WO2011030549A1 - Composition pour le traitement d'une surface métallique, procédé de traitement d'une surface métallique utilisant la composition, et film de revêtement de traitement d'une surface métallique produit au moyen de la composition ou du procédé - Google Patents

Composition pour le traitement d'une surface métallique, procédé de traitement d'une surface métallique utilisant la composition, et film de revêtement de traitement d'une surface métallique produit au moyen de la composition ou du procédé Download PDF

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WO2011030549A1
WO2011030549A1 PCT/JP2010/005523 JP2010005523W WO2011030549A1 WO 2011030549 A1 WO2011030549 A1 WO 2011030549A1 JP 2010005523 W JP2010005523 W JP 2010005523W WO 2011030549 A1 WO2011030549 A1 WO 2011030549A1
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composition
metal surface
resin
surface treatment
metal
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PCT/JP2010/005523
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Japanese (ja)
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屋部幸誠
和智大介
原真純
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日本パーカライジング株式会社
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular 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
    • C08G18/28—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
    • C08G18/58—Epoxy resins
    • C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
    • 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
    • C09D175/04—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
    • 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
    • C09D5/4488—Cathodic paints
    • C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Definitions

  • the present invention relates to a metal surface treatment composition capable of forming a film capable of imparting excellent corrosion resistance and coating appearance to a metal material, particularly a metal structure having a complicated shape, and a metal surface treatment using the same.
  • the present invention relates to a method and a metal surface treatment film using them.
  • electrodeposition coating having high throwing power has been generally used as a method for imparting excellent corrosion resistance to various metal materials, particularly metal structures having complicated shapes.
  • the desired corrosion resistance cannot be obtained only with the electrodeposition coating film obtained by electrodeposition coating. Processing was applied.
  • Electrodeposition coating consists of an anionic electrodeposition coating in which the coating is deposited by anodic electrolysis in an aqueous paint containing an anionic resin emulsion, and an aqueous coating containing a cationic resin emulsion.
  • Cathodic electrolysis can be broadly divided into cationic electrodeposition coating in which a coating film is deposited.
  • cationic electrolysis which does not cause the base metal to elute into the paint during electrolytic treatment, is possible.
  • Electrodeposition coating is advantageous, and cationic electrodeposition coating is widely applied to automobile bodies, automobile parts, home appliances, building materials, etc., which are metal components mainly composed of iron-based materials.
  • Cation electrodeposition coating has a long history in the market, and once it was rust-proof by blending chromium and lead compounds. However, since this also has insufficient rust prevention properties, a ground treatment such as a zinc phosphate chemical conversion treatment was essential.
  • a ground treatment such as a zinc phosphate chemical conversion treatment was essential.
  • chromium and lead compounds have become virtually unusable due to environmental regulations, especially the European ELV regulations, so alternative components have been studied and their effects have been found in bismuth compounds. Is disclosed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5-329159 discloses a resin composition for electrodeposition paints containing at least one pigment coated with a bismuth compound.
  • Patent Document 2 discloses a cationic electrodeposition coating composition comprising an aqueous dispersion paste containing an aqueous dispersion in which an organic acid-modified bismuth compound is present in a water-insoluble form. ing.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-137367 discloses a cationic electrodeposition coating characterized by comprising a colloidal bismuth metal and a resin composition having a sulfonium group and a propargyl group.
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2007-197688 discloses an electrodeposition coating comprising particles of at least one metal compound selected from bismuth hydroxide, a zirconium compound and a tungsten compound, wherein the metal compound is 1 to An electrodeposition paint characterized by being 1000 nm is disclosed.
  • Patent Document 5 Japanese Patent Laid-Open No. 11-80621 discloses a cationic electrodeposition coating composition characterized by containing an aqueous solution of an aliphatic alkoxycarboxylic acid bismuth salt.
  • Patent Document 6 Japanese Patent Laid-Open No. 11-80622 contains an aqueous solution of bismuth salt with two or more organic acids, wherein at least one of the organic acids is an aliphatic hydroxycarboxylic acid.
  • a cationic electrodeposition coating composition characterized by the above is disclosed.
  • Patent Document 7 Japanese Patent Laid-Open No. 11-100533 discloses a cationic electrodeposition coating composition characterized by containing bismuth lactate using lactic acid containing 80% or more of L isomers among optical isomers. Has been.
  • Patent Document 8 Japanese Patent Laid-Open No. 11-106687 includes an aqueous solution of an organic acid bismuth salt containing two or more organic acids, wherein at least one of the organic acids is an aliphatic alkoxycarboxylic acid.
  • a cationic electrodeposition coating composition characterized by the above is disclosed.
  • Patent Documents 1 to 4 are those in which a bismuth compound or metal bismuth insoluble in an aqueous paint is dispersed, and Patent Documents 5 to 8 dissolve at least the bismuth compound until there is no remaining solids, that is, Bi. It is characterized by being added to the paint after being in an ionic state.
  • Patent Document 9 Japanese Patent Application Laid-Open No. 2008-274392 discloses a method of forming a film by coating a metal base material with a film forming agent in at least two stages of multi-stage energization methods, and (i) a film forming agent Is at least one selected from a zirconium compound and, optionally, titanium, cobalt, vanadium, tungsten, molybdenum, copper, zinc, indium, aluminum, bismuth, yttrium, lanthanoid metal, alkali metal and alkaline earth metal A compound containing metal (a) comprising 30 to 20,000 ppm in terms of total metal (in terms of mass) and 1 to 40% by mass of a resin component, and (ii) a first stage using a metal substrate as a cathode performed by energizing the painting of 1 ⁇ 50 V of voltage (V 1) 10 ⁇ 360 seconds, then 2 metal substrate as a cathode Wherein the difference in the
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2008-538383 discloses an aqueous coating composition containing (A) a rare earth metal compound, (B) a base resin having a cationic group, and (C) a curing agent, The coating material is immersed in an aqueous coating composition in which the amount of (A) rare earth metal compound contained in the coating composition is 0.05 to 10% by weight in terms of the rare earth metal relative to the solid content of the coating.
