WO2015147079A1 - Composition de revêtement formé par dépôt électrolytique - Google Patents

Composition de revêtement formé par dépôt électrolytique Download PDF

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WO2015147079A1
WO2015147079A1 PCT/JP2015/059194 JP2015059194W WO2015147079A1 WO 2015147079 A1 WO2015147079 A1 WO 2015147079A1 JP 2015059194 W JP2015059194 W JP 2015059194W WO 2015147079 A1 WO2015147079 A1 WO 2015147079A1
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Prior art keywords
electrodeposition coating
pigment dispersion
acid
coating composition
resin
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PCT/JP2015/059194
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English (en)
Japanese (ja)
Inventor
誠之 小谷
俊雄 印部
治広 宮前
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日本ペイント・オートモーティブコーティングス株式会社
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Publication of WO2015147079A1 publication Critical patent/WO2015147079A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8074—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • 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
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
    • C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4453—Polyepoxides characterised by the nature of the curing agent
    • 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
    • C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
    • C09D5/443—Polyepoxides
    • C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
    • 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
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/04—Electrophoretic coating characterised by the process with organic material
    • C25D13/06—Electrophoretic coating characterised by the process with organic material with polymers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/10—Electrophoretic coating characterised by the process characterised by the additives used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

  • the present invention relates to an electrodeposition coating composition, particularly a cationic electrodeposition coating composition.
  • the cationic electrodeposition coating composition generally contains a resin emulsion, and may further contain a pigment dispersion paste if desired.
  • organotin compounds have been widely used as curing catalysts.
  • the use of organotin compounds is likely to be limited in the future due to recent trends in environmental regulations.
  • alternative catalysts have been developed for some time.
  • bismuth compounds are used as curing catalysts for cationic electrodeposition coating compositions.
  • a method is disclosed in which a bismuth compound such as bismuth oxide or bismuth hydroxide is simply dispersed in a pigment dispersion paste.
  • the catalytic activity of the bismuth compound is low, the coating film cannot be sufficiently cured.
  • the storage stability of the paint and the pigment dispersion paste decreased, aggregation occurred during storage.
  • a method in which a bismuth compound is mixed and dissolved in advance with an amine-containing carboxylic acid such as an amino acid, and the resulting mixture is used for preparing a pigment dispersion paste (Patent Document 1). Also disclosed is a method in which a bismuth compound is mixed and dissolved in advance with lactic acid, and then the resulting mixture is added to a paint (Patent Document 2).
  • the catalytic activity is somewhat increased by the dissolution of the bismuth compound.
  • sufficient curing of the coating film could not be achieved.
  • the present invention solves the above-mentioned conventional problems, and the object is to form a coating film with sufficiently improved solubility of the bismuth compound and excellent curability, film thickness uniformity and corrosion resistance. It is an object of the present invention to provide an electrodeposition coating composition capable of producing
  • the present invention also provides an electrodeposition coating composition having a sufficiently improved solubility of the bismuth compound and capable of forming a coating film excellent in curability, film thickness uniformity and corrosion resistance, and having improved storage stability.
  • the purpose is to provide.
  • an object of this invention is to provide the electrodeposition coating material composition excellent in the storage stability of the pigment dispersion paste which comprises the said electrodeposition coating material composition.
  • the present invention is an electrodeposition coating composition
  • a resin emulsion (1) contains an aminated resin (A) and a blocked isocyanate curing agent (B)
  • the pigment dispersion paste (2) is prepared by mixing a mixture obtained by previously mixing a bismuth compound (C) and an organic acid (D), a pigment dispersion resin (E), and a pigment (F).
  • An electrodeposition coating composition in which the pigment dispersion paste (2) satisfies the following conditions is provided: (I) the molar ratio of the bismuth metal to the organic acid (D) content in the bismuth compound (C) is 1: 0.5 to 1: 4 in Bi: (D); and (ii) the bismuth compound ( The mass ratio of the content of C), pigment dispersion resin (E) and pigment (F) is 1: 0.2 to 1: 0.5 in (C) + (F) :( E).
  • the electrodeposition coating composition of the present invention comprises: The pigment dispersion paste (2) further comprises an amino acid (G),
  • the pigment dispersion paste (2) includes a mixture obtained by previously mixing a bismuth compound (C), an organic acid (D) and an amino acid (G), a pigment dispersion resin (E), and a pigment (F). It is preferable to prepare by mixing.
  • the solubility of the bismuth compound is sufficiently improved, so that a coating film excellent in curability, film thickness uniformity and corrosion resistance can be formed. Furthermore, the electrodeposition coating composition of the present invention and the pigment dispersion paste constituting the electrodeposition coating composition are sufficiently excellent in storage stability.
  • the electrodeposition coating composition of the present invention comprises a resin emulsion (1) and a pigment dispersion paste (2).
  • the resin emulsion (1) contains an aminated resin (A) and a blocked isocyanate curing agent (B), and may further contain other components as desired.
  • the aminated resin (A) is a coating film forming resin constituting the electrodeposition coating film.
  • a cation-modified epoxy resin obtained by modifying an oxirane ring in the resin skeleton with an organic amine compound is preferable.
