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WO2006043727A1 - Agent servant à traiter la surface d'un métal, procédé de traitement de la surface d'une matière métallique et matière métallique traitée en surface - Google Patents

Agent servant à traiter la surface d'un métal, procédé de traitement de la surface d'une matière métallique et matière métallique traitée en surface Download PDF

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Publication number
WO2006043727A1
WO2006043727A1 PCT/JP2005/019837 JP2005019837W WO2006043727A1 WO 2006043727 A1 WO2006043727 A1 WO 2006043727A1 JP 2005019837 W JP2005019837 W JP 2005019837W WO 2006043727 A1 WO2006043727 A1 WO 2006043727A1
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WO
WIPO (PCT)
Prior art keywords
cationic
metal
compound
mass
metal surface
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/019837
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English (en)
Japanese (ja)
Inventor
Kenichiro Oshita
Munenori Tanaka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2004308499A external-priority patent/JP2006118012A/ja
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to CN2005800363396A priority Critical patent/CN101048476B/zh
Publication of WO2006043727A1 publication Critical patent/WO2006043727A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • Metal surface treatment agent Description Metal surface treatment agent, surface treatment method for metal materials, and surface treatment metal materials
  • the present invention provides a sheet coinole made of a metal material, excellent corrosion resistance and excellent alkali resistance on the surface of a molded product, and, in some cases, excellent blacking resistance and excellent yellowing resistance, and does not contain chromium.
  • the present invention relates to a metal surface treatment agent used for forming a film, a metal surface treatment method, and a surface-treated metal material. More specifically, the present invention is excellent in molded products, forged products, sheet coils, etc., such as automobile bodies, automobile parts, building materials, and home appliance parts made of zinc-based steel sheets, steel sheets, and aluminum-based metallic materials.
  • the present invention relates to a surface-treated metal material.
  • Metallic materials such as sub-metallic steel plates and steel plates are corroded and oxidized by oxygen, moisture, and ions contained in the moisture. In addition, it may be washed with an alkaline degreasing agent after molding, and if it is not durable against Al force, it will discolor or corrode early under use.
  • the phenomenon that the inset steel material appears to turn black in a specific environment at high temperature and high humidity is caused by the deterioration of the metal material of the inset layer, and when incorporated into various products. It is regarded as a problem from the viewpoint of quality and design.
  • a metal material surface is brought into contact with a chromium-containing treatment solution such as chromate chromate to deposit a chromate film, or it is applied and dried to the metal surface.
  • a chromium-containing treatment solution such as chromate chromate
  • these inorganic chromate films alone provide short-term protection in a relatively mild environment.
  • the corrosion resistance over a long period or in a harsher environment is insufficient.
  • the formed film is hard, brittle, and lacks lubricity. The problem is that the material is cracked and cracked.
  • a two-layer process is performed in which a chromate film is formed on the surface of a metal material, and a resin film is further formed on the formed chromate film.
  • the chromate film has insufficient performance, and the treatment liquid contains harmful hexavalent chromium. Therefore, wastewater treatment is costly, and the formed film also contains 6 Because it contains chromium, it tends to be avoided from the environmental and safety aspects.
  • a polymer composition for surface treatment of a metal material containing a phenol resin polymer having a specific structure and an acidic compound and a surface treatment method JP-A-7- 2 7 8 4 10
  • a metal surface treatment agent excellent in fingerprint resistance and the like which contains two or more silane coupling agents having a reactive functional group having a specific structure which is different from each other and capable of reacting with each other
  • a treatment method Japanese Patent Laid-Open No.
  • a metal surface treatment agent containing a specific structure silane coupling agent and a phenol resin polymer having a specific structure a metal surface treatment agent containing at least one nitrogen atom-containing epoxy polymer, acrylic resin, urethane resin, etc. and a specific polyvalent cation.
  • Method and treated metal material Japanese Patent Laid-Open No. 10-178089
  • Antifungal agent containing bisphenol A epoxy resin of specific structure (2) Phenolic resin and other polyesters, etc.
  • a processing method using (1) and (2), and a processed metal material Japanese Patent Laid-Open No.
  • the treatment liquid does not contain hexavalent chromium, but the corrosion resistance is insufficient, and the corrosion resistance of the scratched and processed parts is particularly inferior to that of the chromate film.
  • blackening resistance also has the disadvantage that 'I ⁇ bioactivity is insufficient under high temperature and humidity.
  • resin films generally have the property of turning yellow or brown under the influence of heat (yellowing), and have the drawback of being discolored due to the heat generated during press processing during welding. is doing. Therefore, at present, non-chromate metal surfaces that form a film that can simultaneously provide excellent corrosion resistance, alkali resistance and blackening resistance, and even better yellowing resistance in some cases on the surface of metal materials. No treatment agent has been obtained. Disclosure of the invention
  • the present invention has been made to solve the problems of the prior art, and has excellent corrosion resistance and excellent alkali resistance in metal materials, and in some cases, excellent blackening resistance and excellent yellow resistance. It aims at providing the metal surface treatment agent which does not contain chromium used for providing modification
  • the present inventors have found that a cationic water-soluble or aqueous emulsion urethane resin, a phenolic compound, and a vinyl compound. Excellent corrosion resistance by treating the surface of metal materials with a polycondensate with aldehydes, cationic ones, and aqueous surface treatment agents containing zirconium compounds and / or titanium compounds as essential components.
  • the film has excellent blackening resistance in addition to the above-mentioned characteristics.
  • the present invention has been completed by finding that it can be imparted.
  • the present invention provides: (1) a cationic water-soluble or aqueous emulsion resin (A) (hereinafter referred to as a cationic urethane resin (A)), a polycondensate of a phenol compound and an aldehyde, (B) (hereinafter referred to as a cationic phenol polycondensate (B)), and a zirconium compound and / or a titanium compound (C) (hereinafter referred to as a metal compound (C)) in an aqueous medium
  • A cationic water-soluble or aqueous emulsion resin
  • A a cationic urethane resin
  • B a polycondensate of a phenol compound and an aldehyde
  • C zirconium compound and / or a titanium compound
  • a metal compound (C) hereinafter referred to as a metal compound (C)
  • the metal compound (C) is a zirconium compound, and Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo
  • the metal surface treating agent according to the above (1) which contains a compound (D) containing at least one metal selected from (hereinafter referred to as a metal compound (D)).
  • a metal compound (D) containing at least one metal selected from
  • the metal compound (C) is a titanium compound, and Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo
  • the metal surface treating agent may be at least one acid component (E) (hereinafter referred to as an acid) selected from inorganic acids and organic acids.
  • Component (E)) is preferably contained, whereby the corrosion resistance and blackening resistance of the formed skin film are further improved.
  • the metal surface treatment agent of the present invention preferably contains a vanadium compound (F), whereby the corrosion resistance and alkali resistance of the formed film are further improved.
  • the present invention also includes forming a film on the surface of the metal material by applying the metal surface treatment agent according to the above aspect (1), (2) or (3) to the surface of the metal material and then drying.
  • the present invention relates to a surface treatment method for a metal material, and a metal material having a film formed by using the surface treatment method.
  • “Cationic” in the cationic urethane resin (A) ie, cationic water-soluble or aqueous emulsion urethane resin (A)) to be blended in the metal surface treatment agent of the present invention is the molecular structure. It means having a cationic functional group inside. Such cationic functional groups include the following general formula (I), (11), (III) or (IV)
  • R 1 R 2 , R 3 , R 6 , and R 7 are each independently a hydrogen atom, carbon number:! ⁇ 10, preferably:! ⁇ 6 linear or branched alkyl group or 1 to 10 carbon atoms, preferably 1 to 6 linear or branched hydroxyalkyl groups, and R 4 and R 5 independently of each other are 2 to 10 carbon atoms, preferably 2 to 6 linear or branched A branched chain alkylene group, and A— and B_ represent a hydroxide ion or an acid ion).
  • the amount of such a cationic functional group is a cationic urethane resin.
  • (A) is an amount that can stably exist in a dissolved or dispersed state in the metal surface treating agent of the present invention, it is sufficient.