  • a dipping step applying a voltage of less than 50 V as the cathode in the aqueous coating composition, and a pretreatment step, and applying a voltage of 50 to 450 V as the cathode in the aqueous coating composition.
  • a method for forming a multilayer coating film including an electrodeposition coating step of applying a voltage is disclosed.
  • the anticorrosive action of the base metal must be on the surface where Bi contacts with the metal, that is, the interface between the base metal surface and the coating, but in the prior art, the Bi component is uniformly dispersed in the coating and exhibits corrosion resistance. It was estimated that sufficient Bi was not present on the base metal surface.
  • Patent Documents 1 to 4 are those in which a bismuth compound or metal bismuth that is insoluble in an aqueous paint is dispersed.
  • a film is deposited from such a composition, the film is the same as other pigments. Bi is uniformly dispersed therein.
  • Patent Documents 5 to 8 are characterized in that at least the bismuth compound is dissolved until there is no remaining solids, that is, it is added to the paint after being in a Bi ion state. Since the ability is weak, Bi is gradually hydrolyzed when it is put into the composition, and changes to oxide or hydroxide, so long-term stabilization as Bi ion cannot be expected. . As a result, Bi is uniformly dispersed in the film. In these patent documents, the fact that the zinc phosphate-based chemical conversion treatment was used as the base treatment also supports the above-mentioned assumption.
  • Patent Document 9 and Patent Document 10 are techniques for depositing an inorganic film on a base metal and laminating a resin film, which is advantageous in terms of anticorrosion of the base metal. Both the resin film and the resin film have a mechanism that precipitates due to the pH increase on the surface of the base metal by cathodic electrolysis, so that it is not easy to form a laminated film.
  • the present inventors applied an aminopolycarboxylic acid having a high chelating ability in order to make Bi ions exist more stably in the composition, and thus applied to low voltage cathode electrolysis.
  • a reaction mechanism was found in which resin was deposited by such pH increase at the stage where Bi was diffused and reduced by high voltage cathode electrolysis.
  • the coating obtained by this can sufficiently improve the corrosion resistance of the base metal by Bi present in a high concentration on the surface of the base metal as well as the curing catalyst ability of the resin of Bi.
  • the present inventors examined increasing the Bi concentration in order to further enhance the rust prevention effect.
  • the aminopolycarboxylic acid concentration that is a chelating agent may be increased, but in this case, if excessive aminopolycarboxylic acid is incorporated into the coating film, the coating film appearance (specifically, This causes another problem that the glossiness is lowered.
  • the present invention capable of solving the above problems is the following (1) to (10).
  • the present invention (1) contains 5 to 30% by weight of an aqueous resin, 100 to 5000 ppm of trivalent Bi ions, and an aminopolycarboxylic acid in a molar concentration of 0.1 to 5 times the Bi ions, At least a part of the water-based resin is represented by the following formula (1): ⁇ Wherein R1 and R2 are independently of each other-(R) m-X (where R is an alkylene group having 1 to 6 carbon atoms, m is 1 or 0, and X is A metal surface treatment characterized by being a nonionic and / or cationic resin having a nitrogen-containing group capable of forming a chelate with Bi ions in the polymer skeleton, represented by hydrogen, carboxyl, hydroxyl or acyl ⁇ Composition (metal surface treatment composition for depositing an organic-inorganic composite film by electrolysis).
  • R1 and R2 are independently of each other hydrogen, alkyl, hydroxyalkyl, carboxyalkyl (—R—COOH: R is an alkyl group) or alkylcarbonyl (—CO -R: where R is an alkyl group, wherein the alkyl moiety of alkyl, hydroxyalkyl, carboxyalkyl and alkylcarbonyl is a straight, branched or cyclic group having 1 to 6 carbon atoms ( 1) The metal surface treatment composition.
  • the present invention (3) is the metal surface treatment composition of the invention (1) or (2), wherein the aqueous resin is a modified epoxy resin.
  • the modified epoxy resin is bisphenol A type, and the nitrogen-containing group is directly bonded to the benzene ring portion of the phenylene group instead of the glycidyl ether portion in the modified epoxy resin.
  • the metal surface treatment composition according to (3) is bisphenol A type, and the nitrogen-containing group is directly bonded to the benzene ring portion of the phenylene group instead of the glycidyl ether portion in the modified epoxy resin.
  • the bisphenol A type modified epoxy resin (A) comprises, as raw materials, a modified resin (B), an epoxy resin (C) having an epoxy equivalent of 180 to 2500, and a phenol compound (D Or a secondary amino group-containing compound (F) and / or bisphenol A (E), and an aminated product of a modified epoxy resin obtained by reacting them. It is a composition for metal surface treatment.
  • the compound (D) is represented by the following formula (2): (Formula 4) (Wherein R3 is the nitrogen-containing group or hydrogen atom, at least one of R3 is the nitrogen-containing group; R4 is independently hydrogen or an alkyl group having 1 to 2 carbon atoms)
  • the composition for metal surface treatment of the said invention (5) which is an amine addition phenol compound shown by this.
  • the invention (7) provides the metal surface treatment according to any one of the inventions (1) to (6), wherein the molar concentration of the nitrogen-containing group is 0.1 to 200 times with respect to trivalent Bi ions. Composition.
  • the present invention (8) includes a step of depositing a coating film on the surface of a metal material in an electrolytic treatment step using the composition according to any one of the inventions (1) to (7) as a cathode. This is a surface treatment method.
  • the present invention (9) is a metal surface for depositing a film on a metal material, comprising an electrolysis process for subjecting the metal material having a cleaned surface to an electrolysis process, and a water washing and baking process performed after the electrolysis process.
