WO2006043727A1 - Agent for treating metal surface, method of treating surface of metallic material, and surface-treated metallic material - Google Patents

Agent for treating metal surface, method of treating surface of metallic material, and surface-treated metallic material 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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WIPO (PCT)
Prior art keywords
cationic
metal
compound
mass
metal surface
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PCT/JP2005/019837
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French (fr)
Japanese (ja)
Inventor
Kenichiro Oshita
Munenori Tanaka
Original Assignee
Nihon Parkerizing Co., Ltd.
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Filing date
Publication date
Priority claimed from JP2004308499A external-priority patent/JP2006118012A/en
Application filed by Nihon Parkerizing Co., Ltd. filed Critical Nihon Parkerizing Co., Ltd.
Priority to CN2005800363396A priority Critical patent/CN101048476B/en
Publication of WO2006043727A1 publication Critical patent/WO2006043727A1/en

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    • 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

An agent for treating metal surfaces which comprises an aqueous medium and, incorporated therein, (A) a cationic urethane resin which is water-soluble or in an aqueous emulsion form, (B) a cationic polycondensation product obtained from a phenol compound and an aldehyde, and (C) a zirconium compound and/or titanium compound. A coating film formed from the treating agent imparts excellent corrosion resistance and alkali resistance to a metallic material. When the proportion of the urethane resin (A) is equal to or higher than that of the polycondensation product (B), yellowing resistance can be also imparted. By incorporating a metal compound (D) containing a specific metal, excellent blacking resistance also can be imparted. Furthermore, by incorporating an acid ingredient (E) and a vanadium compound (F), a further improvement in performances can be attained.

Description

明 細 書 金属表面処理剤、 金属材料の表面処理方法 及ぴ表面処理金属材料 技術分野  Description Metal surface treatment agent, surface treatment method for metal materials, and surface treatment metal materials
本発明は、 金属を素材としたシートコィノレ、 成形品の表面に優れた耐食性及び 優れた耐アルカリ性、 並びに場合によりさらに、 優れた耐黒変性及び優れた耐黄 変性を付与でき、 力 クロムを含まない皮膜を形成させるために用いる金属表面 処理剤、 金属表面処理方法、 表面処理された金属材料に関する。 さらに詳しくは、 本発明は、 亜鉛系メツキ鋼板、 鋼板、 アルミニウム系金属材料を素材とする自動 車ボディー、 自動車部品、 建材、 家電用部品等の成形加工品、 铸造品、 シートコ ィル等に優れた耐食性及び優れた耐アルカリ性、 並びに場合によりさらに、 優れ た耐黒変性及び優れた耐黄変性を付与し得る、 クロムを含まなレヽ皮膜を形成させ るために用いる表面処理剤、 表面処理方法、 表面処理された金属材料に関する。 背景技術  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. A surface treatment agent used for forming a chromium-containing clay film, a surface treatment method, which can impart excellent corrosion resistance and excellent alkali resistance, and, in some cases, excellent blackening resistance and excellent yellowing resistance, The present invention relates to a surface-treated metal material. Background art
亜 系メツキ鋼板、 鋼板等の金属材料は、 大気中の酸素、 水分、 水分中に含ま れるイオン等によって酸ィヒされ腐食する。 また、 成型加工した後にアルカリ性を 示す脱脂剤により洗浄する場合があり、 アル力リに対して耐久性がないと変色し たり、 使用下で早期に腐食してしまう。 さらに、 高温多湿で特定の環境下におい てはめつき鋼材が黒く変色して見える現象が起こり、 いずれの現象もめつき層金 属材料の劣化に起因するものであり、 様々な製品として組み込まれたときの品質、 意匠性という観点から問題視される。 これらの腐食を防止する方法として、 従来 から、 クロム酸クロメート等のクロムを含有する処理液に金属材料表面を接触さ せてクロメート皮膜を析出させる、 或いは塗布して乾燥させる等して金属表面に クロメート皮膜を形成させる方法がある。 しかしながら、 これらの無機系のクロ メート皮膜単独では、 比較的マイルドな環境下では、 短期的な防鲭性が発揮され るものの、 長期に亘つての或いはより厳しい環境での耐食性は不十分である。 さ らに、 クロメート単独処理を施したシートコイルを切り出して成形力□ェすると、 形成された皮膜が硬質で脆く潤滑性に乏しいため、 皮膜が脱落し外観を損ねるだ けでなく、 十分な加工ができず、 素材に亀裂が生じ割れてしまうという不具合が 生じる。 そこで一般には、 これらすベての性能を満足するためには、 金属材料表 面にクロメート皮膜を形成し、 形成されたクロメート皮膜上に、 さらに樹脂皮膜 を設ける 2層処理が行われている。 また、 クロメート皮膜は性能的に不十分であ るほ力 その処理液中に有害な 6価クロムを有しているため廃水処理に手間ゃコ ストが掛かるほか、 形成された皮膜中にも 6価クロムを含有されているので環境 面、 安全面から敬遠される傾向にある。 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. In addition, 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. As a method of preventing such corrosion, conventionally, 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. There is a method of forming a chromate film. However, these inorganic chromate films alone provide short-term protection in a relatively mild environment. However, the corrosion resistance over a long period or in a harsher environment is insufficient. In addition, when a sheet coil treated with chromate alone is cut out and the forming force is applied, the formed film is hard, brittle, and lacks lubricity. The problem is that the material is cracked and cracked. Therefore, in general, in order to satisfy all of these performances, 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. In addition, 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.
1層処理ですベての性能を満足させようとする試みとしては、 クロメートと樹脂 皮膜とを一度に形成させる樹脂クロメートが検討され、 アルミニウム一亜鉛めつ き鋼板の表面に、 特定の水分散系又は水溶性樹脂と特定量の 6価クロムを配合し た樹脂組成物を塗布する処理方法 （特公平 4— 2 6 7 2号公報） 、 及び無機化合 物の 6価クロムイオン又は 6価クロムイオンと 3価クロムイオン、 及び特定の乳 化重合条件で重合したァクリルェマルジョンを含有する金属表面処理組成物 （特 公平 7— 6 0 7 0号公報） が知られている。 しかしながら、 前述したように、 皮 膜中に含有される 6価クロムは微量ではあるが、 徐々に溶け出す性質を持ってお り、 環境面、 安全面に問題を有している。  As an attempt to satisfy all performance with a single layer treatment, resin chromate that forms chromate and resin film at the same time was studied, and a specific water dispersion system was applied to the surface of the aluminum-zinc plated steel sheet. Or a treatment method of applying a resin composition containing a water-soluble resin and a specific amount of hexavalent chromium (Japanese Patent Publication No. 4-2 6 72), and hexavalent chromium ions or hexavalent chromium ions of inorganic compounds And a trivalent chromium ion, and a metal surface treatment composition containing an acrylic emulsion polymerized under specific emulsion polymerization conditions (Japanese Patent Publication No. 7-600). However, as described above, although the hexavalent chromium contained in the skin is a trace amount, it has the property of gradually leaching and has problems in terms of environment and safety.
クロムを有さないノンクロメート処理液を用いる方法としては、 特定構造のフ ェノール樹脂系重合体と酸性化合物とを含有する金属材料表面処理用重合体組成 物及ぴ表面処理方法 （特開平 7— 2 7 8 4 1 0号公報） 、 互いに異種でかつ互い に反応し得る特定構造の反応性官能基を有する 2種以上のシランカツプリング剤 を含有する耐指紋性等に優れた金属表面処理剤及び処理方法 （特開平 8— 7 3 7 7 5号公報） 、 特定構造のシランカップリング剤と特定構造のフエノール樹脂系 重合体とを含有する金属表面処理剤及ぴ処理方法 （特開平 9— 2 4 1 5 7 6号公 報） 、 少なくとも 1個の窒素原子を有するエポキシ樹脂、 アクリル樹脂、 ウレタ ン樹脂等の有機高分子と特定の多価ァユオンとを含有する金属表面処理剤、 処理 方法及び処理金属材料 （特開平 1 0— 1 7 8 9号公報） 、 （ 1 ) 特定構造のビス フエノール Aエポキシ系樹脂を含有する防鲭剤、 ( 2 ) フエノール系樹脂とそれ 以外のポリエステル等の特定樹脂とを特定比で含有する防鲭剤、 ( 1 ) と （2 ) とを用いる処理方法及び処理金属材料 （特開平 1 0— 6 0 2 3 3号公報） 、 並ぴ に特定構造のフエノール系樹脂化合物と、 バナジウム化合物と、 特定の金属化合 物と、 任意成分としての有機高分子とを含有する金属表面処理剤、 処理方法及び 処理金属材料 （特開 2 0 0 1— 1 8 1 8 6 0号公報） 、 及ぴ特定の水溶性樹脂も しくは水性ェマルジョン樹脂と、 特定構造のフエノール系樹脂化合物と、 特定の 金属化合物とを必須成分とする金属表面処理剤、 処理方法及び処理金属材料 （特 開 2 0 0 3— 1 3 2 5 2号公報） が知られている。 As a method of using a non-chromate treatment liquid not containing chromium, 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 And a treatment method (Japanese Patent Laid-Open No. 8-7 3 7 75), a metal surface treatment agent containing a specific structure silane coupling agent and a phenol resin polymer having a specific structure, and a treatment method 2 4 1 5 7 6)) 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), (1) 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. 10-6023), and a specific structure Metal surface treatment agent, treatment method and treated metal material containing a phenolic resin compound, a vanadium compound, a specific metal compound, and an organic polymer as an optional component 1 8 60)), a metal surface treatment agent comprising a specific water-soluble resin or water-based emulsion resin, a phenol resin compound having a specific structure, and a specific metal compound, a processing method, and Treated metal materials (special issue 2 0 0 3— 1 3 2 5 2 ) It has been known.
しかしながら、 クロムを用いない金属表面処理においては、 処理液が 6価クロ ムを含有しない利点がある反面、 耐食性が不十分で、 特にキズ部、 加工部の耐食 性は、 クロメート皮膜に比べ著しく劣っており、 また、 耐黒変性も高温多湿な環 境下では' I·生能が不十分であるという欠点を有している。 さらに、 一般的に樹脂皮 膜は熱の影響を受け、 黄色や褐色に変色する特性 （黄変性） があり、 溶接時ゃプ レス加工時に発生する熱の影響にて変色してしまう欠点を有している。 したがつ て、 現状では、 金属材料表面に優れた耐食性、 耐アルカリ性及び耐黒変性、 並び に場合によってさらに優れた耐黄変性を同時に付与し得る皮膜を形成するような ノンクロメート系の金属表面処理剤は得られていない。 発明の開示  However, in the metal surface treatment that does not use chromium, there is an advantage that 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. In addition, blackening resistance also has the disadvantage that 'I · bioactivity is insufficient under high temperature and humidity. In addition, 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
本発明は前記従来技術の抱える問題を解決するために成されたものであって、 金属材料に優れた耐食性及び優れた耐ァルカリ性、 並びに場合によってさらに優 れた耐黒変性及び優れた耐黄変性を付与するために用いる、 クロムを含有しない 金属表面処理剤、 金属表面処理方法及び表面処理金属材料を提供することを目的 とする。  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 | denaturation, the metal surface treatment method, and a surface treatment metal material.
本発明者らは、 前記課題を解決する手段について、 鋭意検討した結果、 カチォ ン性の水溶性もしくは水系ェマルジヨンウレタン榭脂、 フエノール系化合物とァ ルデヒド類との重縮合物であってカチオン性のもの、 並びにジルコニウム化合物 及ぴ,又はチタン化合物を必須成分とする水系表面処理剤を用レ、て金属材料表面 を処理することにより、 優れた耐食性及び優れた耐ァルカリ性耐を有する皮膜が 得られること、 及び該水系表面処理剤にさらに他の特定の金属化合物を配合する 場合には、 上記特性に加えさらに優れた耐黒変性を該皮膜に付与し得ることを見 出し、 本発明を完成した。 As a result of intensive studies on the means for solving the above problems, 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 In addition, in addition to the above-mentioned characteristics, 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.
すなわち、 本発明は、 （1) カチオン性の水溶性もしくは水系ェマルジヨンゥ レタン樹脂 (A) (以下、 カチオン性ウレタン樹脂 (A) という） 、 フエノール 系化合物とアルデヒド類との重縮合物であってカチオン性のもの （B) (以下、 カチオン性フエノ一ル系重縮合物 (B) という） 、 並びにジルコニウム化合物及 び/又はチタン化合物 （C) (以下、 金属化合物 (C) という） を水性媒体に配 合してなる金属表面処理剤に関する。 本発明のこの態様によって、 優れた耐食性 及び優れた耐ァルカリ性を有する皮膜を形成させることができる。  That is, 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 The present invention relates to a metal surface treatment agent formed by mixing. According to this aspect of the present invention, a film having excellent corrosion resistance and excellent alkali resistance can be formed.
また、 本発明は、 （2) 金属化合物 (C) がジルコニウム化合物であり、 さら に L i、 Mg、 A l、 Ca、 Mn、 Co、 N i、 Zn、 S r、 W、 Ce及ぴ Mo から選ばれる少なくとも 1種の金属を含有する化合物 (D) (以下、 金属化合物 (D) という） を配合した上記 (1) の金属表面処理剤に関する。 本発明のこの 態様によって、 優れた耐食性及び優れた耐アルカリ性に加え、 優れた耐黒変性を 有する皮膜を形成させることができる。  In the present invention, (2) 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)). According to this aspect of the present invention, it is possible to form a film having excellent blackening resistance in addition to excellent corrosion resistance and excellent alkali resistance.
本発明の上記 (1) 及び （2) の態様において、 カチオン性ウレタン樹脂 In the above aspects (1) and (2) of the present invention, a cationic urethane resin
(A) とカチオン性フエノール系重縮合物 (B) との配合比率は、 固形分質量比 として、 （A) ： (B) =99 ： 1〜1 ： 99であることが好ましいが、 The blending ratio of (A) to the cationic phenol-based polycondensate (B) is preferably (A) :( B) = 99: 1 to 1:99 as a solid content mass ratio,
(A) ： (B) =99 : l〜50 : 50である場合には、 優れた耐食性及び優れ た耐アル力リ性並びに場合により優れた耐黒変性に加え、 優れた耐黄変性を有す る皮膜を形成させることができる。  (A): When (B) = 99: l to 50:50, in addition to excellent corrosion resistance, excellent strength resistance and, in some cases, excellent blackening resistance, excellent yellowing resistance A film can be formed.
また、 本努明は、 （3) 金属化合物 (C) がチタン化合物であり、 さらに L i、 Mg、 A l、 Ca、 Mn、 Co、 N i、 Zn、 S r、 W、 C e及び Moから選ば れる少なくとも 1種の金属を含有する化合物 （D) (すなわち、 金属化合物 (D) ) を配合し、 カチオン性ウレタン樹脂 (A) とカチオン性フエノール系重 縮合物 （B) との配合比率が、 固形分質量比として、 （A) ： (B) =99 ： 1 〜50 ： 50である上記 (1) の金属表面処理剤に関する。 本発明のこの態様に よって、 優れた耐食性、 優れた耐アルカリ性、 優れた耐黒変性及び優れた耐黄変 性を有する皮膜を形成させることができる。 In addition, this effort is as follows: (3) The metal compound (C) is a titanium compound, and Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo A compound containing at least one metal selected from (D) (that is, a metal compound) (D)), and the blending ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is as follows: (A): (B) = 99: 1 to 50: The metal surface treating agent according to (1), which is 50. By this aspect of the present invention, a film having excellent corrosion resistance, excellent alkali resistance, excellent blackening resistance and excellent yellowing resistance can be formed.
また、 本発明の上記 （1) 、 （2) 及び （3) の各態様において、 金属表面処 理剤には無機酸及び有機酸から選ばれる少なくとも 1種の酸成分 （E) (以下、 酸成分 （E) という） を含有させることが好ましく、 それにより、 形成される皮 膜の耐食性及び耐黒変性がさらに向上する。 また、 本発明の上記金属表面処理剤 にはバナジウム化合物 (F) を含有させることが好ましく、 それにより、 形成さ れる皮膜の耐食性及ぴ耐アルカリ性がさらに向上する。  In each of the above aspects (1), (2) and (3) of the present invention, 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.
本発明はまた、 金属材料表面に上記 （1) 、 （2) 又は （3) の態様の金属表 面処理剤を塗布した後、 乾燥することによって該金属材料表面に皮膜を形成させ ることを特徴とする金属材料の表面処理方法、 及び上記表面処理方法を用いて形 成された皮膜を有する金属材料に関する。 発明を実施するための最良の形態  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. BEST MODE FOR CARRYING OUT THE INVENTION
本発明の金属表面処理剤中に配合するカチオン性ゥレタン樹脂 （A) (すな わち、 カチオン性の水溶性もしくは水系ェマルジョンウレタン榭脂 (A) ) にお ける 「カチオン性」 は分子構造中にカチオン性官能基を有することを意味する。 かかるカチオン性官能基としては下記一般式 （I) 、 （1 1) 、 （I I I) 又は (IV) “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)
Figure imgf000007_0001
Figure imgf000007_0001
(式中、 R1 R2、 R3、 R6、 及ぴ R 7は互いに独立に水素原子、 炭素数：！〜 1 0好ましくは：！〜 6の直鎖もしくは分枝鎖のアルキル基又は炭素数 1〜： 10好ま しくは 1〜6の直鎖もしくは分枝鎖のヒドロキシアルキル基を表し、 R4及び R 5は互いに独立に炭素数 2〜 10好ましくは 2〜 6の直鎖もしくは分枝鎖のアル キレン基を表し、 A—及ぴ B_は水酸イオン又は酸イオンを表す） で表される基 などが挙げられる。 かかるカチオン性官能基の量はカチオン性ゥレタン樹脂(Wherein 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) が本発明の金属表面処理剤中に溶解もしくは分散状態で安定に存在し得る 量であればよレ、。 If (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.
一般式 （I) 、 （1 1) 、 （I I I) 及び （I V) において、 R1 R2、 R3、 R6、 及び R7が表す、 炭素数 1〜10のアルキル基としては、 メチル基、 ェチ ル基、 プロピル基、 イソプロピル基、 ブチノレ基、 イソプチノレ基、 ペンチノレ基、 へ キシル基、 ヘプチル基、 ォクチル基、 ノニノレ基、 デシル基等が、 炭素数：！〜 10 のヒドロキシアルキル基としては、 ヒドロキシメチル基、 2—ヒドロキシェチル 基、 1ーヒドロキシェチル基、 3—ヒドロキシプ口ピル基、 4—ヒドロキシプチ ノレ基、 5—ヒドロキシペンチル基、 6—ヒドロキシへキシノレ基、 7—ヒドロキシ ヘプチル基、 8—ヒドロキシォクチル基、 9—ヒドロキシノニル基、 10—ヒド ロキシデシル基等が挙げられる。 一般式 （I I I) 及び （IV) において、 R4 及び R5が表す、 炭素数 2〜10のアルキレン基としては、 エチレン基、 プロピ レン基、 トリメチレン基、 テトラメチレン基、 ペンタメチレン基、 へキサメチレ ン基、 ォクタメチレン基、 2—ェチルーへキシレン基、 デカメチレン基等が挙げ られる。 また、 一般式 （I I ) 及ぴ （I V) において、 A—及び B—が表す酸ィ オンとしてはハロゲンイオン (塩素イオン、 臭素イオン、 フッ素イオン等） 、 硫 酸イオン、 硝酸イオン、 リン酸イオン等の無機酸イオン、 酢酸イオン、 ギ酸ィォ ン等の有機酸イオンが挙げられる。 In the general formulas (I), (11), (III) and (IV), 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. In the general formulas (III) and (IV), 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. In general formulas (II) and (IV), 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.
また本発明で用いるカチオン性ウレタン樹脂 （A) は水溶性のもの又は水系ェ マルジョン形態のものである。  The cationic urethane resin (A) used in the present invention is water-soluble or water-based emulsion.
本発明で用いるカチオン性ウレタン樹脂 （A) は上記したようなカチオン性官 能基を有することが必要であるが、 かかるカチオン性官能基は、 カチオン性フエ ノール系重縮合物 （B ) (すなわち、 フエノール系化合物とアルデヒ ド類との重 縮合物であってカチオン性のもの （B ) ) や化合物 ( C) (すなわち、 ジルコ二 ゥム化合物及び/又はチタン化合物 ( C ) ) や金属化合物 （D) (すなわち、 L i、 M g、 A l、 C a、 Mn、 C o、 N i、 Z n、 S r、 W、 C e及ぴ M oから 選ばれる少なくとも 1種の金属を含有する化合物 (D) ) との相溶性に寄与する。 力チオン性ウレタン樹脂 （A) の水への溶解性又は分散性は該榭脂の水への自己 溶解性又は自己分散性に基づいて達成されてもよく、 またカチオン性界面活性剤 (例えばアルキル 4級アンモ-ゥム塩等） 及び/又はノニオン性界面活性剤 （例 えばアルキルフェニルエーテル等） の助けを借りて達成されてもよい。  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)). 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.).
カチオン性ゥレタン榭脂 (A) としては、 ポリオール、 ポリエーテルポリォー ノレ、 ポリエステルポリオール等のポリオール類と脂肪族、 脂環式もしくは芳香族 ポリイソシァネートとの縮重合物であるウレタン樹脂において、 用いるポリオ一 ルの一部として、 （置換） ァミノ基を有するポリオール又は窒素原子を主鎖中に 有するポリオールを用いることによつて得られるゥレタン樹脂、 該ウレタン樹脂 の窒素原子を 4級化剤で 4級ィ匕したゥレタン樹脂などが挙げられる。  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.