  • R 1 R 2 , R 3 , R 6 and R 7 represent an alkyl group having 1 to 10 carbon atoms as a methyl group , Ethyl group, propyl group, isopropyl group, butinole group, isoptinole group, pentinole group, hexyl group, heptyl group, octyl group, noninore group, decyl group, etc.
  • ⁇ 10 hydroxyalkyl groups include: hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6- Examples include a hydroxyhexenole group, a 7-hydroxyheptyl group, an 8-hydroxyoctyl group, a 9-hydroxynonyl group, and a 10-hydroxydecyl group.
  • the alkylene group having 2 to 10 carbon atoms represented by R 4 and R 5 includes ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethyle Group, octamethylene group, 2-ethylhexylene group, decamethylene group, etc. It is done.
  • the ions represented by A- and B- include halogen ions (chlorine ions, bromine ions, fluorine ions, etc.), sulfate ions, nitrate ions, phosphate ions. Inorganic acid ions such as acetate ions, and organic acid ions such as acetate ions and formate ions.
  • the cationic urethane resin (A) used in the present invention is water-soluble or water-based emulsion.
  • the cationic urethane resin (A) used in the present invention needs to have a cationic functional group as described above.
  • the cationic functional group contains a cationic phenolic polycondensate (B) (that is, , Polycondensates of phenolic compounds and aldehydes that are cationic (B)) and compounds (C) (ie, zirconium compounds and / or titanium compounds (C)) and metal compounds ( D) (i.e., containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo) Contributes to compatibility with compound (D)).
  • B cationic phenolic polycondensate
  • C ie, zirconium compounds and / or titanium compounds
  • D metal compounds
  • the solubility or dispersibility of the force thione urethane resin (A) in water may be achieved based on the self-solubility or self-dispersibility of the resin in water, and a cationic surfactant (eg, alkyl It may be achieved with the help of quaternary ammonium salts, etc.) and / or nonionic surfactants (eg alkylphenyl ethers, etc.).
  • a cationic surfactant eg, alkyl It may be achieved with the help of quaternary ammonium salts, etc.
  • nonionic surfactants eg alkylphenyl ethers, etc.
  • the cationic urethane resin (A) is a urethane resin that is a polycondensation product of polyols such as polyols, polyether polyols, and polyester polyols with aliphatic, alicyclic, or aromatic polyisocyanates.
  • a urethane resin obtained by using a polyol having a (substituted) amino group or a polyol having a nitrogen atom in the main chain as a part of the polyol used, and a quaternizing agent for the nitrogen atom of the urethane resin And 4th grade urethane resin.
  • polyol for example, ethylene glycol, diethylene glycolol, triethyleneglycolanol, 1,2-propylene glycolanol, 1,3 monopropylene glycol, neopentino glycol, 1,2-butylene glycol, 1,3 1-butylene glycol monoole, 1,4-butylene glycolenole, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylonorepro Bread, 1,2-propanediol, 1,3-propanediole, 2-methinole 1,
  • polyether polyol for example, ethylene oxide adducts such as ethylene dalycol, diethylene glycol and triethylene glycol, propylene oxide adducts such as propylene glycolate, dipropylene glycolate and tripropylene glycolate, Examples thereof include ethylene oxide and Z or propylene oxide adducts of the above polyols, polytetramethylene glycol and the like.
  • polyester polyol for example, a direct esterification reaction between the polyol and an ester-forming derivative such as a polyvalent carboxylic acid or an anhydride thereof, a halide or an ester, which is less than the stoichiometric amount, and / or Or obtained by ester exchange reaction; obtained by ring opening of lactone with the above polyol; polycarbonate polyol and the like.
  • an ester-forming derivative such as a polyvalent carboxylic acid or an anhydride thereof, a halide or an ester, which is less than the stoichiometric amount, and / or Or obtained by ester exchange reaction; obtained by ring opening of lactone with the above polyol; polycarbonate polyol and the like.
  • polycarboxylic acids examples include oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipine Acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid Aliphatic dicarboxylic acids such as acid, dimer acid and hydrogenated dimer acid; Cyclohexane dicarboxylic acid and other alicyclic dicarboxylic acids; phthalic acid, isophthalic acid and terephthalic acid.
  • Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid; And tricarboxylic acids such as acid, trimesic acid, and a trimer of castor oil fatty acid; and tetracarboxylic acids such as pyromellitic acid.
  • ester-forming derivatives include acid anhydrides of these polyvalent carboxylic acids; halides of the polyvalent carboxylic acids, halides such as bromides, etc .; methyl esters, ethyl esters, propyl esters, isopropinoles of the polyvalent carboxylic acids.
  • Examples thereof include lower aliphatic esters such as estenole, petitenore estenole, isobutino les enore, and aminoester. Lactones such as ⁇ -force prolacton, ⁇ -force prolacton, £ -force prolacton, dimethinole f -turnip ratataton, ⁇ -valerolactone, y-valerolactone, ⁇ -butyrolacton, etc. Can be mentioned.
  • the (substituted) polyol having an amino group or the polyol having a nitrogen atom in the main chain is represented by the following general formula (V) or (VI) R 1 ⁇ 2
  • R ⁇ R 2 , R 4 , R 5 and R 6 have the same meaning as defined in the general formulas (I) and (III), and R 8 has 2 to 10 carbon atoms, preferably 2 to 6 represents a straight chain or branched chain alkylene group, and one NRiR 2 group is substituted on any carbon thereof.
  • Specific examples of powerful polyols include N, N-dimethylaminodimethylolpropane, N-methyl-N, N-diethanolamine and the like.
  • R 3 C 1, R 3 Br, R 7 C 1, R 7 Br (where R 3 and R 7 are in general formulas (II) and (IV)) Synonymous).
  • the aliphatic, alicyclic or aromatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate. Sulfonate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-sucrose xylene diisocyanate, 4, 4'-dicyclohexyl, isophorone diisocyanate, 3, 3 ' —Dimethoxy 4, 4 '—Biphenoxy diisocyanate, 1,5-Naphthalene diisocyanate, 1,5-Tetrahydronaphthalene diisocyanate, 2,4—Tolylene diisocyanate 2, 6-tolylene diisocyanate, 4, 4, — diphenylmethane diisocyanate.
  • Isocyanate ester hydrogenated xylylene diamine, xylene diisocyanate to 1,4-sic, 4,4,1 dicyclohexylenomethane diisocyanate, 2,4,2-dicyclohexylenomethane diisocyanate
  • an aliphatic or alicyclic polyisocyanate compound such as isophorone diisocyanate
  • the resulting film is preferably excellent in weather resistance.
  • soap-free products that do not use a surfactant as a solubilizer or emulsifier that may adversely affect the adhesion of the film to the metal material and the water resistance of the film Some are more preferred to use less.
  • the weight average molecular weight of the cationic urethane resin (A) is preferably 1,000 to 1,000,000, and more preferably 2,000 to 500,000. When the molecular weight is less than 1,000, the film-forming property is insufficient. On the other hand, when the molecular weight exceeds 1,000,000, the stability of the treatment agent tends to decrease.
  • “Cationic” in (B) means having a cationic functional group.
  • Examples of strong cationic functional groups include the above general formula (I) or (II) Can be mentioned.
  • the cationic phenol polycondensate (B) may have at least one of such cationic functional groups.
  • These cationic functional groups coexist with ammonia or amine corresponding to the cationic functional group represented by the general formula (I) when, for example, polycondensation of a phenolic compound and aldehydes. If necessary, it can be introduced by quaternizing the nitrogen atom with a quaternizing agent.
  • the ratio of the cationic functional group contained in the cationic phenol polycondensate (B) is preferably 0.2 to 3 per benzene ring contained in the cationic phenol polycondensate (B). . If the above numerical value is less than 0.2, the stability of the metal surface treatment agent tends to decrease, and if it exceeds 3, the corrosion resistance of the formed film tends to decrease.
  • the cationic phenol polycondensate (B) used in the present invention is preferably a novolac type phenol polycondensate obtained by carrying out the above polycondensation reaction in the presence of an acidic catalyst.