  • a cation-modified epoxy resin is prepared by a ring-opening reaction by reacting an oxirane ring in a starting material resin molecule with an amine such as a primary amine, a secondary amine or a tertiary amine and / or its acid salt.
  • a typical example of the starting material resin is a polyphenol polyglycidyl ether type epoxy resin which is a reaction product of a polycyclic phenol compound such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolak, and epichlorohydrin.
  • examples of other starting material resins include oxazolidone ring-containing epoxy resins described in JP-A-5-306327. These epoxy resins can be prepared by reacting a diisocyanate compound or a bisurethane compound obtained by blocking an isocyanate group of a diisocyanate compound with a lower alcohol such as methanol or ethanol, and epichlorohydrin.
  • the above starting material resin can be used by extending the chain with a bifunctional polyester polyol, polyether polyol, bisphenol, dibasic carboxylic acid or the like before the oxirane ring-opening reaction with amines.
  • bisphenols may be used for chain extension by using an oxirane ring-opening reaction with amines.
  • ethylene glycol may be added to some oxirane rings for the purpose of adjusting molecular weight or amine equivalent and improving heat flow.
  • Monohydroxy compounds such as mono-2-ethylhexyl ether, ethylene glycol mono n-butyl ether, propylene glycol mono-2-ethylhexyl ether, and / or monocarboxylic acid compounds such as octylic acid can be added and used.
  • Examples of amines that can be used for opening an oxirane ring and introducing an amino group include butylamine, octylamine, diethylamine, dibutylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine , N, N-dimethylbenzylamine, primary amines such as N, N-dimethylethanolamine, secondary amines or tertiary amines and / or their acid salts.
  • ketimine block primary amino group-containing secondary amine such as aminoethylethanolamine methyl isobutyl ketimine, diethylenetriamine diketimine can also be used. These amines must be reacted with at least an equivalent amount relative to the oxirane ring in order to open all the oxirane rings.
  • the number average molecular weight of the aminated resin (A) is preferably 1,000 to 5,000.
  • the number average molecular weight is 1,000 or more, physical properties such as solvent resistance and corrosion resistance of the obtained cured electrodeposition coating film are improved.
  • the number average molecular weight is 5,000 or less, the viscosity of the aminated resin can be easily adjusted to enable smooth synthesis, and handling of emulsified dispersion of the obtained aminated resin (A) is possible. Becomes easier.
  • the number average molecular weight of the aminated resin (A) is more preferably in the range of 1,600 to 3,200.
  • the number average molecular weight is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • cured electrodeposition coating film is sometimes simply referred to as “electrodeposition coating film”.
  • electrodeposited film and “resin film” mean an uncured film mainly composed of a resin, which is deposited on an object to be coated by application of a voltage.
  • the amine value of the aminated resin (A) is preferably in the range of 20 to 100 mgKOH / g.
  • the amine value of the aminated resin (A) is 20 mgKOH / g or more, the emulsion dispersion stability of the aminated resin (A) in the electrodeposition coating composition is improved.
  • the amine value is 100 mgKOH / g or less, the amount of amino groups in the cured electrodeposition coating film becomes appropriate, and there is no possibility of reducing the water resistance of the coating film.
  • the amine value of the aminated resin (A) is more preferably in the range of 20 to 80 mgKOH / g.
  • the hydroxyl value of the aminated resin (A) is preferably in the range of 50 to 400 mgKOH / g.
  • the hydroxyl value is 50 mgKOH / g or more, the cured electrodeposition coating film is cured well.
  • the hydroxyl value is 400 mgKOH / g or less, the amount of the hydroxyl group remaining in the cured electrodeposition coating film becomes appropriate, and there is no possibility of reducing the water resistance of the coating film.
  • the hydroxyl value of the aminated resin (A) is more preferably in the range of 100 to 300 mgKOH / g.
  • an aminated resin having a number average molecular weight of 1,000 to 5,000, an amine value of 20 to 100 mgKOH / g, and a hydroxyl value of 50 to 400 mgKOH / g
  • (A) an aminated resin having a number average molecular weight of 1,000 to 5,000, an amine value of 20 to 100 mgKOH / g, and a hydroxyl value of 50 to 400 mgKOH / g
  • aminated resin (A) if necessary, aminated resins having different amine values and / or hydroxyl values may be used in combination. When two or more kinds of amine resins having different amine values and hydroxyl values are used in combination, the average amine value and the average hydroxyl value calculated based on the mass ratio of the aminated resin used are within the above numerical range. preferable.
  • the aminated resin (A) used in combination is an aminated resin having an amine value of 20 to 50 mgKOH / g and a hydroxyl value of 50 to 300 mgKOH / g, and an amine value of 50 to 200 mgKOH / g.
  • the aminated resin (A) may contain an amino group-containing acrylic resin, an amino group-containing polyester resin, or the like, if necessary.
  • the blocked isocyanate curing agent (B) (hereinafter sometimes simply referred to as “curing agent (B)”) is also a coating film forming resin constituting the electrodeposition coating film.
  • the blocked isocyanate curing agent (B) can be prepared by blocking polyisocyanate with a sealing agent.
  • polyisocyanates examples include aliphatic diisocyanates such as hexamethylene diisocyanate (including trimer), tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, and fats such as 4,4′-methylenebis (cyclohexyl isocyanate).