  • the electrolytic treatment step includes A first step of electrolysis for 10 to 120 seconds at a voltage of 0 to 15 V in a state where the metal material is immersed in the composition of any one of the inventions (1) to (7); The electrolysis is carried out after the first step, in which the metal material is immersed in the composition according to any one of the inventions (1) to (7) and electrolysis is performed at a voltage of 50 to 300 V for 30 to 300 seconds.
  • the “voltages X to Y (V)” in the first step and the second step may be a mode in which a constant voltage is applied within the range of the voltages X to Y or a mode in which the applied voltage is changed over time.
  • the lower limit value “0 V” of “voltage 0 to 15 V” in the first step means not a constant voltage mode but a predetermined voltage in a mode in which the applied voltage is changed over time.
  • the metal Bi and the oxidized Bi formed by the method of the invention (8) or (9) are deposited as Bi in an amount of 20 to 500 mg / m2, the total film thickness is 5 to 40 ⁇ m, and
  • the Bi adhesion distribution (G) on the metal material side from the center of the film thickness is a Bi adhesion distribution that is 55% or more (G / H ⁇ 55%) with respect to the total Bi adhesion quantity (H). It is a metal surface treatment film.
  • FIG. 1 is an EPMA line analysis profile of the film in Example 1.
  • FIG. 2 is a diagram showing appropriate ranges of Al ion concentration and pH.
  • the metal surface treatment composition according to the best mode the metal surface treatment method using the composition, and the metal surface treatment film formed by the method will be described in order.
  • the metal surface treatment composition according to the present invention comprises 5 to 30% by weight of an aqueous resin, 100 to 5000 ppm of trivalent Bi ions, and 0.1 to 5 times the molar concentration of aminopolycarboxylic acid with respect to Bi ions. And at least a portion of the aqueous resin is a nonionic and / or cationic resin having a predetermined substituent.
  • an aqueous resin 100 to 5000 ppm of trivalent Bi ions, and 0.1 to 5 times the molar concentration of aminopolycarboxylic acid with respect to Bi ions.
  • the aqueous resin is a nonionic and / or cationic resin having a predetermined substituent.
  • the aqueous resin according to the present invention is preferably a nonionic resin and a cationic resin.
  • a curing agent such as a blocked polyisocyanate can be arbitrarily added to the water-based resin.
  • aqueous resin is represented by the following formula (1): ⁇ Wherein R1 and R2 are independently of each other-(R) m-X (where R is an alkylene group having 1 to 6 carbon atoms, m is 1 or 0, and X is And a nonionic and / or cationic resin having a nitrogen-containing group capable of forming a chelate with Bi ion in the polymer skeleton, represented by hydrogen, carboxyl, hydroxyl or acyl.
  • R in acyl may be aliphatic or aromatic and preferably has 1 to 6 carbon atoms.
  • R1 and R2 are independently of each other hydrogen, alkyl, hydroxyalkyl, carboxyalkyl or alkylcarbonyl, wherein alkyl, hydroxyalkyl, carboxyalkyl and alkylcarbonyl alkyl
  • the moiety is preferably a linear, branched or cyclic group having 1 to 6 carbon atoms.
  • those containing O (oxygen atom) are preferable from the viewpoint of chelate forming ability, and hydroxyalkyl is most preferable in view of the ease of synthesis.
  • the nitrogen-containing group represented by the formula (1) is present in the polymer skeleton of the nonionic and / or cationic resin.
  • the nonionic resin and / or the cationic resin are not particularly limited, and examples thereof include an epoxy resin, a urethane resin, and an acrylic resin.
  • epoxy resins are preferable, modified epoxy resins are more preferable, and bisphenol A type modified epoxy resins are particularly preferable.
  • a compound containing an ethylene oxide group can also be introduced.
  • this ethylene oxide group has a nonionic activator function, and effects such as improvement of emulsion stability when it is in an emulsion state can be obtained.
  • polyethylene glycol or polyethylene glycol diglycidyl ether the properties of the nonionic resin are exhibited.
  • a bisphenol A-type modified epoxy resin it is preferable to use a bisphenol A ethylene oxide adduct having the same bisphenol A structure.
  • the bisphenol A-type modified epoxy resin includes, as raw materials, a modified resin (B), an epoxy resin (C) having an epoxy equivalent of 180 to 2500, the phenol compound (D) having a nitrogen-containing group, and a secondary amino group-containing compound (F ) Or further using bisphenol A (E) and reacting these, an aminated product of a modified epoxy resin.
  • a modified resin B
  • an epoxy resin C
  • the phenol compound D
  • F secondary amino group-containing compound
  • E bisphenol A
  • modified resin (B) Raw material of modified epoxy resin (A) of bisphenol A type
  • a polyol compound is usually used as the modified resin (B).
  • These are applied for the purpose of improving the plasticity of the epoxy resin.
  • polyol resins such as polyester polyol, polyether polyol, polyurethane polyol, and acrylic polyol, and aromatic condensed compounds having a hydroxyl group by adding phenol to the terminal. More specifically, polycaprolactone diol, polyethylene glycol, polypropylene glycol, xylene formaldehyde resin having a phenolic hydroxyl group and the like can be mentioned.
  • the modification with these compounds is a technique that has been used conventionally since the hydroxyl groups of these compounds and the glycidyl ether portion of the epoxy resin can easily react.
  • these modified resins are contained in an amount of 5 to 30% by weight.
  • the epoxy resin (C) having an epoxy equivalent of 180 to 2500 is particularly preferably an epoxy resin obtained by a reaction between a polyphenol compound and an epihalohydrin, for example, epichlorohydrin, from the viewpoint of the corrosion resistance of the coating film.
  • an epoxy resin obtained by polymerizing bisphenol A as a basic structure exhibits the same effect, and an epoxy equivalent having an epoxy equivalent of 180 to 2500, preferably 180 to 2000, more preferably 180 to 1500 is optimal.