  • the cationic phenol polycondensate (B) used in the present invention is the same as the above-mentioned novolak type phenol polycondensate that is boron-modified, kaen-modified, phosphorus-modified, heavy-metal-modified, nitrogen-modified, and nitrogen-modified. It may be modified by a known method such as oil modification or rosin modification.
  • the phenolic compound used to obtain the cationic phenolic polycondensate (B) used in the present invention is an acidic catalyst and an ammonia or amine amine corresponding to the cationic functional group represented by the general formula (I). It is not particularly limited as long as it can be polycondensed with aldehydes in the presence to form a cationic phenol polycondensate (B).
  • Such phenolic compounds include, for example, phenol, m_cresol, m-ethylphenol, m-propylphenol, m-butynolephenol, p-petitenolevenore, o-petitenoenoenore, resonoresinore, Nodroquinone, Force Teconole, 3-Methoxyphenol, 4-Methoxyphenol, 3-Methinore force Tecol, 4-Methylcatechol, Methylhydroquinone, 2-Methylresorcinol, 2, 3-Dimethylhydroquinone, 2, 5-Dimethylresorcinol, 2-Ethoxyphenol, 4-Ethoxyphenol, 4-Ethynoresolezinores, 3-Ethoxy-4-Methoxyphenol, 2-Propylphenol, 2-Isoisophenol Propinolevenore, 3-Isopropinolephenol, 4-Isopropino Fuweno Nore, 3, 4, 5—Trimethinolephenol,
  • Feno Monore o-Crezo Nore
  • m-Crezo Nole m-Crezo Nole
  • p-Tale Zonole Bisphenol Enore A, 2, 3 xylenol, 3, 5— Xylenol, m-Puchinolehuenol, p_Butinolehuenore, 0-Butinolehuenore, 4
  • Nonole and resornoresinol are preferred, and phenol and bisphenol A are most preferred.
  • the aldehydes used to obtain the cationic phenolic polycondensate (B) used in the present invention are an acidic catalyst and an amine or an amine corresponding to the cationic functional group represented by the general formula (I).
  • aldehydes include, for example, formaldehyde, trioxane, furfural, noraldehyde aldehyde, benzaldehyde, methyl hemiformer nore, ethenole hemihonole meranore, pouch pinole hemihoneno meranore, fuchno les hemihonole mer de sol, fohe les Propyl aldehyde, phenylacetaldehyde, ⁇ -phenyl pill aldehyde, ⁇ -phenyl pill aldehyde Dehydride, o-Hydroxybenzaldehyde, m-Hydroxybenzaldehyde, p-Hydroxybenzaldehyde, o-Black Bendealdehyde, o-Nitrobensaldehyde, m-Nitro Bens aldehyde, p-nitrobenzenes aldeh
  • formaldehyde normal formaldehyde, furfural, benzaldehyde, and salicylaldehyde are preferable, and formaldehyde and paraformaldehyde are most preferable.
  • Examples of the amine used to obtain the cationic quinol-based polycondensate (B) used in the present invention include monomethylamine, dimethinoreamine, trimethinoreamine, monoethinoreamine, jetylamine, triethylamine, isopropylamine, diisopropinole.
  • the quaternizing agent As the quaternizing agent, the quaternizing agent described in the production of the cationic urethane resin (A) can be used.
  • the acidic catalyst used for obtaining the cationic phenol-based polycondensate (B) used in the present invention is not limited to the following examples.
  • hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, sulfur Acid, butyric acid, lactic acid, benzenesulfonic acid, p-toluenesulfonic acid, tartaric acid, boric acid, etc. or salt with metal such as zinc or zinc acetate Can be used. These may be used alone or in combination of two or more.
  • the number average molecular weight of the cationic phenolic polycondensate (B) used in the present invention is preferably in the range of 1,000 to 1,000,000, and in the range of 2,000 to 100,000. More preferred. If the number average molecular weight is less than 1,000, the barrier properties (denseness) of the formed film will be inferior, and the corrosion resistance and alkali resistance will tend to decrease. If the number average molecular weight exceeds 1,000,000, the liquid surface treatment of this metal surface treatment agent will be stable. May be impaired.
  • the metal compound (C) (that is, the zirconium compound and / or the titanium compound (C)) contained in the metal surface treating agent of the present invention is zirconium, titanium oxide, hydroxide, complex compound, inorganic It is preferably a salt with an acid or an organic acid and having good compatibility with the cationic urethane resin (A) and the cationic phenol polycondensate (B).
  • Metal surface treatment agent of the present invention comprising the above-described cationic urethane resin (A), cationic phenol-based polycondensate (B) and metal compound (C) (as described above, the present invention of this embodiment
  • the coating obtained by coating the surface (referred to as aspect (1)) on the metal surface has excellent corrosion resistance and excellent alkali resistance.
  • zirconium In addition, select from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo.
  • the compound (D) containing at least one kind of metal hereinafter referred to as the metal compound (D)
  • the aspect of the present invention in this case is referred to as aspect (2) as described above.
  • the blending ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is expressed as (A):
  • the metal surface treatment agent of the present invention (that is, the embodiment (1)) comprising the cationic urethane resin (A), the cationic phenol polycondensate (B), and the metal compound (C) described above.
  • the metal surface treatment agent on a metal surface has excellent corrosion resistance and excellent alkali resistance.
  • a metal compound in this metal surface treatment agent, a metal compound
  • (C) uses a titanium compound and further contains at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo Compound (D) (that is, metal compound (D)) to be blended, and the mixing ratio of the force and cationic urethane resin (A) to the cationic phenol polycondensate (B) is defined as the solid mass ratio.
  • (A): (B) 9 9 ::!
  • ⁇ 50: 50 in addition to excellent corrosion resistance and excellent alkali resistance, excellent blackening resistance and excellent yellowing resistance can be imparted to the formed film.
  • the aspect of the present invention is referred to as the aspect (3) as described above.
  • Metal compound (D) contained in the metal surface treatment agent of aspects (2) and (3) of the present invention i.e., Li, Mg, Al, Ca, Mn, Co, Ni, Zn,
  • the compound (D)) containing at least one metal selected from Sr, W, Ce and Mo is a salt of the above metal oxide, hydroxide, complex compound, inorganic acid or organic acid. Etc. It is preferable that the resin be compatible with the cationic urethane resin (A) and the cationic phenol polycondensate (B).
  • the metal compound (D) include lithium nitrate, lithium phosphate, lithium lithium, lithium hydroxide, lithium sulfate, lithium carbonate, dilithium oxalate, lithium lithium oxide, magnesium nitrate, Magnesium sulfate, Magnesium carbonate, Magnesium hydroxide, Magnesium fluoride, Anmoem magnesium phosphate, Magnesium hydrogen phosphate, Magnesium oxide, Aluminum nitrate, Aluminum sulfate, Potassium anoleum , Sodium sulfate aluminum sulfate, Aluminum aluminum sulfate, Anoleminum phosphate, Anoleminic carbonate, Aluminum oxide, Aluminum hydroxide, Aluminum iodide, Calcium acetate, Fluorine power Lucium, Calcium phosphinate [ Ca (PH 2 0 2 ) 2 ], cal nitrate Calcium hydroxide, calcium oxalate, calcium oxalate, calcium acetate,
  • Such metal compounds (D) can be used alone or in combination of two or more.
  • Molybdenum (VI) compounds, tungsten (VI) compounds, and manganese (VI) compounds that have been reduced using reducing agents such as alcohols and organic acids can also be used.
  • reducing agents such as alcohols and organic acids
  • the film obtained by applying the metal surface treatment agent of (1) to (3) on the metal surface has excellent corrosion resistance, excellent alkali resistance and, in some cases, excellent blackening resistance and Although it has excellent yellowing resistance, by adding an acid component (E) (that is, at least one acid component (E) selected from inorganic acids and organic acids) to this metal surface treatment agent, The corrosion resistance and blackening resistance of the formed film can be further improved.