  • Aromatic diisocyanates such as cyclic polyisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate and the like can be mentioned.
  • sealants include monovalent alkyl (or aromatic) alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenol carbinol, methylphenyl carbinol; ethylene glycol mono Cellosolves such as hexyl ether and ethylene glycol mono 2-ethylhexyl ether; Polyether type terminal diols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol phenol; ethylene glycol, propylene glycol, 1,4-butanediol, etc.
  • monovalent alkyl (or aromatic) alcohols such as n-butanol, n-hexyl alcohol, 2-ethylhexanol, lauryl alcohol, phenol carbinol, methylphenyl carbinol
  • ethylene glycol mono Cellosolves such as hexyl ether and ethylene glycol mono 2-
  • Polyester type terminal polyols obtained from the following diols and dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid; para-t-butyl Phenols such as phenol and cresol; oximes such as dimethyl ketoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, methyl amyl ketoxime, and cyclohexanone oxime; and lactams represented by ⁇ -caprolactam and ⁇ -butyrolactam are preferably used. .
  • dioxalic acid succinic acid, adipic acid, suberic acid, sebacic acid
  • para-t-butyl Phenols such as phenol and cresol
  • oximes such as dimethyl ketoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, methyl amyl ketoxime, and cyclohe
  • the blocking ratio of the blocked isocyanate curing agent (B) is preferably 100%. Thereby, there exists an advantage that the storage stability of an electrodeposition coating composition becomes favorable.
  • the blocked isocyanate curing agent (B) is a combination of a curing agent prepared by blocking an aliphatic diisocyanate with a sealing agent and a curing agent prepared by blocking an aromatic diisocyanate with a sealing agent. It is preferable to do.
  • the blocked isocyanate curing agent (B) preferentially reacts with the primary amine of the aminated resin (A), and further reacts with a hydroxyl group to be cured.
  • the curing agent at least one curing agent selected from the group consisting of an organic curing agent such as a melamine resin or a phenol resin, a silane coupling agent, and a metal curing agent may be used in combination with the blocked isocyanate curing agent (B). .
  • the resin emulsion can be formed by mixing an organic solvent solution of the aminated resin (A) and an organic solvent solution of the blocked isocyanate curing agent (B) and then neutralizing it with a neutralizing acid.
  • the neutralizing acid include organic acids such as methanesulfonic acid, sulfamic acid, lactic acid, dimethylolpropionic acid, formic acid, and acetic acid.
  • the content of the curing agent (B) is sufficient to react with active hydrogen-containing functional groups such as primary, secondary amino groups and hydroxyl groups in the aminated resin (A) during curing to give a good cured coating film. Amount is needed.
  • the preferable content of the curing agent (B) is 90/10 to 90% expressed by the solid content mass ratio of the aminated resin (A) and the curing agent (B) (aminated resin (A) / curing agent (B)). 50/50, more preferably in the range of 80/20 to 65/35.
  • the solid content of the resin emulsion is usually 25 to 50% by mass, particularly 35 to 45% by mass, based on the total amount of the resin emulsion.
  • the “solid content of the resin emulsion” means the mass of all components that are contained in the resin emulsion and remain solid even after removal of the solvent. Specifically, it means the total amount of the mass of the aminated resin (A), the curing agent (B) and other solid components added as necessary, contained in the resin emulsion.
  • the neutralizing acid is preferably used in an amount of 10 to 100%, more preferably 20 to 70%, as the equivalent ratio of the neutralizing acid to the equivalent of the amino group of the aminated resin (A). Is more preferable.
  • the equivalent ratio of the neutralized acid to the equivalent of the amino group of the aminated resin (A) is defined as the neutralization rate. When the neutralization rate is 10% or more, affinity for water is ensured and water dispersibility is improved.
  • the pigment dispersion paste (2) contains a bismuth compound (C), an organic acid (D), a pigment dispersion resin (E) and a pigment (F), and preferably further contains an amino acid (G).
  • the bismuth compound (C) is a compound containing a bismuth metal, and examples thereof include bismuth oxide, bismuth hydroxide, bismuth nitrate, and mixtures thereof.
  • Preferred bismuth compounds (C) are bismuth oxide and bismuth hydroxide.
  • the bismuth compound (C) is used in a powder form, and the average particle size is usually 0.5 to 20 ⁇ m, preferably 1 to 3 ⁇ m.
  • the average particle diameter is a volume average particle diameter D50, and a value measured by a method described later is used.
  • Organic acid (D) is an organic acid having no amino group, and is, for example, one or more compounds selected from the group consisting of hydroxycarboxylic acids and sulfonic acids.
  • hydroxycarboxylic acid examples include the following compounds: (D1) Monohydroxy monocarboxylic acids having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, particularly aliphatic monohydroxy monocarboxylic acids, such as lactic acid and glycolic acid; (D2) Monohydroxy dicarboxylic acids having 2 to 5 carbon atoms, preferably 2 to 4 carbon atoms, particularly aliphatic monohydroxy dicarboxylic acids, such as hydroxymalonic acid and malic acid; (D3) Dihydroxy monocarboxylic acids having 3 to 7 carbon atoms, preferably 3 to 6 carbon atoms, particularly aliphatic dihydroxy monocarboxylic acids, such as dimethylolpropionic acid (DMPA) and glyceric acid; (D4) Dihydroxy dicarboxylic acids having 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms, particularly aliphatic dihydroxy dicarboxylic acids, such as tartaric acid and glucose.
