Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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
  • C23C22/07—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 phosphates
  • C23C22/08—Orthophosphates
  • C23C22/12—Orthophosphates containing zinc cations
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/21—Urea; Derivatives thereof, e.g. biuret
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
  • C08K5/405—Thioureas; Derivatives thereof
• • 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
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/56—After-treatment
• • 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
  • C23C22/07—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 phosphates
  • C23C22/08—Orthophosphates
  • C23C22/12—Orthophosphates containing zinc cations
  • C23C22/17—Orthophosphates containing zinc cations containing also organic acids
• • 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
  • C23C22/07—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 phosphates
  • C23C22/08—Orthophosphates
  • C23C22/18—Orthophosphates containing manganese cations
• • 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
  • C23C22/07—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 phosphates
  • C23C22/08—Orthophosphates
  • C23C22/20—Orthophosphates containing aluminium cations
• • 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
  • C23C22/46—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 oxalates
  • C23C22/47—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 oxalates containing also phosphates
• • 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
  • C23C22/68—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 solutions with pH between 6 and 8
• • 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
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment
• • 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
  • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
  • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
  • Y10T428/12771—Transition metal-base component
  • Y10T428/12778—Alternative base metals from diverse categories

Definitions

• the present invention relates to a finish for a trivalent chromium chemical conversion film, particularly a finish for forming a hexavalent chromium-free corrosion-resistant film that has few scratches and spots, and is excellent in gloss and corrosion resistance, a finishing method using the same, and a hexavalent chromium-free corrosion resistance
• the present invention relates to a metal article having a film.
• Hexavalent chromium is used as a main component in the formation of the chromate film by chromic acid treatment performed here.
• hexavalent chromium has a bad influence on the human body and the environment, and the movement to regulate the use of hexavalent chromium has become active.
• an alternative technology for hexavalent chromate is strongly demanded in the industrial world.
• a trivalent chromium chemical conversion coating finish containing a trivalent chromium source, a phosphate ion source, a zinc ion source, and a chelating agent capable of forming a complex with trivalent chromium (for example, JP-A-2005-23372).
• the film does not cause problems in insulation and tightening properties.
• this film has a lot of scratches due to contact between the products and green spots caused by liquid pools in the drying process in the finishing process. There may be a problem that spots such as white spots or white spots occur. In addition, there may be a problem that mold occurs in the finish.
• the present invention provides a trivalent chromium chemical conversion film, in particular, a black trivalent chromium chemical conversion film having low insulation, no problem in tightening, excellent gloss and high corrosion resistance, and few scratches and spots.
• An object of the present invention is to provide a water-soluble finish for a trivalent chromium chemical conversion film.
• Another object of the present invention is to provide a finishing method for obtaining the trivalent chromium chemical conversion film.
• Another object of the present invention is to provide a metal article having a hexavalent chromium-free corrosion-resistant coating.
• the present invention relates to a trivalent chromium source, a phosphate ion source, a zinc ion source, a chelating agent capable of forming a complex with trivalent chromium, and polyvinyl alcohol and derivatives thereof for a substrate having a trivalent chromium conversion coating.
• the present invention relates to a trivalent chromium source, a phosphate ion source, a zinc ion source, a chelating agent capable of forming a complex with trivalent chromium, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone and derivatives thereof, and polyalkylene glycol. And a derivative thereof, and a non-ionic water-soluble polymer compound selected from the group consisting of cellulose ethers and derivatives thereof.
• the present invention is also selected from a trivalent chromium source, a phosphate ion source, a zinc ion source, a chelating agent capable of forming a complex with trivalent chromium, and urea, thiourea, dithiothiourea and derivatives thereof.
• the present invention provides a trivalent chromium chemical conversion coating finish characterized by containing an anti-smudge agent.
• the present invention also provides a trivalent chromium source, a phosphate ion source, a zinc ion source, a chelating agent capable of forming a complex with trivalent chromium, the nonionic water-soluble polymer compound, and the stain prevention.
• a finishing agent for a trivalent chromium chemical conversion film characterized by containing an agent.
• the present invention also contains a trivalent chromium complex, a phosphate ion, a zinc ion, a nonionic water-soluble polymer and / or a stain inhibitor, and water, and is in the form of an aqueous solution.