  • these epoxy resins are contained in an amount of 5 to 30% by weight.
  • the phenol compound (D) having the nitrogen-containing group the following formula (2): (Formula 6) (Wherein R3 is the nitrogen-containing group or hydrogen atom, at least one of R3 is the nitrogen-containing group; R4 is independently hydrogen or an alkyl group having 1 to 2 carbon atoms) It is preferable that it is an amine addition phenol compound shown by this. Of these, those having an addition number of R3 of 1 are preferred. When R4 has 1 carbon, that is, a bisphenol A type is preferable. In the modified epoxy resin, the phenol compound having these nitrogen-containing groups is contained in an amount of 5 to 30% by weight.
  • Primary and secondary amines include ammonia; mono- or di-alkylamines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine; monoethanolamine, Alkanolamines such as diethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxypropyl) amine, tri (2-hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol; N-formylmethylamine, N- Formylethylamine, acetamide, N-methylacetamide, N-ethylacetamide, propionic acid amide, N-methylpropionamide, N-ethylpropyleneamide
  • the content (addition amount) of bisphenol A (E) can be changed at an arbitrary ratio in relation to the content (addition amount) of the phenol compound (D) having the nitrogen-containing group.
  • the total amount of both is contained by 5 to 30% by weight.
  • the secondary amino group-containing compound (F) is a cationic property-imparting component for introducing an amino group into an epoxy resin substrate to cationize the epoxy resin.
  • the effect is different.
  • the amine used here contains at least one active hydrogen that reacts with an epoxy group.
  • Examples of the amino group-containing compound used for such purpose include mono- or di-alkylamines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, monoisopropylamine, diisopropylamine, monobutylamine, dibutylamine and the like.
  • Alkanolamines such as monoethanolamine, diethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxypropyl) amine, tri (2-hydroxypropyl) amine, monomethylaminoethanol, monoethylaminoethanol; ethylenediamine, propylene Diamine, Butylenediamine, Hexamethylenediamine, Tetraethylenepentamine, Pentaethylenehexamine, Diethylaminopropylamine, Diethylenetriamine Alkylene polyamine and ketimine of the polyamines such as triethylenetetramine; ethyleneimine, alkylene imine such as propylene imine; piperazine, a cyclic amine such as morpholine, and the like.
  • the secondary amino group-containing compound (F) is contained in an amount of 0.5 to 20% by weight.
  • An epoxy resin having a predetermined epoxy equivalent can be synthesized by adjusting the synthesis temperature and time.
  • the epoxy equivalent is calculated by the epoxy equivalent measurement defined in JIS K7236.
  • the epoxy equivalent at this time is preferably 800 to 10,000, more preferably 800 to 5000, and most preferably 800 to 3000. The greater the epoxy equivalent, the lower the emulsification stability during emulsion preparation.
  • a secondary amino group-containing compound (F) is added to the synthesized modified epoxy resin. While maintaining the modified epoxy resin at 70 ° C. to 110 ° C., the secondary amino group-containing compound (F) is added and synthesis is performed for 1 to 3 hours to obtain an aminated product of the modified epoxy resin.
  • Bi ion in the present invention refers to a Bi component that is not solidified in the composition and is in a completely dissolved state. Specifically, the nitrogen-containing group in the aminopolycarboxylic acid or polymer described later is used. This means that the chelate is constituted by a water-soluble state stably.
  • Aminopolycarboxylic acid is a generic term for chelating agents having an amino group and a plurality of carboxyl groups in the molecule. Specifically, EDTA (ethylenediaminetetraacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), NTA (nitrilotrimethyl). Acetic acid), DTPA (diethylenetriaminepentaacetic acid), TTHA (triethylenetetraminehexaacetic acid) and the like are applicable, and EDTA, HEDTA and NTA are more preferable from the viewpoint of chelate stability with Bi ions.
  • EDTA ethylenediaminetetraacetic acid
  • HEDTA hydroxyethylethylenediaminetriacetic acid
  • NTA nitrilotrimethyl
  • Acetic acid DTPA (diethylenetriaminepentaacetic acid)
  • TTHA triethylenetetraminehexaacetic acid
  • composition component Other ingredients>
  • additives usually used in the paint field such as a pigment, a catalyst, an organic solvent, a pigment dispersant, and a surfactant can be further applied as necessary.
  • pigments include colored pigments such as titanium white and carbon black, extender pigments such as clay, talc and barita, rust preventive pigments such as aluminum tripolyphosphate and zinc phosphate, organic tin compounds such as dibutyltin oxide and dioctyltin oxide, Examples thereof include dialkyltin fatty acids such as dibutyltin laurate and dibutyltin dibenzoate, and tin compounds such as aromatic carboxylates.
  • Al ions may be added from the viewpoint of promoting the precipitation of the aqueous resin (especially in the case of a nonionic resin). Furthermore, even if the composition of the present invention contains metal ions such as Fe ions, Zn ions, and Ce ions in addition to Bi ions and Al ions, the effects of the present invention are not impaired. Rather, these metal ions have the effect of promoting the precipitation of the aqueous resin, although not as much as the Al ions.
  • the Fe ion is more preferably trivalent than divalent.
  • composition component Liquid medium>
  • an aqueous medium is preferable, and water is more preferable.
  • the liquid medium may contain an aqueous solvent other than water (for example, water-soluble alcohols).
  • composition of the metal surface treatment composition according to the present invention will be described.
  • the metal surface treatment composition according to the present invention contains 5 to 30% by weight of an aqueous resin, preferably 10 to 25% by weight, more preferably 10 to 20% by weight, based on the total weight of the composition. Including.
  • the ratio (weight ratio) of the nonionic and / or cationic resin represented by the formula (1) in the total water-based resin is preferably 30 to 100%, and more preferably 70 to 100%. .