  • D1 Monohydroxy monocarboxylic acids
  • the sulfonic acid is an organic sulfonic acid, and examples thereof include alkanesulfonic acids having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms such as methanesulfonic acid and ethanesulfonic acid.
  • Preferred organic acid (D) is one or more compounds selected from the group consisting of monohydroxymonocarboxylic acid, dihydroxymonocarboxylic acid, and alkanesulfonic acid.
  • the molecular weight of the organic acid (D) is not particularly limited, and is usually 60 to 200, preferably 70 to 150.
  • the molecular weight of the organic acid is a value calculated from the molecular formula.
  • the usage form of the organic acid (D) is not particularly limited, and examples thereof include a solid form, a liquid form, a solution form dissolved in a solvent, and particularly an aqueous solution form.
  • the pigment dispersion resin (E) is a resin for dispersing the pigment (F), and is used by being dispersed in an aqueous medium.
  • a pigment dispersion resin having a cationic group such as a modified epoxy resin having at least one selected from a quaternary ammonium group, a tertiary sulfonium group, and a primary amine group can be used.
  • aqueous solvent ion-exchanged water or water containing a small amount of alcohols can be used.
  • the pigment (F) is a pigment usually used in an electrodeposition coating composition.
  • pigments for example, commonly used inorganic and organic pigments, eg colored pigments such as titanium white (titanium dioxide), carbon black and bengara; like kaolin, talc, aluminum silicate, calcium carbonate, mica and clay
  • extender pigments such as iron phosphate, aluminum phosphate, calcium phosphate, aluminum tripolyphosphate, and rust preventive pigments such as aluminum phosphomolybdate and zinc aluminum phosphomolybdate.
  • the amino acid (G) is an organic compound having one or more amino groups and one or more carboxyl groups in one molecule.
  • Preferred amino acids (G) are organic compounds having 1 to 3, in particular 1 amino group and 1 to 3, in particular 1 to 2, carboxyl group in one molecule.
  • the amino acid (G) is preferably an amino acid having 2 to 6 carbon atoms, particularly 2 to 4 carbon atoms, particularly an aliphatic amino acid.
  • the molecular weight of the amino acid (G) is not particularly limited, and is usually 60 to 200, preferably 70 to 150.
  • the molecular weight of the amino acid is a value calculated from the molecular formula.
  • amino acid (G) for example, glycine, aspartic acid or a mixture thereof can be used.
  • the usage form of the amino acid (G) is not particularly limited, and examples thereof include a solid form, a liquid form, and a solution form formed by dissolving in a solvent.
  • the pigment dispersion paste (2) is prepared by further mixing the mixture obtained by previously mixing the bismuth compound (C) and the organic acid (D), the pigment dispersion resin (E), and the pigment (F). Is done.
  • the electrodeposition coating composition of this invention can form the coating film which the solubility of the bismuth compound fully improved and was excellent in sclerosis
  • the storage stability is sufficiently improved in the electrodeposition coating composition and the pigment dispersion paste of the present invention.
  • Bismuth compound solubility, coating film curability, film thickness uniformity and corrosion resistance, and storage stability provided by premixing bismuth compound (C) and organic acid (D) prior to other components
  • C bismuth compound
  • D organic acid
  • the bismuth compound (C) and the organic acid (D) are mixed together with other components without premixing, the bismuth compound (C) is not sufficiently dissolved, so the curability and film thickness uniformity of the resulting coating film And the corrosion resistance can be reduced. Furthermore, the storage stability of the electrodeposition coating composition and the pigment dispersion paste of the present invention can be lowered.
  • the premixing of the bismuth compound (C) and the organic acid (D) (hereinafter sometimes simply referred to as “first mixing”) is performed by stirring the bismuth compound (C) particles in the organic acid (D) aqueous solution, This is achieved by dispersing.
  • the mixing ratio of the bismuth compound (C) and the organic acid (D) during the first mixing is such that the resulting pigment dispersion paste satisfies the following condition (i).
  • the molar ratio of the bismuth metal to the content of the organic acid (D) in the bismuth compound (C) is Bi: (D) 1: 0.5 to 1: 4, preferably 1: 1 to 1: 2. It is.
  • content of the bismuth metal in a bismuth compound (C) is the quantity (mole number) of the bismuth metal in the bismuth compound (C) mixed in 1st mixing.
  • the content of the organic acid (D) is the amount (number of moles) of the organic acid mixed in the first mixing.
  • the organic acid (D) is used in the form of a solution, the amount of the organic acid alone in the solution (Number of moles).
  • the content ratio of the organic acid (D) in the mixture obtained by the first mixing is usually 1 to 20 mass in terms of the ratio of the organic acid (D) alone contained in the aqueous organic acid (D) solution based on the total amount of the mixture. %, Preferably 3 to 15% by mass.
