WO2024257445A1 - Composition de revêtement par électrodéposition cationique, produit revêtu par électrodéposition et procédé de production de produit revêtu par électrodéposition - Google Patents

Composition de revêtement par électrodéposition cationique, produit revêtu par électrodéposition et procédé de production de produit revêtu par électrodéposition Download PDF

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Publication number
WO2024257445A1
WO2024257445A1 PCT/JP2024/013701 JP2024013701W WO2024257445A1 WO 2024257445 A1 WO2024257445 A1 WO 2024257445A1 JP 2024013701 W JP2024013701 W JP 2024013701W WO 2024257445 A1 WO2024257445 A1 WO 2024257445A1
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electrodeposition coating
coating composition
compound
cationic electrodeposition
aminated
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Japanese (ja)
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沙理 中島
雄大 山下
悠斗 森本
祐斗 岩橋
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Nippon Paint Automotive Coatings Co Ltd
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Nippon Paint Automotive Coatings Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • 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
    • C09D7/65—Additives macromolecular

Definitions

  • the present invention relates to a cationic electrocoating composition, an electrocoated article, and a method for producing an electrocoated article.
  • Cationic electrocoating paints are often used as undercoats to impart rust resistance to industrial products such as automobiles. From the viewpoint of rust resistance, it is required that the coating film is formed uniformly on the substrate. However, it is difficult to cover edges in particular with a sufficiently thick coating film, which makes them susceptible to corrosion. For this reason, it has been proposed to increase the viscosity of the paint.
  • Patent Document 1 teaches the addition of polyvinyl formamide polymer to the cationic electrocoating paint.
  • Patent Document 2 teaches the addition of a polyvinyl compound to the cationic electrocoating paint.
  • the present invention aims to solve the above-mentioned conventional problems, and to provide a cationic electrodeposition coating composition that can provide a coating film that has excellent rust prevention properties, especially edge rust prevention properties, and excellent appearance.
  • an aminated epoxy resin A
  • an aminated acrylic resin B
  • a blocked polyisocyanate curing agent C
  • a pigment D
  • E a polyamidine compound or a hydrophobically modified product thereof
  • the polyamidine compound or its hydrophobically modified derivative (E) is represented by the following general formula (I):
  • R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X is an anion.
  • a cationic electrodeposition coating composition having a structural unit represented by the formula:
  • the hydrophobized modified product of the polyamidine compound contains, in addition to the structural unit (I), a cyclized structural unit derived from an unsaturated nitrile or a structural unit represented by the following general formula (X): (In the formula, R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms,
  • the aminated epoxy resin (A) is obtained by reacting an amine compound with an epoxy resin, the amine compound is a combination of two types of amines, a primary amine and a secondary amine,
  • the primary amine has the formula: NH 2 -(CH 2 )n-NR 11 R 12 (In the formula, R 11 and R 12 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group at its terminal, and n represents an integer of 2 to 4.) having
  • the secondary amine has the formula: R13 R14 NH (In the formula, R 13 and R 14 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms and a hydroxyl group at its terminal.) or the amine compound comprises one or more compounds selected from the group consisting of ketimine compounds and diketimine compounds;
  • the cationic electrodeposition coating composition according to [1] or [2].
  • the blocked polyisocyanate curing agent (C) contains an oxime-blocked isocyanate curing agent which is a blocked reaction product between a blocking agent containing an oxime compound and a polyisocyanate, and the polyisocyanate in the blocking reaction contains one or more compounds selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound.
  • the cationic electrodeposition coating composition according to [1] or [2].
  • the present invention provides a cationic electrocoating paint composition that provides a coating film with excellent rust prevention properties, particularly edge rust prevention properties, and excellent appearance, as well as an electrocoated product and a method for producing the same.
  • the polymeric viscous agent interacts with the film-forming resin and pigment to increase the viscosity of the cationic electrodeposition coating composition.
  • the coating composition is prevented from flowing when heated. However, it is difficult to cure the coating composition while covering the edges.
  • a polyamidine compound having a cyclic amidine skeleton (hereinafter referred to as a cyclic polyamidine compound) is added to the paint composition.
  • a cyclic polyamidine compound is added to the paint composition.
  • a polyamidine compound having an electric charge is likely to precipitate on the edge.
  • the paint composition can harden while covering the edge, improving edge rust prevention.
  • the cyclic polyamidine compound may be modified to introduce a hydrophobic group from the viewpoint of paint stability.
  • a compound into which a hydrophobic group has been introduced is referred to as a "hydrophobized modified product" in this specification.
  • the film-forming resin flows to a certain extent when heated, so the surface of the resulting cured coating is leveled, resulting in a good appearance.
  • the cationic electrodeposition coating composition according to this embodiment contains, in addition to the aminated epoxy resin (A), an aminated acrylic resin (B) as a film-forming resin component that reacts with a curing agent to harden. This has the advantage of providing better weather resistance.
  • the cationic electrodeposition coating composition according to this embodiment contains an aminated epoxy resin (A), an aminated acrylic resin (B), a blocked polyisocyanate curing agent (C), a pigment (D), and a polyamidine compound or a hydrophobically modified product thereof (E).
  • the polyamidine compound or its hydrophobized modification (E) is represented by the following general formula: (In the formula, R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X is an anion.) It has a structural unit represented by the following formula:
  • the aminated epoxy resin (A) is a coating film-forming resin.
  • at least one oxirane ring (also called "epoxy group") of the epoxy resin is aminated.
  • the aminated epoxy resin (A) is preferably contained in the electrodeposition coating composition in the form of a resin emulsion together with the blocked polyisocyanate curing agent (C).
  • the number average molecular weight of the aminated epoxy resin (A) is, for example, 1,000 or more and 7,000 or less. When the number average molecular weight is 1,000 or more, the rust prevention and solvent resistance of the resulting cured electrodeposition coating film are likely to be improved. When the number average molecular weight is 7,000 or less, the viscosity of the aminated epoxy resin (A) can be easily adjusted, allowing for smooth synthesis, and in addition, the resulting aminated epoxy resin (A) can be easily emulsified and dispersed.
  • the number average molecular weight of the aminated epoxy resin (A) may be 1,500 or more and 4,000 or less.
  • the number average molecular weight of the aminated epoxy resin (A) is a styrene homopolymer equivalent value measured using gel permeation chromatography.
  • the amine value of the aminated epoxy resin (A) is, for example, 20 mgKOH/g or more and 100 mgKOH/g or less.
  • the amine value of the aminated epoxy resin (A) is 20 mgKOH/g or more, the stability of the emulsion dispersion of the aminated epoxy resin (A) in the coating composition is good.
  • the amine value is 100 mgKOH/g or less, the amount of amino groups in the cured electrodeposition coating film is appropriate, and a decrease in the water resistance of the coating film is suppressed.
  • the amine value of the aminated epoxy resin (A) may be 20 mgKOH/g or more and 80 mgKOH/g or less.
  • the amine value can be determined by the following method in accordance with ASTM D2073. (1) 500 mg of aminated epoxy resin is weighed out accurately into a 200-ml Erlenmeyer flask. (2) Add approximately 50 ml of glacial acetic acid and dissolve uniformly. (3) Add 5 to 6 drops of indicator (methyl violet solution) and stir evenly. (4) Titrate with 0.1 N perchloric acid and acetic acid solution, and the endpoint is when the color turns bright green. (The above (3) and (4) may be replaced by potentiometric titration.)
  • the aminated epoxy resin (A) may have hydroxyl groups, and the hydroxyl value of the aminated epoxy resin (A) is, for example, 150 mgKOH/g or more and 650 mgKOH/g or less.
  • the hydroxyl value is 150 mgKOH/g or more, the curability of the coating composition is enhanced and the appearance of the coating film is improved.
  • the hydroxyl value is 650 mgKOH/g or less, the amount of hydroxyl groups remaining in the cured electrodeposition coating is appropriate, making it easier to improve the water resistance of the coating film.
  • the hydroxyl value of the aminated epoxy resin (A) is 150 mgKOH/g or more, 180 mgKOH/g or more, 200 mgKOH/g or more, 250 mgKOH/g or more, 300 mgKOH/g or more, 350 mgKOH/g or more, 400 mgKOH/g or more, 450 mgKOH/g or more, 500 mgKOH/g or more, 550 mgKOH/g or more, or 600 mgKOH/g or more.
  • the hydroxyl value of the aminated epoxy resin (A) component is 650 mgKOH/g or less, 600 mgKOH/g or less, 550 mgKOH/g or less, 500 mgKOH/g or less, 450 mgKOH/g or less, 400 mgKOH/g or less, 350 mgKOH/g or less, 300 mgKOH/g or less, 250 mgKOH/g or less, or 200 mgKOH/g or less.