• the high molecular weight compound is selected from the group consisting of polyvinyl alcohol and derivatives thereof, polyvinyl pyrrolidone and derivatives thereof, polyalkylene glycol and derivatives thereof, and cellulose ether and derivatives thereof, and the stain inhibitor is urea, thiourea, thiourea dioxide and Provided is a finish for a trivalent chromium chemical conversion film selected from those derivatives.
• the present invention is also applied to a substrate having a black trivalent chromium conversion coating, the black trivalent chromium conversion coating being adhered to the black trivalent chromium conversion coating in the form of an aqueous solution, and then dried.
• a method for finishing a black trivalent chromium conversion coating characterized by the above is provided.
• the present invention also provides a metal article having a metal base, a hexavalent chromium-free corrosion-resistant film having a black trivalent chromium conversion coating provided thereon and a finish layer provided thereon, Contains trivalent chromium, zinc and phosphorus elements, and the total amount of trivalent chromium, zinc and phosphorus elements is 100 parts by weight, 10 to 40 parts by weight of trivalent chromium, 20 to 75 parts by weight of zinc, phosphorus
• the metal article is characterized in that is 3 to 40 parts by weight.
• the barrier coating of the trivalent chromium conversion coating needs to be dense and thick.
• a trivalent chromium chemical conversion film it is difficult to form a barrier film having a thickness comparable to that of hexavalent chromate by chemical conversion treatment alone.
• the hexavalent metal is excellent in luster and corrosion resistance without damaging the tightening property with low insulation with few scratches and spots on the zinc and zinc alloy plating, especially green stains due to liquid pools. Since a chromium-free corrosion-resistant film, particularly a black trivalent chromium chemical conversion film, can be formed, it can be expected to be widely used in various fields such as electronic devices in the future.
• trivalent chromium source used in the finish for a trivalent chromium film of the present invention examples include trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate, and chromium acetate.
• trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate, and chromium acetate.
• hexavalent chromium such as chromic acid or dichromate may be reduced to trivalent with a reducing agent to obtain trivalent chromium.
• These trivalent chromium sources can be used alone or in combination of two or more.
• the concentration is preferably 0.1 g / L to 20 g / L, more preferably 0.3 g / L to 10 g / L in terms of chromium concentration.
• Examples of the phosphate ion source used in the finish for a trivalent chromium film of the present invention include phosphorus oxygen acids such as phosphoric acid and phosphorous acid, and salts thereof, particularly alkali salts. These phosphate ion sources can be used alone or in combination of two or more. The concentration is preferably 0.3 to 70 g / L, more preferably 1 to 40 g / L.
• chromium phosphate can be used as the trivalent chromium source and phosphate ion source.
• chromium phosphate having a structural formula of Cr (H n PO 4 ) (3 / 3-n) (where n is 1 to 2) is used, durability under high temperature and high humidity is used. Are preferable, and those having n of 1 are most preferable.
• Examples of the zinc ion source used in the finish for a trivalent chromium film of the present invention include zinc oxide, zinc carbonate, zinc nitrate, zinc chloride, zinc sulfate, and zinc salts of various organic carboxylic acids. Zinc is preferred. These zinc ion sources can be used alone or in combination of two or more. The concentration is preferably 0.1 g / L to 30 g / L, more preferably 0.5 g / L to 20 g / L in terms of zinc concentration.
• Examples of the chelating agent capable of forming a complex with trivalent chromium used in the finish for a trivalent chromium film of the present invention include polycarboxylic acids such as monocarboxylic acids, dicarboxylic acids and tricarboxylic acids, hydroxycarboxylic acids, and aminocarboxylic acids. Examples include acids (eg, glycine) or salts thereof. Of these, oxalic acid, malonic acid, citric acid, tartaric acid, and malic acid are preferred. These chelating agents can be used alone or in combination of two or more. The concentration is preferably 0.5 to 100 g / L in the aqueous solution, more preferably 1 to 50 g / L.
• the molar ratio of the chelating agent to trivalent chromium is preferably 0.2 to 2 because it affects the corrosion resistance and the finished appearance (treated appearance). More preferably, it is 0.5 to 1.
• the molar ratio of chelating agent to zinc is preferably 0.5 or more, and more preferably 0.7 to 1.
• the nonionic water-soluble polymer compound used in the finishing agent for trivalent chromium film of the present invention is selected from the group consisting of polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone and its derivatives, polyalkylene glycol and its derivatives, and cellulose ether and its derivatives. Selected.