  • the content ratio of the organic acid (D) alone is adjusted by the amount of ion exchange water used. Is done. If the content ratio of the organic acid (D) alone is too small, the bismuth compound (C) cannot be sufficiently dissolved, so that the curability of the resulting coating film can be lowered. On the other hand, even if the content ratio of the organic acid (D) alone is too large, the bismuth compound (C) cannot be sufficiently dissolved, so that the curability of the coating film can be lowered.
  • the temperature of the mixture during the first mixing does not affect the solubility of the bismuth compound (C), and is usually 10 to 30 ° C., preferably room temperature.
  • the stirring speed at the time of the first mixing is not particularly limited as long as stirring sufficient to generate a stirring flow is achieved.
  • the first mixing is preferably performed until the volume average particle diameter D50 of the bismuth compound (C) is 100 nm or less, preferably 50 nm or less, more preferably 20 nm or less.
  • the solubility of the bismuth compound (C) is sufficiently improved, so that the dissolution rate is sufficiently high.
  • the first mixing time for achieving the above average particle diameter is within about 1.5 hours, preferably 0.5 to 1.2 hours.
  • the obtained mixture, the pigment dispersion resin (E) and the pigment (F) are further mixed to prepare a pigment dispersion paste.
  • Mixing of the mixture obtained by the first mixing, the pigment dispersion resin (E) and the pigment (F) (hereinafter sometimes simply referred to as “second mixing”) is achieved by stirring these mixtures.
  • the mixing amount of the pigment dispersion resin (E) and the pigment (F) at the time of the second mixing is such an amount that the obtained pigment dispersion paste satisfies the following condition (ii).
  • the mass ratio of the contents of the bismuth compound (C), the pigment dispersion resin (E) and the pigment (F) is 1: 0.2 to 1: 0.5 when (C) + (F) :( E). Preferably, it is 1: 0.25 to 1: 0.4.
  • content of a bismuth compound (C) is the quantity (mass) of the bismuth compound (C) mixed by 1st mixing.
  • the content of the pigment dispersion resin (E) is the amount (mass) of the pigment dispersion resin mixed in the second mixing.
  • the amount (mass) of the solid content in the solution It is.
  • the content of the pigment (F) is the mass of the pigment mixed in the second mixing.
  • the content of the pigment-dispersed resin (E) in the pigment-dispersed paste is usually 20 to 40 parts by mass in terms of resin solid content with respect to 100 parts by mass of the pigment (F).
  • the temperature of the mixture during the second mixing is not particularly limited, but is preferably 20 to 50 ° C., particularly 30 to 40 ° C. from the viewpoint of pigment dispersion paste stability.
  • the second mixing is usually performed until the dispersed particle size of the pigment is 10 ⁇ m or less.
  • the mixture immediately before the second mixing that is, the mixture immediately before mixing the pigment dispersion resin (E) and the pigment (F) has a bismuth compound dissolution residue amount of 5% or less, particularly 1.5% by mass or less. It is preferable to show.
  • the amount of the bismuth compound dissolution residue is shown as a ratio with respect to the content (charge amount) of the bismuth compound (C) in the mixture, and a value measured by the method described later is used.
  • the content of the bismuth compound (C) contained in the pigment dispersion paste is 0. 0 in terms of metal elements with respect to the solid content of the pigment dispersion paste. It is preferably 5 to 5% by mass, preferably 1 to 3% by mass, more preferably 1 to 2% by mass.
  • the content of the bismuth compound (C) is the amount (mass) of the bismuth compound (C) mixed in the first mixing.
  • the “solid content of the pigment dispersion paste” means the mass of all the components that are contained in the pigment dispersion paste and remain solid even after removal of the solvent. Specifically, it means the total mass of the bismuth compound (C), the pigment dispersion resin (E) and the pigment (F) and other solid components added as necessary, contained in the pigment dispersion paste.
  • Metal element conversion is a metal element conversion coefficient (a coefficient for converting a metal compound amount into a metal element amount to the content of the metal compound.
  • the atomic weight of the metal element in the metal compound is It means a value obtained by dividing the molecular weight of the metal compound.)
  • the target metal element amount For example, when the bismuth compound (C) is bismuth oxide (Bi 2 O 3 , molecular weight 466), the metal element equivalent content of bismuth in the electrodeposition coating composition containing 0.1% by mass of bismuth oxide is 0.8. It is calculated as 0.0897% by mass by the calculation of 1% by mass ⁇ (418 ⁇ 466).
  • the solid content of the pigment dispersion paste is usually 40 to 70% by mass, particularly 50 to 60% by mass, based on the total amount of the pigment dispersion paste.
  • the amino acid (G) is further mixed at the same time when the bismuth compound (C) and the organic acid (D) are premixed (first mixing). That is, it is preferable to mix the amino acid (G) in advance together with the bismuth compound (C) and the organic acid (D). This is because the solubility of the bismuth compound is further improved. This is considered to be because the amino acid (G) having a strong chelating property is coordinated to Bi, thereby improving the dissolution stability of Bi.
  • the mixing ratio of the amino acid (G) during the first mixing is such that the pigment dispersion paste satisfies the following condition (iii).
  • the molar ratio of the content of bismuth metal and amino acid (G) in the bismuth compound (C) is Bi: (G) 1: 0.5 to 1: 4.0, preferably 1: 1 to 1: 2. It is.
  • the bismuth metal content in the bismuth compound (C) is the same as in the condition (i).