上記において、 ポリオールとしては、 例えばエチレングリコール、 ジエチレン グリコーノレ、 トリエチレングリコーノレ、 1 , 2—プロピレングリコーノレ、 1， 3 一プロピレングリコール、 ネォペンチノレグリコール、 1 , 2ーブチレングリコー ノレ、 1 , 3一ブチレングリコ一ノレ、 1 , 4—ブチレングリコーノレ、 へキサメチレ ングリコール、 ビスフエノール A、 水添ビスフヱノール A、 トリメチローノレプロ パン、 1 , 2—プロパンジオール、 1 , 3—プロパンジォーノレ、 2—メチノレー 1，In the above, as the 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,
3 _プロパンジオール、 2—ブチル一 2 _ェチル _ 1， 3一プロパンジォーノレ、3_Propanediol, 2-Butyl-1-2_Ethyl_1,3-Propanediol
1， 4—ブタンジオール、 ネオペンチノレグリコール、 3—メチル一2 , 4—ペン タンジォ一ノレ、 2 , 4一ペンタンジォ一ノレ、 1 , 5—ペンタンジォ一ノレ、 3—メ チル一 1 , 5一ペンタンジオール、 2—メチルー 2 , 4一ペンタンジォーノレ、 2 ,1,4-butanediol, neopentinodiol, 3-methyl-1,2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,1,5 Pentanediol, 2-methyl-2,4-pentanediol, 2,
4—ジェチル一 1， 5一ペンタンジオール、 1 , 6—へキサンジォーノレ、 1 ， 7 一へプタンジオール、 3 , 5—ヘプタンジォール、 1 , 8一オクタンジォーノレ、 2—メチノレ一 1 , 8—オクタンジオール、 1 , 9—ノナンジオール、 1 , 1 0— デカンジオール等の脂肪族ジオールィヒ合物、 トリメチロールェタン、 トリメチロ ールプロパン、 へキシトーノレ類、 ペンチトール類、 グリセリン、 ジグリセリン、 ポリグリセリン、 ペンタエリスリ トーノレ、 ジペンタエリスリ ト一ル、 テトラメチ 口ールプ口パン等の三価以上の脂肪族又は脂環族アルコール化合物等が挙げられ る。 4—Jetyl 1,5,1 pentanediol, 1,6—hexanediol, 1,7 1 heptanediol, 3,5-heptanediol, 1,8 1 octanediol, 2—methinole 1,8— Aliphatic diol compounds such as octanediol, 1,9-nonanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane, hexitoleol, pentitols, glycerin, diglycerin, polyglycerin, pentaerythritol Examples thereof include trivalent or higher aliphatic or alicyclic alcohol compounds such as Tonole, Dipentaerythritol, Tetramethyl Mouth and Mouth Bread.
上記においてポリエーテルポリオールとしては、 例えばエチレンダリコール、 ジエチレングリコール、 トリエチレングリコール等のエチレンォキサイド付加物、 プロピレングリ コーノレ、 ジプロピレングリ コーノレ、 ト リプロピレングリ コーノレ等 のプロピレンォキサイド付加物、 上記のポリオールのエチレンォキサイド及び Z 又はプロピレンォキサイド付加物、 ポリテトラメチレングリコール等が挙げられ る。  In the above, as the 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.
上記においてポリエステノレポリオールとしては、 例えば上記ポリオールとその 化学量論的量より少ない量の、 多価カルボン酸又はその無水物、 ハライド、 エス テル等のエステル形成性誘導体との直接エステル化反応及び/又はェステル交換 反応により得られるもの；ラクトン類を上記ポリオールにより開環して得られる もの；ポリカーボネートポリオールなどが挙げられる。 多価カルボン酸としては、 例えば、 シユウ酸、 マロン酸、 コハク酸、 ダルタル酸、 アジピン酸、 ピメリン酸、 スベリ ン酸、 ァゼライン酸、 セバシン酸、 ドデカン二酸、 2—メチルコハク酸、 2—メチルアジピン酸、 3—メチルアジピン酸、 3—メチルペンタン二酸、 2— メチルオクタン二酸、 3， 8—ジメチルデカン二酸、 3 , 7—ジメチルデカン二 酸、 ダイマー酸、 水添ダイマー酸等の脂肪族ジカルボン酸類；シクロへキサンジ カルボン酸等の脂環式ジカルボン酸類；フタル酸、 イソフタル酸、 テレフタル酸. ナフタレンジカルボン酸等の芳香族ジカルボン酸類； トリメリット酸、 トリメシ ン酸、 ひまし油脂肪酸の三量体等のトリカルボン酸類； ピロメリット酸等のテト ラカルボン酸などが挙げられる。 そのエステル形成性誘導体としては、 これらの 多価カルボン酸の酸無水物；該多価カルボン酸のクロライド、 ブロマイド等のハ ライド；該多価カルボン酸のメチルエステル、 ェチルエステル、 プロピルエステ ノレ、 イソプロピノレエステノレ、 プチノレエステノレ、 イソブチノレエステノレ、 アミノレエス テル等の低級脂肪族エステル等が挙げられる。 上記ラクトン類としては、 Ύ—力 プロラク トン、 δ—力プロラタトン、 £—力プロラク トン、 ジメチノレー f —カブ 口ラタトン、 δ—バレロラクトン、 y一バレロラクトン、 γ—ブチロラク トン等 のラタトン類等が挙げられる。 In the above, as the 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. Examples of polycarboxylic acids 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. Examples of the 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 ラ -force prolacton, δ-force prolacton, £ -force prolacton, dimethinole f -turnip ratataton, δ-valerolactone, y-valerolactone, γ-butyrolacton, etc. Can be mentioned.
上記において、 （置換） ァミノ基を有するポリオール又は窒素原子を主鎖中に 有するポリオールとしては、 下記一般式 (V) 又は （V I) R1 ρ2 In the above, 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 ρ2
\ / 6 \ / 6
| ^ ΗΟ一 R4― Ν I― R5一 OH (VI)| ^ ΗΟ one R 4 - Ν I- R 5 one OH (VI)
ΗΟ R8 ΟΗ ΗΟ R 8 ΟΗ
(式中、 R\ R2、 R4、 R5及び R6前記一般式 （I) 及び （I I I) におい て定義したのと同義であり、 R8は炭素数 2〜1 0好ましくは 2〜6の直鎖もし くは分枝鎖のアルキレン基を表すが、 そのいずれかの炭素上に一 NRiR 2基が 置換している。 ） で表されるポリオールなどが挙げられる。 力かるポリオールの 具体例として、 N, N—ジメチルァミノジメチロールプロパン、 N—メチルー N， N—ジエタノールァミンなどが挙げられる。 また、 4級化剤としては R3C 1、 R3B r、 R7C 1、 R7B r (式中、 R3及ぴ R7は一般式 （I I) 及ぴ （I V) におけると同義である） などが挙げられる。 (Wherein 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. As quaternizing agents, 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).
カチオン性ウレタン樹脂 （A) に関し、 脂肪族、 脂環式もしくは芳香族ポリイ ソシァネートとしては、 テトラメチレンジイソシァネート、 へキサメチレンジィ ソシァネート、 リジンジィソシァネートエステル、 水添キシリレンジイソシァネ ート、 1 , 4ーシク口へキシレンジィソシァネート、 4, 4 ' ージシクロへキシ ト、 イソホロンジイソシァネート、 3, 3 ' —ジメ トキシ一 4, 4' —ビフエ二 レンジィソシァネート、 1, 5—ナフタレンジイソシァネート、 1, 5—テトラ ヒ ドロナフタレンジイソシァネート、 2, 4—トリ レンジィソシァネート、 2， 6—トリレンジイソシァネート、 4, 4， —ジフエニルメタンジィソシァネート. 2, 4 ' —ジフエ二ノレメタンジイソシァネート、 フエ二レンジイソシァネート、 キシリレンジイソシァネート、 テトラメチルキシリレンジイソシァネート等が挙 げられるが、 これらの中でも、 テトラメチレンジイソシァネート、 へキサメチレ ンジィソシァネート、 リジンジィソシァネートエステル、 水添キシリレンジィソ シァネート、 1 , 4ーシク口へキシレンジィソシァネート、 4， 4， 一ジシクロ へキシノレメタンジイソシァネート、 2， 4， ージシクロへキシノレメタンジイソシ ァネート、 ィソホロンジイソシァネート等の脂肪族または脂環式ポリイソシァネ 一ト化合物を用いる場合には、 得られる皮膜が耐候性にも優れたものとなるので 好ましい。 Regarding the cationic urethane resin (A), 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. 2, 4 '— diphenylenolmethane diisocyanate, phenolic diisocyanate, xylylene diisocyanate And tetramethylxylylene diisocyanate. Among these, tetramethylene diisocyanate, hexamethylenediocyanate, lysine diisocyanate. Isocyanate ester, hydrogenated xylylene diamine, xylene diisocyanate to 1,4-sic, 4,4,1 dicyclohexylenomethane diisocyanate, 2,4,2-dicyclohexylenomethane diisocyanate When an aliphatic or alicyclic polyisocyanate compound such as isophorone diisocyanate is used, the resulting film is preferably excellent in weather resistance.
上記したカチオン性ウレタン樹脂 （A) の中で、 皮膜の金属材料への密着性や 皮膜の耐水性へ悪影響を及ぼす恐れがある可溶化剤もしくは乳化剤としての界面 活性剤を使用しないソープフリーのもの或レ、はその使用量を抑えたものがより好 ましい。  Among the above-mentioned cationic urethane resins (A), 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.
カチオン性ゥレタン樹脂 （A) の重量平均分子量は 1， 000〜1, 000, 000であるのが好ましく、 2, 000〜500， 000であるのがより好まし レヽ。 該分子量が 1, 000未満では皮膜形成性が不十分で、 一方 1， 000, 0 00を超えると処理剤の安定性が低下する傾向となる。  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.
本発明の金属表面処理剤中に含有させるカチオン性フエノ一ル系重縮合物 Cationic phenolic polycondensate contained in the metal surface treating agent of the present invention
(B) (すなわち、 フエノール系化合物とアルデヒ ド類との重縮合物であって力 チオン性のもの （B) ) における 「カチオン性」 はカチオン性官能基を有するこ とを意味する。 力かるカチオン性官能基としては前記一般式 (I) 又は （I I) で表されるものを挙げることができる。 カチオン性フエノール系重縮合物 ( B ) はかかるカチオン性官能基の少なくとも 1種を有していればよい。 これらのカチ オン性官能基は、 例えば、 フエノール系化合物とアルデヒ ド類とを重縮合させる 際に、 前記一般式 （I ) で表されるカチオン性官能基に対応するアンモニアもし くはァミンを共存させ、 必要に応じさらに 4級化剤で窒素原子を 4級化すること により導入することができる。 カチオン性フエノール系重縮合物 (B ) に含まれ るカチオン性官能基の割合はカチオン性フエノール系重縮合物 (B ) に含まれる ベンゼン環 1個あたり 0 . 2〜 3個であるのが好ましい。 上記数値が 0 . 2個未 満では、 金属表面処理剤の安定性が低下する傾向になり、 また 3個を超えると、 形成される皮膜の耐食性が低下する傾向になる。 本発明で使用するカチオン性フ エノール系重縮合物 (B ) は上記重縮合反応を酸性触媒の存在下に行って得られ るノボラック型フエノ一ル系重縮合物であることが好まし 、。 また本発明で使用 するカチオン性フエノール系重縮合物 （B ) は上記ノボラック型フエノール系重 縮合物をホウ素変†生、 ケィ素変性、 リン変性、 重金属変 'I生、 窒素変性、 ィォゥ変 性、 油変性、 ロジン変性等の公知の手法により変性ものであってもよい。 “Cationic” in (B) (that is, a polycondensate of phenolic compounds and aldehydes and having a thione property (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. In addition, 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.
本発明で用いるカチオン性フエノール系重縮合物 (B ) を得るために使用され るフエノール系化合物は酸性触媒及び前記一般式 ( I ) で表されるカチオン性官 能基に対応するアンモニアもしくはァミンの存在下にアルデヒド類と重縮合して カチオン性フヱノール系重縮合物 (B ) を生ずることができる限り特に限定され ない。 かかるフエノール系化合物として、 例えばフエノール、 m_クレゾール、 m—ェチルフエノール、 m—プロピルフエノール、 m—ブチノレフエノール、 p— プチノレフエノーノレ、 o—プチノレフエノーノレ、 レゾノレシノーノレ、 ノヽイ ドロキノン、 力テコーノレ、 3—メ トキシフエノーノレ、 4—メ トキシフエノール、 3—メチノレ力 テコール、 4—メチルカテコール、 メチルハイ ドロキノン、 2—メチルレゾルシ ノール、 2 , 3—ジメチルハイ ドロキノン、 2 , 5—ジメチルレゾルシノール、 2—ェトキシフエノーノレ、 4—エトキシフエノーノレ、 4ーェチノレレゾノレシノ一ノレ、 3—エトキシ一 4—メ トキシフエノール、 2—プロぺユルフェノール、 2—イソ プロピノレフエノーノレ、 3—イソプロピノレフェノール、 4—イソプロピノレフヱノー ノレ、 3 , 4 , 5—トリメチノレフエノーノレ、 2—イソプロポキシフエノーノレ、 4 - ピロポキシフエノール、 2—ァリルフエノール、 3 , 4 , 5—トリメ トキシフエ ノーノレ、 4—イソプロピノレー 3—メチノレフエノーノレ、 ピロガローノレ、 フロログリ シノ一ノレ、 1 , 2 , 4—ベンゼントリオール、 5—ィソプロピル一 3—メチルフ エノーノレ、 4一ブトキシフエノーノレ、 4一 t一プチノレ力テコーノレ、 tーブチノレノヽ ィ ドロキノン、 4 - t一ペンチルフエノール、 2 - t—フ"チノレ一 5—メチノレフエ ノール、 2—フエニノレフェノ一ノレ、 3—フエユルフェノーノレ、 4一フエユルフェ ノール、 3—フエノキシフエノー Λ\ 4一フエノキシフエノーノレ、 4—へキシノレ 才キシフエノーノレ、 4一へキサノィルレゾルシノール、 3， 5—ジィソプロピノレ カテコール、 4—へキシルレゾノレシノール、 4一へプチノレォキシフエノーノレ、 3， 5—ジー t—ブチルフエノーノレ、 3 , 5—ジー tーブチルカテコール、 2， 5— ジー t一ブチルハイ ドロキノン、 ジ一 s e c一ブチルフエノール、 4ークミルフ エノーノレ、 ノニノレフエノーノレ、 2—シクロペンチノレフエノーノレ、 4ーシクロペン チルフエノール、 ビスフエノール A、 ビスフエノール Fなどが挙げられる。 これ らは各単独で用いても 2種以上組み合わせて用いてもよい。 これらのうちフエノ 一ノレ、 o—クレゾーノレ、 m—クレゾーノレ、 p—タレゾーノレ、 ビスフエノ一ノレ A、 2 , 3一キシレノール、 3 , 5—キシレノール、 m—プチノレフエノール、 p _ブ チノレフエノーノレ、 0—ブチノレフエノーノレ、 4一フエニノレフエノーノレ、 レゾノレシノ ールが好ましく、 フエノール、 ビスフエノール Aが最も好ましい。 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, 2-Isopropoxyphenol, 4-Pyropoxyphenol, 2-Arylphenol, 3,4,5-Trimethoxyphenol Norole, 4-Isopropinore 3-Methino Leunore, Pirogalonore, Phlorogori Shino-nore, 1, 2, 4-Benzenetriol, 5-Isopropyl-I 3-Methylphenol, 4-Butoxyfenenore, 4-I-Puttinole, Teconole, Tebutinoreno-Droquinone, 4-t-pentylphenol, 2-t-phenol "5-methinolephenol, 2-phenenolenoenole, 3-fuenofenenore, 4-neuenophenol, 3-phenophenole Λ \ 4-eneno Shifenenore, 4-Hexinore Talented Kichenenore, 4-Hexanol Resorcinol, 3, 5-Giso Propinole catechol, 4-hexylresorenosinol, 4-heptinoreoxyphenenole, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcatechol, 2,5-di t-Butylhydroquinone, di-sec sec-butyl phenol, 4-cumyl enol, nonino leuenore, 2-cyclopentino leenore, 4-cyclopentyl phenol, bisphenol A, bisphenol F, etc. Each of these may be used alone or in combination of two or more of these: Feno Monore, o-Crezo Nore, 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.
本発明で用いるカチオン性フエノール系重縮合物 (B ) を得るために使用され るアルデヒド類は酸性触媒及び前記一般式 （I ) で表されるカチオン性官能基に 対応するァンモエアもしくはアミンの存在下に前記フエノ一ノレ系化合物と重縮合 してカチオン性フエノール系重/縮合物 (B ) を生ずることができる限り特に限定 されない。 かかるアルデヒ ド類として、 例えばホルムアルデヒ ド、 トリオキサン、 フルフラール、 ノ ラホルムアルデヒ ド、 ベンズアルデヒ ド、 メチルへミホルマー ノレ、 ェチノレへミホノレマーノレ、 プ口ピノレへミホノレマーノレ、 フチノレへミホノレマーノレ、 フエ二ルへミホルマール、 ァセトアルデヒ ド、 プロピルアルデヒ ド、 フエニルァ セトアルデヒ ド、 α—フエニルプ口ピルアルデヒ ド、 β—フエニルプ口ピルアル デヒ ド、 o—ヒ ドロキシベンズアルデヒ ド、 m—ヒ ドロキシベンズアルデヒ ド、 p—ヒ ドロキシベンズアルデヒ ド、 o—クロ口べンズアルデヒ ド、 o—二トロべ ンズアルデヒ ド、 m—ニトロべンズアルデヒ ド、 p—二トロべンズアルデヒ ド、 o—メチノレベンズアルデヒ ド、 m—メチノレベンズアルデヒ ド、 p—メチノレベンズ アルデヒ ド、 p—ェチルベンズアルデヒ ド、 p—n—ブチルベンズアルデヒ ドな どが挙げられる。 これらは各単独で用いても 2種以上組み合わせて用いてもよレ、。 これらのうちホルムアルデヒ ド、 ノ ラホルムアルデヒ ド、 フルフラール、 ベンズ アルデヒ ド、 サリチルアルデヒ ドが好ましく、 ホルムアルデヒ ド、 パラホルムァ ルデヒ ドが最も好ましい。 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). In addition, there is no particular limitation as long as it can be polycondensed with the phenolic compound to form a cationic phenolic polycondensate (B). Such 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, α-phenyl pill aldehyde, β-phenyl pill aldehyde Dehydride, o-Hydroxybenzaldehyde, m-Hydroxybenzaldehyde, p-Hydroxybenzaldehyde, o-Black Bendealdehyde, o-Nitrobensaldehyde, m-Nitro Bens aldehyde, p-nitrobenzenes aldehyde, o-methinolevens aldehyde, m-methinolevens aldehyde, p-methinolevens aldehyde, p-ethylbenzenes aldehyde, p-n-butylbenzaldehyde And so on. These can be used alone or in combination of two or more. Of these, formaldehyde, normal formaldehyde, furfural, benzaldehyde, and salicylaldehyde are preferable, and formaldehyde and paraformaldehyde are most preferable.
本発明で用いるカチオン性クェノール系重縮合物 （B ) を得るために使用され るァミンとしては、 モノメチルァミン、 ジメチノレアミン、 トリメチノレアミン、 モ ノエチノレアミン、 ジェチルァミン、 トリェチルァミン、 イソプロピルァミン、 ジ イソプロピノレアミン、 n—ブチノレアミン、 ジ一 n—ブチ^^ァミン、 トリー n—ブ チルァミン、 ィソブチルァミン、 ジィソプチルァミン、 s e c—プチ/レアミン、 n—アミルァミン、 ジ一 n—ァミルァミン、 トリー n—アミルァミン、 s e c— アミルァミン、 s e c—へキシルァミン、 2—ェチルへキシルァミン、 ジォクチ ノレアミン、 エタノーノレアミン、 ジエタノーノレアミン、 トリエタノ一ノレアミン、 N ーメチノレエタノールァミン、 N—ェチノレエタノーノレアミン、 N—ブチノレエタノー ノレアミン、 N, N -ジメチルェタノールァミン、 N, N -ジェチルェタノールァ ミン、 N—ェチルジェタノ一^/アミン、 N— n—プチノレジエタノーノレアミン、 N， N—ジ一n _ブチルエタノールァミン、 N—メチルプロパノールァミン、 トリイ ソプロパノールァミンなどが挙げられる。 また 4級化剤としてはカチオン性ウレ タン樹脂 （A) の製造において記載したような 4級化剤を用いることができる。 本発明で用いるカチオン性フエノール系重縮合物 (B ) を得るために使用され る酸性触媒としては以下の例示に限定されるものではないが、 例えば塩酸、 硫酸、 リン酸、 ギ酸、 酢酸、 シユウ酸、 酪酸、 乳酸、 ベンゼンスルホン酸、 p—トルェ ンスルホン酸、 酒石酸、 ホウ酸等又は塩ィ匕亜鉛や酢酸亜鉛のような金属との塩を 用いることができる。 これらは各単独で用いても 2種以上組み合わせて用いても よい。 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. Amine, n-Butanolamine, Di-n-Butylamine, Toly n-Butylamine, Isobutylamine, Disoptylamine, sec-Peti / Reamine, n-Amylamine, Di-n-Amylamine, Tory n-Amylamine, sec—Amylamine, sec—Hexylamine, 2-Ethylhexylamine, Dioctenoreamine, Ethanolenoleamine, Diethanolanolamine, Trietanolenoreamine, N-Methylenoethanolamine, N—Ethenoreethanolamine, N— Butinolee Noreamine, N, N-Dimethylethanolamine, N, N-Jetylethanolamine, N-Ethyljetano-1 / Amine, N—n—Putinoresidenoethanolamine, N, N—Di-n _Butylethanolamine, N-methylpropanolamine, triisopropanolamine, etc. 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. For example, 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.
本発明で用いるカチオン性フエノール系重縮合物 (B) の数平均分子量は 1, 000〜1， 000， 000の範囲であるのが好ましく、 2， 000〜： 100， 000の範囲であるのがより好ましい。 数平均分子量が 1, 000未満では形成 された皮膜のバリア性 （緻密性） が劣り、 耐食性や耐アルカリ性が低下する傾向 となり、 また 1, 000, 000を超えると本金属表面処理剤の液安定性が損な われる可能性がある。  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.
本発明の金属表面処理剤中に含有される金属化合物 （C) (すなわちジルコ二 ゥム化合物及び/又はチタン化合物 （C) ) は、 ジルコニウム又はチタンの酸化 物、 水酸化物、 錯化合物、 無機酸もしくは有機酸との塩等であり、 カチオン性ゥ レタン樹脂 （A) 及ぴカチオン性フエノール系重縮合物 (B) と相溶性の良いも のであることが好ましい。 金属化合物 (C) としては、 例えば、 硝酸ジルコニル Z rO (N03) 2、 酢酸ジルコニル、 硫酸ジルコニル、 炭酸ジルコ二ルアンモ ニゥム （NH4) 2 [Z r (CO3) 2 (OH) 2] 、 ジルコニウムァセチノレアセト ネート Z r (OC (=CH2) CH2COCH3) ) Λ フルォロジルコニウム酸、 硫酸チタニル T i OS〇4、 ジイソプロポキシチタニウムビスァセチルァセトン (C5H702) 2T i [OCH (CH3) 2] 2、 乳酸とチタニウムアルコキシド との反応物、 チタンラウレート、 チタニウムァセチルァセトネート T i (OC (=CH2) CH2COCH3) ) 3、 フルォロチタン酸などを用いることができ る。 これらの金属化合物 (C) は各単独で又は 2種以上組み合わせて用いること ができる。 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). Examples of the metal compound (C) include zirconyl nitrate ZrO (N0 3 ) 2 , zirconyl acetate, zirconyl sulfate, zirconyl carbonate (NH 4 ) 2 [Z r (CO 3 ) 2 (OH) 2 ], zirconium § isethionate Honoré acetonate Z r (OC (= CH 2 ) CH 2 COCH 3)) Λ full O b zirconium acid, titanyl sulfate T i OS_〇 4, diisopropoxy titanium bis § cetyl § seton (C 5 H 7 0 2 ) 2 T i [OCH (CH 3 ) 2 ] 2 , reaction product of lactic acid and titanium alkoxide, titanium laurate, titanium acetyl acetylate T i (OC (= CH 2 ) CH 2 COCH 3 )) 3. Fluorotitanic acid can be used. These metal compounds (C) can be used alone or in combination of two or more.