  • the hydroxyl value of component (A) is 180 to 300 mgKOH/g.
  • the hydroxyl value can be determined by the neutralization titration method using an aqueous potassium hydroxide solution as described in JIS K 0070.
  • the number average molecular weight of the aminated epoxy resin (A) is within the range of 1,000 to 7,000, the amine value is 20 to 100 mgKOH/g, and the hydroxyl value is 150 to 650 mgKOH/g (preferably 150 to 400 mgKOH/g), the rust prevention properties of the coated object are likely to be further improved.
  • the coating composition may contain multiple aminated epoxy resins (A) with different amine values and/or hydroxyl values.
  • the average amine value and average hydroxyl value calculated based on the mass ratio of the multiple aminated epoxy resins (A) are within the above ranges.
  • the multiple aminated epoxy resins (A) contain an aminated epoxy resin with an amine value of 20 to 50 mgKOH/g and a hydroxyl value of 50 to 300 mgKOH/g, and an aminated epoxy resin with an amine value of 50 to 200 mgKOH/g and a hydroxyl value of 200 to 500 mgKOH/g. This makes the core of the emulsion more hydrophobic and the shell more hydrophilic, making it easier to improve the rust prevention properties of the coated object.
  • the above-mentioned aminated epoxy resin (A) can be prepared, for example, by reacting the oxirane ring of the above-mentioned epoxy resin with an amine compound.
  • an amine compound generally used in the production of aminated epoxy resins is used.
  • commonly used amine compounds include primary amines such as butylamine, octylamine, and monoethanolamine; secondary amines such as diethylamine, dibutylamine, methylbutylamine, diethanolamine, and N-methylethanolamine; and complex amines such as diethylenetriamine.
  • the above-mentioned primary amines can form ketimine groups using ketone compounds, thereby controlling the reaction by so-called blocking.
  • amine compounds having a ketimine group or diketimine group examples include ketimine of aminoethylethanolamine and diketimine of diethylenetriamine.
  • Ketone compounds that generate ketimine groups include methyl isopropyl ketone (MIPK), diisobutyl ketone (DIBK), methyl isobutyl ketone (MIBK), diethyl ketone (DEK), ethyl butyl ketone (EBK), ethyl propyl ketone (EPK), dipropyl ketone (DPK), and methyl ethyl ketone (MEK), with methyl isobutyl ketone (MIBK) being preferred.
  • MIPK isopropyl ketone
  • DIBK diisobutyl ketone
  • MIBK methyl isobutyl ketone
  • DEK diethyl ketone
  • EBK ethyl butyl ketone
  • Tertiary amines may be used as amine compounds, and specific examples thereof include triethylamine, N,N-dimethylbenzylamine, and N,N-dimethylethanolamine. These amines may be used alone or in combination of two or more.
  • the amine compound is preferably used in an amount that is 0.9 to 1.2 equivalents per equivalent of epoxy groups in the raw epoxy resin.
  • the reaction conditions for the conversion to amination can be appropriately selected depending on the reaction scale, etc. For example, the reaction can be carried out at 80°C to 150°C for 0.1 to 5 hours, or at 120°C to 150°C for 0.5 to 3 hours.
  • an amine compound having at least one of a primary amino group, a secondary amino group, and a tertiary amino group, excluding ketimines (including diketimines), is used as the amine compound that modifies the oxirane ring (also called the "epoxy group") of the epoxy resin.
  • the amine compound is a combination of two types of amines, a primary amine and a secondary amine
  • the primary amine is represented by the formula: NH 2 -(CH 2 )n-NR 11 R 12 (1)
  • R 11 and R 12 may be the same or different and each represent an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group at its terminal, and n represents an integer of 2 to 4.
  • the secondary amine has the formula: R 13 R 14 NH (2) (In formula (2), R 13 and R 14 represent an alkyl group having 1 to 4 carbon atoms and a hydroxyl group at its terminal.)
  • the primary amino group of the primary amine reacts with the epoxy resin and is consumed, and the remaining amino group is only the secondary amino group, which reacts with the epoxy group of the epoxy resin, so that the reaction proceeds evenly without superiority or inferiority in reactivity, and it is believed that the molecular weight distribution can be controlled.
  • the primary amine has the above formula (1), and R 11 and R 12 are specifically methyl, ethyl, propyl, or butyl, and may have a hydroxyl group at the end. n is 2 to 4, and preferably 3. Specific examples of the primary amine include aminopropyldiethanolamine, dimethylaminopropanediamine, diethylaminopropanediamine, and dibutylaminopropanediamine.
  • the secondary amine is a secondary amine having the above formula (2), in which R 13 and R 14 are bonded to a nitrogen atom, and both R 3 and R 4 have an alkyl group having 1 to 4 carbon atoms and a hydroxyl group. Specific examples of the secondary amine include dimethanolamine and diethanolamine.
  • the amine compound used for the amination may include an amine compound having a ketimine group or a diketimine group.
  • the aminated acrylic resin (B) is a film-forming resin.
  • the aminated acrylic resin (B) has a function as a film-forming resin and a function of mainly imparting weather resistance to the electrodeposition coating film.
  • Amino-containing acrylic resin (B) can be obtained by copolymerizing (i) an amino-containing acrylic monomer, (ii) a hydroxyl-containing acrylic monomer, and (iii) other ethylenically unsaturated monomers. Furthermore, it can also be obtained by copolymerizing an epoxy-containing acrylic monomer (iv) instead of the amino-containing acrylic monomer with a hydroxyl-containing acrylic monomer and other ethylenically unsaturated monomers, and ring-opening the epoxy groups of the resulting copolymer with an amine.
  • amino group-containing acrylic monomers (i) examples include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate.
  • Preferred examples of the hydroxyl group-containing acrylic monomer (ii) include mono(meth)acrylates of alkylene diols such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, polypropylene glycol mono(meth)acrylate, and 1,6-hexanediol mono(meth)acrylate.
  • (meth)acrylamides such as N-hydroxyethyl(meth)acrylamide and N-hydroxypropyl(meth)acrylamide are also preferred, and furthermore, reaction products of hydroxyalkyl mono(meth)acrylates with ⁇ -caprolactone or reaction products of hydroxyalkyl mono(meth)acrylates with six-membered cyclic carbonates can also be suitably used as the hydroxyl group-containing acrylic monomer (ii).
  • Examples of other ethylenically unsaturated monomers (iii) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, styrene, vinyl toluene, ⁇ -methylstyrene, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, etc.
  • an acrylic monomer having a hydroxyl group and other ethylenically unsaturated monomers may be copolymerized with an epoxy group-containing acrylic monomer (iv) such as glycidyl (meth)acrylate, and then a secondary amine may be reacted with the epoxy group.
  • an epoxy group-containing acrylic monomer (iv) such as glycidyl (meth)acrylate
  • Secondary amines that can be used for the reaction with the epoxy group include diethylamine, dibutylamine, dicyclohexylamine, morpholine, diethanolamine, N-methylethanolamine, etc., and amines having a hydroxyl group and a secondary amino group in the molecule are particularly preferred.
  • methyl isobutyl ketone diketimine of diethylenetriamine and methyl isobutyl ketone monoketimine of 2-(2-aminoethylamino)ethanol can also be used.
  • examples of the above epoxy group-containing acrylic monomer (iv) include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc.
  • the polymerization of the acrylic monomers (i) to (iv) can be carried out by a conventional method such as solution polymerization.
  • the number average molecular weight of the copolymer may be, for example, 1000 or more, 1500 or more, or 2000 or more, and may be 50000 or less, 40000 or less, 30000 or less, or 20000 or less.
  • the degree of polymerization can be adjusted, if necessary, by using a chain transfer agent such as dodecyl mercaptan or 2-ethylhexyl thioglycolate.
  • Half-blocked diisocyanates may be added to amino group-containing acrylic polymers via urethane bonds to impart self-crosslinking properties.
  • alicyclic diisocyanates such as isophorone diisocyanate (IPDI), 4,4'-methylenebis(cyclohexyl isocyanate) (hydrogenated MDI), and norbornane diisocyanate (NBDI).
  • a known blocking agent can be used to block one of the isocyanate groups of a diisocyanate to form a half-blocked diisocyanate.