  • the content of amino acid (G) is the amount (number of moles) of amino acid mixed in the first mixture.
  • amino acid (G) is used in the form of a solution, the amount of amino acid alone in the solution (number of moles) It is.
  • the content ratio of the amino acid (G) in the mixture obtained by the first mixing is usually 1 to 16 masses as the ratio of the amino acid (G) alone to the total amount of the mixture. %, Preferably 1.5 to 8% by mass. Even if the content ratio of the amino acid (G) alone is too small or too large, there is a possibility that a further improvement effect on the solubility of the bismuth compound (C) cannot be obtained.
  • the electrodeposition coating composition of the present invention can be prepared by mixing the resin emulsion (1) and the pigment dispersion paste (2).
  • the mixing ratio of the resin emulsion (1) and the pigment dispersion paste (2) is such that the content of the bismuth compound (C) contained in the electrodeposition coating composition is a metal element conversion with respect to the solid content of the electrodeposition coating composition.
  • the ratio is preferably 0.05 to 2.00% by mass, preferably 0.10 to 1.50% by mass, more preferably 0.1 to 1.0% by mass.
  • the content of the bismuth compound (C) is the amount (mass) of the bismuth compound (C) mixed in the first mixing.
  • the “solid content of the electrodeposition coating composition” means the mass of all components that are contained in the electrodeposition coating composition and remain solid even after removal of the solvent. .
  • the mixing ratio of the resin emulsion (1) and the pigment dispersion paste (2) is usually from 1: 0.1 to 1: 0.4 in terms of the solid content mass ratio of (1) :( 2), preferably 1: 0.15 to 1: 0.3.
  • the solid content of the electrodeposition coating composition of the present invention is preferably 1 to 30% by mass with respect to the total amount of the electrodeposition coating composition.
  • the amount of the solid content of the electrodeposition coating composition is less than 1% by mass, the amount of electrodeposition coating deposited decreases, and it may be difficult to ensure sufficient corrosion resistance.
  • the resin solid content of an electrodeposition coating composition exceeds 30 mass%, there exists a possibility that throwing power or a coating external appearance may worsen.
  • the pH of the electrodeposition coating composition of the present invention is preferably 4.5-7.
  • the pH of the electrodeposition coating composition can be set in the above range by adjusting the amount of neutralizing acid used, the amount of free acid added, and the like.
  • the pH of the electrodeposition coating composition can be measured using a commercially available pH meter having a temperature compensation function.
  • the milligram equivalent (MEQ (A)) of the acid with respect to 100 g of the solid content of the electrodeposition coating composition is preferably 40 to 120.
  • the milligram equivalent (MEQ (A)) of the acid with respect to 100 g of the resin solid content of the electrodeposition coating composition can be adjusted by the amount of neutralized acid and the amount of free acid.
  • MEQ (A) is an abbreviation for mg equivalent (acid), and is the sum of mg equivalents of all acids per 100 g of solid content of the paint.
  • This MEQ (A) is obtained by accurately weighing about 10 g of the solid content of the electrodeposition coating composition and dissolving it in about 50 ml of a solvent (THF: tetrahydrofuran), followed by potentiometric titration using a 1/10 N NaOH solution. The amount of acid contained in the electrodeposition coating composition can be quantified and measured.
  • THF tetrahydrofuran
  • the electrodeposition coating composition contains substantially neither a tin compound nor a lead compound.
  • “the electrodeposition coating composition is substantially free of both a tin compound and a lead compound” means that the concentration of the lead compound contained in the electrodeposition coating composition does not exceed 50 ppm as a lead metal element, And it means that the concentration of the organic tin compound does not exceed 50 ppm as a tin metal element.
  • the electrodeposition coating composition of the present invention contains a bismuth compound (C). Therefore, it is not necessary to use a lead compound or an organic tin compound as a curing catalyst. Thereby, the electrodeposition coating composition which does not contain any of a tin compound and a lead compound can be prepared.
  • the electrodeposition coating composition of the present invention comprises additives generally used in the coating field, such as ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoethyl hexyl ether, propylene glycol monobutyl ether, dipropylene glycol.
  • Organic solvents such as monobutyl ether and propylene glycol monophenyl ether, surfactants such as anti-drying agents and antifoaming agents, viscosity modifiers such as acrylic resin fine particles, anti-fogging agents, vanadium salts, copper, iron, manganese, magnesium,
  • An inorganic rust preventive agent such as a calcium salt may be included as necessary.
  • auxiliary complexing agents may be mixed depending on the purpose.
  • These additives may be added during the production of the resin emulsion, may be added during the second mixing during the production of the pigment dispersion paste, or during or after the mixing of the resin emulsion and the pigment dispersion paste. It may be added.
  • the electrodeposition coating composition of the present invention may contain other film forming resin components in addition to the aminated resin (A).
  • film forming resin components include acrylic resin, polyester resin, urethane resin, butadiene resin, phenol resin, xylene resin, and the like.
  • the aminated resin which does not correspond to the aminated resin (A) as described above may be used.
  • Phenol resins and xylene resins are preferred as other film-forming resin components that can be included in the electrodeposition coating composition.
  • the phenol resin and xylene resin include xylene resins having 2 or more and 10 or less aromatic rings.