上記したカチオン性ウレタン樹脂 （A) 、 カチオン性フエノール系重縮合物 (B) 及び金属化合物 (C) を配合してなる本発明の金属表面処理剤 （既述のご とく、 この態様の本発明は態様 (1) と称せられる） を金属表面上に塗布して得 られる皮膜は、 優れた耐食性及び優れた耐アルカリ性を有するが、 この金属表面 処理剤おいて、 金属化合物 (C) としてジルコニウムィ匕合物を用い、 さらに L i、 Mg、 Al、 Ca、 Mn、 Co、 Ni、 Zn、 S r、 W、 Ce及び Moから選ば れる少なくとも 1種の金属を含有する化合物 （D) (以下、 金属化合物 (D) と いう） を配合する場合には、 形成される皮膜に、 優れた耐食性及び優れた耐アル 力リ性に加え、 優れた耐黒変性を付与することができる。 この場合の本発明の態 様は既述のごとく、 態様 (2) と称せられる。 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. In this metal surface treatment agent, zirconium In addition, select from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo. When the compound (D) containing at least one kind of metal (hereinafter referred to as the metal compound (D)) is blended, in addition to excellent corrosion resistance and excellent strength resistance, Excellent blackening resistance can be imparted. The aspect of the present invention in this case is referred to as aspect (2) as described above.
態様 （1) 及ぴ （2) においては、 カチオン性ウレタン樹脂 （A) とカチオン 性フエノール系重縮合物 (B) との配合比率は、 固形分質量比として、 （A) ： In the aspect (1) and (2), the blending ratio of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is expressed as (A):
(B) =99 ： 1〜1 ： 99であるのが好ましい。 この配合比率は、 固形分質量 比として、 （A) ： (B) =99 ： ：！〜 50 ： 50であるのがより好ましく、 こ の場合には、 形成される皮膜に、 優れた耐食性及び優れた耐アルカリ性並びに場 合により優れた耐黒変性を付与することができることに加え、 さらに優れた耐黄 変性を付与することができる。 (B) It is preferable that = 99: 1 to 1:99. This blending ratio is (A) :( B) = 99 ::! ~ 50: 50 is more preferable. In this case, in addition to being able to impart excellent corrosion resistance and excellent alkali resistance to the formed film, and in some cases, excellent blackening resistance, Excellent yellowing resistance can be imparted.
また、 上記したカチオン性ウレタン樹脂 （A) 、 カチオン性フエノール系重縮 合物 (B) 及び金属化合物 (C) を配合してなる本発明の金属表面処理剤 （すな わち態様 （1) の本発明） を金属表面上に塗布して得られる皮膜は、 優れた耐食 性及び優れた耐アルカリ性を有するが、 この金属表面処理剤おいて、 金属化合物 Further, 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. Of the present invention) on a metal surface has excellent corrosion resistance and excellent alkali resistance. In this metal surface treatment agent, a metal compound
(C) としてチタン化合物を用い、 さらに L i、 Mg、 A l、 C a、 Mn、 C o、 N i、 Zn、 S r、 W、 C e及び Moから選ばれる少なくとも 1種の金属を含有 する化合物 (D) (すなわち金属化合物 (D) ) を配合し、 力 、 カチオン性ゥ レタン樹脂 （A) とカチオン性フエノール系重縮合物 (B) との配合比率を、 固 形分質量比として、 （A) ： (B) =9 9 ： ：！〜 50 ： 50とする場合には、 形 成される皮膜に、 優れた耐食性及び優れた耐アルカリ性に加え、 優れた耐黒変性 及び優れた耐黄変性を付与することができる。 この場合の本発明の態様は既述の ごとく、 態、様 (3) と称せられる。 (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 ::! In the case of ˜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. In this case, the aspect of the present invention is referred to as the aspect (3) as described above.
本発明の態様 (2) 及び （3) の金属表面処理剤中に含有される金属化合物 (D) (すなわち、 L i、 Mg、 A l、 C a、 Mn、 C o、 N i、 Zn、 S r、 W、 C e及び Moから選ばれる少なくとも 1種の金属を含有する化合物 （D) ) は、 上記金属の酸ィ匕物、 水酸化物、 錯化合物、 無機酸もしくは有機酸との塩等で あり、 カチオン性ウレタン樹脂 （A) 及ぴカチオン性フエノール系重縮合物 (B) と相溶性の良レ、ものであることが好ましい。 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).
上記金属化合物 (D) として具体的には、 例えば硝酸リチウム、 リン酸リチウ ム、 フツイ匕リチウム、 水酸ィ匕リチウム、 硫酸リチウム、 炭酸リチウム、 シユウ酸 二リチウム、 酸ィ匕リチウム、 硝酸マグネシウム、 硫酸マグネシウム、 炭酸マグネ シゥム、 水酸化マグネシゥム、 フッ化マグネシゥム、 リン酸ァンモェムマグネシ ゥム、 リン酸水素マグネシウム、 酸化マグネシウム、 硝酸アルミニウム、 硫酸ァ ルミ二ゥム、 硫酸カリウムァノレミニゥム、 硫酸ナトリウムァノレミニゥム、 硫酸ァ ンモニゥムアルミニウム、 リン酸ァノレミニゥム、 炭酸ァノレミニゥム、 酸化アルミ 二ゥム、 水酸化アルミニウム、 ヨウ化アルミニウム、 酢酸カルシウム、 フッ化力 ルシゥム、 ホスフィン酸カルシウム [Ca (PH202) 2] 、 硝酸カルシウム、 水酸化カルシウム、 シユウ酸カルシウム、 酸ィヒカルシウム、 酢酸カルシウム、 過 マンガン酸 HMnO4、 過マンガン酸カリウム、 過マンガン酸ナトリウム、 リン 酸二水素マンガン Mn (H2P04) 2、 硝酸マンガン Mn (N03) 2、 硫酸マン ガン （I I) 、 (I I I) もしくは （I V；) 、 フッ化マンガン (I I) もしくは (1 1 1) 、 炭酸マンガン、 酢酸マンガン （I I) もしくは （I I I) 、 硫酸ァ ンモニゥムマンガン、 マンガンァセチルァセトネート Mn (OC (=CH2) C H2COCH3) ) 3、 ヨウ化マンガン、 酸化マンガン、 水酸化マンガン、 塩ィ匕コ バルト、 クロ口ペンタアンミンコバルト塩化物 [C o C 1 (NH3) 5] C l、 へキサアンミンコバルト塩化物 [Co (NH3) 6] C 12、 クロム酸コノ レト、 硫酸コバルト、 硫酸アンモ-ゥムコバルト、 硝酸コバルト、 酸化コバルト二アル ミニゥム C o O · A 1203、 水酸化コバルト、 リン酸コノ レト、 硝酸ニッケル、 硫酸ニッケル、 炭酸ニッケル、 ニッケルァセチルァセトネート N i (OC (=C H2) CH2COCH3) ) 3、 塩ィ匕ニッケル、 へキサアンミンニッケル塩ィ匕物 Specific examples of 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, HMnO 4 permanganate, potassium permanganate, sodium permanganate, manganese dihydrogen phosphate Mn (H 2 P0 4 ) 2 , manganese nitrate Mn ( N0 3 ) 2 , Mangan sulfate (II), (III) or (IV;), Manganese fluoride (II) or (1 1 1), Manganese carbonate, Manganese acetate (II) or (III) Manganese manganese, manganese acetyl cetate Mn (OC (= CH 2 ) CH 2 COCH 3 )) 3, manganese iodide, manganese oxide, manganese hydroxide, salt 匕 balt, black pentaammine cobalt chloride [C o C 1 (NH 3 ) 5 ] C l, hexamminecobalt chloride [Co (NH 3 ) 6 ] C 1 2 , Colinate chromate, cobalt sulfate, ammonium cobalt sulfate, cobalt nitrate, oxidation Koval Two Al Miniumu C o O · A 1 2 0 3, cobalt hydroxide, phosphoric acid Kono Leto, nickel nitrate, nickel sulfate, nickel carbonate, nickel § cetyl § Seto sulfonate N i (OC (= CH 2 ) CH 2 COCH 3 ) 3 , Nickel salt, Hexammine nickel salt
[N i (NH3) 6] C l 2、 酸ィ匕ニッケル、 水酸化ニッケル、 硫酸亜鉛、 炭酸亜 鉛、 塩化亜鉛、 ヨウ化亜鉛、 亜鉛ァセチルァセトネート Zn (OC (=CH2) CH2COCH3) ) 2、 リン酸二水素亜鉛、 硝酸ストロンチウム、 硫酸ストロン チウム、 炭酸ストロンチウム、 塩化ストロンチウム、 ストロンチウムァセチルァ セトネート S r (OC (=CH2) CH2COCH3) ) 2、 メタタングステン酸 H6 [H2W12O40] 、 メタタングステン酸アンモニゥム （NH4) 6 [H2W12 O40] 、 メタタングステン酸ナトリウム、 パラタングステン酸 H10 [W12046 H10] 、 パラタングステン酸アンモニゥム、 パラタングステン酸ナトリウム、 酸化セリウム、 酢酸セリウム Ce (CH3C02) 3、 硝酸セリウム （I I I) も しくは （IV) 、 硫酸セリウム、 塩化セリウム、 酸ィ匕モリブデン、 モリブデン酸 H2Mo04、 モリプデン酸アンモニゥム、 パラモリブデン酸アンモニゥム、 モ リブデン酸ナトリウム、 モリプドリン酸化合物 （例えば、 モリブドリン酸ァンモ ニゥム （NH4) 3 [Ρ04Μο 12036] · 3H20、 モリブドリン酸ナトリゥム Na 3 [Ρ04 · 12Μο 03] · ηΗ20等） 等が挙げられる。 かかる金属化合 物 （D) は各単独で又は 2種以上組み合わせて用いることができる。 モリブデン (V I) 化合物、 タングステン (VI) 化合物、 マンガン (V I) 化合物につい ては、 アルコール類、 有機酸類等の還元剤を用いて還元したものも使用可能であ る。 これら金属化合物の中で、 Mg、 N i又は C oの化合物を用いることが耐食 性及び耐黒変性を向上させる上で特に好ましい。 [N i (NH 3 ) 6 ] C l 2 , nickel oxide, nickel hydroxide, zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetylylacetonate Zn (OC (= CH 2 ) CH 2 COCH 3 )) 2 , zinc dihydrogen phosphate, strontium nitrate, strontium sulfate, strontium carbonate, strontium chloride, strontium acetylene Cetonate S r (OC (= CH 2 ) CH 2 COCH 3 )) 2 , metatungstic acid H 6 [H 2 W 12 O 40 ], metatungstate ammonium (NH 4 ) 6 [H 2 W 12 O 40 ], Sodium metatungstate, paratungstic acid H 10 [W 12 0 46 H 10 ], ammonium paratungstate, sodium paratungstate, cerium oxide, cerium acetate Ce (CH 3 C0 2 ) 3 , cerium nitrate (III) or (IV), cerium sulfate, cerium chloride, molybdenum oxide, molybdenum molybdate H 2 Mo0 4 , ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdophosphoric acid compounds (eg, ammonium molybdate (NH 4 ) 3 [Ρ0 4 Μο 12 0 36 ] · 3H 2 0, sodium molybdophosphate Na 3 [Ρ0 4 · 12Μο 0 3 ] · ηΗ 2 0 etc.). 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. Among these metal compounds, it is particularly preferable to use a compound of Mg, Ni or Co from the viewpoint of improving corrosion resistance and blackening resistance.
上記したカチオン性ウレタン樹脂 （A) 、 カチオン性フエノール系重縮合物 (B) 及ぴ金属化合物 (C) (すなわち、 ジルコニウム化合物及ぴ Z又はチタン 化合物） 並びに場合により金属化合物 (D) を配合してなる本発明の態様 （1) 〜 （3) の金属表面処理剤を金属表面上に塗布して得られる皮膜は、 優れた耐食 性及び優れた耐ァルカリ性並びに場合により優れた耐黒変性及び優れた耐黄変性 を有するが、 この金属表面処理剤中に、 さらに酸成分 (E) (すなわち、 無機酸 及び有機酸から選ばれる少なくとも 1種の酸成分 (E) ) を配合することにより、 形成される皮膜の耐食性及び耐黒変性をさらに向上させることができる。  A cationic urethane resin (A), a cationic phenol polycondensate (B), a metal compound (C) (ie, a zirconium compound and a Z or titanium compound), and optionally a metal compound (D). 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.
酸成分 （E) としての無機酸としては、 水溶性のものを用いることができ、 例 えばオノレトリン酸、 メタリン酸、 ホスホン酸、 ポリリン酸 （特にピロリン酸、 ト リリン酸等のオルトリン酸多量体など） などのリン酸系の酸；フッ化水素酸；フ ルォロジルコニウム酸、 フルォロチタン酸などのフルォロ金属酸；硝酸；硫酸な どが挙げられる。 また、 有機酸としてはカルボキシル基もしくはスルホン基を有 するものなどで水溶 1生のものを用いることができ、 例えば酢酸、 プロピオン酸、 シユウ酸、 酒石酸、 りんご酸、 ダルコン酸、 タンニン酸、 ギ酸、 ァスコルビン酸 などが挙げられる。 かかる酸成分 （E) は各単独で又は 2種以上組み合わせて用 いることができる。 これらのうち、 特にフッ化水素酸、 硝酸、 硫酸、 リン酸が好 ましい。 酸成分 （E) は、 本発明の金属表面処理剤と金属材料が接触した際に、 前記金属材料の表面をエッチングする働きを主に担い、 耐食性及び皮膜密着性As the inorganic acid as the acid component (E), water-soluble ones can be used. For example, onoletriic acid, metaphosphoric acid, phosphonic acid, polyphosphoric acid (especially orthophosphoric acid multimers such as pyrophosphoric acid, triphosphoric acid, etc.) And phosphoric acid acids such as hydrofluoric acid, fluorometallic acids such as fluorozirconic acid and fluorotitanic acid, nitric acid and sulfuric acid. In addition, the organic acid has a carboxyl group or a sulfone group. For example, 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
(金属表面への密着性） をさらに向上させる。 特に硝酸は高湿潤条件下での耐黒 変性をさらに向上させる効果も併せ持つ。 また、 酸成分 （E) は本発明の金属表 面処理剤の液安定性もさらに向上させる。 (Adhesion to metal surface) is further improved. 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.
本発明の上記 (1) 〜 （3) の態様の金属表面処理剤中に、 さらにバナジウム 化合物 （F) を配合することにより、 形成される皮膜の耐食性及ぴ耐アルカリ性 をさらに向上させることができる。 力かるバナジウム化合物 (F) としては、 ノ ナジゥムの酸ィ匕数が 5価、 4価又は 3価のバナジゥム化合物を用いることができ、 例えば五酸化バナジウム V205、 メタバナジン酸 HV〇3、 メタバナジン酸アンモ 二ゥム、 メタバナジン酸ナトリウム、 ォキシ三塩化バナジウム VOC 13等の酸 ィ匕数 5価のバナジウム化合物；三酸ィ匕バナジウム V203、 二酸ィ匕バナジウム V02、 ォキシ硫酸バナジウム voso4、 バナジウムォキシァセチルァセテート v〇 By further adding the vanadium compound (F) to the metal surface treatment agent according to the above aspects (1) to (3) of the present invention, the corrosion resistance and alkali resistance of the formed film can be further improved. . As the powerful vanadium compound (F), 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〇
(OC (=CH2) CH2COCH3) ) 2、 バナジウムァセチルアセテート V (O C (=CH2) CH2COCH3) ) 3、 三塩化バナジウム VC 13、 リンバナドモリ ブデン酸 H15— x [ P V12.XM o xO40] · n H20 (6<x< 12, nく 30) 等の酸 化数 3価又は 4価のバナジウム化合物が挙げられる。 これらのバナジウム化合物 は各単独で又は 2種以上組み合わせて用いることができる。 (OC (= CH 2 ) CH 2 COCH 3 )) 2 , vanadium acetyl acetate V (OC (= CH 2 ) CH 2 COCH 3 )) 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.
本発明の上記 (1) 〜 （3) の態様の金属表面処理剤がバナジウム化合物 (F) として酸ィ匕数 3価又は 4価のバナジウム化合物を含有していることが、 よ り一層の高耐食性維持、 耐アルカリ性の点から好ましい。 すなわち、 バナジウム 化合物 (F) に占める酸ィヒ数 3価又は 4価のバナジウム化合物の割合が、 （V3+ + V4+) /V (式中、 V3+、 V4\ Vはそれぞれバナジウム化合物 (F) 中の酸ィ匕 数 3価のバナジウム質量、 酸化数 4価のバナジウム質量、 全バナジウム質量を表 す） として、 0 . 1〜1 . 0であるのが好ましく、 0 . 2〜1 . 0であるのがよ り好ましく、 0 . 4〜1 . 0であるのが最も好ましい。 It is even higher that 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.
本発明の上記 ( 1 ) 〜 （3 ) の態様の金属表面処理剤中に 3価もしくは 4価の バナジウム化合物を含有させる方法としては、 前記したような 3価もしくは 4価 のバナジウム化合物を用いる他、 5価のバナジウム化合物を予め還元剤を用いて 3価又は 4価に還元したものを用いることができる。 用いる還元剤は無機系、 有 機系いずれでも良いが、 有機系が好ましく、 例えばメタノール、 エタノール、 ィ ソプロパノール、 エチレンダリコール等のアルコール類； ホルムァノレデヒ ド、 ァ セトアルデヒ ド、 フルフラ一ル等のァルデヒ ド化合物； ァセチルァセトン、 ァセ ト酢酸ェチル、 ジピバロィルメタン、 3—メチルペンタンジオン等のカルボニル 化合物；ギ酸、 酢酸、 プロピオン酸、 酒石酸、 ァスコルビン酸、 グノレコン酸、 ク ェン酸、 リンゴ酸等の有機酸； トリェチルァミン、 トリエタノールァミン、 ェチ レンジァミン、 ピリジン、 イミダゾー \ ピロ一^ モノレホリン、 ピぺラジン等 のァミン化合物；ホルムアミド、 ァセトアミ ド、 プロピオンアミ ド、 Ν—メチル プロピオンアミ ド等の酸アミド化合物；グリシン、 ァラニン、 ピロリン、 グルタ ミン酸等のアミノ酸類；グルコース、 マンノース、 ガラクトース等の単糖類；麦 芽糖、 ショ糖、 デンプン、 セルロース等の天然多糖類；アミノトリ （メチレンホ スホン酸） 、 1—ヒ ドロキシェチリデンー 1， 1 'ージホスホン酸、 エチレンジ アミンテトラ （メチレンホスホン酸） 、 フィチン酸等の有機リン酸；没食子酸、 タンニン酸、 フミン酸、 リダニンスルホン酸、 ポリフヱノール等の天然高分子； ポリビュルアルコール、 ポリエチレングリコール、 ポリアクリル酸、 ポリアクリ ルァミ ド、 ポリエチレンイミン、 水溶性ナイ口ン等の合成高分子； E D Τ Α等の ァミノカルボン酸などが挙げられる。  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. For example, 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, Ν-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 EDΤ.
前記有機系還元剤は、 バナジウム化合物を還元する作用を有するだけでなく、 処理液中のバナジウム化合物の安定性を著しく向上させ、 本発明の上記 （1 ) 〜 ( 3 ) の態様の金属表面処理剤の優れた耐食性付与効果を長時間維持させること ができる。 また、 前記有機系還元剤は均一な皮膜形成にも効果があるため、 耐食 性の向上も期待できる。 次に、 本発明の態様 (1) 〜 （3) の金属表面処理剤中の各成分の使用量につ いて説明する。 本発明の態様 (1) 及び （2) の金属表面処理剤中に配合される カチオン生ウレタン樹脂 （A) とカチオン性フエノーノレ系重,縮合物 （B) との配 合比率は、 固形分質量比として、 （A) ： (B) =99 ： 1〜1 ： 99であるの が好ましい。 カチオン性フエノール系重縮合物 (B) の配合比率が 99 ： 1を下 回ると、 形成される皮膜の耐食性が不十分になり、 他方、 カチオン性ウレタン樹 月旨 （A) が 1 ： 99を下回ると、 耐食性や耐アルカリ性が不十分になる傾向とな る。 上記比率を （A) ： (B) =99 ： ：！〜 50 ： 50の範囲内とする場合には、 既述の効果に加えさらに、 得られる皮膜に優れた耐黄変性を付与することができ ることが見出された。 上記比率は （A) ： (B) =90 ： 10〜60 ： 40であ るのがより一層好ましい。 カチオン性フエノール系重縮合物 (B) の配合比率が 50 : 50を超えると、 耐黄変性が不十分になる。 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. In addition, since the organic reducing agent is effective in forming a uniform film, it can be expected to improve the corrosion resistance. Next, 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. In the embodiment (1) and (2) of the present invention, the mixing ratio between the cationic raw urethane resin (A) and the cationic phenolic polycondensate (B) is the solid mass. The ratio is preferably (A) :( B) = 99: 1 to 1:99. If the blending ratio of the cationic phenolic polycondensate (B) is less than 99: 1, the corrosion resistance of the formed film will be insufficient, while the cationic urethane resin (A) will have a ratio of 1:99. If it is lower, the corrosion resistance and alkali resistance tend to be insufficient. The above ratio is (A) :( B) = 99 ::! In the range of ˜50: 50, it was found that, in addition to the effects described above, excellent yellowing resistance can be imparted to the resulting film. The ratio is more preferably (A) :( B) = 90: 10-60: 40. When the blending ratio of the cationic phenol polycondensate (B) exceeds 50:50, yellowing resistance becomes insufficient.
本発明の態様 (3) の場合には、 金属表面処理剤中に配合されるカチオン性ゥ レタン樹脂 （A) とカチオン性フエノール系重縮合物 (B) との配合比率は、 固 形分質量比として、 （A) ： (B) =99 ： ：!〜 50 ： 50であることが必要で あり、 得られる皮膜に優れた耐黄変性を付与することができる。 上記比率は In the case of the embodiment (3) of the present invention, 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 ratio must be (A) :( B) = 99 ::! To 50:50, and excellent yellowing resistance can be imparted to the resulting film. The above ratio is
(A) ： (B) =90： 10〜60 ： 40であるのが好ましい。 カチオン性フヱ ノール系重縮合物 （B) の配合比率が 99 ： 1を下回ると、 形成される皮膜の耐 食性が不十分になる傾向となり、 他方、 カチオン性フエノール系重縮合物 (B) の配合比率が 50 ： 50を超えると、 耐黄変性が不十分になる。 (A): (B) = 90: It is preferable that it is 10-60: 40. When 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. On the other hand, the cationic phenol polycondensate (B) When the blending ratio of exceeds 50:50, yellowing resistance becomes insufficient.