  • the inorganic acid as the acid component (E), water-soluble ones can be used.
  • phosphoric acid acids such as hydrofluoric acid, fluorometallic acids such as fluorozirconic acid and fluorotitanic acid, nitric acid and sulfuric acid.
  • the organic acid has a carboxyl group or a sulfone group.
  • acetic acid, propionic acid, oxalic acid, tartaric acid, malic acid, darconic acid, tannic acid, formic acid, ascorbic acid and the like can be used.
  • These acid components (E) can be used alone or in combination of two or more. Of these, hydrofluoric acid, nitric acid, sulfuric acid, and phosphoric acid are particularly preferred.
  • the acid component (E) is mainly responsible for etching the surface of the metal material when the metal surface treatment agent of the present invention and the metal material are in contact with each other. Corrosion resistance and film adhesion
  • Nitric acid in particular has the effect of further improving blackening resistance under high-humidity conditions.
  • the acid component (E) further improves the liquid stability of the metal surface treating agent of the present invention.
  • the corrosion resistance and alkali resistance of the formed film can be further improved.
  • a pentavalent, tetravalent or trivalent vanadium compound having an acid number of nonadium can be used, for example, vanadium pentoxide V 2 0 5 , metavanadate HV 0 3 , Ammonium metavanadate, Sodium metavanadate, Vanadium trichloride VOC 1 3 and other pentavalent vanadium compounds; Vanadium triacid V 2 0 3 , Vanadium diacid V0 2 , Oxysulfuric acid Vanadium voso 4 ⁇ Vanadium oxycetyl acetate v ⁇
  • vanadium trichloride VC 1 3 vanadium trichloride VC 1 3
  • phosphovanadomo budenic acid H 15 — x [ PV 12. X M o x O 40] ⁇ n H 2 0 (6 ⁇ x ⁇ 12, n rather 30) oxidation number trivalent, etc., or tetravalent vanadium compounds.
  • These vanadium compounds can be used alone or in combination of two or more.
  • the metal surface treatment agent according to the above aspects (1) to (3) of the present invention contains a trivalent or tetravalent vanadium compound having an acid number as the vanadium compound (F). It is preferable from the viewpoint of maintaining corrosion resistance and alkali resistance. That is, the proportion of trivalent or tetravalent vanadium compound in the vanadium compound (F) is (V 3+ + V 4+ ) / V (where V 3+ and V 4 ⁇ V are respectively Number of acids in vanadium compound (F) Mass of trivalent vanadium, oxidation number of tetravalent vanadium, total vanadium ) Is preferably from 0.1 to 1.0, more preferably from 0.2 to 1.0, and most preferably from 0.4 to 1.0.
  • Examples of the method for incorporating the trivalent or tetravalent vanadium compound in the metal surface treatment agent according to the above aspects (1) to (3) of the present invention include the use of the trivalent or tetravalent vanadium compound as described above.
  • a pentavalent vanadium compound that has been previously reduced to trivalent or tetravalent using a reducing agent can be used.
  • the reducing agent to be used may be either inorganic or organic, but is preferably organic.
  • alcohols such as methanol, ethanol, isopropanol, and ethylene dallicol
  • aldehydes such as formaldehyde, acetoaldehyde, furfural, etc.
  • Carbonyl compounds such as acetylylaceton, acetoacetate, dipivaloylmethane, 3-methylpentanedione; formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, gnoreconic acid, citrate, malic acid
  • Organic acids such as: Triethylamine, Triethanolamine, Ethylenediamine, Pyridine, Imidazo ⁇ Pyro-monorephorin, Piperazine, Amamine compounds: Formamide, Acetamide, Propionamide, ⁇ -Methylpropionamide, etc.
  • Acid amide compound Amino acids such as lysine, alanine, pyrroline and glutamic acid; monosaccharides such as glucose, mannose and galactose; natural polysaccharides such as maltose, sucrose, starch and cellulose; aminotri (methylene phosphonic acid) Drokishylidene 1,1'-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), organic phosphoric acid such as phytic acid; natural polymers such as gallic acid, tannic acid, humic acid, lidanesulfonic acid, polyphenol; poly Examples include synthetic alcohols such as butyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyethyleneimine, and water-soluble naphthalene; and aminocarboxylic acids such as ED ⁇ .
  • Amino acids such as lysine, alanine, pyrroline and glutamic acid
  • monosaccharides such as glucose, mannose and galact
  • the organic reducing agent not only has the effect of reducing the vanadium compound, but also significantly improves the stability of the vanadium compound in the treatment liquid, and the metal surface treatment according to the above aspects (1) to (3) of the present invention.
  • the excellent corrosion resistance imparting effect of the agent can be maintained for a long time.
  • the organic reducing agent is effective in forming a uniform film, it can be expected to improve the corrosion resistance.
  • the amount of each component used in the metal surface treatment agent according to embodiments (1) to (3) of the present invention will be described.
  • the mixing ratio between the cationic raw urethane resin (A) and the cationic phenolic polycondensate (B) is the solid mass.
  • the blending ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) blended in the metal surface treatment agent is the solid mass.
  • the above ratio is
  • (A): (B) 90: It is preferable that it is 10-60: 40.
  • the blending ratio of the cationic phenol polycondensate (B) is less than 99: 1, the corrosion resistance of the formed film tends to be insufficient.
  • the cationic phenol polycondensate (B) When the blending ratio of exceeds 50:50, yellowing resistance becomes insufficient.
  • the compounding amount of the metal compound (C) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass as a metal (zirconium and / or titanium).
  • the compounding amount of the metal compound (C) is within the above range, sufficient corrosion resistance and liquid stability can be ensured.
  • the total solid content of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) contained in the metal surface treatment agent of the embodiments (2) and (3) of the present invention is 1
  • the metal compound (D) that is, at least one selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo
  • the compounding amount of the compound (D)) containing the metal is preferably 0.01 to 10 parts by mass as the metal (the metal as a whole when two or more metals are included). More preferably, it is 5 parts by mass.
  • the above compounding amount of the metal compound (D) is 0.0.
  • the amount is less than 1 part by mass, blackening resistance cannot be imparted to the metal surface, and if it exceeds 10 parts by mass, the barrier properties (denseness) of the skin will decrease and the corrosion resistance will tend to decrease.
  • An acid component (E) as an optional component is blended with the metal surface treatment agent of aspects (1) to (3) of the present invention.
  • the acid component itself containing no water is 1-30.
  • the amount is preferably part by mass, more preferably 5 to 20 parts by mass.
  • the content of the acid component (E) is less than 1 part by mass, the etching action on the metal surface becomes insufficient, and as a result, the adhesion between the metal material and the film is inferior, and the corrosion resistance tends to decrease.
  • the content of the acid component (E) exceeds 30 parts by mass, the etching action becomes excessive, and it becomes difficult to form a uniform film, and each performance such as corrosion resistance and blackening resistance tends to decrease. .
  • the blending amount thereof includes the cationic urethane resin (A) and the force thione phenol.
  • the vanadium is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass. If the content of the vanadium compound (F) is less than 0.01 part by mass, the effect of the vanadium compound (F) to further improve the corrosion resistance and the alkali resistance is not exhibited. The barrier property (denseness) is lowered, and the corrosion resistance and alkali resistance tend to be rather impaired.
  • the metal surface treatment agent according to the embodiments (1) to (3) of the present invention includes polyolefin wax, ester-based soot, hydrocarbon-based soot, etc. Arrange at least one selected from water-based wax Can be combined.
  • the amount is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass as a solid content.
  • a silane coupling agent can be blended with the metal surface treatment agents of the embodiments (1) to (3) of the present invention.
  • the type of the silane coupling agent is not particularly limited.
  • a silane coupling agent Is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass as a solid content.
  • the aqueous medium used in the metal surface treatment agents of embodiments (1) to (3) of the present invention is usually water, but a small amount (for example, 10% by volume or less of the entire aqueous medium) for the purpose of improving the drying property of the film. ) Alcohols, ketones, and cellosolve water-soluble organic solvents may be used in combination.