  • blocking agents include alcohols such as n-butanol, 2-ethylhexanol, ethylene glycol monobutyl ether, and cyclohexanol; phenols such as phenol, nitrophenol, cresol, and nonylphenol; oximes such as dimethyl ketoxime, methyl ethyl ketoxime, and methyl isobutyl ketoxime; and lactams such as ⁇ -caprolactam.
  • the aminated acrylic resin (B) can be designed to have a lower SP value than the aminated epoxy resin (A).
  • aminated epoxy resin (A) in combination with aminated acrylic resin (B) having a lower SP value than the aminated epoxy resin (A), at least a portion of the aminated epoxy resin (A) migrates to the metal substrate side during baking after electrodeposition coating, improving corrosion resistance, and at least a portion of the aminated acrylic resin (B) migrates to the coating film surface side, improving weather resistance, for example, as a single cured electrodeposition coating film.
  • the SP values of the aminated epoxy resin (A) and the aminated acrylic resin (B) can be determined by calculation based on the SP values of the homopolymers of the constituent monomers that make up the resins and the weight fractions of each constituent monomer in the monomer mixture.
  • the aminated acrylic resin (B) also preferably contains hydroxyl groups.
  • the hydroxyl value of the aminated acrylic resin (B) may be, for example, 20 to 250 mgKOH/g or more.
  • the hydroxyl value of the aminated acrylic resin (B) may be 40 mgKOH/g or more, 50 mgKOH/g or more, or 55 mgKOH/g or more, and may be 200 mgKOH/g or less, 180 mgKOH/g or less, or 160 mgKOH/g or less.
  • the monomer composition can be configured so that the hydroxyl value falls within the above range by a method well known to those skilled in the art.
  • the amine value of the aminated acrylic resin (B) may be, for example, 20 to 100.
  • the amine value of the aminated acrylic resin (B) may be 20 or more, 30 or more, or 35 or more, and may be 95 or less, 90 or less, 85 or less, or 80 or less.
  • the monomer composition can be configured so that the amine value of the aminated acrylic resin (B) falls within the above range by a method well known to those skilled in the art.
  • the resin solids mass ratio of aminated epoxy resin (A) to aminated acrylic resin (B) in aminated acrylic resin (A):(B) may be in the range of 5:95 to 30:70, or in the range of 10:90 to 40:60.
  • the coating composition may contain, as necessary, an aminated resin other than the aminated epoxy resin (A) and the aminated acrylic resin (B), such as an aminated polyester resin.
  • the coating composition may also contain other film-forming resins other than the above-mentioned aminated resins.
  • other film-forming resins include hydroxyl-containing acrylic resins, hydroxyl-containing polyester resins, urethane resins, butadiene resins, phenolic resins, and xylene resins.
  • film-forming resins contained in the coating composition that react with a curing agent to form a coating film 80% by mass or more, further 90% by mass or more, and particularly 100% by mass may be composed of the aminated epoxy resin (A) and the aminated acrylic resin (B).
  • the blocked polyisocyanate curing agent (C) (hereinafter sometimes simply referred to as curing agent (C)) also constitutes the electrodeposition coating film.
  • the blocked polyisocyanate curing agent (C) reacts preferentially with the amine groups of the aminated epoxy resin (A) and the aminated acrylic resin (B), and further reacts with the hydroxyl groups to cure the aminated epoxy resin (A) and the aminated acrylic resin (B).
  • the blocked polyisocyanate curing agent (C) can be prepared by blocking a polyisocyanate compound with a blocking agent.
  • polyisocyanate compound examples include: Aliphatic polyisocyanate compounds having 3 to 12 carbon atoms, such as hexamethylene diisocyanate (including trimer), 2,2,4-trimethylhexane diisocyanate, and lysine diisocyanate; Alicyclic polyisocyanate compounds such as 1,4-cyclohexane diisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methylcyclohexane diisocyanate, isopropylidenedicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethylcyclohexane (hydrogenated XDI), hydrogenated TDI, 2,5- or 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane (also referred to as norbornane diisocyan
  • the isocyanurate of hexamethylene diisocyanate is included in the aliphatic polyisocyanate compound.
  • the polyisocyanate compound may be used alone or in combination with two or more other polyisocyanate compounds.
  • an adduct or prepolymer obtained by reacting the above polyisocyanate compound with a polyhydric alcohol such as ethylene glycol, propylene glycol, trimethylolpropane, or hexanetriol at an NCO/OH ratio of 2 or more may also be used to prepare the blocked isocyanate curing agent (C).
  • blocking agents examples include monovalent alkyl (or aromatic) alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenol carbinol, and methylphenyl carbinol; cellosolves such as ethylene glycol monohexyl ether and ethylene glycol mono 2-ethylhexyl ether; polyether-type diols at both ends such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol phenol; polyester-type polyols at both ends obtained from diols such as ethylene glycol, propylene glycol, and 1,4-butanediol and dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, and sebacic acid; phenols such as para-t-butylphenol and cresol; oximes such as dimethyl ketoxime,
  • the blocked polyisocyanate curing agent (C) contains an oxime-blocked isocyanate curing agent which is a blocked reaction product between a blocking agent containing an oxime compound and a polyisocyanate, and the polyisocyanate in the blocking reaction contains one or more compounds selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound. Examples of the embodiment include the above-mentioned oximes. Blocking with oximes has the effect of lowering the curing temperature of the electrodeposition coating composition.
  • the curability of the electrodeposition coating film is specifically evaluated by baking at 135°C for 25 minutes.
  • high curability is obtained by curing at 135°C for 25 minutes, it can be judged that the low-temperature curability is high.
  • the blocked polyisocyanate curing agent (C) contains an oxime-blocked isocyanate curing agent which is a blocked reaction product between a blocking agent containing an oxime compound and a polyisocyanate, and the polyisocyanate in the blocking reaction contains an aliphatic polyisocyanate compound and/or an alicyclic polyisocyanate compound.
  • the embodiments include:
  • the blocked polyisocyanate curing agent (C) contains an oxime-blocked isocyanate curing agent which is a blocked reaction product between a blocking agent containing an oxime compound and a polyisocyanate, and the polyisocyanate in the blocking reaction contains at least an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound.
  • the embodiments include:
  • the blocked polyisocyanate curing agent is preferably a combination of an aliphatic polyisocyanate compound and an alicyclic polyisocyanate compound as the polyisocyanate curing agent before blocking, since this alleviates the internal stress in the curing agent.
  • the mass ratio of the aliphatic polyisocyanate compound/alicyclic polyisocyanate compound is 5/95 to 95/5, preferably 20/80 to 80/20, and more preferably 30/70 to 70/30.
  • the content of the blocked polyisocyanate curing agent (C) is set taking into consideration the structure of the curable resin (specifically, the combination of the aminated epoxy resin (A) and the aminated acrylic resin (B)). Specifically, a sufficient amount of curing agent is used to react with the active hydrogen-containing functional groups, such as primary amino groups, secondary amino groups, and hydroxyl groups, of the curable resin.
  • the curing agent is blended, for example, so that the solids mass ratio of the curable resin to the blocked polyisocyanate curing agent (C) (referred to as curable resin/curing agent) is 90/10 to 50/50, more preferably 80/20 to 65/35.
  • the fluidity and curing speed of the electrodeposition coating composition are controlled by the solids mass ratio of the curable resin to the curing agent.
  • the content of the curing agent (typically, curing agent (C)) is set taking into consideration the amount and structure of the film-forming resin (typically, aminated epoxy resin (A) and aminated acrylic resin (B)). Specifically, a sufficient amount of curing agent is used to react with the active hydrogen-containing functional groups, such as primary amino groups, secondary amino groups, and hydroxyl groups, of the film-forming resin.
  • the curing agent is blended, for example, so that the solids mass ratio of the film-forming resin to the curing agent (film-forming resin/curing agent) is 90/10 to 50/50, more preferably 80/20 to 65/35.
  • the fluidity and curing speed of the paint composition are controlled by the solids mass ratio of the film-forming resin to the curing agent.
  • the coating composition may contain a curing agent other than the blocked polyisocyanate curing agent (C) as necessary.
  • a curing agent other than the blocked polyisocyanate curing agent (C) examples include organic curing agents such as melamine resins or phenolic resins, silane coupling agents, and metal curing agents.
  • organic curing agents such as melamine resins or phenolic resins, silane coupling agents, and metal curing agents.
  • 80% by mass or more, even 90% by mass or more, and particularly 100% by mass may be the blocked polyisocyanate curing agent (C).
  • the pigment is a pigment that is generally used in coating compositions.