本発明の態様 (1) 〜 （3) の金属表面処理剤中に含有されるカチオン性ウレ タン樹脂 (A) とカチオン性フエノール系重縮合物 (B) との合計固形分を 10 0質量部とした場合、 金属化合物 (C) の配合量は、 金属 （ジルコニウム及び/ 又はチタン） として 0. 1〜20質量部であるのが好ましく、 1〜10質量部で あるのがより好ましい。 金属化合物 （C) の配合量が上記範囲内である場合、 十 分な耐食性や液安定性を確保することができる。  100 parts by mass of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B) contained in the metal surface treatment agent according to embodiments (1) to (3) of the present invention In this case, 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). When the compounding amount of the metal compound (C) is within the above range, sufficient corrosion resistance and liquid stability can be ensured.
本発明の態様 （2) 及び （3) の金属表面処理剤中に含有されるカチオン性ゥ レタン樹脂 （A) とカチオン性フエノール系重縮合物 (B) との合計固形分を 1 00質量部とした場合、 金属化合物 (D) (すなわち、 L i、 Mg、 A l、 Ca、 Mn、 Co、 N i、 Zn、 S r、 W、 C e及び M oから選ばれる少なくとも 1種 の金属を含有する化合物 (D) ) の配合量は、 金属 （2種以上の金属が含まれる 場合全体としての金属） として 0. 01〜10質量部であるのが好ましく、 0. ：!〜 5質量部であるのがより好ましい。 金属化合物 （D) の上記配合量が 0. 0The 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 When it is 00 parts by mass, 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.
1質量部を下回ると金属表面に耐黒変性を付与できず、 10質量部を上回ると皮 膜のバリア性 （緻密性） が低下し、 耐食性が低下する傾向になる。 If 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.
本発明の態様 (1) 〜 （3) の金属表面処理剤に任意成分としての酸成分 (E) (すなわち、 無機酸及び有機酸から選ばれる少なくとも 1種の酸成分 (E) ) を配合する場合、 その配合量は、 カチオン性ウレタン樹脂 （A) とカチ オン性フエノール系重縮合物 （B) との合計固形分を 100質量部とした場合、 水を含まない酸成分そのものとして 1〜30質量部であるのが好ましく、 5〜2 0質量部であるのがより好ましい。 酸成分 （E) の上記含有量が 1質量部を下回 ると金属表面へのエッチング作用が不十分となり、 その結果金属素材と皮膜との 密着性が劣り、 耐食性が低下する傾向となる。 また、 酸成分 (E) の上記含有量 が 30質量部を超えるとエッチング作用が過大となり、 均一な皮膜を形成させる ことが困難となり、 耐食性、 耐黒変性等の各性能が低下する傾向になる。  An acid component (E) as an optional component (that is, at least one acid component (E) selected from inorganic acids and organic acids) is blended with the metal surface treatment agent of aspects (1) to (3) of the present invention. When the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is 100 parts by mass, 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. When 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. In addition, if 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. .
本発明の態様 (1) 〜 （3) の金属表面処理剤に任意成分としてのバナジウム 化合物 (F) を配合する場合、 その配合量は、 カチオン性ウレタン樹脂 （A) と 力チオン性フヱノ一ル系重縮合物 (B) との合計固形分を 100質量部とした場 合、 バナジウムとして 0. 01〜20質量部であるのが好ましく、 0. 1〜10 質量部であるのがより好ましい。 バナジウム化合物 (F) の上記含有量が 0. 0 1質量部を下回ると耐食性及び耐ァルカリ性をさらに向上させるというバナジゥ ム化合物 (F) の効果が発揮されず、 20質量部を超えると皮膜のバリア性 （緻 密性） が低下し、 耐食性及び耐アルカリ性がむしろ損われる傾向になる。  In the case where the vanadium compound (F) as an optional component is blended with the metal surface treatment agent according to the embodiments (1) to (3) of the present invention, the blending amount thereof includes the cationic urethane resin (A) and the force thione phenol. When the total solid content with the system polycondensate (B) is 100 parts by mass, 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.
さらに、 形成される皮膜の潤滑性、 加工性を上げるために、 本発明の態様 (1) 〜 (3) の金属表面処理剤に、 ポリオレフイン系ワックス、 エステル系ヮ ッタス、 炭化水素系ヮッタス等の水系ワックスから選ばれる少なくとも 1種を配 合することができる。 本発明の金属表面処理剤中に含有されるカチオン性ウレタ ン樹脂 （A) とカチオン性フエノール系重縮合物 （B ) との合計固形分を 1 0 0 質量部とした場合、 水系ワックスの配合量は固形分として 0 . 5〜 3 0質量部で あることが好ましく、 1〜2 0質量部であることがより好ましい。 Furthermore, in order to improve the lubricity and workability of the film to be formed, 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. When the total solid content of the cationic urea resin (A) and the cationic phenolic polycondensate (B) contained in the metal surface treating agent of the present invention is 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass as a solid content.
さらに、 形成される皮膜の耐食性や耐アルカリ性をさらに向上させるために、 本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤に、 シランカップリング剤を配合 することができる。 かかるシランカップリング剤の種類は特に限定されず、 例え ばビニノレトリクロロシラン、 ビニノレトリス ( β—メ トキシエトキシシラン) 、 ビ ニルトリエトキシシラン、 ビュルトリメ トキシシラン、 γ― (メタクリロイノレ才 キシプロピル） トリメ トキシシラン、 β— ( 3 , 4一エポキシシクロへキシル） ェチルトリメ トキシシラン、 γ—グリシドキシプロピルトリエトキシシラン、 γ 一グリシドキシプロピルメチルジェトキシシラン、 Ν— ( —アミノエチル) ーァミノプロビルトリメ トキシシラン、 Ν— —アミノエチノレ) γ—アミノブ 口ピルメチルジメ トキシシラン、 γ—ァミノプロピルトリエトキシシラン、 Ν— フエ-ルー γ—アミノプロビルトリメ トキシシラン、 γ—メルカプトプロビルト リメ トキシシラン、 γ—クロ口プロピルトリメ トキシシラン、 ゥレイ ドプロピル トリエトキシシランなどが挙げられる。 これらは各単独で又は 2種以上組み合わ せて用いることができる。 本発明の金属表面処理剤中に含有されるカチオン性ゥ レタン樹脂 （Α) とカチオン性フエノール系重縮合物 （Β) との合計固形分を 1 0 0質量部とした場合、 シランカップリング剤の配合量は固形分として 0 . 5〜 1 5質量部であることが好ましく、 1〜1 0質量部であることがより好ましレ、。 本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤で用いる水性媒体は通常水であ るが、 皮膜の乾燥性の改善などの目的で少量 （例えば水性媒体全体の 1 0容量％ 以下） のアルコール、 ケトン、 セロソルプ系の水溶性有機溶剤を併用をしてもよ レ、。 この他に、 界面活个生剤、 消泡剤、 レべリング剤、 防菌防ばい剤、 着色剤など を本発明の金属表面処理剤の液安定性や皮膜†生能を損なわない範囲で添加し得る。 本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤の合計固形分濃度の下限につい ては、 本発明の効果が達成しうる限り特に制限はないが、 上限については液安定 性の観点から制限される。 本発明の金属表面処理剤の合計固形分濃度は 0 . 1〜 4 0質量％の範囲に調整するのが好ましく、 1〜 3 0質量％の範囲に調整するの がより好ましく、 5〜2 5質量％の範囲に調整するのが最も好ましい。 Furthermore, in order to further improve the corrosion resistance and alkali resistance of the formed film, 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. For example, vinylenotrichlorosilane, vinylenotris (β-methoxyethoxysilane), vinyltriethoxysilane, burtrimethoxysilane, γ- (methacryloylenoyloxypropyl) trimethoxysilane, β — (3,4 monoepoxycyclohexyl) etyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyljetoxysilane, Ν— (—aminoethyl) aminoprovir trimethoxysilane, Ν--Aminoethynole) γ-Aminobutylpyrumethyldimethyoxysilane, γ-aminopropyltriethoxysilane, Ν-Ferru γ-Aminopropyl trimethoxysilane, γ-mercaptoprovir trimethyoxysilane, γ-Black mouthpiece Examples include propyltrimethoxysilane and ureidopropyltriethoxysilane. These can be used alone or in combination of two or more. When the total solid content of the cationic urethane resin (Α) and the cationic phenolic polycondensate (Β) contained in the metal surface treatment agent of the present invention is 100 parts by mass, 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. In addition, 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. Can be added. 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.
次に、 本発明の表面処理方法について述べる。  Next, the surface treatment method of the present invention will be described.
本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤及び表面処理方法は、 令延鋼板、 炭素鋼板、 ケィ素鋼板などの鋼板、 メツキ鋼板、 アルミニウム系金属材料に適し ている。 メツキ鋼板は、 例えば電気亜鉛メツキ、 溶融亜鉛メツキ、 5 5 %アルミ 亜鉛メッキ、 5 %アルミ亜鉛メッキ、 アルミメツキ、 鉄亜鉛メツキなどのメッキ 処理が施された亜鉛含有メツキ鋼板を包含する。 アルミニウム系金属材料は、 純 アルミニウム材、 アルミニウム合金材、 アルミニウムダイキャスト材等のアルミ ニゥム又はアルミニウム合金を主成分とする金属材料を包含する。  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. Examples of 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.
本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤による処理に先立つ前処理工程 については特に制限はないが、 通常は、 本処理を行う前に被処理金属に付着した 油分、 汚れを取り除くために、 アルカリ脱脂剤又は酸性脱脂剤で洗浄するカヽ 湯 洗、 溶剤洗浄等を行い、 その後、 必要に応じて酸、 アルカリなどによる表面調整 を行う。 金属材料表面の洗浄においては、 洗浄剤が金属材料表面になるべく残留 しないように洗浄後に水洗することが好ましい。  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.
本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤による処理は、 金属表面処理剤 を塗布した後、 乾燥することにより行う。 塗布方法については特に制限はなく、 金属材料表面に処理剤をロール転写させて塗り付けるロールコート法、 或いはシ ャワーリンガー等によって流し掛けた後ロールで絞るもしくはエアーナイフで液 切りをする方法、 処理液中に金属材料を浸漬する方法、 金属材料に処理剤をスプ レーする方法などから適宜選択すればょレヽ。 本処理剤の溶媒は水が主体であるた め、 処理液温度は 0〜 6 0 °Cであるのが好ましく、 5〜 4 0 °Cであるのがより好 ましい。  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. There are no particular restrictions on the application method, and a roll coating method in which a treatment agent is roll-transferred and applied to the surface of a metal material, or a method of squeezing with a roll after pouring with a shower ringer or draining with an air knife, in a processing solution You can select the appropriate method from the method of immersing a metal material in the metal and the method of spraying the treatment agent on the metal material. Since 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.
本発明の態様 ( 1 ) 〜 （3 ) の金属表面処理剤を塗布した後の乾燥工程につい ては、 カチオン性ウレタン樹脂 （A) 及ぴカチオン性フエノール系重縮合物 (B) の硬ィ匕を促進する必要がなく付着水の除去だけ行う場合は、 必ずしも熱を 必要とせず風乾、 もしくはエアーブロー等の物理的除去でも構わないが、 カチォ ン性ウレタン樹脂 （A) 及びカチオン性フエノール系重縮合物 （B) の硬化を促 進し又は軟ィ匕による被覆効果を高めるためには加熱乾燥する必要がある。 その場 合の温度は、 50〜250°Cが好ましく、 60〜220°Cがより好ましい。 In the drying step after the application of the metal surface treatment agent according to embodiments (1) to (3) of the present invention, 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.
形成される皮膜の付着量は乾燥皮膜質量として 30〜5, 00 OmgZm2が 好ましく、 50〜3， 00 OmgZm2がより好ましい。 前記乾燥皮膜質量が 3 Omg /m2未満である場合には十分な耐食性及ぴ耐黒変性が得られず、 5， 0 0 Omg / 2を超えると金属材料との密着性ゃ耐黄変性が低下する。 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. When 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.
次に本発明の作用について述べる。 本発明の態様 （1) 〜 （3) の金属表面処 理剤において各成分は以下のような働きを有していると推察されるが、 本発明は 以下の推察によつて何ら制限されるものではな！/、。  Next, the operation of the present invention will be described. Aspects of the present invention It is inferred that 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! /.
本発明の態様 (1) 〜 （3) の金属表面処理剤は、 金属材料に塗布され乾燥さ れる工程において、 金属材料表面と反応し密着性の良好な皮膜を形成すると共に 樹脂成分が造膜し、 優れた耐食性を素材に付与するものと考えられる。 カチオン 性フエノール系重縮合物 (B) と金属化合物 (C) (すなわち、 ジルコニウムィ匕 合物及び/又はチタン化合物） は、 処理剤塗布時又は加熱乾燥工程において、 緻 密な 3次元構造を形成して造膜すると共に、 金属表面と反応して固着する。 この 際に、 前記金属表面処理剤中に酸成分 （E) が含有されることにより、 エツチン グ作用が高まり、 より金属表面との反応性が高まることによって、 より強固な皮 膜が金属表面との界面に形成される。  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. At this time, 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.
このようにして形成された皮膜が優れた耐食性を有するのは、 形成された皮膜 の金属表面パリア一性 （緻密性） によることの他、 次のことが考えられる。 すな わち、 本発明処理剤に含有されるカチオン性フエノール系重縮合物 （B) は共鳴 安定化構造を有する化合物であり、 金属化合物 (C) (すなわち、 ジルコニウム 化合物及ひブ又はチタン化合物） 、 金属化合物 (D) 中の Mn、 Co、 N i、 W、 Ceもしくは Moを含有する化合物、 及びバナジウム化合物 (F) は遷移金属化 合物である。 カチオン性フエノール系重縮合物 （B) 、 金属化合物 (C) 及び M n、 Co、 N i、 W、 Ceもしくは Moを含有する化合物、 並びに任意的なバナ ジゥム化合物 ( F ) とで形成される皮膜は、 金属表面と反応し固着することによ つて、 素材金属の外殻軌道と重なる程度に十分近い距離となり、 その結果、 腐食 によって生ずる電子を φ軌道を利用して非局在ィ匕する作用を持ち、 そのことによ つて、 表面電位が均一に保たれ、 優れた耐食性 （平面部のみならず、 切断端面、 キズ部） を付与すると考えられる。 従来のクロメート皮膜の防食機構としては、 溶解性のある 6価のクロムが溶け出し、 金属表面露出部に再析出する自己補修作 用が一般的に言われているが、 本発明者らは、 クロメート皮膜の防食機構はクロ ムの高いカチオノイド性 （金属表面への高い固着反応性） と優れた （腐食電子 の） 非局在化作用に起因する、 本発明の処理剤と同様の防食機構であると考えて いる。 The reason why the film formed in this way has excellent corrosion resistance is considered to be due to the metal surface paria uniformity (denseness) of the formed film as follows. That is, 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 compound containing Mn, Co, Ni, W, Ce or Mo in the metal compound (D), and the vanadium compound (F) are transition metal compounds. Cationic phenolic polycondensates (B), metal compounds (C) and compounds containing Mn, Co, Ni, W, Ce or Mo, and optional vana 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. As 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.
また、 金属化合物 (D) は金属基材表面に塩基性ィ匕合物を形成したり、 或いは 金属基材表面を改質することで金属基材表面を不活性化し、 金属基材の黒変を防 止し、 かつ耐食性を向上させる。  In addition, 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.
一方、 カチオン性ウレタン樹脂 （A) は、 金属界面に形成された前記皮膜上に 形成され （すなわち、 2層構造を持つ） 、 バリアー性 （緻密性） を高めることに よって耐食性を向上させる効果がある他、 加工性を高める効果がある。  On the other hand, 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.
また、 カチオン性ウレタン樹脂 （A) とカチオン性フエノール系重縮合物 (B ) とを組合せ、 力 両者の比率を限定することで耐水性が改善され、 皮膜が 溶解し難くなり、 耐ァルカリ性の向上につながる。  In addition, by combining the cationic urethane resin (A) with the cationic phenol polycondensate (B) and limiting the ratio of both forces, the water resistance is improved, the film is difficult to dissolve, and the alkali resistance is reduced. It leads to improvement.
耐黄変性 （耐熱性） に関しては、 カチオン性フエノール系重縮合物 (B ) は芳 香環を有しているため、 加熱により変色しやすい傾向があるが、 カチオン性ウレ タン樹脂 （A) とカチオン性フエノール系重縮合物 (B ) との使用比率をカチォ ン性ウレタン樹脂 （A) が同量以上となるようにすることで、 耐食性、 耐黒変性 及ぴ耐アル力リ性を維持しながら、 耐黄変性を付与/向上させることができる。 実施例  Regarding yellowing resistance (heat resistance), the cationic phenolic polycondensate (B) has an aromatic ring and therefore tends to be discolored by heating. However, the cationic urethane resin (A) and Maintaining corrosion resistance, blackening resistance and strength resistance by making the ratio of use with the cationic phenolic polycondensate (B) equal to or greater than that of the cationic urethane resin (A). However, yellowing resistance can be imparted / improved. Example
以下に実施例及び比較例によつて本発明を説明するが、 本実施例は単なる一例 に過ぎず、 本発明を限定するものではない。 実施例及び比較例において使用した 被処理金属材料、 成分 （A) 〜 （F) 及び処理方法 （前処理及ぴ本発明処理） 、 並びに評価方法、 評価結果の説明、 処理剤組成及び処理方法 （表 1〜4、 8〜1 0、 13〜15) 及び評価結果 （表 5〜7、 11〜： 12、 16〜： 17) をこの順 序で以下に記載する。 The present invention will be described below with reference to examples and comparative examples. However, the present examples are merely examples and do not limit the present invention. Used in Examples and Comparative Examples Metal material to be treated, components (A) to (F) and treatment method (pretreatment and treatment of the present invention), evaluation method, explanation of evaluation results, treatment agent composition and treatment method (Tables 1 to 4, 8 to 1) 0, 13-15) and evaluation results (Tables 5-7, 11-: 12, 16-: 17) are listed below in this order.
(1) 被処理金属材料  (1) Metal material to be treated
I 電気亜鉛メツキ鋼板 （板厚： 0. 8 mm)  I Electro-galvanized steel sheet (thickness: 0.8 mm)
Π 溶融亜鉛メツキ鋼板 （板厚： 0. 8 mm)  Π Hot-dip galvanized steel sheet (thickness: 0.8 mm)
ΙΠ 5 %アルミ亜鉛メッキ鋼板 （板厚： 0. 6 mm)  ΙΠ 5% aluminum galvanized steel sheet (thickness: 0.6 mm)
IV 55%アルミ亜鉛メツキ鋼板 （板厚： 0. 4 mm)  IV 55% aluminum zinc plated steel sheet (thickness: 0.4 mm)
(2) 金属表面処理剤成分  (2) Metal surface treatment component
(2-1) カチオン性ウレタン樹脂 （A)  (2-1) Cationic urethane resin (A)
カチオン性ウレタン樹脂 （A1) Cationic urethane resin (A1)
ポリエーテルポリオール （合成成分：テトラメチレングリコール及ぴェチレン グリコール、 分子量 1500) 150質量部、 トリメチロールプロパン 6質量部、 N—メチルー N, N—ジエタノールァミン 24質量部、 イソホロンジイソシァネ ート 94質量部及びメチルェチルケトン 13, 5質量部を反応容器に入れ、 70〜 75°Cに保ちながら 1時間反応させてウレタンプレボリマーを生成させた。 つい で該反応容器にジメチル硫酸 15質量部を入れ、 50〜 60 °Cで 30〜 60分間 反応させて、 カチオン性ゥレタンプレポリマーを生成させた。 ついで該反応容器 に水 576質量部を入れ、 混合物を均一に乳ィヒさせた後、 メチルェチルケトンを 回収して水溶性のカチオン性ウレタン樹脂 （A1) を得た。  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).
カチオン性ウレタン榭脂 （A2) Cationic urethane resin (A2)
ポリエステルポリオール （合成成分：イソフタル酸、 ァジピン酸及ぴ 1 , 6— へキサンジオール、 エチレンダリコール、 分子量 1700) 135質量部、 トリ メチロールプロパン 5質量部、 N—メチル一 N， N—ジエタノールァミン 22質 量部、 イソホロンジイソシァネート 86質量部及ぴメチルェチルケトン 120質 量部を反応容器に入れ、 70〜75°Cに保ちながら 1時間反応させてウレタンプ レポリマーを生成させた。 該反応容器にジメチル硫酸 17質量部を入れ、 50〜 60°Cで 30〜6 0分間反応させてカチオン性ウレタンプレボリマーを生成させ た。 ついで該反応容器に水 6 1 5質量部を入れ、 混合物を均一に乳化させた後、 メチルェチルケトンを回収して水溶性のカチオン性ゥレタン樹脂 (A 2 ) を得た。 カチオン性ポリウレタン樹脂 （A3) 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. Into the reaction vessel, 17 parts by mass of dimethyl sulfate was added, Cationic urethane prepolymers were produced by reacting at 60 ° C. for 30 to 60 minutes. Next, 61. 5 parts by mass of water was placed in the reaction vessel to uniformly emulsify the mixture, and then methyl ethyl ketone was recovered to obtain a water-soluble cationic urea resin (A 2). Cationic polyurethane resin (A3)
ポリカーボネートポリオール (合成成分： 1. 6一へキサンカーボネートジォ ール、 エチレングリコール、 分子量 2000) 1 30質量部、 トリメチロールプ 口パン 4質量部、 N—メチル一 N, N—ジエタノールァミン 2 1質量部、 イソホ 口ンジィソシァネート 75質量部及びメチルェチルケトン 1 1 5質量部を反応容 器に入れ、 70〜75 °Cに保ちながら 1時間反応をさせてウレタンプレポリマー を生成させた。 ついで該反応容器にジメチル硫酸 22質量部を入れ、 50〜 6 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
0°Cで 30〜60分間反応させてカチオン性ウレタンプレポリマーを生成させた。 ついで該反応容器に水 6 33質量部を入れ、 混合物を均一に乳化させた後、 メチ ルェチルケトンを回収して水溶性の力チオン性ポリウレタン樹脂 （A 3 ) を得た。 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).