  • surface active agents, antifoaming agents, leveling agents, antibacterial and antifungal agents, coloring agents, and the like are included within the range that does not impair the liquid stability and film ⁇ viability of the metal surface treatment agent of the present invention.
  • the lower limit of the total solid content concentration of the metal surface treatment agents of aspects (1) to (3) of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but the upper limit is liquid stable. Limited in terms of sex.
  • the total solid concentration of the metal surface treatment agent of the present invention is preferably adjusted to a range of 0.1 to 40% by mass, more preferably adjusted to a range of 1 to 30% by mass, and 5 to 25. It is most preferable to adjust to the mass% range.
  • the metal surface treatment agent and the surface treatment method according to aspects (1) to (3) of the present invention are suitable for steel sheets such as extended steel sheets, carbon steel sheets, and key steel sheets, plating steel sheets, and aluminum-based metal materials.
  • the steel plate include zinc-containing plating steel plates that have been subjected to plating treatment such as electrogalvanizing, hot-dip galvanizing, 55% aluminum galvanizing, 5% aluminum galvanizing, aluminum plating, and iron-zinc plating.
  • the aluminum-based metal material includes a metal material mainly composed of aluminum or aluminum alloy such as pure aluminum material, aluminum alloy material, and aluminum die-cast material.
  • pretreatment step prior to the treatment with the metal surface treatment agent of aspects (1) to (3) of the present invention there is no particular limitation on the pretreatment step prior to the treatment with the metal surface treatment agent of aspects (1) to (3) of the present invention. Usually, however, oil and dirt adhering to the metal to be treated before this treatment are removed. In order to remove it, perform washing with alkaline degreasing agent or acidic degreasing agent, washing with solvent, washing with solvent, etc., and then adjust the surface with acid or alkali as necessary. In cleaning the surface of the metal material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the metal material.
  • the treatment with the metal surface treatment agent according to embodiments (1) to (3) of the present invention is performed by applying the metal surface treatment agent and then drying.
  • the solvent of this treatment agent is mainly water
  • the treatment liquid temperature is preferably 0 to 60 ° C, more preferably 5 to 40 ° C.
  • the hardening of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is performed. If it is only necessary to remove the adhering water without promoting Although it is not necessary, it may be air-dried or physically removed by air blow, etc., but it accelerates the curing of cationic urethane resin (A) and cationic phenolic polycondensate (B) or has a coating effect by softness. In order to increase the temperature, it is necessary to heat and dry. In this case, the temperature is preferably 50 to 250 ° C, more preferably 60 to 220 ° C.
  • the amount of the film formed is preferably 30 to 5,000 OmgZm 2 and more preferably 50 to 3,000 OmgZm 2 as the dry film mass.
  • the dry film mass is less than 3 Omg / m 2 , sufficient corrosion resistance and blackening resistance cannot be obtained, and when it exceeds 5,000 Omg / 2 , adhesion to a metal material can cause yellowing resistance. descend.
  • each component in the metal surface treating agent of (1) to (3) has the following functions, but the present invention is not limited by the following inferences. Not a thing! /.
  • the metal surface treating agent of aspects (1) to (3) of the present invention reacts with the surface of the metal material to form a film having good adhesion in the step of being applied to the metal material and dried, and the resin component is formed into a film. Therefore, it is considered that the material has excellent corrosion resistance.
  • Cationic phenolic polycondensate (B) and metal compound (C) (that is, zirconium compound and / or titanium compound) form a dense three-dimensional structure when applying the treatment agent or in the heat drying process. Then, it forms a film and reacts with and adheres to the metal surface.
  • the acid component (E) is contained in the metal surface treatment agent, so that the etching action is enhanced and the reactivity with the metal surface is further increased, so that a stronger skin film is formed with the metal surface. Formed at the interface.
  • the cationic phenol-based polycondensate (B) contained in the treatment agent of the present invention is a compound having a resonance-stabilized structure, and is a metal compound (C) (that is, a zirconium compound and a titanium or titanium compound).
  • a metal compound (C) that is, a zirconium compound and a titanium or titanium compound.
  • a compound containing Mn, Co, Ni, W, Ce or Mo in the metal compound (D), and the vanadium compound (F) are transition metal compounds.
  • the film formed with the zinc compound (F) reacts and adheres to the metal surface, so that the distance is close enough to overlap with the outer shell orbit of the material metal. It is considered that the surface potential is kept uniform and excellent corrosion resistance (not only the flat part, but also the cut end face and the flawed part) is imparted.
  • a conventional anti-corrosion mechanism of chromate film self-repairing action in which soluble hexavalent chromium is dissolved and re-deposited on the exposed metal surface is generally said.
  • the anti-corrosion mechanism of the chromate film is the same anti-corrosion mechanism as the treatment agent of the present invention due to the high cationogenicity of chromium (high adhesion reactivity to the metal surface) and excellent delocalization action (of corrosion electrons). I think there is.
  • the metal compound (D) forms a basic compound on the surface of the metal substrate, or deactivates the metal substrate surface by modifying the surface of the metal substrate, thereby blackening the metal substrate. To prevent corrosion and improve corrosion resistance.
  • the cationic urethane resin (A) is formed on the film formed on the metal interface (that is, has a two-layer structure) and has an effect of improving the corrosion resistance by increasing the barrier property (denseness). In addition, it has the effect of improving processability.
  • the cationic phenolic polycondensate (B) has an aromatic ring and therefore tends to be discolored by heating.
  • yellowing resistance can be imparted / improved.
  • Electro-galvanized steel sheet (thickness: 0.8 mm)
  • Hot-dip galvanized steel sheet (thickness: 0.8 mm)
  • Polyether polyol (synthesis components: tetramethylene glycol and ethylene glycol, molecular weight 1500) 150 parts by mass, trimethylolpropane 6 parts by mass, N-methyl-N, N-diethanolamine 24 parts by mass, isophorone diisocyanate 94 parts by mass and 13,5 parts by mass of methyl ethyl ketone were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer. Next, 15 parts by mass of dimethyl sulfuric acid was placed in the reaction vessel and reacted at 50 to 60 ° C. for 30 to 60 minutes to produce a cationic uretan prepolymer. Next, 576 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly milked. Then, methyl ethyl ketone was recovered to obtain a water-soluble cationic urethane resin (A1).
  • A1 water-soluble cationic urethan
  • Polyester polyol (Synthetic components: isophthalic acid, adipic acid and 1, 6-hexanediol, ethylene dalycol, molecular weight 1700) 135 parts by mass, trimethylolpropane 5 parts by mass, N-methyl-1-N, N-diethanolamine 22 parts by mass, 86 parts by mass of isophorone diisocyanate and 120 parts by mass of methyl ethyl ketone were placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C. to produce a urethane prepolymer.
  • Polycarbonate polyol (Synthetic components: 1.6 Monohexane carbonate diol, ethylene glycol, molecular weight 2000) 1 30 parts by mass, 4 parts by weight of trimethylol bread, N-methyl-1-N, N-diethanolamine 2 1 part by weight, 75 parts by weight of isophosphonate isocyanate and methyl ethyl ketone 1 1 5 parts by weight are placed in a reaction vessel and reacted for 1 hour while maintaining at 70 to 75 ° C to produce a urethane prepolymer. I let you. Next, 22 parts by mass of dimethyl sulfate was placed in the reaction vessel, and 50 to 6
  • a cationic urethane prepolymer was produced by reacting at 0 ° C. for 30 to 60 minutes. Next, 633 parts by mass of water was placed in the reaction vessel, and the mixture was uniformly emulsified. Then, methyl ethyl ketone was recovered to obtain a water-soluble force thione polyurethane resin (A 3).
  • a 100 OmL flask equipped with a reflux condenser was charged with 1 mol (108 g) of O-taresol and 0.3 g of p-toluenesulfonic acid as a catalyst, and the internal temperature was raised to 100 ° C. 85 mol (69 g) was added over 1 hour and reacted at 100 ° C for 2 hours under reflux. After that, the reaction vessel is allowed to cool in water, and after the aqueous layer separated into the upper layer disappears, the aqueous layer is removed by decantation, and further heated and stirred until the temperature reaches 170 to 175 ° C. The reaction and water were removed.