  • the smaller the ratio of the resin represented by the formula (1) the lower the chelating ability, and it cannot contribute to the stability of Bi. Further, if the total water-based resin content is too low, the amount of film deposition is insufficient, and if the content is too high, it is economically disadvantageous.
  • the molar concentration of the nitrogen-containing group represented by the formula (1) in the metal surface treatment composition according to the present invention is 0.1 to 200 times, 0 times the trivalent Bi ion. It is more preferably 5 to 100 times, and further preferably 1.0 to 50 times.
  • the metal surface treatment composition according to the present invention contains 100 to 5000 ppm of trivalent Bi ions. More preferred is 500 to 4000 ppm, and most preferred is 1000 to 3000 ppm. If the Bi ion concentration is too low, a sufficient amount of Bi adhesion necessary for improving the corrosion resistance cannot be obtained. If the Bi ion concentration is too high, the electrical conductivity of the composition becomes too high, and the coating on the metal material having a complicated shape is increased. As a result, the Bi adhesion amount becomes excessive and the film adhesion may be impaired.
  • the Bi ion concentration in the composition can be determined by solid-liquid separation of the composition using an ultracentrifuge, and the liquid phase can be quantified using high frequency inductively coupled plasma emission spectrometry (ICP) or atomic absorption spectrometry (AA). .
  • ICP inductively coupled plasma emission spectrometry
  • AA atomic absorption spectrometry
  • the metal surface treatment composition according to the present invention contains aminopolycarboxylic acid at a molar concentration of 0.1 to 5 times with respect to Bi ions.
  • a molar concentration of 0.1 to 4 times is more preferable, and a molar concentration of 0.1 to 3 times is most preferable.
  • Bi ions are hydrolyzed in the composition and become oxides, so that the effective Bi ion concentration is lowered, and as a result, a sufficient amount of Bi deposition cannot be obtained.
  • Bi ions will be overstabilized and a sufficient amount of Bi will not be obtained.
  • the excessive aminopolycarboxylic acid may cause gelation of the cationic resin, and is incorporated into the coating film during electrolysis, thereby deteriorating the appearance of the coating film.
  • the composition according to the present invention contains an aminopolycarboxylic acid, but particularly when combined with a cationic resin, the presence of excess aminopolycarboxylic acid sometimes causes gelation of the cationic resin. There is. In such a case, the amount of the cation group of the cationic resin is reduced or a nonionic resin is used (or the cationic resin and the nonionic resin are mixed, and the total amount of cation groups is relatively reduced. (Decrease) is preferred. By the way, in this case, another problem that the resin does not precipitate so much even when the pH is increased may occur.
  • the problem can be solved by including Al ions.
  • ionic Al becomes a fine hydroxide colloid due to the increase in pH of the metal surface by cathodic electrolysis, and when it completely loses zeta charge around pH 9 and begins to agglomerate rapidly, the surrounding resin is also involved and precipitates. Presumed to be.
  • the Al component in this embodiment must be in the form of ions in the composition.
  • metal ions are usually stabilized by the presence of a chelating agent, but in the case of Al ions, there is no or rare chelating agent that is stable enough to prevent the formation of hydroxide colloid accompanying pH increase. .
  • chelating agent such as acetic acid, formic acid, sulfamic acid, and lactic acid, and aminopolycarboxylic acids that are usually blended in electrodeposition coating compositions do not have a chelating ability to stabilize Al ions.
  • Al ions can be added using an Al compound.
  • the Al compound is not particularly limited, but can be added in the form of an inorganic acid salt such as nitrate or sulfate, or an organic acid salt such as lactate or acetate.
  • ⁇ Log ((A ⁇ 1.93 ⁇ 10 ⁇ 15 ) 1/3 ) is obtained from the solubility product of Al hydroxide at 25 ° C .: 1.92 ⁇ 10 ⁇ 32 . That is, when the pH is exceeded, Al ions precipitate as hydroxides and can no longer be ions.
  • 25 ° C. is a typical temperature during storage and use of the composition.
  • the effects of the present invention are not impaired even if the composition of the present invention contains metal ions such as Fe ions, Zn ions, and Ce ions in addition to Bi ions and Al ions. Rather, these metal ions have the effect of promoting the precipitation of the aqueous resin, although not as much as the Al ions.
  • the Fe ion is more preferably trivalent than divalent.
  • the pH of the metal surface treatment composition according to the present invention is not particularly limited, but is usually adjusted to a range of 2.0 to 7.0, preferably 3.0 to 6.5. it can.
  • the temperature of the metal surface treatment composition according to the present invention is not particularly limited, but when the film is deposited by electrolytic treatment, it is usually used within a range of 15 to 40 ° C, preferably 20 to 35 ° C. it can.
  • a method for producing a metal surface treatment composition according to the present invention will be described.
  • the case where an aminated product of a modified epoxy resin is used as the aqueous resin will be described as an example.
  • a neutralized acid is added to the synthesized aminated product of the modified epoxy resin, mixed with stirring, and then diluted with water to prepare a resin emulsion having a predetermined concentration.
  • the neutralizing acid formic acid, acetic acid, lactic acid, sulfamic acid and the like are used.
  • a curing agent it is preferable to add a curing agent, a curing catalyst, an organic solvent, etc. before adding the neutralizing acid.
  • a uniform emulsion By adding in advance, a uniform emulsion can be obtained.
  • block polyisocyanate is an addition reaction product of approximately the theoretical amount of a polyisocyanate compound and an isocyanate blocking agent.
  • examples of the polyisocyanate compound used here include tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate (usually referred to as “MDI”), Aromatic, aliphatic or alicyclic polyisocyanate compounds such as crude MDI, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, isophorone diisocyanate; cyclized polymers of these polyisocyanate compounds; Isocyanate biuret; ethylene glycol, propylene glycol
  • the isocyanate blocking agent is blocked by adding to the isocyanate group of the polyisocyanate compound, and the blocked polyisocyanate compound produced by the addition is stable at room temperature, but the baking temperature of the coating film (usually about 100). When heated to about 200 ° C., it is desirable that the blocking agent dissociates to regenerate free isocyanate groups.