(2-2) カチオン' I生フヱノ一ル系重縮合物 (B)  (2-2) Cation 'I raw phenolic polycondensate (B)
カチオン性フエノ一ル系重縮合物 (B 1) Cationic phenolic polycondensate (B 1)
還流冷却機を備えた 1 000 m Lのフラスコ内に、 ビスフエノール A 1モル (228 g) 及び触媒として p—トルエンスルホン酸 0. 3 gを仕込み、 内部温 度を 1 00°Cまで上げ、 ホルムアルデヒド水溶液 0. 8 5モル （69 g) を 1時 間かけて添加し、 1 00°Cで 2時間還流下に反応させた。 その後、 反応容器を水 冷静置し、 上層に分離する水層の濁りがなくなつてから、 デカンテーシヨンして 水層を除去し、 さらに 1 70〜1 75°Cになるまで加熱攪拌して、 未反応分及び 水分を除去した。  Into a 1 000 mL flask equipped with a reflux condenser was charged 1 mol (228 g) of bisphenol A and 0.3 g of p-toluenesulfonic acid as a catalyst, and the internal temperature was raised to 100 ° C. 0.85 mol (69 g) of an aqueous formaldehyde solution was added over 1 hour and reacted at 100 ° C. under reflux for 2 hours. After that, leave the reaction vessel in water-cooled condition, and after the aqueous layer separated into the upper layer disappears, remove the aqueous layer by decantation, and further heat and stir until it reaches 170-175 ° C. Unreacted content and water were removed.
次に、 1 00°Cまで温度を下げ、 プチルセ口ソルプ 234 gを添加して重縮合 物を完全に溶解させた後、 純水 234 gを加え、 系内の温度が 50°Cまで下がつ たところで、 ジエタノールァミン 1モル (75 g) を添カロし、 これにホルムアル デヒド水溶液 1モル （8 1. 1 g ) を 50 °Cで約 1時間かけて滴下した。 さらに、 80°Cまで温度を上げ、 約 3時間攪拌しながら反応を続けカチオン性フエノール 系重縮合物 (B 1) を得た。 力チオン性フェノ一ル系重縮合物 (B 2) Next, the temperature was lowered to 100 ° C, and 234 g of ptylcete sorp was added to completely dissolve the polycondensate. Then, 234 g of pure water was added, and the temperature in the system was lowered to 50 ° C. Then, 1 mol (75 g) of diethanolamine was added, and 1 mol (81.1 g) of an aqueous formaldehyde solution was added dropwise at 50 ° C. over about 1 hour. Further, the temperature was raised to 80 ° C., and the reaction was continued with stirring for about 3 hours to obtain a cationic phenol polycondensate (B 1). Force thione phenol polycondensate (B 2)
還流冷却機を備えた 100 OmLのフラスコ内に、 フエノール 1モル （96g) 及ぴ触媒として p—トルエンスルホン酸 0 · 3 gを仕込み、 内部温度を 100。C まで上げ、 ホルムアルデヒド水溶液 0. 7モル （56.8 g) を 1時間かけて添加し 100°Cで 2時間還流下に反応させた。 その後、 反応容器を水冷静置し、 上層に 分離する水層の濁りがなくなつてから、 デカンテーシヨンして水層を除去し、 さ らに 170〜175°Cになるまで加熱攪拌して、 未反応分及ぴ水分を除去した。 次に、 100°Cまで温度を下げ、 ブチルセ口ソルブ 234 gを添加して重縮合 物を完全に溶解させた後、 純水 234 gを加え、 系内の温度が 50°Cまで下がつ たところで、 N—メチルプロパノ一ルァミン 1モル (89 g) を添カロし、 これに ホルムアルデヒド水溶液 0. 7モル （56. 8 g ) を 50。Cで約 1時間かけて滴 下した。 さらに、 80°Cまで温度を上げ、 約 3時間攪拌しながら反応を続けカチ オン性フエノール系重縮合物 （B2) を得た。  A 100 OmL flask equipped with a reflux condenser was charged with 1 mol (96 g) of phenol and 0 · 3 g of p-toluenesulfonic acid as a catalyst, and the internal temperature was 100. C was added, and 0.7 mol (56.8 g) of an aqueous formaldehyde solution was added over 1 hour, and the mixture was reacted at 100 ° C for 2 hours under reflux. Then, leave the reaction vessel in water-cooled condition, and after the aqueous layer separated into the upper layer disappears, decant and remove the aqueous layer, and further heat and stir until 170 ~ 175 ° C. Unreacted components and water were removed. Next, the temperature is lowered to 100 ° C, and 234 g of butyl caffeosolve is added to completely dissolve the polycondensate. Then, 234 g of pure water is added, and the temperature in the system is lowered to 50 ° C. At the same time, 1 mol (89 g) of N-methylpropanolamine was added, and then 0.7 mol (56.8 g) of an aqueous formaldehyde solution was added to 50 mol. C was added dropwise over about 1 hour. Further, the temperature was raised to 80 ° C., and the reaction was continued with stirring for about 3 hours to obtain a cationic phenol polycondensate (B2).
カチオン性フエノ一ル系重縮合物 (B 3) Cationic phenolic polycondensate (B 3)
還流冷却機を備えた 100 OmLのフラスコ内に、 O—タレゾール 1モル （1 08 g) 及び触媒として p—トルエンスルホン酸 0. 3 gを仕込み、 内部温度を 100°Cまで上げ、 ホルムアルデヒド水溶液 0. 85モル （69 g) を 1時間か けて添加し、 100°Cで 2時間還流下に反応させた。 その後、 反応容器を水冷静 置し、 上層に分離する水層の濁りがなくなつてから、 デカンテーシヨンして水層 を除去し、 さらに 170〜 175 °Cになるまで加熱攪拌して、 未反応分及び水分 を除去した。  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.
次に、 100°Cまで温度を下げ、 プチルセ口ソルブ 234 gを添加して重縮合 物を完全に溶解させた後、 純水 234 gをカロえ、 系内の温度が 50°Cまで下がつ たところで、 N, N—ジェチルエタノールァミン 1モル （117 g) を添加し、 これにホルムアルデヒド水溶液 1モル （81. 1 g) を 50°Cで約 1時間かけて 滴下した。 さらに、 80°Cまで温度を上げ、 約 3時間攪拌しながら反応を続け力 チオン性フエノール系重縮合物 （B3) を得た。  Next, the temperature was lowered to 100 ° C, and 234 g of butyl solvate was added to completely dissolve the polycondensate. Then, 234 g of pure water was removed and the temperature in the system was lowered to 50 ° C. Then, 1 mol (117 g) of N, N-jetylethanolamine was added, and 1 mol (81.1 g) of an aqueous formaldehyde solution was added dropwise thereto at 50 ° C. over about 1 hour. Furthermore, the temperature was raised to 80 ° C and the reaction was continued with stirring for about 3 hours to obtain a force thione phenol polycondensate (B3).
(2— 3) 金属化合物 （C) C I ：炭酸ジルコニウムアンモニゥム(2-3) Metal compounds (C) CI: Ammonium zirconium carbonate
C 2 ： フノレオ口ジルコニウム酸 C 2: Funoleo mouth zirconium acid
C 3 ：チタンラクテート  C3: Titanium lactate
C 4 ：フルォロチタン酸  C4: Fluorotitanic acid
(2-4) 金属化合物 (D)  (2-4) Metal compound (D)
D 1 ：酸ィ匕リチウム  D 1: Lithium acid
D 2 ：硝酸マグネシウム  D 2: Magnesium nitrate
D 3 ：酸化マグネシウム  D 3: Magnesium oxide
D 4 ：ァノレミニゥムァセチルァセトネート D 5 ： フッ化カルシウム  D 4: Anoleminium cetylacetonate D 5: Calcium fluoride
D 6 ：硝酸コバルト  D 6: Cobalt nitrate
D 7 ：硝酸ニッケル  D 7: Nickel nitrate
D8 ：炭酸ニッケル  D8: Nickel carbonate
D 9 ：硝酸ストロンチウム  D 9: Strontium nitrate
D 10 ：酸化モリブデン D 10: Molybdenum oxide
D 1 1 ：メタタングステン酸アンモニゥム D 1 1: Ammonium metatungstate
D 12 ：酸化セリゥム D 12: Ceric oxide
D 13 ：酸化亜鉛  D 13: Zinc oxide
D 14 ：亜鉛ァセチルァセトネート D 15 ：炭酸マンガン  D 14: Zinc acetyl chloride acetate D 15: Manganese carbonate
D 16 ：酸化マンガン  D 16: Manganese oxide
D 17 ： リン酸ニ水素マンガン  D 17: Manganese dihydrogen phosphate
(2— 5) 酸成分 （E)  (2-5) Acid component (E)
E 1 ： フッ化水素酸  E 1: Hydrofluoric acid
E 2 ： リン酸 E 2: Phosphoric acid
E 3 ：硝酸  E 3: Nitric acid
E 4 ：クェン酸  E 4 ： Chenic acid
E 5 ：シュゥ酸 (2-6) バナジウム化合物 (F) E 5: Oxalic acid (2-6) Vanadium compounds (F)
F 1 ：メタバナジン酸アンモニゥム  F 1: Ammonium metavanadate
F 3 ： リン酸バナジウム F 3: Vanadium phosphate
F 4 ：ォキシ硫酸バナジウム  F 4: Vanadium oxysulfate
(3) 処理方法  (3) Processing method
(3-1) 脱脂  (3-1) Degreasing
日本パーカライジング （株） 製アル力リ脱脂剤パルクリーン 364 S (20 g /L建浴、 60°C、 10秒スプレー、 スプレー圧 0. 5 k gZcm2) で素材を 脱月旨した後、 スプレー水洗を 10秒行つた。 Nippon Parkerizing Co., Ltd. Al-powered degreasing agent Pulclean 364 S (20 g / L building bath, 60 ° C, 10 seconds spray, spray pressure 0.5 kgZcm 2 ) Rinse for 10 seconds.
(3-2) 塗布及び乾燥  (3-2) Application and drying
I ：固形分濃度 10質量％に調整した金属表面処理剤 （媒体：水） を乾燥質量が 70 OmgZm2になるようにバーコート塗布し、 80。C (PMT：到達板温） で乾燥した。 I: Bar coating was applied to a metal surface treatment agent (medium: water) adjusted to a solid content concentration of 10% by mass so that the dry mass was 70 OmgZm 2 . Dried at C (PMT: ultimate plate temperature).
I I ：固形分濃度 16質量％に調整した金属表面処理剤 （媒体：水） を乾燥質量 が 100 Omg/m2になるようにバーコート塗布し、 150°C (PMT) で乾 燥した。 II: 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).
(4) 評価方法  (4) Evaluation method
(4-1) 耐食性  (4-1) Corrosion resistance
実施例、 比較例において作製した処理板試料について、 無加工 （平面部） 、 N Tカッターで素地到達までクロスカットしたもの （クロスカット部） 、 エリクセ ン 7 mm押し出し加工したもの （加工部） について、 耐食性試験を行った。 評価 方法は次の通りである。  For the processed plate samples prepared in the examples and comparative examples, no processing (planar part), cross-cutting to the base with an NT cutter (cross-cut part), extruding elixir 7 mm (processing part) A corrosion resistance test was performed. The evaluation method is as follows.
(平面部） 塩水噴霧試験法 J I S— Z— 2371に基づき塩水噴霧 360時間後 の白鲭発生面積を求め評価した。  (Flat part) Based on the salt spray test method JIS-Z-2371, the area where white haze occurred after 360 hours of salt spray was determined and evaluated.
評価基準：白鲭発生面積◎ 5 %未満、 〇 5 %以上〜 10 %未満、 Δ 10 %以上 〜 30 %未満、 X 30 %以上〜 50 %未満、 X X 50 %以上。 (クロスカツト部) 塩水噴霧試験法 J I S— Z— 2371に基づき塩水噴霧 36 0時間後の白鲭発生状況を肉眼で評価した。 Evaluation criteria: Area where white birch occurs ◎ Less than 5%, 〇 5% or more to less than 10%, Δ10% or more to less than 30%, X 30% or more to less than 50%, XX 50% or more. (Cross cut part) Salt spray test method Based on JIS-Z-2371, the occurrence of white mist after 360 hours of salt spray was evaluated with the naked eye.
評価基準：白鲭発生状況◎ほとんど鲭なし、 〇クロスカツト部に白鲭が発生し ていない部分が多い、 △クロスカット部の全てが白鲭になっているが、 流れ鲭な し、 Xクロスカツト部から流れ鲭が発生。 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.
(加工部） 塩水噴霧試験法 J I S— Z _ 2371に基づき塩水噴霧 360時間後 の白鲭発生状況を肉眼で評価した。  (Processing part) Based on the salt spray test method JIS—Z — 2371, the occurrence of white mist after 360 hours of salt spray was evaluated with the naked eye.
評価基準：白鲭発生状況◎ほとんど鲭なし、 〇加工部に白鲭が発生していない 部分が多い、 △加工部の全てが白鲭になっているが、 流れ鲭なし、 X加工部から 流れ鲭が発生。 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.
(4-2) 耐ァルカリ性  (4-2) Resistance to alkali
処理板試料に、 日本パー力ラィジング （株） 製アル力リ脱脂剤パルクリーン 3 64 Sを 20 g Z L水に建浴し 65 °Cに調整した脱脂剤水溶液を 5分間スプレー し、 水洗した後、 80°Cで乾燥した。 この板について、 上記 (4-1) に記載し た条件、 評価法で耐食性を評価した。  After spraying the treated plate sample with degreasing aqueous solution adjusted to 65 ° C for 5 minutes after basking Alpari degreasing agent Palclean 3 64 S manufactured by Nippon Parr Rising Co., Ltd. in 20 g ZL water and washing with water And dried at 80 ° C. The corrosion resistance of this plate was evaluated using the conditions and evaluation method described in (4-1) above.
(4-3) 耐黒変性  (4-3) Blackening resistance
処理板試料を温度 70 °C、 湿度 95 %雰囲気に 12日間放置した後、 外観を肉 眼で観察し評価した。  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.
評価基準：◎白鲭発生なし、 黒変なし、 〇白鲭発生なし、 黒変僅かにあり、 △白 鲭発生あり、 黒変僅かにあり、 X白鲭発生あり、 黒変かなりあり。 Evaluation criteria: ◎ No white wrinkle occurrence, no black discoloration, 〇No white discoloration occurrence, slight black discoloration, △ white flaw occurrence, slight black discoloration, X white discoloration occurrence, black discoloration considerably.
(4-4) 耐黄変性  (4-4) Yellowing resistance
処理板試料を温度 250°C雰囲気に 2時間放置した後、 外観を肉眼で観察し評 価し 7こ。  After the treated plate sample is left in an atmosphere of 250 ° C for 2 hours, the appearance is observed and evaluated with the naked eye.
評価基準：◎変色なし、 〇僅かに黄変、 △全面黄変、 X全面黄褐色。 本発明の態様 （1 ) についての金属表面処理剤の組成及び処理方法並びに試験評 価結果 Evaluation criteria: ◎ No discoloration, ○ Slightly yellow, △ All yellow, X All tan. Composition of metal surface treatment agent and treatment method and test evaluation results for embodiment (1) of the present invention
実施例 1 0 1〜： 1 7 7及び比較例 1 0 1〜 1 0 5の金属表面処理剤の組成及び 処理方法を表 1〜4に、 試験評価結果を表 5〜 7に示す。 表 5〜 7から明らかな ように、 本発明の態様 （1 ) の金属表面処理剤を用いて形成された皮膜を有する 実施例 1 0 1〜 1 4 3及ぴ 1 4 5〜： 1 7 7の金属材料は耐食性、 耐ァルカリ性、 及ぴ耐黄変性が良好で、 有害なクロムを含んでいないため安全性が高く、 平面部、 クロスカツト部、 加工部のいずれもクロメート処理と同等以上の優れた耐食性を 有していることが判る。 また、 (A) / (B ) の比が ( B ) リツチである実施例 1 4 4の金属材料は耐黄変性は劣っていたが、 耐食性及び耐ァルカリは優れてい た。 他方、 皮膜がカチオン性ウレタン樹脂 （A) を含まない比較例 1 0 1の金属 材料、 皮膜が本発明の金属表面処理剤の必須成分であるカチオン性フェノール系 重縮合物 (B ) を含まない比較例 1 0 2の金属材料、 金属化合物 (C) (すなわ ちジ コニゥム化合物及び/又はチタン化合物） を含まない比較例 1 0 3、  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. As is apparent from Tables 5 to 7, 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. Further, the metal material of 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. On the other hand, the metal material of Comparative Example 10 0 in which the film does not contain the cationic urethane resin (A), and the film does not contain the cationic phenol polycondensate (B) that is an essential component of the metal surface treatment agent of the present invention. 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),
(A) / (Β ) の比が本発明の範囲を外れる比較例 1 0 4の金属材料は耐食性、 耐アルカリ及ぴ耐黄変性のすべてにおいて明らかに劣っていた。 また、 また、 ク 口メート （ジンクロム 3 3 6 0 Η) 処理した比較例 1 0 5の金属材料は、 耐アル カリ†生が劣っていた。 The metal material of Comparative Example 10 4 in which the ratio (A) / (Β) was outside the scope of the present invention was clearly inferior in all of corrosion resistance, alkali resistance and yellowing resistance. In addition, the metal material of Comparative Example 10 5 treated with cucumber mate (zinc chromium 33 60 Η) had poor alkali resistance.