  • pigments include color pigments such as titanium white (titanium dioxide), carbon black, and red iron oxide; extender pigments such as kaolin, talc, aluminum silicate, calcium carbonate, mica, and clay; and rust-preventive pigments such as iron phosphate, aluminum phosphate, calcium phosphate, aluminum tripolyphosphate, aluminum phosphomolybdate, and aluminum zinc phosphomolybdate.
  • the coating composition may contain an extender pigment in that edge rust prevention can be further improved.
  • the extender pigment can moderately interact with the cyclic polyamidine compound.
  • the solid content of the paint composition refers to all components contained in the paint composition that remain in a solid form even after the solvent is removed. Specifically, the solid content of the paint composition refers to solid components contained in the paint composition, such as aminated epoxy resin (A), aminated acrylic resin (B), blocked polyisocyanate curing agent (C), pigment (D), and cyclic polyamidine compound or its hydrophobized modified form (E), as well as pigment dispersing resins that are included as necessary.
  • A aminated epoxy resin
  • B aminated acrylic resin
  • C blocked polyisocyanate curing agent
  • pigment D
  • E cyclic polyamidine compound or its hydrophobized modified form
  • Pigments are typically added to paint compositions as a pigment dispersion paste that contains a pigment dispersing resin and a pigment.
  • the pigment dispersion resin is a resin for dispersing a pigment.
  • the pigment dispersion resin include pigment dispersion resins having a cationic group, such as modified epoxy resins having at least one selected from a quaternary ammonium group, a tertiary sulfonium group, and a primary amino group.
  • Specific examples of the pigment dispersion resin include quaternary ammonium group-containing epoxy resins and tertiary sulfonium group-containing epoxy resins.
  • the aqueous solvent include ion-exchanged water and ion-exchanged water containing a small amount of alcohol.
  • the cyclic polyamidine compound or its hydrophobically modified derivative (E) is represented by the following general formula: (In the formula, R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X is an anion.) It has a structural unit represented by the following formula:
  • Polyamidine compounds with such a cyclic structure are prone to depositing on edges because they have an electric charge, and also increase the viscosity of the paint composition. This is thought to improve the rust prevention properties of the edges.
  • R 1 and R 2 may each independently be a hydrogen atom.
  • X represents an anion, for example, a halogen ion.
  • the halogen ion include F - , Cl - , Br - , and I - .
  • the halogen ion may be Cl - because it is easily available.
  • the cyclic polyamidine compound (E) can be synthesized, for example, by hydrolyzing a copolymer of N-vinylcarboxylic acid amide and an unsaturated nitrile in the presence of an acid. During hydrolysis in the presence of an acid, the amide group derived from the N-vinylcarboxylic acid amide is hydrolyzed and reacts with the cyano group of the unsaturated nitrile to form a cyclic amidine skeleton.
  • N-vinyl carboxylic acid amides examples include N-vinyl acetamide, N-vinyl-N-methyl acetamide, N-vinyl formamide, N-methyl-N-vinyl formamide, N-vinyl propionic acid amide, and N-vinyl butyric acid amide. These may be used alone or in combination of two or more.
  • the unsaturated nitrile may have, for example, 3 to 18 carbon atoms, or 3 to 9 carbon atoms.
  • Specific examples of unsaturated nitriles include acrylonitrile; ⁇ -alkyl acrylonitriles such as methacrylonitrile and ethacrylonitrile; fumaronitrile; and ⁇ -halogenoacrylonitriles such as ⁇ -chloroacrylonitrile and ⁇ -bromoacrylonitrile. These may be used alone or in combination of two or more.
  • the acid used for hydrolysis is, for example, a strong inorganic acid, specific examples of which include hydrochloric acid, nitric acid, and p-toluenesulfonic acid.
  • the cyclic polyamidine compound (E) may be a partial hydrolysis product of a copolymer of N-vinyl carboxylic acid amide and an unsaturated nitrile. It can be explained using the chemical formula as follows:
  • R 4 , R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
  • the copolymer of the general formula (II) represents a state in which each monomer is polymerized alternately, but in reality, it is composed of the following N-vinyl carboxylic acid amide constituent unit (III) and the unsaturated nitrile constituent unit (IV) bonded randomly: (In the above formulas (III) and (IV), R 4 to R 6 have the same meanings as defined above.)
  • the ratio of the number of structural units (I) to the total number of structural units (I) and structural units (II) in one molecule of the cyclic polyamidine compound (E): I/(I+II) may be 5% or more, 10% or more, or 20% or more.
  • the ratio: I/(I+II) may be 100%, 90% or less, or 80% or less.
  • hydrophobization has the advantage of improving the stability of the coating material when it is formed into a coating material (cationic electrodeposition coating composition). More specifically, hydrophobizing the polyamidine compound has the advantage of improving the storage stability when the polyamidine compound is mixed with a resin emulsion containing the aminated epoxy resin (A) and a curing agent.
  • the hydrophobization modification is mainly carried out by the following two methods. In the first method of hydrophobization modification, when the unsaturated nitrile structural units (IV) are arranged next to each other, a cyclization reaction between the nitrile groups occurs with an acid, producing a cyclized structural unit.
  • the formation of the nitrile cyclized structural unit can be expressed by the following chemical reaction formula:
  • two nitrile groups (CN) are cyclized to form the above-mentioned nitrogen atom-containing six-membered ring structure (aminopyridine structure or six-membered pyridine derivative-like structure), and this nitrile cyclized structural unit has higher hydrophobicity than other parts, so that it can be hydrophobized.
  • the first method of hydrophobic modification involves heating the reaction in the presence of an acid.
  • the acid is, for example, a weak acid such as acetic acid, formic acid, lactic acid, phosphoric acid, oxalic acid, or hydrogen sulfide, and the heating condition is preferably 70 to 98°C.
  • the amount of acid added is preferably 5 to 40 parts by mass, more preferably 8 to 25 parts by mass, per 100 parts by mass of the polyamidine compound.
  • the reaction time can be appropriately selected depending on the heating conditions and the amount of acid added, and can be selected, for example, in the range of 3 to 80 hours, more preferably 6 to 46 hours. In the above reaction, pressurized conditions may be added to accelerate the reaction.
  • the second method of hydrophobic modification is to further react the amidine ring represented by the above formula (I) with an alkyl halide compound to bond an alkyl group to the amidine ring and impart hydrophobicity.
  • This reaction is represented by the following reaction formula: (In the above reaction scheme, R 1 to R 3 and X are defined as above, and Hal represents a halogen atom.)
  • the second method of hydrophobic modification involves heating in the presence of an alkali to carry out the reaction.
  • Reaction conditions include, for example, pH 4.0 to 6.5 and the addition of an alkaline substance such as sodium hydroxide, potassium hydroxide, or aqueous ammonia. Heating conditions are preferably 80°C to 98°C.
  • the reaction time can be appropriately selected depending on the heating conditions, pH conditions, and the type of alkaline substance used, and can be selected, for example, within the range of 2 to 36 hours, and more preferably 10 to 24 hours. Pressurized conditions may be added to accelerate the reaction.
  • R 3 includes at least one of a substituted or unsubstituted linear or branched alkyl group having 3 to 12 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms.
  • R 3 includes an alkyl group (e.g., n-propyl group, sec-propyl group, n-butyl group, sec-butyl group, hexyl group, n-pentyl group, sec-pentyl group, neopentyl group, heptyl group, pentyl group, octyl group, etc.); or an aromatic group (e.g., benzyl group, naphthalene group, etc.).
  • any substituent that does not affect the hydrophobic modification can be used without any particular limitation.
  • an alkenyl group having 3 to 6 carbon atoms for example, an alkenyl group having 3 to 6 carbon atoms, an alkyl ether group having 3 to 6 carbon atoms, etc. are included.
  • the above alkyl group and aromatic group preferably have no substituent.
  • the halogen atom in the alkyl halide include a chlorine atom, a bromine atom, and a fluorine atom.
  • the alkyl halide (R 3 -Hal) is chlorohexane, bromohexane, chloropentane, bromopentane, iodohexane, iodopentane, chloroheptane, bromoheptane, iodoheptane, chlorooctane, bromooctane, iodooctane, and the like.
  • the weight average molecular weight of the cyclic polyamidine compound or its hydrophobically modified product (E) is, for example, 50,000 or more. This allows the effect of improving edge rust prevention to be obtained with a small amount.
  • the weight average molecular weight of the cyclic polyamidine compound or its hydrophobically modified product (E) may be 80,000 or more, 100,000 or more, or 300,000 or more.