  • Pulclean 364 S (20 g / L building bath, 60 ° C, 10 seconds spray, spray pressure 0.5 kgZcm 2 ) Rinse for 10 seconds.
  • a metal surface treatment agent (medium: water) adjusted to a solid content concentration of 16% by mass was applied by bar coating so that the dry mass was 100 Omg / m 2 and dried at 150 ° C. (PMT).
  • Evaluation criteria White wrinkle occurrence condition ⁇ Almost no wrinkle, ⁇ Many cross cut parts do not have white wrinkles, ⁇ All cross cut parts are white wrinkles, but there is no flow, X cross cut part A flow trap occurs.
  • Evaluation criteria White wrinkle occurrence condition ⁇ Almost no wrinkle, ⁇ Many white wrinkles are not generated in the processing part, ⁇ All the processing parts are white wrinkles, but there is no flow flaw, flow from the X processing part A wrinkle occurs.
  • the treated plate sample was left in an atmosphere of 70 ° C and 95% humidity for 12 days, and then the appearance was visually observed and evaluated.
  • Tables 1 to 4 show the compositions and treatment methods of the metal surface treatment agents of Examples 1 0 1 to 1: 7 7 and Comparative Examples 1 0 1 to 1 0 5 and Tables 5 to 7 show the test evaluation results.
  • Examples 1 0 1 to 1 4 3 and 1 4 5 to 1 7 7 having a film formed by using the metal surface treatment agent of embodiment (1) of the present invention This metal material has good corrosion resistance, alkali resistance, and yellowing resistance, and is safe because it does not contain harmful chromium, and the flat part, cross-cut part, and processed part are all superior to or better than chromate treatment. It can be seen that it has high corrosion resistance.
  • Example 14 4 in which the ratio of (A) / (B) was (B) Rich was inferior in yellowing resistance, but was excellent in corrosion resistance and alkali resistance.
  • Comparative Example 1 0 3 which does not contain the metal material of Comparative Example 10 2 and the metal compound (C) (that is, a diconium compound and / or a titanium compound),
  • the metal material of Comparative Example 10 4 in which the ratio (A) / ( ⁇ ) was outside the scope of the present invention was clearly inferior in all of corrosion resistance, alkali resistance and yellowing resistance.
  • the metal material of Comparative Example 10 5 treated with cucumber mate (zinc chromium 33 60 ⁇ ) had poor alkali resistance.
  • Treatment method Composition of metal surface treatment agent (mass 0 / o)
  • Example 101 I A1 B1 50/50 C2 (3.0) E2 (26.3) F4 (0.4) 100 1000
  • Example 102 I A1 B1 60/40 Cl (6.0) E3 (14.1), E4 (0.1) Fl (l.2 ) 100 1000
  • Example 103 I A1 B1 70/30 C2 (3.0) E2 (14.1) F2 (0.4) 100 1000
  • Example 104 I A1 B1 90/10 C2 (1.5) El (1.7), E2 (10.5) F2 ( 1.9) 100 1000
  • Example 105 I A1 B1 95/5 C2 (l.5) El (1.7), E2 (ll.7) F2 (0.5) 100 1000
  • Example 106 I A1 B1 99/1 CI (8.2) El (1.7), E2 (19.4) F2 (10.1) 100 1000
  • Example 107 I A1 B1 59/41 C2 (10.7) E2 (17.1), E3 (2.5) F4 (0.4) 100 1000
  • Example 108 I A1 B1 81 / 19 CI (12.2)
  • composition of the treatment method the metal surface treatment agent (wt 0/0)
  • Example 139 I A3 B1 70/30 C2 (3.0) E2 (9.9) F2 (l.5) 100 1000
  • Example 140 I A1 B2 70/30 C2 (3.0) E2 (9.9) F2 (l.5) 100 1000
  • Example 141 I A1 B3 70/30 C2 (3.0) E 2 (9.9) F2 (l.5 ) 100 1000
  • Example 142 I A1 B1 60/40 CI (1.0) El (1.9), E5 (4.4) F4 (0.5) 100 1000
  • composition of the treatment method the metal surface treatment agent (wt 0/0)
  • Example 143 I A1 B1 60/40 Cl (lO) El (1.9), E5 (4.4) F4 (0.5) 50 2500
  • Example 144 I A1 B1 20/80 C2 (l.2) E2 (5.3) F4 (0.1 ) 100 1000
  • Example 145 I A1 B1 65/35 C4 (2.8) El (l.1), E5 (1.7) Fl (3.7) 100 1000
  • Example 146 I A1 B1 80/20 C3 (12.0) E2 (14.1) F3 (1.7) 100 1000
  • Example 147 I A1 B1 51/49 C4 (0.3) E3 (6.0), E5 (0.4) F3 (1.0) 100 1000
  • Example 148 I A1 B1 65/35 C4 (L 7) E2 ( 9.4) F2 (0.7) 100 1000
  • Example 149 I A1 B1 90/10 C3 (1.5) E2 (26.9) F3 (15.7) 100 1000
  • Example 150 I A1 B1 61/39 C3 (1.0) E1 (1.9), E5 (4.5) F
  • composition of the treatment method the metal surface treatment agent (wt 0/0)
  • Example 163 I A1 B1 65/35 C3 (2.9) E2 (7.6), E4 (9.9) 100 1000
  • Example 164 I A1 B1 61/39 C3 (l.0) E1 (1.9), E5 (4.5) 100 1000
  • Example 165 I A1 B1 90/10 C4 (0.9) El (l.3), E2 (1.4) 100 1000
  • Example 166 I A1 B1 97/3 C4 (l.0) E1 (1.8), E2 (1.3) 100 1000
  • Example 170 I A1 B1 95/5 C3 (0.8) 100 1000
  • Example 172 II A1 B1 80/20 C3 (12.0) E2 (14.1) F3 (l.
  • (A) is a cationic urethane
  • (B) is a cationic phenolic polycondensate
  • (C) is a metal compound (dinoleconium compound and Z or titanium compound)
  • (E) Represents an acid component
  • (F) represents a vanadium compound.
  • * 1 is the solid content ratio (mass ratio)
  • * 2 and * 4 are zirconium and / or titanium and vanadium, respectively, with respect to 100 parts by mass of the total solid content of component (A) and component (B).
  • * 3 is the total content of component (A) and component (B), and is the ratio of the water-free acid component itself to the total solid content of 100 parts by mass
  • Example 138 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 139 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 140 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 141 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 142 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 143 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 144 ⁇ ⁇ ⁇ ⁇ ⁇ X
  • Example 145 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 146 ⁇ ⁇ ⁇ ⁇ ⁇ Example 147 ⁇ ⁇ ⁇ ⁇ ⁇ Example 148 ⁇ ⁇ ⁇ ⁇ ⁇ Example 149 ⁇ ⁇ ⁇ ⁇ ⁇ Example 150 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 151 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 152 ⁇ ⁇ ⁇ ⁇ ⁇ Example 153 ⁇
  • Examples 2 0 1 to 2 5 1 and Comparative Examples 2 0 1 to 2 0 6 show the compositions and treatment methods of metal surface treatment agents in Tables 8 to 10 and Tables 1 1 and 12 show the test evaluation results. .
  • Examples 2 0 1 to 2 5 50 having a coating formed using the metal surface treatment agent of the present invention have corrosion resistance, alkali resistance, and black resistance. Denature and yellowing resistance are good, it does not contain harmful chromium, it is highly safe, and the flat part, cross force part, and processed part have excellent corrosion resistance equivalent to or better than chromate treatment.
  • Example 2 51 in which the ratio of (A) / (B) was (B) Rich was inferior in yellowing resistance, but was excellent in corrosion resistance, alkali resistance and blackening resistance.