表 1 table 1
処理方法 金属表面処理剤の組成 (質量0 /o) Treatment method Composition of metal surface treatment agent (mass 0 / o)
金属  Metal
実施例 PMT*6  Example PMT * 6
材料 (A)/(B) (0 (E) (F)  Material (A) / (B) (0 (E) (F)
(A) (B) (°C) (mg/m2) (A) (B) (° C) (mg / m 2 )
*1 *2 *4 *5  * 1 * 2 * 4 * 5
実施例 101 I A1 B1 50/50 C2(3.0) E2(26.3) F4(0.4) 100 1000 実施例 102 I A1 B1 60/40 Cl(6.0) E3(14.1),E4(0.1) Fl(l.2) 100 1000 実施例 103 I A1 B1 70/30 C2(3.0) E2(14.1) F2(0.4) 100 1000 実施例 104 I A1 B1 90/10 C2(1.5) El (1.7), E2(10.5) F2(1.9) 100 1000 実施例 105 I A1 B1 95/5 C2(l.5) El (1.7)， E2(ll.7) F2(0.5) 100 1000 実施例 106 I A1 B1 99/1 CI (8.2) El (1.7)， E2(19.4) F2(10.1) 100 1000 実施例 107 I A1 B1 59/41 C2(10.7) E2(17.1), E3(2.5) F4(0.4) 100 1000 実施例 108 I A1 B1 81/19 CI (12.2) El (1.9), E2(23.6) F4(0.6) 100 1000 実施例 109 I A1 B1 95/5 C2(1.5) E2(11.7) F3(0.4) 100 1000 実施例 110 I A1 B1 99/1 CI (8.2) El (1.7)， E2(19.4) F2(10.1) 100 1000 実施例 111 I A1 B1 50/50 C2(3.0) E2(26.3) F2(0.4) 100 1000 実施例 112 I A1 B1 65/35 C2(2.9) E2(14.3) F4(0.7) 100 1000 実施例 113 I A1 B1 70/30 C2(3.0) E2 (14.1) F2(l.5) 100 1000 実施例 114 I A1 B1 80/20 CI (3.4) E2(14.1) F3(1.5) 100 1000 実施例 115 I A1 B1 95/5 C2C1.5) El (1.7), E2(11.7) F3(l.9) 100 1000 実施例 116 I A1 B1 98/2 CI (8.1) El(l.7), E2(19.4) F2(10.0) 100 1000 実施例 117 I A1 B1 60/40 CI (1.0) El (3.1), E5(7.4) F4(0.5) 100 1000 実施例 118 I A1 B1 70/30 C2(3.0) E2(14.1) F3(0.8) 100 1000 実施例 119 I A1 B1 59/41 C2(10.7) F4(0.4) 100 1000 実施例 120 I A1 B1 70/30 C2(3.0) F2(1.5) 100 1000 実施例 121 I A1 B1 81/19 CI (12.2) F4(0.6) 100 1000 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) El (1.9), E2 (23.6) F4 (0.6) 100 1000 Example 109 I A1 B1 95/5 C2 (1.5) E2 (11.7) F3 (0.4) 100 1000 Example 110 I A1 B1 99 / 1 CI (8.2) El (1.7), E2 (19.4) F2 (10.1) 100 1000 Example 111 I A1 B1 50/50 C2 (3.0) E2 (26.3) F2 (0.4) 100 1000 Example 112 I A1 B1 65/35 C2 (2.9) E2 (14.3) F4 (0.7) 100 1000 Example 113 I A1 B1 70/30 C2 (3.0) E2 (14.1) F2 (l.5) 100 1000 Example 114 I A1 B1 80 / 20 CI (3.4) E2 (14.1) F3 (1.5) 100 1000 Example 115 I A1 B1 95/5 C2C1.5) El (1.7), E2 (11.7) F3 (l.9) 100 1000 Example 116 I A1 B1 98/2 CI (8.1) El (l.7), E2 (19.4) F2 (10.0) 100 1000 Example 117 I A1 B1 60/40 CI (1.0 ) El (3.1), E5 (7.4) F4 (0.5) 100 1000 Example 118 I A1 B1 70/30 C2 (3.0) E2 (14.1) F3 (0.8) 100 1000 Example 119 I A1 B1 59/41 C2 ( 10.7) F4 (0.4) 100 1000 Example 120 I A1 B1 70/30 C2 (3.0) F2 (1.5) 100 1000 Example 121 I A1 B1 81/19 CI (12.2) F4 (0.6) 100 1000
表 2 Table 2
処理方法 金属表面処理剤の組成 (質量0 /0) The composition of the treatment method the metal surface treatment agent (wt 0/0)
金属  Metal
実施例 PMT*5  Example PMT * 5
材料 (E) (F)  Material (E) (F)
(A) (0  (A) (0
(B) (。c) (mg/m2) (B) (.c) (mg / m 2 )
*2 *3 *4  * 2 * 3 * 4
実施例 122 I A1 B1 90/10 C2(1.5) F2(1.9) 100 1000 実施例 123 I A1 . B1 99/1 C1 (8.2) F2(10.1) 100 1000 実施例 124 I A1 B1 60/40 C1 (1.0) F2(0.5) 100 1000 実施例 125 I A1 B1 50/50 C2(3.0) E2(13.2) 100 1000 実施例 126 I A1 B1 60/40 CI (1.0) El (1.9)， E5(4.4) 100 1000 実施例 127 I A1 B1 70/30 C2(3.0) E2 (9.9) 100 1000 実施例 128 I A1 B1 90/10 C2(l.5) El (1.5), E2 (9.5) 100 1000 実施例 129 I A1 B1 95/5 C2(l.5) E2(ll.1) 100 1000 実施例 130 I A1 B1 98/2 CI (8.1) El (1.7), E2(19.0) 100 1000 実施例 131 I A1 B1 50/50 C2(3.0) E2(13.2) 100 1000 実施例 132 I A1 B1 65/35 C2(2.9) E2(9.3) 100 1000 実施例 133 I A1 B1 70/30 C2(3.0) E2(9.9) 100 1000 実施例 134 I A1 B1 80/20 CI (3.4) E2(ll.3) 100 1000 実施例 135 I A1 B1 95/5 C2(l.5) El (1.6), E2(ll.1) 100 1000 実施例 136 I A1 B1 60/40 CI (1.0) 100 1000 実施例 137 I A1 B1 70/30 C2(3.0) 100 1000 実施例 138 I A2 B1 70/30 C2(3.0) E2(9.9) F2(l.5) 100 1000 実施例 139 I A3 B1 70/30 C2(3.0) E2(9.9) F2(l.5) 100 1000 実施例 140 I A1 B2 70/30 C2(3.0) E2(9.9) F2(l.5) 100 1000 実施例 141 I A1 B3 70/30 C2(3.0) E 2(9.9) F2(l.5) 100 1000 実施例 142 I A1 B1 60/40 CI (1.0) El (1.9), E5(4.4) F4(0.5) 100 1000 Example 122 I A1 B1 90/10 C2 (1.5) F2 (1.9) 100 1000 Example 123 I A1 .B1 99/1 C1 (8.2) F2 (10.1) 100 1000 Example 124 I A1 B1 60/40 C1 ( 1.0) F2 (0.5) 100 1000 Example 125 I A1 B1 50/50 C2 (3.0) E2 (13.2) 100 1000 Example 126 I A1 B1 60/40 CI (1.0) El (1.9), E5 (4.4) 100 1000 Example 127 I A1 B1 70/30 C2 (3.0) E2 (9.9) 100 1000 Example 128 I A1 B1 90/10 C2 (l.5) El (1.5), E2 (9.5) 100 1000 Example 129 I A1 B1 95/5 C2 (l.5) E2 (ll.1) 100 1000 Example 130 I A1 B1 98/2 CI (8.1) El (1.7), E2 (19.0) 100 1000 Example 131 I A1 B1 50 / 50 C2 (3.0) E2 (13.2) 100 1000 Example 132 I A1 B1 65/35 C2 (2.9) E2 (9.3) 100 1000 Example 133 I A1 B1 70/30 C2 (3.0) E2 (9.9) 100 1000 Example 134 I A1 B1 80/20 CI (3.4) E2 (ll.3) 100 1000 Example 135 I A1 B1 95/5 C2 (l.5) El (1.6), E2 (ll.1) 100 1000 Example 136 I A1 B1 60/40 CI (1.0) 100 1000 Example 137 I A1 B1 70/30 C2 (3.0) 100 1000 Example 138 I A2 B1 70/30 C2 (3.0) E2 (9.9) F2 (l. 5) 100 1000 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
表 table
処理方法 金属表面処理剤の組成 (質量0 /0) The composition of the treatment method the metal surface treatment agent (wt 0/0)
金属  Metal
実施例 PMT*5  Example PMT * 5
材料 (A)/(B) (0 (E) (F)  Material (A) / (B) (0 (E) (F)
(A) (B) (。c) (rag/m2) (A) (B) (.c) (rag / m 2 )
*1 *2 *3 *4  * 1 * 2 * 3 * 4
実施例 143 I A1 B1 60/40 Cl(l.O) El (1.9)， E5(4.4) F4(0.5) 50 2500 実施例 144 I A1 B1 20/80 C2(l.2) E2(5.3) F4(0.1) 100 1000 実施例 145 I A1 B1 65/35 C4(2.8) El(l.1),E5(1.7) Fl(3.7) 100 1000 実施例 146 I A1 B1 80/20 C3(12.0) E2(14.1) F3(1.7) 100 1000 実施例 147 I A1 B1 51/49 C4(0.3) E3(6.0),E5(0.4) F3 (1.0) 100 1000 実施例 148 I A1 B1 65/35 C4(L 7) E2(9.4) F2(0.7) 100 1000 実施例 149 I A1 B1 90/10 C3(1.5) E2(26.9) F3(15.7) 100 1000 実施例 150 I A1 B1 61/39 C3 (1.0) E1(1.9),E5(4.5) F3(0.3) 100 1000 実施例 151 I A1 B1 90/10 C4(0.9) El(l.3),E2(1.4) F2(l.7) 100 1000 実施例 152 I A1 B1 50/50 C4(3.0) E2(5.9),E4(7.6) Fl (0.3) 100 1000 実施例 153 I A1 B1 65/35 C3(2.9) E2(7.6),E4(9.9) F4(0.2) 100 1000 実施例 154 I A1 B1 90/10 C4(0.9) E1(1.3),E2(15.7) F3(0.6) 100 1000 実施例 155 I A1 B1 95/5 C3(0.8) E1(1.8),E2(1.2) F3(0.2) 100 1000 実施例 156 I A1 B1 97/3 C4(l.0) El(l.8),E2(1.3) F2(l.5) 100 1000 実施例 157 I A1 B1 50/50 C4(0.3) F3(l.0) 100 1000 実施例 158 I A1 B1 50/50 C4(3.0) F1(0.3) 100 1000 実施例 159 I A1 B1 65/35 C3(2.9) Fl (0.2) 100 1000 実施例 160 I A1 B1 90/10 C4(0.9) F3(0.6) 100 1000 実施例 161 I A1 B1 95/5 C3(0.8) F3(0.2) 100 1000 実施例 162 I A1 B1 97/3 C4(l.0) F2(l.5) 100 1000 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) F3 (0.3) 100 1000 Example 151 I A1 B1 90/10 C4 (0.9) El (l.3), E2 (1.4) F2 (l.7) 100 1000 Example 152 I A1 B1 50/50 C4 (3.0) E2 (5.9), E4 (7.6) Fl (0.3) 100 1000 Example 153 I A1 B1 65/35 C3 (2.9) E2 (7.6), E4 (9.9) F4 (0.2) 100 1000 Example 154 I A1 B1 90/10 C4 (0.9) E1 (1.3), E2 (15.7) F3 (0.6) 100 1000 Example 155 I A1 B1 95/5 C3 (0.8) E1 (1.8), E2 (1.2) F3 (0.2 ) 100 1000 Example 156 I A1 B1 97/3 C4 (l.0) El (l.8), E2 (1.3) F2 (l.5) 100 1000 Example 157 I A1 B1 50/50 C4 (0.3) F3 (l.0) 100 1000 Actual Example 158 I A1 B1 50/50 C4 (3.0) F1 (0.3) 100 1000 Example 159 I A1 B1 65/35 C3 (2.9) Fl (0.2) 100 1000 Example 160 I A1 B1 90/10 C4 (0.9) F3 (0.6) 100 1000 Example 161 I A1 B1 95/5 C3 (0.8) F3 (0.2) 100 1000 Example 162 I A1 B1 97/3 C4 (l.0) F2 (l.5) 100 1000
表 4 Table 4
処理方法 金属表面処理剤の組成 (質量0 /0) The composition of the treatment method the metal surface treatment agent (wt 0/0)
金属  Metal
実施例 P T*5  Example P T * 5
材料 (A)/(B) I (0 (E) (F)  Material (A) / (B) I (0 (E) (F)
(A) (B) (°C) (mg/m2) (A) (B) (° C) (mg / m 2 )
*1 *2 *3 *4  * 1 * 2 * 3 * 4
実施例 163 I A1 B1 65/35 C3 (2.9) E2(7.6),E4(9.9) 100 1000 実施例 164 I A1 B1 61/39 C3(l.0) E1(1.9),E5(4.5) 100 1000 実施例 165 I A1 B1 90/10 C4(0.9) El(l.3)，E2(1.4) 100 1000 実施例 166 I A1 B1 97/3 C4(l.0) E1(1.8)，E2(1.3) 100 1000 実施例 167 I A1 B1 50/50 C4(3.0) 100 1000 実施例 168 I A1 B1 65/35 C3 (2.9) 100 1000 実施例 169 I A1 B1 90/10 C4(0.9) 100 1000 実施例 170 I A1 B1 95/5 C3(0.8) 100 1000 実施例 171 I A1 B1 97/3 C4(l.0) 100 1000 実施例 172 II A1 B1 80/20 C3(12.0) E2(14.1) F3(l.7) 100 1000 実施例 173 III A1 B1 80/20 C3(12.0) E2(14.1) F3(l.7) 100 1000 実施例 174 IV A1 B1 80/20 C3 (12.0) E2(14.1) F3(l.7) 100 1000 実施例 175 I A1 B1 65/35 C4(2.8) El(l.1),E5(1.7) Fl (3.7) 100 1000 実施例 176 I A1 B1 65/35 C4(l.7) E2(9.4) F2(0.7) 100 1000 実施例 177 I A1 B1 65/35 C4(2.8) El(l.1),E5(1.7) Fl (3.7) 100 1000 比較例 101 I 実施例 103の組成より成分 (A)のみ除いた 100 1000 比較例 102 I 実施例 103の組成より成分 (B)のみ除いた 100 1000 比較例 103 I 実施例 103の組成より成分 (C)のみ除いた 100 1000 比較例 104 I A1 B1 99.5/0.5 CI (8.3) El(l.7),E2(19.3) F2(10.1) 100 1000 比較例 105 I クロメー卜 *6 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 167 I A1 B1 50/50 C4 (3.0) 100 1000 Example 168 I A1 B1 65/35 C3 (2.9) 100 1000 Example 169 I A1 B1 90/10 C4 (0.9) 100 1000 Example 170 I A1 B1 95/5 C3 (0.8) 100 1000 Example 171 I A1 B1 97/3 C4 (l.0) 100 1000 Example 172 II A1 B1 80/20 C3 (12.0) E2 (14.1) F3 (l. 7) 100 1000 Example 173 III A1 B1 80/20 C3 (12.0) E2 (14.1) F3 (l.7) 100 1000 Example 174 IV A1 B1 80/20 C3 (12.0) E2 (14.1) F3 (l. 7) 100 1000 Example 175 I A1 B1 65/35 C4 (2.8) El (l.1), E5 (1.7) Fl (3.7) 100 1000 Example 176 I A1 B1 65/35 C4 (l.7) E2 (9.4) F2 (0.7) 100 1000 Example 177 I A1 B1 65/35 C4 (2.8) El (l.1), E5 (1.7) Fl (3.7) 100 1000 Comparative Example 101 I Composition from the composition of Example 103 100 (excluding (A) only) 100 Comparative Example 102 I Component from the composition of Example 103 (B) 100 1000 Comparative Example 103 I Excluding only component (C) from the composition of Example 103 100 1000 Comparative Example 104 I A1 B1 99.5 / 0.5 CI (8.3) El (l.7), E2 (19.3) F2 ( 10.1) 100 1000 Comparative Example 105 I Chrome * 6
表 1〜4において、 (A) はカチオン性ウレタン榭月旨、 (B) はカチオン性フ ヱノーノレ系重縮合物、 （C) は金属化合物 （ジノレコニゥム化合物及び Z又はチタ ン化合物） 、 (E) は酸成分、 （F) はバナジウム化合物を表す。 また、 * 1は 固形分配合比率 （質量比） 、 * 2及び * 4は成分 （A) と成分 (B) との合計固 形分 100質量部に対する、 それぞれジルコニウム及び/又はチタン、 並びにバ ナジゥムとしての配合割合 （質量部） 、 * 3は成分 （A) と成分 （B) との合計 固形分 100質量部に対する、 水を含まない酸成分そのものとしての配合割合In Tables 1 to 4, (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, and (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
(質量部） をそれぞれ表す。 * 5は到達板温である。 * 6は日本パー力ライジン グ （株） 製の塗布クロメートであるジンクロム 3360Hをクロム付着量で 20 mgZm2になるようにロールコートし、 100°C (PMT) で加熱乾燥した。 (Parts by mass) respectively. * 5 is the ultimate plate temperature. * 6 was roll-coated with Zinchrome 3360H, a coating chromate made by Nippon Pariki Rising Co., Ltd. so that the amount of chromium deposited was 20 mgZm 2 and dried by heating at 100 ° C (PMT).
表 5 Table 5
耐食性 麵アルカリ性  Corrosion resistance 麵 Alkaline
耐黄 クロスかクト クロスか:  Yellow or cross cloth:
平面部 加工部 平面部 加工部 変性 部 部  Flat part Machining part Flat part Machining part Modification part
実施例 101 ◎ ◎ © ◎ 〇 〇 〇 実施例 102 ◎ ◎ ◎ ◎ ◎ ◎ 実施例 103 ◎ ◎ ◎ ◎ ◎ ◎ 実施例 104 ◎ ◎ ◎ ◎ ◎ ◎ 実施例 105 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 106 ◎ ◎ ◎ ◎ 〇 〇 〇 実施例 107 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 108 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 109 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 110 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 111 ◎ ◎ ◎ ◎ 〇 〇 〇 実施例 112 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 113 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 114 ◎ ◎ ◎ ◎ ◎ ◎ 実施例 115 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 116 ◎ ◎ ◎ ◎ ◎ ◎ ® 実施例 117 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 118 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 119 〇 〇 〇 〇 〇 〇 ◎ 実施例 120 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 121 ◎ ◎ ◎ ◎ ◎ © 実施例 122 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 123 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 124 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 125 ◎ ◎ ◎ 〇 〇 〇 〇 実施例 126 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 127 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 128 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 129 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 130 ◎ o 〇 〇 〇 〇 ◎ 実施例 131 ◎ ◎ ◎ 〇 0 〇 〇 実施例 132 ◎ ◎ ◎ ◎ ◎ ◎ 実施例 133 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 134 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 135 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 136 〇 〇 〇 o 〇 o ◎ 実施例 137 ◎ © ◎ ◎ ◎ ◎ ◎ 表 6 Example 101 ◎ ◎ © ◎ 〇 〇 〇 Example 102 ◎ ◎ ◎ ◎ ◎ ◎ Example 103 ◎ ◎ ◎ ◎ ◎ ◎ Example 104 ◎ ◎ ◎ ◎ ◎ ◎ Example 105 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 106 ◎ ◎ ◎ ◎ 〇 〇 Example 107 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 108 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 109 ◎ ◎ ◎ ◎ ◎ ◎ Example 110 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 111 ◎ ◎ ◎ ◎ 〇 〇 Example 112 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 113 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 114 ◎ ◎ ◎ ◎ ◎ ◎ Example 115 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 116 ◎ ◎ ◎ ◎ ◎ ◎ Example 117 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 118 ◎ ◎ ◎ ◎ ◎ ◎ Example 119 〇 〇 〇 〇 ◎ ◎ Example 120 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 121 ◎ ◎ ◎ ◎ ◎ © Example 122 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 123 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 124 ◎ ◎ ◎ ◎ ◎ ◎ Example 125 ◎ ◎ 〇 〇 〇 Example 126 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 127 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 128 ◎ ◎ ◎ ◎ ◎ ◎ Example 129 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 130 ◎ o 〇 〇 〇 ◎ Example 131 ◎ ◎ ◎ 〇 〇 〇 Example Example 132 ◎ ◎ ◎ ◎ ◎ ◎ Example 133 ◎ ◎ ◎ ◎ ◎ ◎ Example 134 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 135 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 136 ○ ○ ○ o ○ o ◎ Example 137 ◎ © ◎ ◎ ◎ ◎ ◎ Table 6
耐食性 ァルカリ性  Corrosion resistance
耐黄 クロスかット クロス;！ /ット  Yellow-resistant cross or cross! / T
平面部 加工部 平面部 加工部 変性 部 部  Flat part Machining part Flat part Machining part Modification part
実施例 138 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 139 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 140 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 141 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 142 〇 〇 〇 〇 〇 0 〇 実施例 143 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 144 ◎ ◎ © ◎ ◎ X 実施例 145 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 146 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 147 ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 148 ◎ ◎ ◎ ◎ ◎ 〇 実施例 149 ◎ ◎ ◎ ◎ 〇 〇 ◎ 実施例 150 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 151 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 152 ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 153 ◎ ◎ ◎ © ◎ ◎ ◎ 実施例 154 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 155 ◎ ◎ ◎ ◎ ◎ ◎ 実施例 156 ◎ 〇 ◎ ◎ 〇 ◎ ◎ 実施例 157 ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 158 ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 159 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 160 〇 〇 〇 〇 〇 〇 ◎ 実施例 161 ◎ ◎ 〇 〇 〇 ◎ 実施例 162 ◎ 〇 ◎ 〇 〇 © ◎ 実施例 163 ◎ ◎ © ◎ ◎ ◎ 実施例 164 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 165 ◎ ◎ 〇 〇 〇 ◎ . 実施例 166 ◎ 〇 〇 ◎ 〇 〇 .◎ 実施例 167 ◎ 〇 〇 ◎ 〇 〇 〇 実施例 168 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 169 〇 〇 〇 〇 〇 〇 ◎ 実施例 170 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 m ◎ 〇 〇 〇 〇 〇 ◎ 実施例 172 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 173 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 174 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 表 7 Example 138 ◎ ◎ ◎ ◎ ◎ ◎ Example 139 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 140 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 141 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 142 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Example 143 ◎ ◎ ◎ ◎ ◎ ◎ Example 144 ◎ ◎ © ◎ ◎ X Example 145 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 146 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 147 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 148 ◎ ◎ ◎ ◎ 〇 Example 149 ◎ ◎ ◎ ◎ 〇 ◎ Example 150 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 151 ◎ ◎ ◎ ◎ ◎ ◎ Example 152 ◎ ◎ ◎ ◎ ◎ ◎ Example 153 ◎ ◎ ◎ © ◎ ◎ ◎ Example 154 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 155 ◎ ◎ ◎ ◎ ◎ ◎ Example 156 ◎ ◎ ◎ ◎ ◎ ◎ Example 157 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 158 ◎ ◎ ◎ ◎ ◎ ◎ Example 159 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 160 〇 〇 〇 〇 〇 Example 163 ◎ ◎ 〇 〇 〇 ◎ Example 162 ◎ ◎ ◎ 〇 〇 Example 163 ◎ ◎ © ◎ ◎ ◎ Example 164 ◎ ◎ ◎ ◎ ◎ ◎ Example 165 ◎ ◎ 〇 〇 〇 ◎ Example 166 ◎ ◎ 〇 〇 〇 〇 〇 〇 Example 167 ◎ 〇 ◎ 〇 〇 〇 Example 168 ◎ ◎ ◎ ◎ ◎ ◎ Example 169 〇 〇 〇 〇 ◎ Example 170 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example m ◎ 〇 〇 〇 〇 ◎ Example 172 ◎ ◎ ◎ ◎ ◎ ◎ Example 173 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 174 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Table 7
耐食性 翻 'アル力リ '  Corrosion resistance
耐黄 クロス iiット ク Pス ト  Yellow Resistant Cross ii Stick P St
平面部 加工部 平面部 加工部 変性 部 部  Flat part Machining part Flat part Machining part Modification part
実施例 175 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 176 ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 177 ◎ ◎ ◎ ◎ ◎ ◎ 比較例 101 厶 Δ X Δ X X X 比較例 102 X Δ X X 厶 X Δ 比較例 103 X X X X X X X X △ 比較例 104 厶 △ X Δ Δ 厶 Δ 比較例 105 ◎ 〇 〇 厶 X X ◎ Example 175 ◎ ◎ ◎ ◎ ◎ ◎ Example 176 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 177 ◎ ◎ ◎ ◎ ◎ ◎ Comparative Example 101 厶 Δ X Δ XXX Comparative Example 102 X Δ XX 厶 X Δ Comparative Example 103 XXXXXXXX △ Comparative example 104 厶 △ X Δ Δ 厶 Δ Comparative example 105 ◎ ○ ○ XX XX ◎
本発明の態様 （2 ) についての金属表面処理剤の組成及び処理方法並びに試験評 価結果 Composition of metal surface treatment agent and treatment method and test evaluation results for embodiment (2) of the present invention
実施例 2 0 1〜 2 5 1及ぴ比較例 2 0 1〜 2 0 6の金属表面処理剤の組成及び 処理方法を表 8〜 1 0に、 試験評価結果を表 1 1及び 1 2に示す。 表 1 1及び 1 2から明らかなように、 本発明の金属表面処理剤を用いて形成された皮膜を有す る実施例 2 0 1〜 2 5 0の金属材料は耐食性、 耐ァルカリ、 耐黒変性及び耐黄変 性が良好で、 有害なクロムを含んでいないため安全性が高く、 平面部、 クロス力 ット部、 加工部のいずれもクロメート処理と同等以上の優れた耐食性を有してい ることが判る。 また、 （A) / (B ) の比が (B ) リツチである実施例 2 5 1の 金属材料は耐黄変性は劣っていたが、 耐食性、 耐アルカリ及ぴ耐黒変性は優れて いた。 他方、 皮膜がカチオン性ウレタン樹脂 （A) を含まない比較例 2 0 1の金 属材料、 皮膜が本発明の金属表面処理剤の必須成分である力チオン性フェノール 系重縮合物 （B ) を含まない比較例 2 0 2の金属材料、 皮膜がジルコニウム化合 物 （C) を含まない比較例 2 0 3、 及ぴ （A) / (B ) の比が本発明の範囲を外 れる比較例 2 0 5の金属材料は耐食性、 耐ァルカリ、 耐黒変性及ぴ耐黄変性のす ベてにおいて明らかに劣っていた。 また、 皮膜が金属化合物 (D) (すなわち、 L i、 M g、 A l、 C a、 Mn、 C o、 N i、 Z n、 S r、 W、 C e及び M oか ら選ばれる少なくとも 1種の金属を含有する化合物 (D) ) を含まない比較例 2 0 4は耐黒変性が不十分であった。 また、 クロメート （ジンクロム 3 3 6 0 H) 処理した比較例 2 0 6の金属材料は、 耐ァルカリ性が劣っていた。 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. . As is apparent from Tables 11 and 12, 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. I understand that Further, the metal material of 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. On the other hand, the metal material of Comparative Example 210 in which the film does not contain the cationic urethane resin (A), the force thione phenol polycondensate (B) whose film is an essential component of the metal surface treatment agent of the present invention. 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 metal material No. 5 was clearly inferior in all of corrosion resistance, alkali resistance, blackness resistance and yellowing resistance. Further, 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.