  • Examples of the blocking agent satisfying such requirements include lactam compounds such as ⁇ -caprolactam and ⁇ -butyrolactam; oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime; phenols such as phenol, para-t-butylphenol and cresol.
  • lactam compounds such as ⁇ -caprolactam and ⁇ -butyrolactam
  • oxime compounds such as methyl ethyl ketoxime and cyclohexanone oxime
  • phenols such as phenol, para-t-butylphenol and cresol.
  • Compounds; aliphatic alcohols such as n-butanol and 2-ethylhexanol; aromatic alkyl alcohols such as phenyl carbinol and methyl phenyl carbinol; ether alcohol compounds such as ethylene glycol monobutyl ether and diethylene glycol monoethyl ether
  • These blocking agents can be used alone or
  • the Bi ion aqueous solution can be obtained by dissolving a predetermined concentration of polyaminocarboxylic acid in water, adding bismuth nitrate pentahydrate thereto and stirring at 50 to 70 ° C. until dissolved.
  • pigments are added here to improve the performance of the coating film or for coloring.
  • a dispersion resin is used, and a dispersion (paste) is used in advance.
  • the metal surface treatment composition according to the present invention is used for the purpose of preventing various metals from corrosion.
  • the metal material is not particularly limited, but steel materials such as cold-rolled steel plates, hot-rolled steel plates, cast materials, steel pipes, etc., and zinc-based plating treatment and / or aluminum-based plating are performed on those steel materials. Materials, aluminum alloy plates, aluminum castings, magnesium alloy plates, magnesium castings, and the like. It is particularly suitable for use in metal structures having complicated shapes, for example, automobile bodies, automobile parts, home appliances, building materials, etc., which are metal structures mainly composed of iron-based materials.
  • the usage method (metal surface treatment method) according to the present invention includes a step of depositing a coating film on the surface of a metal material in an electrolytic treatment step using the above-described metal surface treatment composition as a cathode. More preferably, the method of use (metal surface treatment method) according to the present invention comprises an electrolytic treatment step of performing electrolytic treatment on a metal material whose surface has been cleaned in order to deposit a film on the metal material; It includes a water washing and baking process performed after the treatment process.
  • the electrolytic treatment process characteristic of this method will be described in detail.
  • This electrolytic treatment step includes a first step of electrolysis at a voltage of 0 to 15 V for 10 to 120 seconds in a state where the metal material is immersed in a metal surface treatment composition, and a metal surface treatment composition.
  • the first step is a step mainly performed for preferentially attaching Bi
  • the second step is a step mainly performed for precipitating the resin preferentially.
  • Bi that is in direct contact with the metal material, that is, the presence of the interface Bi that exists at the interface between the metal material and the film is necessary.
  • the order of the first step and the second step is required. And conditions are extremely important.
  • the voltage in the first step is 0 to 15 V, and electrolysis is preferably performed for 10 to 120 seconds.
  • the voltage is lower than the lower limit, that is, when electrolysis is performed using the metal material as an anode, the metal material is eluted in the composition, not only reducing the stability of the composition, but also the interface Bi necessary for improving the corrosion resistance. It will not adhere sufficiently.
  • the upper limit is exceeded, resin deposition starts before Bi is preferentially deposited on the metal surface, so that sufficient corrosion resistance cannot be obtained.
  • the voltage in the second step is 50 to 300 V, and electrolysis is preferably performed for 30 to 300 seconds.
  • the voltage is lower than the lower limit, the amount of the resin film deposited is insufficient.
  • the voltage is higher than the upper limit, the resin film is excessively deposited, which is economically disadvantageous, and the finished appearance of the film may be impaired.
  • the two-stage electrolytic treatment in the present invention is not necessarily performed in the same tank, and may be performed in different tanks.
  • the two-stage electrolytic treatment is performed in two tanks, it is possible to adjust the Bi concentration and the resin concentration in accordance with the first stroke and the second stroke in the first tank and the second tank, thereby achieving cost merit. For example, by reducing the Bi concentration in the second tank, the amount of Bi contained in the carry-out liquid can be reduced, leading to cost reduction.
  • the metal surface treatment film according to the present invention is obtained by the treatment method of the present invention using the metal surface treatment composition of the present invention.
  • Bi which exists in a film
  • membrane exists with the form of a metal and an oxide.
  • Bi deposited by cathodic electrolysis is basically reduced Bi metal Bi, but a part of it is oxidized in particular in the coating baking process to become an oxide.
  • Bi stabilization by the aminopolycarboxylic acid is insufficient due to an increase in pH on the surface of the film, so that it also precipitates as oxidized Bi especially on the film surface side.
  • the Bi adhesion amount is preferably 20 to 500 mg / m2, more preferably 30 to 400 mg / m2, and most preferably 50 to 300 mg / m2. If the amount of Bi deposited is too low, sufficient corrosion resistance cannot be obtained. If it is too high, improvement in corrosion resistance can no longer be expected, and film adhesion may be impaired.
  • the amount of Bi attached can be determined by fluorescent X-ray spectroscopic analysis.
  • the “metal Bi adhesion amount” and “oxidized Bi adhesion amount” in the claims and in the present specification are values determined by the fluorescent X-ray spectroscopic analysis.
  • the total film thickness of the obtained film is preferably 5 to 40 ⁇ m, more preferably 5 to 30 ⁇ m, and most preferably 7 to 25 ⁇ m. If it is too thin, sufficient corrosion resistance cannot be obtained, and if it is too thick, not only is it economically disadvantageous, but the throwing power may be lowered.