  • Comparative Example 2 not including Comparative Example 2 0 2 Comparative Example 2 where the coating does not contain zirconium compound (C) and Comparative Example 2 where the ratio of (A) / (B) is outside the scope of the present invention
  • the coating is at least selected from the metal compounds (D) (i.e., Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo) Comparative Example 2 0 4 containing no compound (D)) containing one kind of metal had insufficient blackening resistance. Further, the metal material of Comparative Example 2 06 treated with chromate (zinc chromium 3 3 60 H) was inferior in alkali resistance.
  • the metal compounds (D) i.e., Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo
  • composition of the treatment method the metal surface treatment agent (wt 0/0)
  • Example 222 I A1 B1 90/10 C2 (l.5) D3 (0.7) F2 (l.9) 100 1000
  • Example 223 I A1 B1 99/1 C1 (8.2) D5 (0.6), D9 (0.4) F2 (10.1) 100 1000
  • Example 224 I A1 B1 60/40 Cl (l.0) D1 (0.7), D5 (0.5) F2 (0.5) 100 1000
  • Example 225 I A1 B1 50/50 C2 (3.0) D4 ( 4.7) E2 (13.2) 100 1000
  • Example 226 I A1 B1 60/40 CI (1.0) D1 (0.7), D5 (0.5) E1 (1.9), E5 (4.4) 100 1000
  • Example 227 I A1 B1 70/30 C2 (3.0) D7 (l.5) E2 (9.9) 100 1000
  • Example 228 I A1 B1 90/10 C2 (1.5) D3 (0.7) El (l.5), E2 (9.5) 100 1000
  • Example 229 I A1 B1 95/5 C2 (l
  • Treatment method Composition of metal surface treatment agent (mass%)
  • Example 243 I A1 B1 60/40 C1 (1.0) Dl (0.7), D5 (0.5) E1 (1.9), E5 (4.4) F4 (0.5) 50 2500
  • Example 44 I A1 B1 80/20 C2 (3.4) D15 (0.3) E2 (14.1), E3 (2.5) F2 (l.5) 100 1000
  • Example 245 I A1 B1 80/20 C2 (6.8) D15 (1.0) F2 (2.l) 100 1000
  • Example 246 I A1 B1 80/20 C2 ⁇ 3.4) D16 (0.3) E2 (14.1), E3 (2.5) 100 1000
  • Example 248 II A1 B1 65 / 35 C2 (2.9) D8 (l.3) E2 (14.3) F4 (0.7) 100 1000
  • Example 249 III A1 B1 65/35 C2 (2.9) D8 (l.3) E2 (14.3) F4 (0.7) 100 1000
  • Example 250 A1 B1 65/
  • (A) is a cationic urethane resin
  • (B) is a cationic phenol polycondensate
  • (C) is a zirconium compound
  • (D) is a metal compound
  • (E) represents an acid component
  • (F) represents a vanadium compound.
  • * 1 is the solid content ratio (mass ratio)
  • * 2, * 3, and * 5 are zirconium, metal, and vanadium for 100 parts by mass of the total solid content of component (A) and component (B), respectively.
  • * 4 indicates the blending ratio (parts by mass) of the acid component itself without water to the total solid content of 100 parts by weight of component (A) and component (B).
  • the * 6 is the ultimate temperature.
  • * 7 Rohn coating was applied to Zinchrome 3360H, a coating material made by Nihon Parkerizing Co., Ltd., so that the amount of chromium deposited was 2 Omg / m 2 and dried at 100 ° C (PMT).
  • Example 201 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 202 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 203 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 204 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 205 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 206 ⁇ ⁇ ⁇ ⁇ O ⁇ ⁇ Example 207 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 208 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 209 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 210 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 211 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 212 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 213 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Example 238 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 239 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 240 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 241 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 242 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 243 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 244 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 245 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 246 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 247 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 248 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 249 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 250 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 251 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Examples 3 0 1 to 3 4 2 and Comparative Examples 3 0 1 to 3 0 6 The composition and treatment method of metal surface treatment agents are shown in Tables 13 to 15 and the test evaluation results are shown in Tables 16 and 17. Show. As is clear from Tables 16 and 17, Examples 3 0 1 to 3 4 2 having a coating formed using the metal surface treatment agent of the present invention have corrosion resistance, alkali resistance, and resistance to corrosion. It has good black and yellowing resistance and is safe because it does not contain harmful chromium, and the flat part, cross-cut part and processed part all have excellent corrosion resistance 3 ⁇ 4fe equivalent to or better than chromate treatment. I understand that.
  • the metal material of Comparative Example 301 in which the film does not contain the cationic urethane resin (A), and the metal material, film in the Comparative Example 302, in which the film does not contain the cationic phenol polycondensate (B).
  • the metal material of Comparative Example 30 3 containing no titanium compound (C), and the ratio of (A) Z (B) is outside the scope of the present invention.
  • the metal material of Comparative Example 3 0 5 is corrosion resistant and alkali resistant. It was clearly inferior in all of blacking resistance and yellowing resistance.
  • the coating is at least one selected from metal compounds (D) (ie, Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo)
  • the metal material of Comparative Example 30 4 which does not contain the compound (D)) containing a seed metal had insufficient blackening resistance.
  • the metal material of Comparative Example 3 06 treated with chromate (zinc chromium 3 360 H) was inferior in corrosion resistance of the processed part after alkaline degreasing.
  • composition of the treatment method the metal surface treatment agent (wt 0/0)
  • Example 301 I A1 B1 65/35 C4 (2.8) Dl (lO) El (l.1), E5 (1.7) Fl (3.7) 100 1000
  • Example 302 I A1 B1 80/20 C3 (12.0) D5 (8.0 ) E2 (14.1) F3 (l.7) 100 1000
  • Example 303 I A1 B1 51/49 C4 (0.3) D6 (2.8) E3 (6.0), E5 (0.4) F3 (1.0) 100 1000
  • Example 304 I A1 B1 65/35 C4 (1.7) D7 (1.4) E2 (9.4) F2 (0.7) 100 1000
  • Example 305 I A1 B1 90/10 C3 (1.5) D4 (0.5) E2 (26.9) F3 (15.7) 100 1000
  • Example 306 I A1 B1 61 ⁇ / 39 C3 (1.0) Dl (0.7), D10 (0.5) El (1.9), E5 (4.5) F3 (0.3) 100 1000
  • Example 307 I A1 B1 90/10 C4 (0.9) D17 (0.2
  • Treatment method Composition of metal surface treatment agent (mass 0 )
  • Example 322 I A1 B1 97/3 C4 (1.0) D17 (0.2) El (l.8), E2 (1.3) 100 1000
  • Example 323 I A1 B1 50/50 C4 (3.0) D6 (0.1), D8 ( l.5) 100 1000
  • Example 324 I A1 B1 65/35 C3 (2.9) D10 (0.7), D11 (0.3) 100 1000
  • Example 325 I A1 B1
  • Treatment method Composition of metal surface treatment agent (mass%)
  • Comparative Example 301 I Only component (A) was removed from the composition of Example 304 100 1000 Comparative Example 302 I Only component (B) was removed from the composition of Example 304 100 1000 Comparative Example 303 I Component from the composition of Example 304 ( 100) Excluding only C 1000 Comparative Example 304 I Excluding component (D) from the composition of Example 304 100 1000 Comparative Example 305 I A1 B1 22/78 C3 (5.5) D15 (5.5) El (2 2), E2 (2. 2) F2 (0. 7) 100 1000 Comparative Example 306 I Chrome * 7
  • (A) is a cationic urethane resin
  • (B) is a cationic phenol polycondensate
  • (C) is a titanium compound
  • (D) is a metal compound
  • (E) is an acid component
  • (F ) Represents a vanadium compound.
  • * 1 is the solid content ratio (mass ratio)
  • * 2 * 3 and * 5 are the total solid content of 100 parts by weight of component (A) and component (B), respectively titanium, metal and Mixing ratio (parts by mass) as vanadium
  • * 4 represents the mixing ratio (parts by mass) as the acid component itself without water with respect to 100 parts by mass of the total solid content of component (A) and component (B).
  • * 6 is the ultimate plate temperature.