Figure imgf000043_0001
Figure imgf000043_0001
表 9 Table 9
処理方法 金属表面処理剤の組成 （質量0 /0) The composition of the treatment method the metal surface treatment agent (wt 0/0)
金属  Metal
実施例 P T*6  Example P T * 6
材料 (D) (E) (F)  Material (D) (E) (F)
(A) (B) (0 (°C) (rag/m2) (A) (B) (0 (° C) (rag / m 2 )
*2 *3 *4 *5  * 2 * 3 * 4 * 5
実施例 222 I A1 B1 90/10 C2(l.5) D3(0.7) F2(l.9) 100 1000 実施例 223 I A1 B1 99/1 C1 (8.2) D5(0.6),D9(0.4) F2(10.1) 100 1000 実施例 224 I A1 B1 60/40 Cl(l.0) D1(0.7),D5(0.5) F2(0.5) 100 1000 実施例 225 I A1 B1 50/50 C2(3.0) D4(4.7) E2(13.2) 100 1000 実施例 226 I A1 B1 60/40 CI (1.0) D1(0.7),D5(0.5) E1(1.9),E5(4.4) 100 1000 実施例 227 I A1 B1 70/30 C2(3.0) D7(l.5) E2(9.9) 100 1000 実施例 228 I A1 B1 90/10 C2(1.5) D3(0.7) El(l.5),E2(9.5) 100 1000 実施例 229 I A1 B1 95/5 C2(l.5) D3(1.0) E2(ll.1) 100 1000 実施例 230 I A1 B1 98/2 CI (8.1) D5(0.6),D9(0.4) El(l.7),E2(19.0) 100 1000 実施例 231 I A1 B1 50/50 C2(3.0) D14(l.5) . E2(13.2) 100 1000 実施例 232 I A1 B1 65/35 C2(2.9) D8(1.3) E2(9.3) 100 1000 実施例 233 I A1 B1 70/30 C2(3.0) D2(0.3) E2(9.9) 100 1000 実施例 234 I A1 B1 80/20 CI (3. ) D6(0.3),D7(0.3) E2(ll.3) 100 1000 実施例 235 I A1 B1 95/5 C2(l.5) D3(1.0) E1(1.6)，E2(1L 1) 100 1000 実施例 236 I A1 B1 60/40 CI (1.0) Dl (0.7), D5(0.5) 100 1000 実施例 237 I A1 B1 70/30 C2(3.0) D7(1.5) 100 1000 実施例 238 I A2 B1 70/30 C2(3.0) D2(0.3) E2(9.9) F2(l.5) 100 1000 実施例 239 I A3 B1 70/30 C2(3.0) D2(0.3) E2(9.9) F2(l.5) 100 1000 実施例 240 I A1 B2 70/30 C2(3.0) D2(0.3) E2(9.9) F2(l.5) 100 1000 実施例 241 I A1 B3 70/30 C2(3.0) D2(0.3) E2(9.9) F2 (1.5) 100 1000 実施例 242 I A1 B1 60/40 Cl(l.0) D1(0.7), D5(0.5) E1(1.9),E5(4.4) F4(0.5) 100 30 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.5) D3 (1.0) E2 (ll.1) 100 1000 Example 230 I A1 B1 98/2 CI (8.1) D5 (0.6), D9 (0.4) El (l.7 ), E2 (19.0) 100 1000 Example 231 I A1 B1 50/50 C2 (3.0) D14 (l.5) .E2 (13.2) 100 1000 Example 232 I A1 B1 65/35 C2 (2.9) D8 (1.3 ) E2 (9.3) 100 1000 Example 233 I A1 B1 70/30 C2 (3.0) D2 (0.3) E2 (9.9) 100 1000 Example 234 I A1 B1 80/20 CI (3.) D6 (0.3), D7 (0.3) E2 (ll.3) 100 1000 Example 235 I A1 B1 95/5 C2 (l.5) D3 (1.0) E1 (1.6), E2 (1L 1) 100 1000 Example 236 I A1 B1 60 / 40 CI (1.0) Dl (0.7), D5 (0.5) 100 100 0 Example 237 I A1 B1 70/30 C2 (3.0) D7 (1.5) 100 1000 Example 238 I A2 B1 70/30 C2 (3.0) D2 (0.3) E2 (9.9) F2 (l.5) 100 1000 Implementation Example 239 I A3 B1 70/30 C2 (3.0) D2 (0.3) E2 (9.9) F2 (l.5) 100 1000 Example 240 I A1 B2 70/30 C2 (3.0) D2 (0.3) E2 (9.9) F2 (l.5) 100 1000 Example 241 I A1 B3 70/30 C2 (3.0) D2 (0.3) E2 (9.9) F2 (1.5) 100 1000 Example 242 I A1 B1 60/40 Cl (l.0) D1 (0.7), D5 (0.5) E1 (1.9), E5 (4.4) F4 (0.5) 100 30
表 10 Table 10
処理方法 金属表面処理剤の組成 （質量％)  Treatment method Composition of metal surface treatment agent (mass%)
実施例 金属  Examples Metal
P T*6 付着量 比較例 材料 (C) (D) (E) (F)  P T * 6 Adhesion amount Comparative example Material (C) (D) (E) (F)
(A) (B) (°C) (mg/m2) (A) (B) (° C) (mg / m 2 )
*2 *3 *4 *5  * 2 * 3 * 4 * 5
実施例 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 実施例 44 I A1 B1 80/20 C2(3.4) D15(0.3) E2(14.1),E3(2.5) F2(l.5) 100 1000 実施例 245 I A1 B1 80/20 C2(6.8) D15(1.0) F2(2.l) 100 1000 実施例 246 I A1 B1 80/20 C2<3.4) D16(0.3) E2(14.1),E3(2.5) 100 1000 実施例 247 I A1 B1 80/20 C2(6.8) D16(1.0) 100 1000 実施例 248 II A1 B1 65/35 C2(2.9) D8(l.3) E2(14.3) F4(0.7) 100 1000 実施例 249 III A1 B1 65/35 C2(2.9) D8(l.3) E2(14.3) F4(0.7) 100 1000 実施例 250 IV A1 B1 65/35 C2(2.9) D8(l.3) E2(14.3) F4(0.7) 100 1000 実施例 251 I A1 B1 20/80 C2(1.2) D13(1.9) E2(5.3) F4(0.1) 100 1000 比較例 201 I 実施例 203の組成より成分 (A)のみ除いた 100 1000 比較例 202 I 実施例 203の組成より成分 (B)のみ除レ、た 100 1000 比較例 203 I 実施例 203の組成より成分 (C)のみ除いた 100 1000 比較例 204 I 実施例 203の組成より成分 (D)のみ除いた 100 1000 比較例 205 I A1 B1 99.5/0.5 CI (8.3) D9(0.4) 、、 El (1.7),E2(19.3) F2(10.1) 100 1000 比較例 206 I クロメ —ト *7 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 247 I A1 B1 80/20 C2 (6.8) D16 (1.0) 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 IV A1 B1 65/35 C2 (2.9) D8 (l.3) E2 (14.3) F4 (0.7) 100 1000 Example 251 I A1 B1 20/80 C2 (1.2) D13 (1.9) E2 (5.3 ) F4 (0.1) 100 1000 Comparative Example 201 I Only component (A) was removed from the composition of Example 203 100 1000 Comparative Example 202 I Only component (B) was removed from the composition of Example 203 100 1000 Comparative Example 203 I 100 1000 comparative example in which only component (C) was removed from the composition of Example 203 100 I Comparative example 205 I A1 B1 99.5 / 0.5 CI (8.3) D9 ( 0. 4),, El (1.7), E2 (19.3) F2 (10.1) 100 1000 Comparative Example 206 I Chromate * 7
表 8〜10において、 （A) はカチオン性ウレタン樹脂、 （B) はカチオン性 フエノール系重縮合物、 （C) はジルコニウム化合物、 (D) は金属化合物、In Tables 8 to 10, (A) is a cationic urethane resin, (B) is a cationic phenol polycondensate, (C) is a zirconium compound, (D) is a metal compound,
(E) は酸成分、 (F) はバナジウム化合物を表す。 また、 * 1は固形分配合比 率 （質量比） 、 *2、 * 3及び * 5は成分 （A) と成分 （B) との合計固形分 1 00質量部に対する、 それぞれジルコニウム、 金属及びバナジウムとしての配合 割合 （質量部） 、 *4は成分 （A) と成分 （B) との合計固形分 100質量部に 対する、 水を含まない酸成分そのものとしての配合割合 （質量部） をそれぞれ表 す。 * 6は到達板温である。 * 7は日本パーカライジング （株） 製の塗布ク口メ 一トであるジンクロム 3360Hをクロム付着量で 2 Omg/m2になるように ローノレコートし、 100°C (PMT) で加熱乾燥した。 (E) represents an acid component, and (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).
表 1 1 Table 1 1
耐食性 而:アル力リ性  Corrosion resistance
耐黒 耐黄 タロスカット  Black resistance Yellow resistance Taros cut
平面部 加工部 平面部 加工部 変性 変性 部  Flat part Machining part Flat part Machining part Denaturation Modification part
実施例 201 ◎ ◎ ◎ ◎ 〇 〇 〇 〇 実施例 202 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 203 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 204 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 205 ◎ ◎ ◎ ◎ ◎ ◎ ◎ © 実施例 206 ◎ ◎ ◎ ◎ 〇 O ◎ 〇 実施例 207 ◎ ◎ ◎ ◎ ◎ © ◎ ◎ 実施例 208 ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ 実施例 209 ◎ © ◎ ◎ ◎ ◎ ◎ ◎ 実施例 210 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 211 ◎ ◎ ◎ ◎ 〇 〇 〇 〇 実施例 212 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 213 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 214 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 215 ◎ ◎ © ◎ ◎ ◎ ◎ ◎ 実施例 216 ◎ ◎ ◎ ◎ ® ◎ 〇 ◎ 実施例 217 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 218 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 219 〇 〇 〇 〇 〇 〇 〇 ◎ 実施例 220 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 221 ◎ ◎ ◎ ◎ ◎ ◎ o 実施例 222 ◎ ◎ ◎ ◎ ◎ ◎ ◎ © 実施例 223 ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ 実施例 224 ◎ ◎ ◎ ◎ ◎ ◎ o ◎ 実施例 225 ◎ ◎ ◎ o 〇 〇 o 〇 実施例 226 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 227 ◎ ◎ ◎ ◎ ® ◎ ◎ ◎ 実施例 228 ◎ ◎ ◎ ◎ © ◎ ◎ ◎ 実施例 229 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 230 ◎ 〇 〇 〇 〇 〇 〇 ◎ 実施例 231 ◎ ◎ ◎ 〇 〇 〇 〇 〇 実施例 232 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 233 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 234 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 235 ◎ ◎ ◎ ◎ ◎ © ◎ ◎ 実施例 236 〇 〇 0 〇 〇 〇 〇 ◎ 実施例 237 ◎ ◎ ◎ ◎ ◎ © ◎ 表 1 2 Example 201 ◎ ◎ ◎ ◎ 〇 〇 〇 Example 202 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 203 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 204 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 205 ◎ ◎ ◎ ◎ ◎ ◎ ◎ © Example 206 ◎ ◎ ◎ ◎ 〇 O ◎ 〇 Example 207 ◎ ◎ ◎ ◎ ◎ © ◎ ◎ Example 208 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 209 ◎ © ◎ ◎ ◎ ◎ ◎ ◎ Example 210 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 211 ◎ ◎ ◎ ◎ 〇 〇 〇 Example 212 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 213 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 214 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 215 ◎ ◎ © ◎ ◎ ◎ ◎ ◎ Example 216 ◎ ◎ ◎ ◎ ® ◎ ◎ ◎ Example 217 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 218 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 219 〇 〇 〇 〇 〇 ◎ Example 220 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 221 ◎ ◎ ◎ ◎ ◎ ◎ o Example 222 ◎ ◎ ◎ ◎ ◎ ◎ ◎ © Example 223 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 224 ◎ ◎ ◎ ◎ ◎ ◎ o ◎ Example 225 ◎ ◎ ◎ o ○ ○ o ○ Example 226 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 227 ◎ ◎ ◎ ◎ ® ◎ ◎ ◎ Example 228 ◎ ◎ ◎ ◎ © ◎ ◎ ◎ Example 229 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 230 ◎ 〇 〇 〇 〇 〇 Example 231 ◎ ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 Example 232 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 233 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 234 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 235 ◎ ◎ ◎ ◎ ◎ © ◎ ◎ Example 236 〇 〇 〇 〇 〇 〇 〇 〇 〇 ◎ ◎ Example 237 ◎ ◎ ◎ ◎ ◎ © ◎ Table 1 2
耐食性 ϋ 'アル力リ ' 14  Corrosion resistance ϋ 'Al strength' 14
耐黒 耐黄 クロスカット  Black resistance Yellow resistance Cross cut
平面部 加工部 平面部 加工部 変性 変性 部  Flat part Machining part Flat part Machining part Denaturation Modification part
実施例 238 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 239 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 240 ◎ ◎ ◎ ◎ © ◎ ◎ ◎ 実施例 241 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 242 〇 〇 〇 〇 〇 〇 〇 〇 実施例 243 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 244 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 245 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 実施例 246 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 247 ◎ ◎ ◎ 〇 〇 〇 〇 ◎ 実施例 248 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 249 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 250 ◎ ◎ © ◎ ◎ ◎ ◎ ◎ 実施例 251 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ 比較例 201 Δ Δ X Δ X X Δ X 比較例 202 X 厶 X X △ X 厶 Δ 比較例 203 X X X X X X X X Δ Δ 比較例 204 © ◎ ◎ ◎ ◎ ◎ △ ◎ 比較例 205 厶 Δ X Δ 厶 X Δ Δ 比較例 206 O Δ Δ X X X Δ ◎ Example 238 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 239 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 240 ◎ ◎ ◎ ◎ © ◎ ◎ ◎ Example 241 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 242 〇 〇 〇 ○ ○ ○ ○ ○ Example 243 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 244 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 245 ◎ ◎ ◎ ◎ ◎ ◎ Example 246 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 247 ◎ ◎ ◎ 〇 〇 〇 ◎ Example 248 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 249 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 250 ◎ ◎ © ◎ ◎ ◎ ◎ ◎ Example 251 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ Comparative Example 201 Δ Δ X Δ XX Δ X Comparative Example 202 X 厶 XX △ X 厶 Δ Comparative Example 203 XXXXXXXX Δ Δ Comparative Example 204 © ◎ ◎ ◎ ◎ ◎ △ ◎ Comparative Example 205 厶 Δ X Δ 厶 X Δ Δ Comparative Example 206 O Δ Δ XXX Δ ◎
本発明の態様 ( 3 ) についての金属表面処理剤の組成及び処理方法並びに試験評 価結果 Composition of metal surface treatment agent and treatment method and test evaluation results for embodiment (3) of the present invention
実施例 3 0 1〜 3 4 2及ぴ比較例 3 0 1〜 3 0 6の金属表面処理剤の組成及び 処理方法を表 1 3〜 1 5に、 試験評価結果を表 1 6及び 1 7に示す。 表 1 6及び 1 7から明らかなように、 本発明の金属表面処理剤を用いて形成された皮膜を有 する実施例 3 0 1〜 3 4 2の金属材料は耐食十生、 耐ァルカリ、 耐黒変性及び耐黄 変性が良好で、 有害なクロムを含んでいないため安全性が高く、 平面部、 クロス カツト部、 加工部のいずれもクロメート処理と同等以上の優れた耐食 ¾feを有して いることが判る。 他方、 皮膜がカチオン性ウレタン樹脂 （A) を含まない比較例 3 0 1の金属材料、 皮膜がカチオン性フエノール系重縮合物 ( B ) を含まない比 較例 3 0 2の金属材料、 皮膜がチタン化合物 (C) を含まない比較例 3 0 3の金 属材科、 及び （A) Z (B ) の比が本発明の範囲を外れる比較例 3 0 5の金属材 料は耐食性、 耐アルカリ、 耐黒変性及ぴ耐黄変性のすべてにおいて明らかに劣つ ていた。 また、 皮膜が金属化合物 （D) (すなわち、 L i、 M g、 A l、 C a、 Mn、 C o、 N i、 Z n、 S r、 W、 C e及び M oから選ばれる少なくとも 1種 の金属を含有する化合物 (D) ) を含まない比較例 3 0 4の金属材料は耐黒変性 が不十分であった。 また、 クロメート （ジンクロム 3 3 6 0 H) 処理した比較例 3 0 6の金属材料は、 アルカリ脱脂後の加工部の耐食性が劣っていた。 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 ¾fe equivalent to or better than chromate treatment. I understand that. On the other hand, 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. Further, 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. Further, 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.
表 13 Table 13
処理方法 金属表面処理剤の組成 （質量0 /0) The composition of the treatment method the metal surface treatment agent (wt 0/0)
金属  Metal
実施例 PMT*6 付着量 材料 (c) (D) (E) (F)  Example PMT * 6 Amount deposited Material (c) (D) (E) (F)
(A) (B) (°C) (mg/m2) (A) (B) (° C) (mg / m 2 )
*2 *3 *4 *5  * 2 * 3 * 4 * 5
実施例 301 I A1 B1 65/35 C4(2.8) Dl(l.O) El(l.1),E5(1.7) Fl(3.7) 100 1000 実施例 302 I A1 B1 80/20 C3(12.0) D5(8.0) E2(14.1) F3(l.7) 100 1000 実施例 303 I A1 B1 51/49 C4(0.3) D6(2.8) E3(6.0),E5(0.4) F3(1.0) 100 1000 実施例 304 I A1 B1 65/35 C4(1.7) D7(1.4) E2(9.4) F2(0.7) 100 1000 実施例 305 I A1 B1 90/10 C3(1.5) D4(0.5) E2 (26.9) F3(15.7) 100 1000 実施例 306 I A1 B1 61 ΐ/39 C3 (1.0) Dl (0.7),D10(0.5) El (1.9)， E5 (4.5) F3 (0.3) 100 1000 実施例 307 I A1 B1 90/10 C4(0.9) D17 (0.2),D15(0.2) El(l.3),E2(1.4) F2(l.7) 100 1000 実施例 308 I A1 B1 50/50 C4(3.0) D6(0.1), D8(l.5) E2(5, 9),E4(7.6) F1(0.3) 100 1000 実施例 309 I A1 B1 65/35 C3(2.9) D10(0.7),D11(0.3) E2(7.6),E4(9.9) F4(0.2) 100 1000 実施例 310 I A1 B1 90/10 C4(0.9) D4(0.9),D14(0.8) E1(1.3),E2(15.7) F3(0.6) 100 1000 実施例 311 I A1 B1 95/5 C3(0.8) D17(0.7) E1(1.8),E2(1.2) F3(0.2) 100 1000 実施例 312 I A1 B1 97/3 C4(1.0) D17(0.2) El(l.8)，E2(1.3) F2(1.5) 100 1000 実施例 313 I A1 B1 50/50 C4(0.3) D6(2.8) F3(1.0) 100 1000 実施例 314 I A1 B1 50/50 C4(3.0) D6(0.1)，D8(1.5) F1(0.3) 100 1000 実施例 315 I A1 B1 65/35 C3(2.9) D10(0.7)，D11(0.3) F1(0.2) 100 1000 実施例 316 I A1 B1 90/10 C4(0.9) D4(0.9), D14(0.8) F3(0.6) 100 1000 実施例 317 I A1 B1 95/5 C3(0.8) D17(0.7) F3(0.2) 100 1000 実施例 318 I A1 B1 97/3 C4(1.0) D17(0.2) F2(1.5) 100 1000 実施例 319 I A1 B1 65/35 C3(2.9) D10(0.7)，D11(0.3) E2(7.6),E4(9.9) 100 1000 実施例 320 I A1 B1 61/39 C3(1.0) Dl (0.7),D10(0.5) E1(1.9),E5(4.5) 100 1000 実施例 321 I A1 B1 90/10 C4(0.9) D17(0.2),D15(0.2) E1(1.3),E2(1.4) 100 1000 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 ΐ / 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), D15 (0.2) El (l.3), E2 (1.4) F2 (l.7) 100 1000 Example 308 I A1 B1 50/50 C4 (3.0) D6 (0.1), D8 (l. 5) E2 (5, 9), E4 (7.6) F1 (0.3) 100 1000 Example 309 I A1 B1 65/35 C3 (2.9) D10 (0.7), D11 (0.3) E2 (7.6), E4 (9.9) F4 (0.2) 100 1000 Example 310 I A1 B1 90/10 C4 (0.9) D4 (0.9), D14 (0.8) E1 (1.3), E2 (15.7) F3 (0.6) 100 1000 Example 311 I A1 B1 95 / 5 C3 (0.8) D17 (0.7) E1 (1.8), E2 (1.2) F3 (0.2) 100 1000 Example 312 I A1 B1 97/3 C4 (1.0) D17 (0.2) El (l.8), E2 (1.3) F2 (1.5) 100 1000 Example 313 I A1 B1 50/50 C4 (0. 3) D6 (2.8) F3 (1.0) 100 1000 Example 314 I A1 B1 50/50 C4 (3.0) D6 (0.1), D8 (1.5) F1 (0.3) 100 1000 Example 315 I A1 B1 65/35 C3 (2.9) D10 (0.7), D11 (0.3) F1 (0.2) 100 1000 Example 316 I A1 B1 90/10 C4 (0.9) D4 (0.9), D14 (0.8) F3 (0.6) 100 1000 Example 317 I A1 B1 95/5 C3 (0.8) D17 (0.7) F3 (0.2) 100 1000 Example 318 I A1 B1 97/3 C4 (1.0) D17 (0.2) F2 (1.5) 100 1000 Example 319 I A1 B1 65 / 35 C3 (2.9) D10 (0.7), D11 (0.3) E2 (7.6), E4 (9.9) 100 1000 Example 320 I A1 B1 61/39 C3 (1.0) Dl (0.7), D10 (0.5) E1 (1.9 ), E5 (4.5) 100 1000 Example 321 I A1 B1 90/10 C4 (0.9) D17 (0.2), D15 (0.2) E1 (1.3), E2 (1.4) 100 1000
表 14 Table 14
処理方法 金属表面処理剤の組成 （質量0） Treatment method Composition of metal surface treatment agent (mass 0 )
金属  Metal
実施例 PMT*6  Example PMT * 6
材料  Material
(A) (B) (0 (D) (E) (F)  (A) (B) (0 (D) (E) (F)
(°C) (rag/m2) *2 *3 *4 *5 (° C) (rag / m 2 ) * 2 * 3 * 4 * 5
実施例 322 I A1 B1 97/3 C4(1.0) D17(0.2) El(l.8), E2 (1.3) 100 1000 実施例 323 I A1 B1 50/50 C4(3.0) D6(0.1), D8(l.5) 100 1000 実施例 324 I A1 B1 65/35 C3(2.9) D10(0.7),D11(0.3) 100 1000 実施例 325 I A1 B1  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
3 90/10 C4(0.9) D4(0.9),D14(0.8) 100 1000 実施例 326 I A1 B1 95/5 C3(0.8) D17(0.7) 100 1000 実施例 327 I A1 B1 97/3 C4(l.0) D17(0.2) 100 1000 実施例 328 II A1 B1 80/20 C3(12.0) D5(8.0) E2(14.1) F3(l.7) 100 1000 実施例 329 III A1 B1 80/20 C3(12.0) D5(8.0) E2(14.1) F3(1.7) 100 1000 実施例 330 IV A1 B1 80/20 C3(12.0) D5(8.0) E2(14.1) F3(L 7) 100 1000 実施例 331 I A1 B1 65/35 C4(2.8) D9(l.0) El(l.1),E5(1.7) Fl(3.7) 100 1000 実施例 332 I A1 B1 65/35 C4(l.7) D9(1.4) E2(9.4) F2(0.7) 100 1000 実施例 333 I A1 B1 65/35 C4(2.8) D12(1.0) El(l.1),E5(1.7) Fl(3.7) 100 1000 実施例 334 I A1 B1 90/10 C4(0.9) D4(0.9),D13(0.8) El(l.3),E2(15.7) F3(0.6) 100 1000 実施例 335 I A1 B1 70/30 C4(1.8) D3(0.7) E2(14.1) F2(1.5) 100 1000 実施例 336 I A1 B1 95/5 C4(0.5) D2(1.4) El (2.6), E2 (15.6) Fl(5.5) 100 1000 実施例 337 I A1 B1 95/5 C4(2.0) D2(l.0) E1(2.4),E2(19.4) F3(l.7) 100 1000 実施例 338 I A1 B1 95/5 C4(2-.0) D3(l.0) F3(l.7) 100 1000 実施例 339 I A1 B1 70/30 C4(1.9) D2(0.7) F2(l.5) 100 1000 実施例 340 I A1 B1 95/5 C4(0.5) D3 (1. ) El (2.6),E2(15.6) 100 1000 実施例 341 I A1 B1 95/5 C4(2.0) D3(1.0) E1(2.4),E2(19.4) 100 1000 実施例 342 I A1 B1 50/50 C4(6.0) D3(l.3) E2(25) 100 1000 3 90/10 C4 (0.9) D4 (0.9), D14 (0.8) 100 1000 Example 326 I A1 B1 95/5 C3 (0.8) D17 (0.7) 100 1000 Example 327 I A1 B1 97/3 C4 (l .0) D17 (0.2) 100 1000 Example 328 II A1 B1 80/20 C3 (12.0) D5 (8.0) E2 (14.1) F3 (l.7) 100 1000 Example 329 III A1 B1 80/20 C3 (12.0 ) D5 (8.0) E2 (14.1) F3 (1.7) 100 1000 Example 330 IV A1 B1 80/20 C3 (12.0) D5 (8.0) E2 (14.1) F3 (L 7) 100 1000 Example 331 I A1 B1 65 / 35 C4 (2.8) D9 (l.0) El (l.1), E5 (1.7) Fl (3.7) 100 1000 Example 332 I A1 B1 65/35 C4 (l.7) D9 (1.4) E2 ( 9.4) F2 (0.7) 100 1000 Example 333 I A1 B1 65/35 C4 (2.8) D12 (1.0) El (l.1), E5 (1.7) Fl (3.7) 100 1000 Example 334 I A1 B1 90 / 10 C4 (0.9) D4 (0.9), D13 (0.8) El (l.3), E2 (15.7) F3 (0.6) 100 1000 Example 335 I A1 B1 70/30 C4 (1.8) D3 (0.7) E2 ( 14.1) F2 (1.5) 100 1000 Example 336 I A1 B1 95/5 C4 (0.5) D2 (1.4) El (2.6), E2 (15.6) Fl (5.5) 100 1000 Example 337 I A1 B1 95/5 C4 (2.0) D2 (l.0) E1 (2.4), E2 (19.4) F3 (l.7) 100 1000 Example 338 I A1 B1 95/5 C4 (2-.0) D3 (l.0) F3 ( l.7) 100 1000 Example 339 I A1 B1 70/30 C4 (1.9) D2 (0.7) F2 (l.5) 100 1000 Example 340 I A1 B1 95/5 C4 (0.5) D3 (1.) El (2.6), E2 (15.6) 100 1000 Example 341 I A1 B1 95/5 C4 (2.0) D3 (1.0) E1 (2.4), E2 (19.4) 100 1000 Example 342 I A1 B1 50/50 C4 (6.0) D3 (l.3) E2 (25) 100 1000
表 1 5 Table 15
処理方法 金属表面処理剤の組成 （質量％)  Treatment method Composition of metal surface treatment agent (mass%)
金属  Metal
実施例 P T*6  Example P T * 6
材料 (C) (D) (E) (F)  Material (C) (D) (E) (F)
(A) (B) (°C) (mg/ra2) (A) (B) (° C) (mg / ra 2 )
*2 *3 *4 *5  * 2 * 3 * 4 * 5
比較例 301 I 実施例 304の組成より成分 （A) のみ除いた 100 1000 比較例 302 I 実施例 304の組成より成分 （B) のみ除いた 100 1000 比較例 303 I 実施例 304の組成より成分 (C) のみ除いた 100 1000 比較例 304 I 実施例 304の組成より成分 (D) のみ除いた 100 1000 比較例 305 I A1 B1 22/78 C3 (5. 5) D15 (5. 5) El (2. 2) , E2 (2. 2) F2 (0. 7) 100 1000 比較例 306 I クロメー卜 *7 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
表 13〜15において、 （A) はカチオン性ウレタン樹脂、 (B) はカチオン 性フエノール系重縮合物、 （C) はチタン化合物、 （D) は金属化合物、 (E) は酸成分、 （F) はバナジウム化合物を表す。 また、 * 1は固形分配合比率 （質 量比） 、 *2、 * 3及ぴ * 5は成分 （A) と成分 （B) との合計固形分 100質 量部に対する、 それぞれチタン、 金属及びバナジウムとしての配合割合 （質量 部） 、 *4は成分 （A) と成分 (B) との合計固形分 100質量部に対する、 水 を含まない酸成分そのものとしての配合割合 （質量部） をそれぞれ表す。 * 6は 到達板温である。 * 7は日本パーカライジング （株） 製の塗布クロメートである ジンクロム 3360Hをクロム付着量で 2 OmgZm2になるようにロールコー トし、 100°C (PMT) で加熱乾燥した。 In Tables 13 to 15, (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).