  • the film thickness can be measured by an electromagnetic induction type film thickness meter if the base metal is a magnetic metal, or by an eddy current film thickness meter if the base metal is a non-magnetic metal.
  • the Bi adhesion amount B on the metal material side from the center of the film thickness is a Bi adhesion distribution in which the total Bi adhesion amount: 55% or more (B / A ⁇ 55%) with respect to A. preferable. It is more preferably 58% or more, and most preferably 60% or more. If it is too low, sufficient corrosion resistance cannot be obtained. Note that if it exceeds 90%, the Bi concentration on the surface side of the film is extremely lowered and the function of Bi as a curing catalyst is lost.
  • the Bi adhesion distribution in the film can be measured by performing a line analysis on the film cross section using EPMA.
  • the position of the base metal / film interface and the film surface is specified from the backscattered electron image taken at the same time, and the integrated value of Bi intensity in the film by EPMA line analysis: the integrated value of only the base metal side from the center of A and film thickness: B can be obtained and B / A can be calculated.
  • Bi ion aqueous solution (B2, see below): To 100 g, 1.7 g of phenol compound (D1) previously dissolved in 50 g of ethanol was added and stirred while heating to 60 ° C. About the obtained solution, it has confirmed that the phenolic compound (D1) was chelating Bi by using a liquid chromatography mass spectrometry. In this case, the phenol compound (D1) has a molar concentration of 1.0 times that of Bi.
  • Bi ion aqueous solution (B2, see below): A solvent solution of bisphenol A dissolved in 50 g of ethanol in advance: 1.1 g was added to 100 g, followed by stirring while heating to 60 ° C. By using liquid chromatography mass spectrometry for the resulting solution, it was confirmed that bisphenol A did not chelate Bi. In this case, bisphenol A has a molar concentration of 1.0 times that of Bi.
  • Bi ion aqueous solution (B2, see below): 100 g of phenol compound (D2) previously dissolved in 50 g of ethanol: 1.5 g was added and stirred while heating to 60 ° C. About the obtained solution, it was able to confirm that the phenol compound (D2) was chelating Bi by using liquid chromatography mass spectrometry. In this case, the phenol compound (D2) has a molar concentration of 1.0 times that of Bi.
  • Bi ion aqueous solution (B2, see below): Phenol compound (D3) dissolved in ethanol 50 g in advance in 100 g: 1.6 g was added and stirred while heating to 60 ° C. About the obtained solution, it was able to confirm that the phenol compound (D3) was chelating Bi by using a liquid chromatography mass spectrometry. In this case, the phenol compound (D3) has a molar concentration of 1.0 times that of Bi.
  • Bi ion aqueous solution (B2, see below): Phenol compound (D4) dissolved in ethanol 50 g in advance in 100 g: 1.5 g was added and stirred while heating to 60 ° C. About the obtained solution, it was able to confirm that the phenol compound (D4) was chelating Bi by using a liquid chromatography mass spectrometry. In this case, the phenol compound (D4) has a molar concentration of 1.0 times that of Bi.
  • Bi ion aqueous solution (B2, see below): Phenol compound (D5) dissolved in ethanol 50 g in advance in 100 g: 1.4 g was added and stirred while heating to 60 ° C. About the obtained solution, it was able to confirm that the phenol compound (D5) was chelating Bi by using a liquid chromatography mass spectrometry. In this case, the phenol compound (D5) has a molar concentration of 1.0 times that of Bi.
  • Bi ion aqueous solution (B2, see below): 1.2 g of a phenol compound (D6) previously dissolved in 50 g of ethanol was added to 100 g, and the mixture was stirred while heating to 60 ° C. About the obtained solution, it was able to confirm that the phenol compound (D6) was chelating Bi by using a liquid chromatography mass spectrometry. In this case, the phenol compound (D6) has a molar concentration of 1.0 times that of Bi.
  • Epoxy resin # 828 manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 180
  • 114.0 g in a 1000 ml separable flask equipped with a thermometer, condenser, and stirrer, polycaprolactone diol Plaxel 208 (Daicel Chemical Co., Ltd.) as a modified resin 41.5 g, bisphenol A: 45.6 g, and 0.1 g of dimethylbenzylamine were added, and the reaction was performed at 130 ° C. until the epoxy equivalent was 1000.
  • Production Example 2 In Production Example 1, in place of bisphenol A, 31.9 g of bisphenol A and 20.8 g of phenol compound (D1) were used, and a similar reaction was performed to obtain an aqueous resin emulsion (A2).
  • Production Example 3 In Production Example 1, instead of bisphenol A, 13.7 g of bisphenol A and 48.4 g of phenol compound (D1) were used, and a similar reaction was performed to obtain an aqueous resin emulsion (A3).
  • Epoxy resin # 828 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 180): 114.0 g in a 2000 ml separable flask equipped with a thermometer, condenser and stirrer, polycaprolactone diol Plaxel 208 (Daicel Chemical Co., Ltd.) as a modified resin 41.5 g, bisphenol A: 31.9 g, phenol compound (D1): 20.8 g, bisphenol A ethylene oxide adduct / New Pole BPE-100 (manufactured by Sanyo Chemical Industries): 100.2 g, 0.1 g of dimethylbenzylamine was added, and the reaction was carried out at 130 ° C. until the epoxy equivalent reached 1500.
  • HEDTA 13.3 g was dissolved in 500 g, heated to 60 ° C., and then bismuth nitrate pentahydrate: 23.2 g was added to completely dissolve the solid content. Stir until Distilled water was further added so that the total amount was finally 1.0 L, and Bi ion aqueous solution (B1) was produced.
  • B1 Bi ion aqueous solution
  • HEDTA has a molar concentration of 1.0 times that of Bi.
  • Distilled water 6.65 g of HEDTA was dissolved in 500 g and heated to 60 ° C., and then bismuth nitrate pentahydrate: 23.2 g was added and stirred.