  • the weight average molecular weight of the cyclic polyamidine compound or its hydrophobically modified product (E) may be 4 million or less, 3.5 million or less, 3.2 million or less, or 3 million or less. In one embodiment, the weight average molecular weight of the cyclic polyamidine compound or its hydrophobically modified product (E) may be 50,000 or more and 4 million or less, or 80,000 or more and 3.2 million or less.
  • the weight average molecular weight of the cyclic polyamidine compound or its hydrophobically modified derivative (E) in this disclosure is measured using a molecular weight measuring device (such as DLS-7000 manufactured by Otsuka Electronics) using the static light scattering method.
  • a molecular weight measuring device such as DLS-7000 manufactured by Otsuka Electronics
  • the solid content mass of the cyclic polyamidine compound or its hydrophobized modified product (E) may be 0.2 ppm or more of the solid content mass of the cationic electrodeposition coating composition.
  • the solid content mass of the cyclic polyamidine compound or its hydrophobized modified product (E) may be 1,200 ppm or less. Even if the amount of the cyclic polyamidine compound or its hydrophobized modified product (E) added is so small, the effect of improving edge rust prevention can be obtained.
  • the solid content mass of the cyclic polyamidine compound or its hydrophobized modified product (E) may be 1 ppm or more, 2 ppm or more, or 50 ppm or more.
  • the solid content mass of the cyclic polyamidine compound or its hydrophobized modified product (E) may be 1,000 ppm or less, 700 ppm or less, or 200 ppm or less. In one embodiment, the solid content mass of the cyclic polyamidine compound or its hydrophobized modified product (E) is 20 ppm or more and 1,200 ppm or less, may be 25 ppm or more and 1,000 ppm or less, may be 25 ppm or more and 700 ppm or less, or may be 50 ppm or more and 200 ppm or less.
  • the coating composition may contain a curing catalyst.
  • the curing catalyst is not particularly limited, and any known catalyst in the coating field can be used.
  • the curing catalyst include organic tin compounds and bismuth compounds.
  • the organic tin compounds include dibutyltin oxide, dioctyltin oxide, dioctyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dibenzoate, and dioctyltin dibenzoate.
  • bismuth compounds examples include bismuth oxide, bismuth hydroxide, bismuth subsalicylate, and bismuth subnitrate.
  • a curing catalyst containing a bismuth compound can be used.
  • the content of the curing catalyst may be 0.5 mass % or less of the solid content of the coating composition, and may be 0.25 mass % or less.
  • the coating composition may further include a metal nitrite.
  • the metal nitrite can further improve edge rust prevention.
  • an alkali metal nitrite or an alkaline earth metal nitrite is preferable, and an alkaline earth metal nitrite is more preferable.
  • the metal nitrite for example, calcium nitrite, sodium nitrite, potassium nitrite, magnesium nitrite, strontium nitrite, barium nitrite, and zinc nitrite can be mentioned.
  • the content of metal nitrite is, for example, 0.001% by mass or more and 0.2% by mass or less, calculated as the metal element of the metal component, relative to the total mass of the coating-forming resin and the hardener.
  • the coating composition may contain additives commonly used in the coating field, such as organic solvents, surfactants such as drying inhibitors and defoamers, viscosity modifiers such as acrylic resin particles, anti-repellent agents, and inorganic rust inhibitors, as necessary.
  • organic solvents include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and propylene glycol monophenyl ether.
  • examples of inorganic rust inhibitors include vanadium salts, copper salts, iron salts, manganese salts, magnesium salts, and calcium salts.
  • auxiliary complexing agents buffering agents, smoothing agents, stress relief agents, gloss agents, semi-gloss agents, antioxidants, and ultraviolet absorbing agents may also be included depending on the purpose.
  • the coating composition is prepared by mixing a resin emulsion containing a film-forming resin (typically, an aminated epoxy resin (A) and an aminated acrylic resin (B)) and a curing agent (typically, a blocked polyisocyanate curing agent (C)), a pigment dispersion paste containing a pigment (D), and a cyclic polyamidine compound or a hydrophobically modified product thereof (E: hereinafter, when simply referred to as a "cyclic polyamidine compound (E)", this may also represent "a cyclic polyamidine or a hydrophobically modified product thereof (E)") by a commonly used method.
  • a resin emulsion containing a film-forming resin typically, an aminated epoxy resin (A) and an aminated acrylic resin (B)
  • a curing agent typically, a blocked polyisocyanate curing agent (C)
  • E cyclic polyamidine compound or
  • the cyclic polyamidine compound or its hydrophobically modified form (E), other components and additives may be added to the resin emulsion, or to the pigment dispersion paste, or may be added during or after mixing of the resin emulsion and the pigment dispersion paste.
  • the cyclic polyamidine compound or its hydrophobically modified form (E), etc. are added to these, for example, in the form of an aqueous solution.
  • the aminated epoxy resin (A), the aminated acrylic resin (B), and optionally other film-forming resins, as well as the blocked polyisocyanate curing agent (C) and other curing agents are each dissolved in an organic solvent to prepare a solution, and these solutions are mixed and then neutralized with a neutralizing acid, thereby enabling the preparation of the resin emulsion.
  • each of the aminated epoxy resin (A) and the aminated acrylic resin (B) can be prepared as a resin emulsion.
  • the aminated epoxy resin (A), other film-forming resins as required, the blocked polyisocyanate curing agent (C) and other curing agents are dissolved in an organic solvent to prepare a solution, and these solutions are mixed and neutralized with a neutralizing acid to prepare the epoxy resin emulsion.
  • the aminated acrylic resin (B), other film-forming resins as required, the blocked polyisocyanate curing agent (C) and other curing agents are dissolved in an organic solvent to prepare a solution, and these solutions are mixed and neutralized with a neutralizing acid to prepare the acrylic resin emulsion.
  • Examples of the neutralizing acid include organic acids such as methanesulfonic acid, sulfamic acid, lactic acid, dimethylolpropionic acid, formic acid, and acetic acid.
  • the neutralizing acid may be one or more selected from the group consisting of formic acid, acetic acid, and lactic acid.
  • the solid content of the resin emulsion may be, for example, 25% by mass or more and 50% by mass or less, and 35% by mass or more and 45% by mass or less, based on the total amount of the resin emulsion.
  • the solid content of the resin emulsion refers to all components contained in the resin emulsion that remain in a solid form even after the solvent is removed.
  • the solid content of the resin emulsion refers to the aminated epoxy resin (A), aminated acrylic resin (B), blocked polyisocyanate curing agent (C), and other solid components added as necessary that are contained in the resin emulsion.
  • the amount of neutralizing acid used may be 10% or more and 100% or less, or 20% or more and 70% or less, in terms of the equivalent ratio of the neutralizing acid to the equivalent of the amino group in the aminated epoxy resin.
  • the equivalent ratio of the neutralizing acid to the equivalent of the amino group in the aminated epoxy resin is referred to as the neutralization rate.
  • a neutralization rate of 10% or more ensures affinity to water and provides good water dispersibility.
  • the pigment dispersion paste is prepared by mixing a pigment dispersion resin and a pigment.
  • the solid content of the pigment dispersion resin in the pigment dispersion paste is not particularly limited, and may be, for example, 20 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the pigment.
  • the solids content of the pigment dispersion paste may be, for example, 40% by mass or more and 70% by mass or less, and may be 50% by mass or more and 60% by mass or less.
  • the solid content of the pigment dispersion paste refers to all components contained in the pigment dispersion paste that remain in a solid form even after the solvent is removed. Specifically, the solid content of the pigment dispersion paste refers to the pigment dispersion resin, pigment, and other solid components that are added as necessary that are contained in the pigment dispersion paste.
  • An electrodeposition coating film is formed by electrocoating a substrate with the coating composition.
  • An electrodeposition-coated article having an electrodeposition coating film is produced by a method (production method 1) comprising the steps of immersing an article to be coated in the cationic electrodeposition coating composition according to this embodiment, applying a voltage between the article to be coated and a counter electrode to form an uncured electrodeposition coating film on the article to be coated, and heating the coating film at a temperature of 75°C or higher and 200°C or lower to obtain a cured electrodeposition coating film.
  • the cationic electrodeposition coating composition contains an aminated epoxy resin (A), an aminated acrylic resin (B), a blocked polyisocyanate curing agent (C), a pigment (D), and a cyclic polyamidine compound or a hydrophobized modified product thereof (E).
  • the voltage is, for example, 50 V or more and 450 V or less.
  • the bath liquid temperature is, for example, 10° C. or more and 45° C. or less.
  • the time for which the voltage is applied is not particularly limited, and is, for example, 2 minutes or more and 5 minutes or less.