  • the electrodeposition coating composition of the present invention can be used for electrodeposition coating and electrodeposition coating film formation on an object to be coated.
  • a voltage is applied between an object to be coated and a cathode. Thereby, an electrodeposition film deposits on a to-be-coated article.
  • electrodeposition coating is performed by applying a voltage of 50 to 450 V after the object to be coated is immersed in the electrodeposition coating composition. If the applied voltage is less than 50V, electrodeposition may be insufficient, and if it exceeds 450V, the coating film may be destroyed and an abnormal appearance may be obtained.
  • the bath temperature of the coating composition is usually adjusted to 10 to 45 ° C.
  • the voltage application time varies depending on the electrodeposition conditions, but can generally be 2 to 5 minutes.
  • the film thickness of the electrodeposition film is the film thickness of the electrodeposition film finally obtained by heat curing.
  • the film thickness is preferably 5 to 40 ⁇ m, more preferably 10 to 25 ⁇ m. If the film thickness of the electrodeposition coating film is less than 5 ⁇ m, the corrosion resistance may be insufficient. On the other hand, if it exceeds 40 ⁇ m, it leads to waste of paint.
  • the electrodeposition film obtained as described above is heat-cured by heating at 120 to 260 ° C., preferably 140 to 220 ° C. for 10 to 30 minutes after completion of the electrodeposition process, or after washing with water. An electrodeposition coating film is formed.
  • various objects that can be energized can be used.
  • coatings that can be used include cold-rolled steel sheets, hot-rolled steel sheets, stainless steel, electrogalvanized steel sheets, hot-dip galvanized steel sheets, zinc-aluminum alloy-plated steel sheets, zinc-iron alloy-plated steel sheets, zinc-magnesium alloy-based plating Examples include steel plates, zinc-aluminum-magnesium alloy-based plated steel plates, aluminum-based plated steel plates, aluminum-silicon alloy-based plated steel plates, and tin-based plated steel plates.
  • Production Example 1 Production of pigment dispersion resin 385 parts of bisphenol A type epoxy resin (trade name DER-331J, manufactured by Dow Chemical Company), 120 parts of bisphenol A in a reaction vessel equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer. Charge 95 parts octyl acid and 1 part 2-ethyl-4-methylimidazole 1% solution, react at 160-170 ° C. for 1 hour in a nitrogen atmosphere, then cool to 120 ° C., then 2-ethylhexanolated half-blocked 198 parts of a methyl isobutyl ketone solution of tolylene diisocyanate (solid content 95%) was added. After the reaction mixture was kept at 120-130 ° C.
  • aminated resin (cation-modified epoxy resin).
  • the number average molecular weight of this resin was 2,560, the amine value was 50 mgKOH / g (of which the amine value derived from the primary amine was 14 mgKOH / g), and the hydroxyl value was 240 mgKOH / g.
  • Production Example 3-2 Production of Blocked Isocyanate Curing Agent (2) 1,340 parts of 4,4′-diphenylmethane diisocyanate and 277 parts of MIBK were charged into a reaction vessel, which was heated to 80 ° C., and then 226 parts of ⁇ -caprolactam was added to butyl cellosolve. What was dissolved in 944 parts was dripped at 80 degreeC over 2 hours. Furthermore, after heating at 100 degreeC for 4 hours, in the measurement of IR spectrum, it confirmed that the absorption based on an isocyanate group disappeared, and after standing to cool, MIBK349 parts were added and block isocyanate hardening
  • Production Example 4 Production of Resin Emulsion 350 g (solid content) of the aminated resin obtained in Production Example 2, 75 g (solid content) of the blocked isocyanate curing agent (1) obtained in Production Example 3-1, and Production Example 3-2
  • the obtained blocked isocyanate curing agent (2) (75 g, solid content) was mixed, and ethylene glycol mono-2-ethylhexyl ether was added to 3% (15 g) based on the solid content.
  • formic acid and acetic acid are equimolarly added so that the total addition amount thereof is equivalent to a resin neutralization rate of 40%, neutralized, and slowly diluted with ion-exchanged water.
  • Methyl isobutyl ketone was removed under reduced pressure to obtain a resin emulsion.
  • Example 1 Manufacture of pigment dispersion paste Based on the composition shown in Table 1, bismuth oxide was added thereto while mixing and stirring ion exchange water and 50% aqueous lactic acid solution, and stirred at 1000 rpm for 1 hour at room temperature (first mixing) ). Thereafter, the mixture was filtered with 508 mesh to remove the dissolution residue, thereby obtaining a uniform mixture. Based on the composition shown in Table 1, the pigment dispersion resin and the pigment obtained in Production Example 1 were further mixed with the obtained mixture using a sand mill and stirred at 2000 rpm for 1 hour at 40 ° C. (Second mixture). Under the present circumstances, the average particle diameter of the bismuth compound in the mixture just before mixing a pigment dispersion resin and a pigment was measured.
  • the average particle size is a volume average particle size D50, and ion exchange is performed using a laser Doppler particle size analyzer (manufactured by Nikkiso Co., Ltd., “Microtrac UPA150”) so that the signal level is appropriate. Diluted with water and measured.