  • Distilled water was further added so that the total amount was finally 1.0 L, and a thin turbid Bi ionic liquid (B2) was produced.
  • HEDTA is 0.5 times the molar concentration of Bi.
  • Distilled water was further added so that the total amount became 1.0 L finally, and a cloudy Bi ionic liquid (B3) was produced.
  • HEDTA has a molar concentration of 0.2 times that of Bi.
  • HEDTA has a molar concentration of 0.1 times that of Bi.
  • EDTA 6.99 g was dissolved in distilled water: 500 g, heated to 60 ° C., bismuth nitrate pentahydrate: 23.2 g was added, and the mixture was stirred until the solid content was completely dissolved.
  • Distilled water was further added so that the total amount was finally 1.0 L, and Bi ion aqueous solution (B5) was produced.
  • EDTA is 0.5 times the molar concentration of Bi.
  • Distilled water was further added so as to be 0 L to prepare a Bi ion aqueous solution (B6).
  • NTA has a molar concentration of 5.0 times that of Bi.
  • composition A pigment dispersion paste and Bi additive in an amount of 4.0% by weight of an inorganic solid are blended in a resin emulsion in an amount of 16.0% by weight of the combination shown in Table 1, and a composition is prepared.
  • Each concentration was adjusted by diluting with deionized water.
  • the pH of the treatment solution was 5.
  • Example 12 it adjusted to Al concentration: 200ppm and pH4 using the aluminum nitrate nonahydrate and nitric acid.
  • Electrolytic conditions After electrolysis at 8V for 60 seconds as an electrolytic step (1), an electrolytic treatment was immediately performed at 180V for 180 seconds as an electrolytic step (2).
  • test plate A cold rolled steel plate: SPCC (JIS 3141) 70 ⁇ 150 ⁇ 0.8 mm (hereinafter abbreviated as SPC) was used as a test plate, and its surface was preliminarily a strong alkaline degreasing agent “FC-E2001” manufactured by Nihon Parkerizing Co., Ltd. Was degreased by spraying for 120 seconds. After the degreasing treatment, it was washed with spray water for 30 seconds, immersed in the compositions shown in Examples and Comparative Examples, and subjected to cathode electrolytic treatment under the electrolytic conditions shown in Examples and Comparative Examples. The test plate after completion of electrolysis was immediately rinsed with deionized water for 30 seconds and baked at 180 ° C. for 20 minutes in an electric oven.
  • FC-E2001 strong alkaline degreasing agent
  • film thickness measurement Measured using an electromagnetic induction film thickness meter.
  • Bi adhesion amount quantified by fluorescent X-ray spectroscopic analysis.
  • Bi adhesion distribution Sample cross section was analyzed by EPMA line analysis. See below for specific methods.
  • a line analysis profile is an average value of characteristic X-ray intensity calculated in an arbitrary width in the one-dimensional direction of an analysis area based on mapping analysis data, and can be interpreted as a line analysis having a width.
  • the measurement conditions are as follows.
  • Measuring instrument EPMA-1610 type electron gun manufactured by Shimadzu Corporation: CeB6 cathode beam current: 50 nA, beam voltage: 15 kV, beam diameter: 1 ⁇ m ⁇ or less Integration number: once, sampling time per point: 100 ms
  • Spectroscopic crystal PET (Bi M ⁇ )
  • FIG. 1 shows the analysis result of the film obtained in Example 1 as a representative profile.
  • Corrosion resistance test method and evaluation method A cross-cut was applied to a resin-coated plate produced by cathodic electrolysis, a salt spray test (JIS-Z2371) was performed, and the maximum swell width on one side of the cross-cut portion after 1500 hours was measured. Based on the measurement results, the evaluation was made with less than 2 mm: ⁇ , 2 mm or more and less than 3 mm: ⁇ , 3 mm or more and less than 4 mm: ⁇ , 4 mm or more: x. The results are shown in Table 2.

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Abstract

La présente invention a pour objet une composition pour le traitement d'une surface métallique, qui permet la formation d'un film de revêtement qui peut conférer une excellente résistance à la corrosion et un excellent aspect de film de revêtement à un matériau métallique, en particulier à une structure métallique ayant une géométrie complexe. La présente invention concerne spécifiquement une composition pour le traitement d'une surface métallique, qui comprend de 5 à 30 % en poids d'une résine aqueuse, de 100 à 5 000 ppm d'un ion Bi trivalent, et un acide aminopolycarboxylique dans une concentration molaire de 0,1 à 5 fois la concentration de l'ion Bi. La composition est caractérisée en ce qu'au moins une partie de la résine aqueuse comprend une résine non ionique et/ou cationique représentée par la formule (1) [dans laquelle R1 et R2 représentent indépendamment un groupe représenté par la formule : -(R)m-X (dans laquelle R représente un groupe alkylène ayant de 1 à 6 atomes de carbone ; m représente 1 ou 0 ; et X représente un atome d'hydrogène, un groupe carboxyle, un groupe hydroxyle, ou un groupe acyle)] et contenant, dans son squelette de polymère, un groupe azoté capable d'être lié à l'ion Bi pour former un chélate.
PCT/JP2010/005523 2009-09-14 2010-09-09 Composition pour le traitement d'une surface métallique, procédé de traitement d'une surface métallique utilisant la composition, et film de revêtement de traitement d'une surface métallique produit au moyen de la composition ou du procédé WO2011030549A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2013011790A1 (fr) * 2011-07-19 2013-01-24 日本パーカライジング株式会社 Composition aqueuse pour le traitement des surfaces métalliques, procédé de traitement des surfaces métalliques l'utilisant, procédé de production d'un matériau métallique portant un film, et film pour le traitement des surfaces métalliques associé
WO2017187900A1 (fr) * 2016-04-25 2017-11-02 日東化成株式会社 Composition d'enrobage par électrodéposition et son procédé de fabrication

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