  • the material of the substrate is not particularly limited as long as it is capable of conducting electricity.
  • the shape of the substrate is not particularly limited either, and may be flat or may be a complex three-dimensional shape.
  • Examples of substrates include cold-rolled steel sheets, hot-rolled steel sheets, stainless steel, electrogalvanized steel sheets, hot-dip galvanized steel sheets, zinc-aluminum alloy-based plated steel sheets, zinc-iron alloy-based plated steel sheets, zinc-magnesium alloy-based plated steel sheets, zinc-aluminum-magnesium alloy-based plated steel sheets, aluminum-based plated steel sheets, aluminum-silicon alloy-based plated steel sheets, tin-based plated steel sheets, and those that have been subjected to chemical conversion treatment (for example, surface treatment using phosphates, zirconium salts, etc.).
  • the substrate may be surface-conditioned with a zinc-based, titanium-based, or manganese-based surface conditioner prior to chemical conversion treatment. This makes the crystal
  • the curing temperature may be 100° C. or higher, or may be 110° C. or higher.
  • the curing temperature may be, for example, 180° C. or lower, or may be 150° C. or lower.
  • the heating time is not particularly limited, and is, for example, 10 to 30 minutes.
  • the electrodeposition-coated product has a substrate and an electrodeposition coating film formed on the substrate by the cationic electrodeposition coating composition.
  • the electrodeposition coating film is cured.
  • the electrodeposition-coated product is produced, for example, by the method described above.
  • the electrodeposition-coated product has excellent rust prevention properties, particularly edge rust prevention properties.
  • the electrodeposition-coated product further has a good appearance.
  • the thickness of the electrocoating film after curing may be 5 ⁇ m or more and 60 ⁇ m or less.
  • the thickness of the electrocoating film after curing may be 10 ⁇ m or more.
  • the thickness of the electrocoating film after curing may be 25 ⁇ m or less.
  • Edge rust prevention is evaluated, for example, by a salt spray test (35°C x 72 hours) in accordance with JIS Z 2371 (2000) performed on a cured electrocoating film with a thickness of 25 to 50 ⁇ m. If the number of rust particles on the edge of the coated object is less than 5 particles/cm2 after the salt spray test, the edge rust prevention can be evaluated as excellent.
  • the cyclic polyamidine compound may be used as a pretreatment agent for electrodeposition coating (electrodeposition pretreatment agent).
  • the electrodeposition pretreatment layer containing the cyclic polyamidine compound is also deposited on the edge portion, so that a coating film having excellent edge rust prevention properties can be obtained.
  • an electrodeposition-coated article having an electrodeposition coating film can also be produced by a method comprising the steps of applying an electrodeposition pretreatment agent containing a cyclic polyamidine compound or a hydrophobically modified form (E) to an object to be coated, immersing the object to which the electrodeposition pretreatment agent has been applied in a cationic electrodeposition paint composition, and then applying a voltage between the object to be coated and a counter electrode to form an uncured electrodeposition coating film on the object to be coated, and heating the uncured electrodeposition coating film at a temperature of 75°C or higher and 200°C or lower to obtain a cured electrodeposition coating film.
  • an electrodeposition pretreatment agent containing a cyclic polyamidine compound or a hydrophobically modified form (E) immersing the object to which the electrodeposition pretreatment agent has been applied in a cationic electrodeposition paint composition, and then applying a voltage between the object to be coated and a counter electrode to form an uncured electrodeposition coating film on the object to be coated, and heating the un
  • the cationic electrodeposition coating composition used in manufacturing method 2 contains aminated epoxy resin (A), aminated acrylic resin (B), blocked polyisocyanate curing agent (C), and pigment (D).
  • the cyclic polyamidine compound or its hydrophobically modified form (E) is contained in the electrodeposition pretreatment agent, which is applied to the substrate prior to the application of the cationic electrodeposition coating composition.
  • the cationic electrodeposition coating composition containing aminated epoxy resin (A), aminated acrylic resin (B), blocked polyisocyanate curing agent (C), and pigment (D) and the electrodeposition pretreatment agent containing the cyclic polyamidine compound or its hydrophobically modified form (E) are used in combination as a coating set.
  • Electroposition pretreatment agent containing a cyclic polyamidine compound or a hydrophobically modified form (E) thereof is applied to the substrate.
  • the electrodeposition pretreatment agent is, for example, an aqueous solution of the cyclic polyamidine compound or a hydrophobically modified form (E) thereof.
  • the concentration of the cyclic polyamidine compound is, for example, 10% by mass.
  • the method of application is not particularly limited, and the substrate may be immersed in the electrodeposition pretreatment agent, or the electrodeposition pretreatment agent may be applied to the substrate.
  • Application methods include coating and spraying. After the electrodeposition pretreatment agent has been applied, a voltage may be applied to the substrate. The voltage is, for example, 50 V or more and 450 V or less. The bath liquid temperature is, for example, 10°C or more and 45°C or less. The time for which the voltage is applied is not particularly limited, and is, for example, 2 minutes or more and 5 minutes or less. After the electrodeposition pretreatment agent has been applied, the substrate may be subjected to the next process without applying a voltage.
  • the substrate may be the same as that in manufacturing method 1.
  • the application of the electrodeposition pretreatment agent is carried out after the above-mentioned surface conditioning treatment and chemical conversion treatment, and before electrodeposition coating.
  • the thickness of the electrocoating film after curing may be 5 ⁇ m or more and 60 ⁇ m or less.
  • the thickness of the electrocoating film after curing may be 10 ⁇ m or more.
  • the thickness of the electrocoating film after curing may be 25 ⁇ m or less.
  • Electrodeposition coating 2 According to the production method 2, there can be obtained an electrodeposition coated article comprising a substrate, an electrodeposition pretreatment layer formed on the substrate and containing a cyclic polyamidine compound or a hydrophobically modified product thereof (E), and an electrodeposition coating film formed from a cationic electrodeposition coating composition containing an aminated epoxy resin (A), a blocked polyisocyanate curing agent (C) and a pigment (D).
  • a cationic electrodeposition coating composition containing an aminated epoxy resin (A), a blocked polyisocyanate curing agent (C) and a pigment (D).
  • an electrodeposition coating can be obtained that includes a substrate and an electrodeposition coating film formed on the substrate.
  • the electrodeposition coating film is formed from a cationic electrodeposition coating composition that includes an aminated epoxy resin (A), an aminated acrylic resin (B), a blocked polyisocyanate curing agent (C) and a pigment (D), and further includes at least a portion of the cyclic polyamidine compound or its hydrophobized modified form (E) contained in the electrodeposition pretreatment agent.
  • the cationic electrodeposition coating composition according to this embodiment has the advantage of providing good weather resistance by containing aminated epoxy resin (A) and aminated acrylic resin (B) as coating film-forming resins that react with a curing agent. Therefore, the cationic electrodeposition coating composition according to this embodiment has the advantage that it can be suitably used in coating aspects in which the formation of an undercoat coating film and/or a topcoat coating film that are generally formed on an electrodeposition coating film is omitted, such as the coating of specific parts or components of an automobile body.
  • Production Example 1-1 Production of aminated epoxy resin (A1) 26 parts of butyl cellosolve, 940 parts of bisphenol A type epoxy resin (trade name DER-331J, manufactured by Dow Chemical Company), 380 parts of bisphenol A, 58 parts of phenol, and 2 parts of dimethylbenzylamine were added to a reaction vessel, and the internal temperature was maintained at 120°C. The reaction was continued until the epoxy equivalent reached 1100 g/eq, and then the reaction vessel was cooled until the temperature inside the reaction vessel reached 110°C.
  • A1 aminated epoxy resin
  • Production Example 1-2 Production of aminated epoxy resin (A2) 12 parts of butyl cellosolve, 940 parts of bisphenol A type epoxy resin (trade name DER-331J, manufactured by Dow Chemical Company), 325 parts of bisphenol A, 4.2 parts of phenol, and 2 parts of dimethylbenzylamine were added, and the temperature inside the reaction vessel was kept at 120° C. and reacted until the epoxy equivalent reached 620 g/eq, and then cooled until the temperature inside the reaction vessel reached 110° C. Then, a mixture of 110 parts of diethanolamine (DETA) and 70 parts of diethylaminopropanediamine (DEAPA) was added, and the mixture was reacted at 140° C. for 1 hour to obtain aminated epoxy resin (A2).