  • Examples 2 to 7 and Comparative Examples 1 to 8 In the production of the pigment dispersion paste, the types and addition amounts of the bismuth compound and the organic acid, the ion exchange water, the pigment dispersion resin solution, and the addition amounts of the pigment were changed as shown in Table 1. Furthermore, in the production of the electrodeposition coating composition, the mixing ratio of the resin emulsion and the pigment dispersion paste was changed to a ratio that achieves the “bismuth compound content in the electrodeposition coating composition” shown in Table 1. . Except for these changes, an electrodeposition coating composition was obtained in the same manner as in Example 1. In addition, when using an amino acid, the amino acid was mixed simultaneously with the organic acid.
  • the content ratio of the organic acid (D) at the time of the first mixing is a ratio of the organic acid (D) alone in the aqueous solution of the organic acid (D) to the total amount of the mixture at the time of the first mixing.
  • the content ratio of the amino acid (G) at the time of the first mixing is a ratio of the amino acid (G) alone in the amino acid (G) aqueous solution to the total amount of the mixture at the time of the first mixing.
  • the content of the bismuth compound (C) is a ratio with respect to the solid content of the pigment dispersion paste (2) and is a value in terms of a metal element.
  • the content of the bismuth compound (C) is a ratio to the solid content of the electrodeposition coating composition, and is a value in terms of a metal element.
  • the particle diameter of the bismuth compound is the average particle diameter of the bismuth compound (C) immediately before the first mixing.
  • the particle diameter of the bismuth compound is the average particle diameter of the bismuth compound (C) in the mixture immediately before removal of the dissolved residue.
  • a cold rolled steel sheet (JIS G3141, SPCC-SD) was degreased by being immersed in Surf Cleaner EC90 (manufactured by Nippon Paint Co., Ltd.) at 50 ° C. for 2 minutes. Next, it was immersed in Surffine GL1 (manufactured by Nippon Paint Co., Ltd.) at room temperature for 30 seconds and immersed in Surfdyne 6350 (manufactured by Nippon Paint Co., Ltd.) at 35 ° C. for 2 minutes. Washed with deionized water.
  • the average particle size of the bismuth compound in the mixture immediately before mixing the pigment dispersion resin and the pigment was measured.
  • the average particle diameter is a volume average particle diameter D50
  • the dispersion is diluted with ion-exchanged water so that the signal level is appropriate using a laser Doppler particle size analyzer (manufactured by Nikkiso Co., Ltd., “Microtrac UPA150”).
  • the solubility of the bismuth compound was evaluated according to the following criteria. Evaluation criteria A: D50 10 nm or less.
  • ⁇ D50 more than 10 nm and 20 nm or less; ⁇ ⁇ ; D50 more than 20 nm and less than 50 nm; ⁇ : D50 more than 50 nm and less than 100 nm (no problem in practical use); X: D50 more than 100 nm and 500 nm or less (practical problem); XX; D50 More than 500 nm.
  • Evaluation criteria pass easily through 508 mesh (manufactured by NBC Meshtec); ⁇ : Difficult to pass through 508 mesh (no problem in practical use); X: Cannot pass 508 mesh (practical problem).
  • the electrodeposition coating film coated in accordance with the above evaluation method was immersed in acetone and heated to reflux at 56 ° C. for 4 hours. After the reflux, the electrodeposition coating film was dried, and the coating film residual rate was determined from the following formula from the coating film mass before and after immersion in acetone, and the curability was evaluated.
  • the electrodeposition coating composition of the present invention is useful, for example, as an undercoating paint for automobiles.

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Abstract

L'invention se rapporte à une composition de revêtement formé par dépôt électrolytique dans laquelle la dissolubilité de composés du bismuth est suffisamment améliorée et qui permet de former un film de revêtement ayant d'excellentes aptitude au durcissement, uniformité d'épaisseur de film et de résistance à la corrosion. La composition de revêtement formé par dépôt électrolytique selon la présente invention comprend une émulsion de résine (1) et une pâte de dispersion de pigment (2). L'émulsion de résine (1) comprend une résine aminée (A) et un agent durcisseur isocyanate séquencé (B). La pâte de dispersion de pigment (2) est préparée par mélange de : un mélange obtenu par mélange à l'avance d'un composé du bismuth (C) et d'un acide organique (D) ; une résine de dispersion de pigment (E) ; et un pigment (F). La pâte de dispersion de pigment (2) satisfait aux conditions suivantes : (i) le rapport molaire en termes de teneur entre le bismuth métallique présent dans le composé du bismuth (C) et l'acide organique (D) est Bi:(D) = 1:0,5 à 1:4 ; et (ii) le rapport massique en termes de teneur entre le composé du bismuth (C) plus le pigment (F) et la résine de dispersion de pigment (E) est (C) + (F):(E) = 1:0,2 à 1:0,5.
PCT/JP2015/059194 2014-03-26 2015-03-25 Composition de revêtement formé par dépôt électrolytique WO2015147079A1 (fr)

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CN114867796A (zh) * 2019-12-19 2022-08-05 巴斯夫涂料有限公司 含灯黑颜料的电沉积涂料组合物

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EP3467056B1 (fr) 2016-05-31 2021-07-14 Nippon Paint Automotive Coatings Co., Ltd. Composition de revêtement par électrodéposition cationique

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