  • * 7 Zinc chrome 3360H, a coating chromate made by Nihon Parkerizing Co., Ltd., was roll-coated so that the amount of chromium deposited was 2 OmgZm 2 and dried at 100 ° C (PMT
  • Example 301 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 302 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 303 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 304 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 305 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 306 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 307 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 308 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 309 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 310 ⁇ ⁇ ⁇ ⁇ Example 311 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 312 ⁇ ⁇ ⁇ ⁇ 0 ⁇ ⁇ ⁇ Example 313 ⁇ ® ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 314 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 315 ⁇ ⁇ ⁇ ⁇
  • Example 316 o ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 317 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 318 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 319 ⁇ ⁇ ⁇ ⁇ ⁇ Example 320 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 321 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 322 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 323 ⁇ ⁇ ⁇ o ⁇ ⁇ ⁇ Example 324 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 325 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 326 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 327 000 0 ⁇ ⁇ ⁇ ⁇ ⁇ Example 328 ⁇ ⁇ ⁇ ⁇ ⁇ Example 329 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 330 ⁇
  • Example 338 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 339 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 340 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 341 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Example 342 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Comparative example 301 ⁇ ⁇ X ⁇ XX ⁇ ⁇ Comparative example 302 X ⁇ XX ⁇ ⁇ ⁇ Comparative example 303 XXXXXXXX ⁇ ⁇ Comparative example 304 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ Comparative example 305 ⁇ ⁇ X ⁇ X ⁇ ⁇ X Comparative Example 306 ⁇ ⁇ ⁇ XXX ⁇ ⁇

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Abstract

L'invention concerne un agent servant à traiter des surfaces de métaux lequel comprend un milieu aqueux et, incorporés dans celui-ci, (A) une résine uréthane cationique qui est soluble dans l'eau ou dans une forme d'émulsion aqueuse, (B) un produit de polycondensation cationique obtenu à partir d'un composé phénol et d'un aldéhyde et (C) un composé du zirconium et/ou un composé du titane. Un film de revêtement formé à partir de l'agent de traitement confère d'excellentes résistance à la corrosion et résistance aux alcalis à une matière métallique. Lorsque la proportion de la résine uréthane (A) est supérieure ou égale à celle du produit de polycondensation (B), on peut également conférer une résistance au jaunissement. En incorporant un composé métal (D) contenant un métal spécifique, on peut également conférer une excellente résistance à la coloration en noir. En outre, en incorporant un ingrédient acide (E) et un composé du vanadium (F), on peut parvenir à atteindre une amélioration supplémentaire en termes de performances.
PCT/JP2005/019837 2004-10-22 2005-10-21 Agent servant à traiter la surface d'un métal, procédé de traitement de la surface d'une matière métallique et matière métallique traitée en surface Ceased WO2006043727A1 (fr)

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WO2011080165A1 (fr) * 2009-12-31 2011-07-07 Henkel Ag & Co. Kgaa Composition et solution de traitement de surface pour métaux légers ou alliages de ceux-ci et procédé de traitement de surface
US20130084453A1 (en) * 2010-02-26 2013-04-04 Jfe Steel Corporation Surface treatment agent for zinc or zinc alloy coated steel sheet, zinc or zinc alloy coated steel sheet, and method of producing the steel sheet
CN103451666A (zh) * 2013-09-16 2013-12-18 杨震宇 一种金属清洗剂
WO2014035690A1 (fr) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du lithium, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
WO2014035691A1 (fr) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du molybdène, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
CN104404492A (zh) * 2014-12-24 2015-03-11 湖南金裕化工有限公司 无铬钝化液、制备方法及其使用方法
CN102625818B (zh) * 2009-09-11 2015-03-25 日本帕卡濑精株式会社 用于多层表面处理钢板的粘接层形成用组合物
EP2794955A4 (fr) * 2011-12-23 2015-09-02 Posco Composition de revêtement de conversion, feuille d'acier traitée en surface et son procédé de fabrication
JPWO2016103491A1 (ja) * 2014-12-26 2017-08-24 日本パーカライジング株式会社 どぶ漬け溶融亜鉛メッキ鋼板用塗料、どぶ漬け溶融亜鉛メッキ鋼板の処理方法、表面処理どぶ漬け溶融亜鉛メッキ鋼板の製造方法、および、表面処理溶融亜鉛メッキ鋼板
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

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KR101262497B1 (ko) * 2011-03-28 2013-05-08 주식회사 노루코일코팅 강판의 흑변 방지용 피막 형성 조성물 및 상기 조성물에 의해 피막이 형성된 강판 및 피막 형성방법
JP5707582B2 (ja) * 2011-07-15 2015-04-30 日本パーカライジング株式会社 水系金属表面処理剤及びその処理剤で処理してなる金属材料
CN103254755B (zh) * 2013-05-27 2016-01-27 宝山钢铁股份有限公司 具有优异耐候性、耐蚀性和耐碱性的热镀铝锌钢板及其制备方法和表面处理剂

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CN102625818B (zh) * 2009-09-11 2015-03-25 日本帕卡濑精株式会社 用于多层表面处理钢板的粘接层形成用组合物
WO2011080165A1 (fr) * 2009-12-31 2011-07-07 Henkel Ag & Co. Kgaa Composition et solution de traitement de surface pour métaux légers ou alliages de ceux-ci et procédé de traitement de surface
US20130084453A1 (en) * 2010-02-26 2013-04-04 Jfe Steel Corporation Surface treatment agent for zinc or zinc alloy coated steel sheet, zinc or zinc alloy coated steel sheet, and method of producing the steel sheet
US9512331B2 (en) * 2010-02-26 2016-12-06 Jfe Steel Corporation Surface treatment agent for zinc or zinc alloy coated steel sheet, zinc or zinc alloy coated steel sheet, and method of producing the steel sheet
US9683294B2 (en) 2011-12-23 2017-06-20 Posco Conversion coating composition, surface treated steel sheet, and method for manufacturing the same
EP2794955A4 (fr) * 2011-12-23 2015-09-02 Posco Composition de revêtement de conversion, feuille d'acier traitée en surface et son procédé de fabrication
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
WO2014035691A1 (fr) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du molybdène, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
RU2609585C2 (ru) * 2012-08-29 2017-02-02 Ппг Индастриз Огайо, Инк. Циркониевые композиции для предварительной обработки, содержащие литий, соответствующие способы обработки металлических субстратов и соответствующие металлические субстраты с покрытиями
RU2611610C2 (ru) * 2012-08-29 2017-02-28 Ппг Индастриз Огайо, Инк. Циркониевые композиции предварительной обработки, содержащие молибден, соответствующие способы обработки металлических субстратов и соответствующие металлические субстраты с покрытиями
WO2014035690A1 (fr) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Compositions de prétraitement du zirconium qui contiennent du lithium, procédés associés permettant de traiter des substrats métalliques et substrats métalliques recouverts associés
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
CN103451666A (zh) * 2013-09-16 2013-12-18 杨震宇 一种金属清洗剂
CN104404492B (zh) * 2014-12-24 2017-07-11 湖南金裕化工有限公司 无铬钝化液、制备方法及其使用方法
CN104404492A (zh) * 2014-12-24 2015-03-11 湖南金裕化工有限公司 无铬钝化液、制备方法及其使用方法
JPWO2016103491A1 (ja) * 2014-12-26 2017-08-24 日本パーカライジング株式会社 どぶ漬け溶融亜鉛メッキ鋼板用塗料、どぶ漬け溶融亜鉛メッキ鋼板の処理方法、表面処理どぶ漬け溶融亜鉛メッキ鋼板の製造方法、および、表面処理溶融亜鉛メッキ鋼板
US10435806B2 (en) 2015-10-12 2019-10-08 Prc-Desoto International, Inc. Methods for electrolytically depositing pretreatment compositions
US11591707B2 (en) 2015-10-12 2023-02-28 Ppg Industries Ohio, Inc. Methods for electrolytically depositing pretreatment compositions
US12104272B2 (en) 2015-10-12 2024-10-01 Prc-Desoto International, Inc. Treated substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

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