  • DETA diethanolamine
  • DEAPA diethylaminopropanediamine
  • Production Example 2-1 Production of blocked polyisocyanate curing agent (C1) 222 parts of isophorone diisocyanate was placed in a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a thermometer, and diluted with 56 parts of methyl isobutyl ketone (MIBK), after which 0.2 parts of butyltin laurate was added and the temperature was raised to 50° C., after which 17 parts of methyl ethyl ketoxime was added so that the temperature of the contents did not exceed 70° C. The mixture was then kept at 70° C.
  • MIBK methyl isobutyl ketone
  • Production Example 2-2 Production of blocked polyisocyanate curing agent (curing agent C2) 165 parts of isocyanurate of hexamethylene diisocyanate (trade name Sumidur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) and 24 parts of MIBK were charged into a reaction vessel and heated to 60°C. 75 parts of methyl ethyl ketoxime (MEK oxime) were added dropwise over 2 hours. After further heating at 70°C for 2 hours, it was confirmed that the absorption based on the isocyanate group disappeared in the measurement of the IR spectrum. Then, 36 parts of butyl cellosolve was added to obtain a blocked polyisocyanate curing agent (C2).
  • curing agent C2 165 parts of isocyanurate of hexamethylene diisocyanate (trade name Sumidur N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) and 24 parts of MIBK were charged into a reaction vessel and heated to
  • Production Example 2-3 Production of blocked polyisocyanate curing agent (C3) 1,400 parts of polymeric MDI (MDI: diphenylmethane diisocyanate) was charged into a reaction vessel and heated to 60°C. A mixture of 330 parts of butyl diglycol ether (BDG) and 950 parts of butyl cellosolve (BC) was added dropwise to the reaction vessel over 2 hours at 60°C. After further heating at 75°C for 4 hours, it was confirmed that the absorption due to the isocyanate group disappeared in the measurement of the IR spectrum, and after cooling, 27 parts of methyl isobutyl ketone (MIBK) was added to obtain a blocked polyisocyanate curing agent (C3).
  • MDI diphenylmethane diisocyanate
  • Production Example 3 Production of aminated acrylic resin (B1) 82 parts of MIBK was charged into a five-neck flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a nitrogen inlet tube, and heated and maintained at 115°C under a nitrogen atmosphere. A mixture of 24 parts of glycidyl methacrylate, 25 parts of hydroxyethyl methacrylate, 40 parts of methyl methacrylate, 25 parts of styrene, 35 parts of n-butyl acrylate, and 8 parts of t-butylperoxy 2-ethylhexanoic acid was added dropwise from the dropping funnel over a period of 3 hours.
  • the temperature was maintained at 115°C for about 1 hour, and then 3 parts of t-butylperoxy 2-ethylhexanoic acid was added dropwise, and the mixture was maintained at 115°C for about 30 minutes to obtain an acrylic resin solution with a solid content of 64%. Thereafter, the mixture was concentrated under reduced pressure to a nonvolatile content of 73%, and after cooling, 3 parts of N-methylethanolamine and 10 parts of 2-ethylaminoethanol were added thereto, and the mixture was reacted at 120° C. for 2 hours in a nitrogen atmosphere to obtain a solution of aminated acrylic resin (B1) with a solid content of approximately 76%.
  • the obtained aminated acrylic resin (B1) had a number average molecular weight (Mn) of 7,000 and a glass transition temperature (Tg) of 30°C.
  • Production Example 3-1 Production of aminated acrylic resin emulsion (Em-1) 240 parts of the aminated acrylic resin (B) solution obtained in Production Example 3 and 85 parts of the blocked isocyanate curing agent (C2) obtained in Production Example 2-2 were added and stirred for 30 minutes. Thereafter, 4.5 parts of acetic acid was added, and the mixture was diluted with ion-exchanged water to a nonvolatile content of 24%, and then concentrated under reduced pressure to a nonvolatile content of 30% to obtain aminated acrylic resin emulsion (Em-1).
  • Em-1 Production of aminated acrylic resin emulsion (Em-1) 240 parts of the aminated acrylic resin (B) solution obtained in Production Example 3 and 85 parts of the blocked isocyanate curing agent (C2) obtained in Production Example 2-2 were added and stirred for 30 minutes. Thereafter, 4.5 parts of acetic acid was added, and the mixture was diluted with ion-exchanged water to a nonvolatile content of 24%
  • Preparation Example 4 Preparation of pigment dispersion resin 2220 parts of isophorone diisocyanate and 342.1 parts of methyl isobutyl ketone were charged into a reaction vessel equipped with a stirring device, a cooling tube, a nitrogen introduction tube and a thermometer. The temperature was raised to 50°C, and 2.2 parts of dibutyltin laurate were further charged, and the temperature was raised to 60°C, and 878.7 parts of methyl ethyl ketone oxime were further charged. After that, the mixture was kept at 60°C for 1 hour, and it was confirmed that the NCO equivalent was 348, and 890 parts of dimethylethanolamine were further charged.
  • the mixture was further kept at 60°C for 1 hour, and it was confirmed by IR that the NCO peak had disappeared.
  • a reaction vessel equipped with a stirrer, cooling tube, nitrogen inlet tube, and thermometer was charged with 940.0 parts of bisphenol A epoxy resin (DER-331J, Dow Chemical Company) and 38.5 parts of methanol, and then 0.1 parts of dibutyltin dilaurate was added. After heating this to 50°C, 87.1 parts of tolylene diisocyanate were added. The temperature was further raised to 100°C and 1.4 parts of N,N-dimethylbenzylamine were added, and then the mixture was kept at 130°C for 2 hours. At this time, methanol was fractionated using a fractionating tube. This was cooled to 115°C, and methyl isobutyl ketone was added until the solids concentration reached 90%.
  • Example 1 Preparation of cationic electrodeposition coating composition (preparation of epoxy resin emulsion) 400 g (solid content) of aminated epoxy resin (A1) obtained in Production Example 1-1, 80 g (solid content) of blocked polyisocyanate curing agent (C1) obtained in Production Example 2-1, and 80 g (solid content) of blocked polyisocyanate curing agent (C2) obtained in Production Example 2-2 were mixed, and ethylene glycol mono-2-ethylhexyl ether was added so that the amount was 3% (15 g) based on the solid content. Next, formic acid was added to neutralize the mixture to a neutralization rate of 40%, and ion-exchanged water was added to slowly dilute the mixture to obtain an epoxy resin emulsion.
  • the cyclic polyamidine compound (E1) has a structural unit of the following formula:
  • a cold-rolled steel sheet (JIS G3141, SPCC-SD) was prepared as a coating substrate. This steel sheet was degreased by immersing it in Surf Cleaner EC90 (manufactured by Nippon Paint Surf Chemicals) at 50°C for 2 minutes. It was then immersed in Surfdyne EC3200 (manufactured by Nippon Paint Surf Chemicals, zirconium conversion treatment agent) at 35°C for 90 seconds. It was then rinsed with deionized water.
  • Surf Cleaner EC90 manufactured by Nippon Paint Surf Chemicals
  • Surfdyne EC3200 manufactured by Nippon Paint Surf Chemicals, zirconium conversion treatment agent
  • the viscosity was adjusted by adding a required amount of 2-ethylhexyl glycol to the cationic electrodeposition coating composition obtained above so that the thickness of the electrodeposition coating film after curing would be 20 ⁇ m.
  • voltage application was immediately started. The voltage was increased for 30 seconds, and after reaching 180 V, it was maintained for 150 seconds. This caused an uncured electrodeposition coating film to be deposited on the substrate.
  • the obtained uncured electrodeposition coating film was heated and cured at 135°C for 25 minutes to obtain an electrodeposition coated object (single coating film) with a cured electrodeposition coating film thickness of 20 ⁇ m.
  • Example 2 A cationic electrodeposition coating composition was produced in the same manner as in Example 1, except that the aminated epoxy resin (A2) obtained in Production Example 1-2 was used instead of the aminated epoxy resin (A1) obtained in Production Example 1-1. Using the resulting cationic electrodeposition coating composition, an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 1.
  • polyamidine compound E2 hydrophobic modified polyamidine compound having an unsaturated nitrile cyclization segment (two nitrile groups (CN) are cyclized) unit.
  • a cationic electrodeposition coating composition was obtained by the same procedure as in Example 1, except that the hydrophobized modified product (E2) of the polyamidine compound obtained above was added in place of the polyamidine compound (E1) so that the solid content was 100 ppm of the solid content mass of the cationic electrodeposition coating composition.
  • an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 1.
  • Example 1 A cationic electrodeposition coating composition was produced in the same manner as in Example 1, except that the aminated acrylic resin (B1) and the polyamidine compound (E1) were not used. Using the resulting cationic electrodeposition coating composition, an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 1.
