.5 parts of 3-aminopropyltrimethoxysilane and 0.04 parts of methoquinone were placed in a flask and heated to 80°C, and air was introduced into the liquid and bubbled while stirring.
  • Silyl group-containing modified polyisocyanate X2 89.5 parts of 3-aminopropyltrimethoxysilane, 0.04 parts of methoquinone, and 4 parts of "Swasol 1000" (naphtha-based solvent, product name, manufactured by Maruzen Petrochemical Co., Ltd.) were placed in a flask, and air was introduced into the liquid to bubble and stir, and 104 parts of isobornyl acrylate was added dropwise over 2 hours, and then the mixture was kept at 50 ° C. for 1 hour. The mixture was further aged at 50 ° C.
  • Silyl group-containing modified polyisocyanate X3 In a flask under a nitrogen atmosphere, 89 parts of methyl acetate, which is a linear saturated ester, and 179 parts of 3-aminopropyltrimethoxysilane were placed and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide was added as a catalyst, and the mixture was stirred and heated to 70°C and aged for one day. The reaction rate of 3-aminopropyltrimethoxysilane was 97%, and methanol was by-produced in an amount approximately equimolar to the reacted 3-aminopropyltrimethoxysilane.
  • Molecular sieve 3A Union Showa Co., Ltd., trade name, sodium calcium aminosilicate, pore size 0.25 nm
  • Molecular sieve 5A Union Showa Co., Ltd., trade name, sodium calcium aminosilicate, pore size 0.42 nm
  • Molecular sieve 13X Union Showa Co., Ltd., trade name, sodium calcium aminosilicate, pore size 1.0 nm
  • each of the coating compositions No. 1 to 30 was air spray coated (pressure 0.4 MPa) on a shot blasted general structural rolled steel material SS-400 (size 2.3 ⁇ 150 ⁇ 300 mm, Ra: 3.9 ⁇ m Ry: 34 ⁇ m Rz: 23 ⁇ m) so that the dry film thickness was 80 ⁇ m, and after setting at 20 ° C for 10 minutes, it was heated and dried at 60 ° C for 30 minutes using an electric hot air dryer, and further aged at 20 ° C for 168 hours to obtain test panels of each of the coating compositions No. 1 to 30.
  • Pencil hardness In accordance with JIS K 5600-5-4:1999, a pencil core was placed on each test plate at an angle of about 45° to the test plate surface, and the core was pressed against the test plate surface hard enough not to break, while moving forward at a uniform speed for about 10 mm. The hardness symbol of the hardest pencil that did not break the coating film was taken as the pencil hardness.
  • the pencil hardness symbols are in accordance with JIS S6006 (2020). A: 2H or more B: H or more and less than 2H C: F or more and less than H D: Less than F
  • each test coated plate had a cross cut on the test coating surface reaching the base material, and was sprayed with a 5% aqueous sodium chloride solution adjusted to a pH of 7.0 in an atmosphere of 35°C for 168 hours, after which the width of a bulge on one side from the cut was evaluated.
  • the 60 degree gloss retention (GR %) is 70 or more and less than 80, or the color difference ( ⁇ E) is 2.0 or more and less than 3.0.

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Abstract

Cette composition de revêtement ayant une haute teneur en solides contient un ester d'acide polyaspartique (A), un composé polyisocyanate (B), un agent de couplage au silane contenant un groupe époxy (C), et un polyol (D) ayant un poids moléculaire moyen en poids de 250-2300 et une valeur hydroxyle de 50-800.
PCT/JP2024/007239 2023-03-31 2024-02-28 Composition de revêtement à haute teneur en solides Pending WO2024202850A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011074390A (ja) * 2009-10-01 2011-04-14 Bayer Materialscience Ag アロファネート基及びシラン基を含む高官能性ポリイソシアネート
WO2016063884A1 (fr) * 2014-10-21 2016-04-28 株式会社カネカ Ester d'acide polyaspartique modifié et composition de résine durcissable
JP2017149858A (ja) * 2016-02-25 2017-08-31 Dic株式会社 印刷インキ、ポリウレタンポリウレア樹脂の製造方法、及び印刷物
WO2018163953A1 (fr) * 2017-03-07 2018-09-13 旭化成株式会社 Composition de matériau de revêtement polyaspartique, film de revêtement, et article revêtu
WO2021175852A1 (fr) * 2020-03-03 2021-09-10 Jotun A/S Revêtement
JP7409757B1 (ja) * 2023-03-31 2024-01-09 関西ペイント株式会社 高固形分塗料組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011074390A (ja) * 2009-10-01 2011-04-14 Bayer Materialscience Ag アロファネート基及びシラン基を含む高官能性ポリイソシアネート
WO2016063884A1 (fr) * 2014-10-21 2016-04-28 株式会社カネカ Ester d'acide polyaspartique modifié et composition de résine durcissable
JP2017149858A (ja) * 2016-02-25 2017-08-31 Dic株式会社 印刷インキ、ポリウレタンポリウレア樹脂の製造方法、及び印刷物
WO2018163953A1 (fr) * 2017-03-07 2018-09-13 旭化成株式会社 Composition de matériau de revêtement polyaspartique, film de revêtement, et article revêtu
WO2021175852A1 (fr) * 2020-03-03 2021-09-10 Jotun A/S Revêtement
JP7409757B1 (ja) * 2023-03-31 2024-01-09 関西ペイント株式会社 高固形分塗料組成物

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