表 1 6 Table 1 6
耐食性 アルカリ性  Corrosion resistance Alkaline
耐黒 耐黄 クロスカット クロス; *ット 平面部 加工部 平面部 加工部 変性 変性 部 部  Black resistance Yellow resistance Cross cut Cross; *
実施例 301 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 302 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 303 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 304 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 305 ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ 実施例 306 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 307 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 308 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 309 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 310 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 311 ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ 実施例 312 ◎ 〇 ◎ © 0 ◎ ◎ ◎ 実施例 313 © ® ◎ ◎ ◎ ◎ ◎ 〇 実施例 314 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 実施例 315 ◎ ◎ ◎ ◎ ◎ ◎ . 〇 ◎ 実施例 316 〇 o 〇 〇 〇 〇 〇 ◎ 実施例 317 ◎ ◎ ◎ 〇 〇 〇 〇 ◎ 実施例 318 ◎ 〇 ◎ 〇 〇 ◎ 〇 ◎ 実施例 319 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 320 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 321 ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ 実施例 322 ◎ 〇 〇 ◎ 〇 〇 . ◎ ◎ 実施例 323 ◎ 〇 〇 ◎ o 〇 〇 〇 実施例 324 ◎ ◎ ◎ ◎ ◎ ◎ 〇 © 実施例 325 〇 〇 〇 〇 〇 〇 〇 © 実施例 326 © ◎ ◎ ◎ ◎ 〇 ◎ 実施例 327 〇 0 〇 〇 〇 〇 ◎ 実施例 328 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 329 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 330 ◎ ◎ ◎ ◎ ◎ ◎ © ◎ 実施例 331 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 332 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 333 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 334 ◎ ◎ ◎ ◎ ◎ © ◎ ◎ 実施例 335 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 実施例 336 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 337 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ W 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 © ® ◎ ◎ ◎ ◎ ◎ 〇 Example 314 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 Example 315 ◎ ◎ ◎ ◎ ◎ ◎. ◎ ◎ Example 316 〇 o 〇 〇 〇 〇 ◎ Example 317 ◎ ◎ ◎ 〇 〇 〇 〇 ◎ Example 318 ◎ ◎ ◎ 〇 ◎ ◎ ◎ Example 319 ◎ ◎ ◎ ◎ ◎ Example 320 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 321 ◎ ◎ ◎ 〇 〇 ◎ ◎ ◎ Example 322 ◎ 〇 ◎ ◎ 〇 〇 ◎ ◎ ◎ Example 323 ◎ 〇 〇 ◎ o 〇 〇 〇 Example 324 ◎ ◎ ◎ ◎ ◎ ◎ 〇 © Example 325 〇 〇 〇 〇 〇 〇 © Example 326 © ◎ ◎ ◎ ◎ 〇 ◎ Example 327 000 0 〇 〇 〇 ◎ ◎ Example 328 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 329 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 330 ◎ ◎ ◎ ◎ ◎ © ◎ Example 331 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 332 ◎ ◎ ◎ ◎ ◎ Example 333 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 334 ◎ ◎ ◎ ◎ ◎ © ◎ ◎ Example 335 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 336 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 337 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ W
54 54
表 1 7 Table 1 7
耐食性 赚 -ァルカリ 4  Corrosion resistance 赚 -Alcali 4
耐黒 耐黄 タロスカット クロスカット  Black resistance Yellow resistance Taros cut Cross cut
平面部 加工部 平面部 加工部 変性 変性 部 部  Flat part Machining part Flat part Machining part Modification Modification part
実施例 338 © 〇 ◎ © 〇 ◎ ◎ ◎ 実施例 339 ◎ © ◎ ◎ ◎ ◎ ◎ ◎ 実施例 340 ◎ ◎ © ◎ © ◎ ◎ ◎ 実施例 341 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 実施例 342 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 比較例 301 Δ Δ X Δ X X Δ 〇 比較例 302 X 厶 X X Δ X Δ X 比較例 303 X X X X X X X X 厶 Δ 比較例 304 ◎ ◎ ◎ ◎ ◎ ◎ 厶 〇 比較例 305 Δ Δ X Δ 厶 X 厶 X 比較例 306 〇 Δ 厶 X X X Δ ◎  Example 338 © ○ ◎ © ○ ◎ ◎ ◎ Example 339 ◎ © ◎ ◎ ◎ ◎ ◎ ◎ Example 340 ◎ ◎ © ◎ © ◎ ◎ ◎ Example 341 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 342 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Comparative example 301 Δ Δ X Δ XX Δ 〇 Comparative example 302 X 厶 XX Δ X Δ X Comparative example 303 XXXXXXXX 厶 Δ Comparative example 304 ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 Comparative example 305 Δ Δ X Δ X 厶 X Comparative Example 306 ○ Δ 厶 XXX Δ ◎

Claims

請 求 の 範 囲 The scope of the claims
1 カチオン性の水溶性もしくは水系ェマルジヨンウレタン樹脂 （A) (以下、 カチオン性ウレタン樹脂 (A) という） 、 フエノール系化合物とアルデ ヒド類との重縮合物であってカチオン性のもの （B) (以下、 カチオン性フエノ 一ル系重縮合物 (B) という） 、 並びにジルコ二ゥム化合物及び/又はチタン化 合物 (C) (以下、 金属化合物 (C) という） を水性媒体に配合してなる金属表 面処理剤であって、 カチオン性ウレタン樹脂 （A) とカチオン性フエノール系重 縮合物 （B) との配合比率が、 固形分質量比として、 （A) ： (B) =99 ： 1 〜1 : 99でぁり、 金属化合物 (C) の配合割合が、 カチオン性ウレタン樹月旨1 Cationic water-soluble or aqueous emulsion urethane resin (A) (hereinafter referred to as cationic urethane resin (A)), a polycondensation product of phenolic compounds and aldehydes that are cationic (B ) (Hereinafter referred to as a cationic phenolic polycondensate (B)), and a zirconium compound and / or a titanium compound (C) (hereinafter referred to as a metal compound (C)) in an aqueous medium. The compounding ratio of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) is expressed as the solid content mass ratio as follows: (A): (B) = 99: 1 to 1 : 99, the compounding ratio of the metal compound (C) is cationic urethane
(A) とカチオン性フエノール系重縮合物 (B) との合計固形分 100質量部に 対し、 ジルコニウム及び/又はチタンとして 0. 1〜20質量部である該金属表 面処理剤。 This metal surface treating agent is 0.1 to 20 parts by mass as zirconium and / or titanium with respect to 100 parts by mass of the total solid content of (A) and the cationic phenolic polycondensate (B).
2 金属化合物 (C) がジルコ二ゥム化合物であり、 さらに L i、 Mg、 Al、 Ca、 Mn、 Co、 N i、 Zn、 S r、 W、 C e及び M oから選ばれる少 なくとも 1種の金属を含有する化合物 (D) (以下、 金属化合物 （D) という） を、 その配合割合がカチオン性ウレタン樹脂 （A) とカチオン性フエノール系重 縮合物 (B) との合計固形分 100質量部に対し、 該金属として 0. 01〜10 質量部となるように配合した請求項 1記載の金属表面処理剤。  2 The metal compound (C) is a zirconium compound, and at least selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo Compound (D) containing one type of metal (hereinafter referred to as metal compound (D)), the total solid content of the cationic urethane resin (A) and cationic phenol polycondensate (B) The metal surface treating agent according to claim 1, wherein the metal surface treatment agent is blended so as to be 0.01 to 10 parts by mass as the metal with respect to 100 parts by mass.
3 カチオン性ウレタン樹脂 （A) とカチオン性フエノール系重縮合物 3 Cationic Urethane Resin (A) and Cationic Phenolic Polycondensate
(B) との配合比率が、 固形分質量比として、 （A) ： (B) =99 : 1〜5 0： 50である請求項 1記載の金属表面処理剤。 The metal surface treatment agent according to claim 1, wherein the blending ratio with (B) is (A) :( B) = 99: 1 to 50:50 as a solid content mass ratio.
4 カチオン性ウレタン樹脂 （A) とカチオン性フエノール系重縮合物 (B) との配合比率が、 固形分質量比として、 （A) ： (B) =99 : 1〜5 0： 50である請求項 2記載の金属表面処理剤。  4 The mixing ratio of the cationic urethane resin (A) to the cationic phenol polycondensate (B) is (A) :( B) = 99: 1 to 50:50 Item 2. The metal surface treatment agent according to Item 2.
5 金属化合物 （C) がチタン化合物であり、 さらに L i、 Mg、 A l、 Ca、 Mn、 C o、 N i、 Zn、 S r、 W、 C e及ぴ Moから選ばれる少なくと も 1種の金属を含有する化合物 (D) (すなわち、 金属化合物 (D) ) を配合し、 カチオン性ウレタン樹脂 （A) とカチオン性フエノール系重縮合物 （B) との配 合比率が、 固形分質量比として、 （A) ： (B) =99 ： ：！〜 50 ： 50である 請求項 1記載の金属表面処理剤。 5 The metal compound (C) is a titanium compound, and at least 1 selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo. Compound (D) containing a metal of some kind (that is, metal compound (D)), The mixing ratio of the cationic urethane resin (A) to the cationic phenol polycondensate (B) is (A) :( B) = 99 ::! The metal surface treatment agent according to claim 1, which is ˜50: 50.
6 無機酸及び有機酸から選ばれる少なくとも 1種の酸成分 （E) (以下、 酸成分 （E) という） を、 その配合割合が、 カチオン性ウレタン樹脂 （A) と力 チォン性フエノ一ル系重縮合物 （ B ) との合計固形分 100質量部に対し、 水を 含まなレ、酸成分そのものとして 1〜 30質量部となるように配合した請求項 1記 載の金属表面処理剤。  6 At least one acid component (E) selected from inorganic acids and organic acids (hereinafter referred to as “acid component (E)”) is mixed in the proportion of cationic urethane resin (A) and strong phenolic phenol. The metal surface treating agent according to claim 1, wherein the total solid content of the polycondensate (B) is 100 parts by mass with respect to 100 parts by mass of water and the acid component itself is blended so as to be 1 to 30 parts by mass.
7 無機酸及び有機酸から選ばれる少なくとも 1種の酸成分 （E) (以下、 酸成分 （E) という） を、 その配合割合が、 カチオン性ウレタン樹脂 （A) と力 チオン性フエノール系重縮合物 (B) との合計固形分 100質量部に対し、 水を 含まなレ、酸成分そのものとして：！〜 30質量部となるように配合した請求項 2記 載の金属表面処理剤。  7 At least one acid component (E) selected from inorganic acids and organic acids (hereinafter referred to as “acid component (E)”) is mixed with cationic urethane resin (A) and thione phenol polycondensation. For 100 parts by mass of the total solid content with the product (B), the acid component itself: The metal surface treating agent according to claim 2, which is blended so as to be -30 mass parts.
8 無機酸及び有機酸から選ばれる少なくとも 1種の酸成分 （E) (以下、 酸成分 （E) という） を、 その配合割合が、 カチオン性ウレタン樹脂 （A) と力 チオン性フエノール系重縮合物 (B) との合計固形分 100質量部に対し、 水を 含まなレ、酸成分そのものとして 1〜 30質量部となるように配合した請求項 5記 載の金属表面処理剤。  8 At least one acid component (E) selected from inorganic acids and organic acids (hereinafter referred to as “acid component (E)”) is mixed with cationic urethane resin (A) and thione phenol polycondensation. The metal surface treating agent according to claim 5, which is blended so that the total solid content with the product (B) is 1 to 30 parts by mass as the acid component itself, without water.
9 バナジウム化合物 (F) を、 その配合割合が、 カチオン性ウレタン樹 脂 （A) とカチオン性フヱノール系重縮合物 （B) との合計固形分 100質量部 に対し、 バナジウムとして 0. 01〜20質量部となるように配合した請求項 1 記載の金属表面処理剤。  9 The vanadium compound (F) is mixed in an amount of 0.01 to 20 as vanadium with respect to 100 parts by mass of the total solid content of the cationic urethane resin (A) and the cationic phenol polycondensate (B). The metal surface treating agent according to claim 1, formulated so as to be part by mass.
10 バナジウム化合物 （F) を、 その配合割合が、 カチオン"生ウレタン 樹脂 （A) とカチオン性フエノール系重縮合物 (B) との合計固形分 100質量 部に対し、 バナジゥムとして 0. 01〜20質量部となるように配合した請求項 2記載の金属表面処理剤。  10 Vanadium compound (F) was added in a vanadium amount of 0.01 to 20 per 100 parts by mass of the total solid content of cationic raw green resin (A) and cationic phenol polycondensate (B). 3. The metal surface treatment agent according to claim 2, which is blended so as to be part by mass.
1 1 バナジウム化合物 (F) を、 その配合割合が、 カチオン性ウレタン 樹月旨 （A) とカチオン性フエノール系重縮合物 (B) との合計固形分 100質量 部に対し、 バナジウムとして 0. 0 1〜20質量部となるように配合した請求項 5記載の金属表面処理剤。 1 1 The total solid content of the vanadium compound (F) is 100% by mass with the proportion of the cationic urethane, Kitsuki (A) and the cationic phenol polycondensate (B). 6. The metal surface treatment agent according to claim 5, wherein the metal surface treatment agent is blended so as to have a content of 0.01 to 20 parts by mass as vanadium with respect to parts.
1 2 カチオン性ウレタン樹脂 （A) において、 該樹脂にカチオン性を与 える官能基が下記一般式 （I) 、 （1 1) 、 （I I I) 又は （I V)  1 2 In the cationic urethane resin (A), the functional group imparting cationicity to the resin is represented by the following general formula (I), (11), (I I I) or (IV)
R1 R1 R 1 R 1
N R3 A NR 3 A
R2 R 2
R0 R6 R 0 R 6
N ― N― R、 (IV) N ― N― R, (IV)
R Β' R Β '
(式中、 I 1、 R2、 R3、 R6、 及び R 7は互いに独立に水素原子、 炭素数 1〜1 0の直鎖もしくは分枝鎖のアルキル基又は炭素数：！〜 1 0の直鎖もしくは分枝鎖 のヒドロキシアルキル基を表し、 R4及び R5は互いに独立に炭素数 2〜1 0の 直鎖もしくは分枝鎖のアルキレン基を表し、 A—及ぴ B—は水酸イオン又は酸ィ オンを表す） で表される基である請求項 1、 2又は 5記載の金属表面処理剤。 (In the formula, I 1 , R 2 , R 3 , R 6 and R 7 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or carbon number:! To 10. R 4 and R 5 independently of each other represent a linear or branched alkylene group having 2 to 10 carbon atoms, and A— and B— represent water. The metal surface treatment agent according to claim 1, 2 or 5, wherein the metal surface treatment agent is a group represented by the following formula:
1 3 カチオン性ウレタン樹脂 (A) がポリオールとポリイソシァネート との重縮合物であるウレタン榭脂において、 用いるポリオールの一部として、 非 置換もしくは置換アミノ基を有するポリオール又は窒素原子を主鎖中に有するポ リオールを用いることによつて得られるゥレタン樹脂である力、 又は該ウレタン 榭脂の窒素原子を 4級化したウレタン樹脂である請求項 1、 2又は 5記載の金属 表面処理剤。  1 3 In the urethane resin in which the cationic urethane resin (A) is a polycondensate of a polyol and a polyisocyanate, as a part of the polyol used, a polyol having an unsubstituted or substituted amino group or a nitrogen atom as the main chain The metal surface treatment agent according to claim 1, 2 or 5, wherein the metal surface treatment agent is a urethane resin obtained by quaternizing a nitrogen atom of the urethane resin, or a force that is a urethane resin obtained by using polyol contained therein.
14 カチオン性フエノール系重縮合物 (B) がフエノール系化合物とァ ルデヒドとを重縮合させる際に、 アンモニアもしくはアミンを共存させることに よつて得られる重縮合物であるカゝ、 又は該重縮合物の窒素原子を 4級化したもの である請求項 1、 2又は 5記載の金属表面処理剤。 1 5 金属材料表面に、 請求項 1〜 1 1の!/、ずれか 1項に記載の金属表面 処理剤を塗布した後、 乾燥することによって該金属材料表面に皮膜を形成させる ことを特徴とする金属材料の表面処理方法。 14 Cationic phenolic polycondensate (B) is a polycondensate obtained by the coexistence of ammonia or an amine when the phenolic compound and aldehyde are polycondensed, or the polycondensation The metal surface treating agent according to claim 1, 2 or 5, wherein the nitrogen atom of the product is quaternized. 1. The metal surface treatment agent according to claim 1 is applied to the surface of the metal material, and then a film is formed on the surface of the metal material by drying. A surface treatment method for a metal material.
1 6 請求項 1 5記載の表面処理方法を用いて形成された皮膜を有する金 属材料。  1 6 A metal material having a film formed by using the surface treatment method according to claim 15.
PCT/JP2005/019837 2004-10-22 2005-10-21 Agent for treating metal surface, method of treating surface of metallic material, and surface-treated metallic material WO2006043727A1 (en)

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