  • Example 2 A cationic electrodeposition coating composition was produced in the same manner as in Example 2, except that the aminated acrylic resin (B1) and the polyamidine compound (D1) were not used. Using the resulting cationic electrodeposition coating composition, an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 2.
  • Example 3 A cationic electrodeposition coating composition was produced in the same manner as in Example 1, except that the aminated acrylic resin (B1) and the polyamidine compound (D1) were not used, and the polyisocyanate curing agent (C3) was used instead of the polyisocyanate curing agent (C1+C2). Using the resulting cationic electrodeposition coating composition, an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 1.
  • Example 4 A cationic electrodeposition coating composition was produced in the same manner as in Example 1, except that no polyamidine compound (D1) was used. Using the resulting cationic electrodeposition coating composition, an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 1.
  • Example 5 A cationic electrodeposition coating composition was produced in the same manner as in Example 1, except that the aminated acrylic resin (B1) was not used. Using the resulting cationic electrodeposition coating composition, an electrodeposition coated product (single layer coating film) was prepared in the same manner as in Example 1.
  • Example 6 A cationic electrodeposition coating composition was obtained in the same manner as in Example 1, except that a commercially available viscosity modifier, poly-N-vinylacetamide (weight average molecular weight 50,000: product name GE191-107, manufactured by Showa Denko K.K.), was added instead of the polyamidine compound (D1), and an electrodeposition coated article (single-layer coating film) was produced.
  • a commercially available viscosity modifier poly-N-vinylacetamide (weight average molecular weight 50,000: product name GE191-107, manufactured by Showa Denko K.K.)
  • D1 polyamidine compound
  • the edge of the coated article is the region extending from the apex of the blade toward the blade body by 5 mm, and exists on both the front and back surfaces of the blade.
  • the total area of the edge is 10 cm2 , which is the blade length (100 mm) x the width of the region (5 mm x 2). If there are less than 50 rust particles on the edge (10 cm2 ), the edge rust prevention can be evaluated as good.
  • the paint was diluted with a No. 4 Ford cup for 30 seconds at 20°C and then air sprayed to a dry film thickness of 40 ⁇ m to form an uncured clear coating film. After setting for 7 minutes, the coating was baked at 140°C for 25 minutes for curing to form a multi-layer coating film.
  • the test piece having the multi-layer coating film prepared above was attached to a Spark Xenon Weather Meter SX2-75 (manufactured by Suga Test Instruments Co., Ltd.), and accelerated exposure was performed for 1000 hours under conditions of simulated sunlight with an illuminance of 180 W/ m2 according to the xenon lamp method of JIS K5600-7-7.
  • the test piece was then immersed in 40°C warm water for 24 hours, dried at room temperature for 1 hour, and then a tape peeling test was performed to visually confirm the presence or absence of peeling of the intermediate coating film, and judged as ⁇ (no peeling) or ⁇ (peel-off was confirmed).
  • the tape peeling test was performed according to JIS K5600.
  • test piece was immersed in pure water and kept at 40°C for 24 hours, and then adhesive cellophane tape (registered trademark) was attached to the test piece, and the tape was rapidly peeled off at 20°C, and the presence or absence of peeling of the intermediate and topcoat coating film was visually confirmed.
  • adhesive cellophane tape registered trademark
  • Example 3 is an example using a cationic electrocoating coating composition using a polyamidine compound hydrophobized by the general formula (X), and has the advantage of good long-term storage stability of the resin emulsion.
  • Comparative Examples 1 to 3 are examples in which the aminated acrylic resin (B) and the polyamidine compound (D) are not used, with Comparative Example 1 being a comparative example for Example 1, Comparative Example 2 being a comparative example for Example 2, and Comparative Example 3 being an example in which the polyisocyanate curing agent in Example 1 is changed to blocked polymeric MDI and the aminated acrylic resin (B) and the polyamidine compound (D) are not used, and all of these have poor edge rust prevention and weather resistance (single layer coating).
  • the evaluation of the gel fraction is B, and it can be seen that the curing property is poor. In the example of Comparative Example 3, this is believed to be because the curing temperature is high when using blocked polymeric MDI.
  • Comparative Example 4 is an example in which the polyamidine compound (E) is not used in Example 1, and it is clear that the edge rust prevention is poor.
  • Comparative Example 5 is an example in which the aminated acrylic resin (B) is not used in Example 1, and the weather resistance is poor in a single layer coating film consisting of only a cationic electrodeposition coating film.
  • Comparative Example 6 is an example in which a commercially available thickener (poly N-vinylacetamide) is used in place of the polyamidine compound (E), and the coating appearance (surface roughness Ra of the single layer coating film) tends to deteriorate.
  • the cationic electrocoating paint composition of the present invention provides a coating film that is excellent in curability, rust prevention, especially edge rust prevention, as well as coating appearance and weather resistance. Therefore, the cationic electrocoating paint composition of the present invention is suitable for coating substrates that have edges.
  • an aminated epoxy resin A
  • an aminated acrylic resin B
  • a blocked polyisocyanate curing agent C
  • a pigment D
  • E a polyamidine compound or a hydrophobically modified product thereof
  • the polyamidine compound or its hydrophobically modified derivative (E) is represented by the following general formula (I):
  • R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and X is an anion.
  • a cationic electrodeposition coating composition having a structural unit represented by the formula:
  • the hydrophobized modified product of the polyamidine compound contains, in addition to the structural unit (I), a cyclized structural unit derived from an unsaturated nitrile or a structural unit represented by the following general formula (X): (In the formula, R 1 and R 2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and R 3 is
  • the aminated epoxy resin (A) is obtained by reacting an amine compound with an epoxy resin, the amine compound is a combination of two types of amines, a primary amine and a secondary amine,
  • the primary amine has the formula: NH 2 -(CH 2 )n-NR 11 R 12 (In the formula, R 11 and R 12 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms which may have a hydroxyl group at its terminal, and n represents an integer of 2 to 4.) having
  • the secondary amine has the formula: R13 R14 NH (In the formula, R 13 and R 14 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms and a hydroxyl group at its terminal.) or the amine compound comprises one or more compounds selected from the group consisting of ketimine compounds and diketimine compounds;
  • the cationic electrodeposition coating composition according to any one of [1] to [6].
  • the blocked polyisocyanate curing agent (C) contains an oxime-blocked isocyanate curing agent which is a blocked reaction product between a blocking agent containing an oxime compound and a polyisocyanate, and the polyisocyanate in the blocking reaction contains one or more compounds selected from the group consisting of an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound.
  • the cationic electrodeposition coating composition according to any one of [1] to [7].

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Abstract

L'invention concerne une composition de revêtement par électrodéposition cationique permettant de former un film de revêtement présentant d'excellentes propriétés de prévention de rouille et d'aspect de film de revêtement.　Cette composition de revêtement par électrodéposition cationique comprend (A) une résine époxydique aminée, (B) une résine acrylique aminée, (C) un agent de durcissement polyisocyanate bloqué, (D) un pigment, et (E) un composé polyamidine ou un corps modifié hydrophobisé associé, le composé polyamidine ou le corps modifié hydrophobisé associé (E) ayant un motif structural représenté par la formule générale (I) (dans la formule, R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe hydrocarboné ayant de 1 à 3 atomes de carbone, et X représente un anion).
PCT/JP2024/013701 2023-06-14 2024-04-03 Composition de revêtement par électrodéposition cationique, produit revêtu par électrodéposition et procédé de production de produit revêtu par électrodéposition Ceased WO2024257445A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000026790A (ja) * 1998-07-09 2000-01-25 Mitsubishi Chemicals Corp コーティング用重合体組成物及びその製造法
JP2009183889A (ja) * 2008-02-07 2009-08-20 Daiyanitorikkusu Kk 汚泥の脱水処理方法
JP2011524934A (ja) * 2008-06-19 2011-09-08 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 電着組成物および方法
WO2020262549A1 (fr) * 2019-06-28 2020-12-30 関西ペイント株式会社 Composition de peinture par électrodéposition cationique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000026790A (ja) * 1998-07-09 2000-01-25 Mitsubishi Chemicals Corp コーティング用重合体組成物及びその製造法
JP2009183889A (ja) * 2008-02-07 2009-08-20 Daiyanitorikkusu Kk 汚泥の脱水処理方法
JP2011524934A (ja) * 2008-06-19 2011-09-08 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング 電着組成物および方法
WO2020262549A1 (fr) * 2019-06-28 2020-12-30 関西ペイント株式会社 Composition de peinture par électrodéposition cationique

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