• polyvinyl alcohol and derivatives thereof include polyvinyl alcohol and sulfonic acid-modified polyvinyl alcohol. Examples include, but are not limited to, PVA NL05, GM-13, and Gocelan L3266 from Nippon Synthetic Chemical.
• polyvinyl pyrrolidone and derivatives thereof include polyvinyl pyrrolidone and vinyl acetate / vinyl pyridone copolymers. Examples thereof include, but are not limited to, K-30, K-30W, K-90, etc. of Nippon Shokubai.
• polyalkylene glycol and derivatives thereof include polyethylene glycol, polypropylene glycol, and ether derivatives thereof. Examples include NOF PEG-200, PEG-1000 and PEG-4000, NOF UNIOL D-700 and D-2000, NOF UNIOR TG-1000, and the like. However, it is not limited to this.
• cellulose ether and derivatives thereof include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethylpropyl cellulose and the like. Examples include, but are not limited to, the Shin-Etsu Chemical Metrows SM, SH, and SH types. These nonionic water-soluble polymer compounds can be used alone or in combination of two or more.
• the concentration of the nonionic water-soluble polymer compound is preferably 0.01 g / L to 50 g / L, more preferably 0.1 g / L to 10 g / L. However, even if it exceeds 50 g / L, there is no problem in performance, but further effects cannot be expected.
• the addition of these nonionic water-soluble polymer compounds particularly contributes to the prevention of rubbing scratches, and thus improves the corrosion resistance in addition to improving the appearance of the trivalent chromium conversion coating.
• the trivalent chromium chemical conversion finish of the present invention provides a hexavalent chromium-free corrosion-resistant chemical conversion film, particularly black trivalent chromium chemical conversion, which has low insulation, gloss without rubbing scratches without impairing tightening properties, and excellent corrosion resistance. A film can be formed.
• the stain inhibitor used in the finish for a trivalent chromium film of the present invention is selected from the group consisting of urea, thiourea, dithiothiourea and derivatives thereof.
• urea, thiourea, dithiothiourea and derivatives thereof include compounds represented by the following general formula.
• R 1 to R 4 are each independently a hydrogen atom, a chain hydrocarbon group, a cyclic hydrocarbon group, an aralkyl group or an aryl group.
• the chain hydrocarbon group of R 1 to R 4 is preferably a chain hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, Examples include an ethyl group, a linear or branched propyl group, a butyl group, and a hexyl group.
• the cyclic hydrocarbon group is preferably a cyclic hydrocarbon group having 3 to 8 carbon atoms, more preferably a cyclic hydrocarbon group having 5 to 6 carbon atoms, and examples thereof include a cyclopentyl group and a cyclohexyl group.
• Preferred examples of the aralkyl group include a benzyl group and a phenethyl group. These phenyl groups may be substituted with alkyl groups or the like.
• R 1 to R 4 are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• stain preventing agent examples include, for example, urea, N-methylurea, N-ethylurea, N-butylurea, N, N′-dimethylurea, phenylurea, benzylurea, ethoxyphenylurea, thiourea, N- Examples include methylthiourea, N-ethylthiourea, N, N′-dimethylthiourea, phenylthiourea, benzylthiourea, ethoxyphenylthiourea, thiourea dioxide, N-methylthiourea dioxide, and N-ethylthiourea dioxide.
• the concentration of the stain inhibitor is preferably 0.01 g / L to 30 g / L, more preferably 0.1 g / L to 15 g / L.
• the addition of these stain-preventing agents contributes particularly to the prevention of stains, in particular to the prevention of green stains caused by liquid pools, and also improves the corrosion resistance.
• the trivalent chromium chemical conversion coating film of the present invention is a hexavalent chromium-free corrosion-resistant chemical film, particularly a black trivalent chromium chemical conversion film, which has low insulation, excellent gloss and corrosion resistance without impairing tightening properties. Can be formed.
• the gloss is low in insulation and has no scratches and spots without impairing the tightening property.
• a hexavalent chromium-free corrosion-resistant chemical conversion film having excellent corrosion resistance, particularly a black trivalent chromium chemical conversion film, can be formed.
• the concentration of each additive is within the range of the additive concentration, and the total concentration is 0.01 g / L to 50 g / L. And more preferably 0.1 g / L to 15 g / L.
• the finishing agent for trivalent chromium film of the present invention preferably further contains a mold suppressing component.
• a mold suppressing component By containing the mold inhibitory component in the above-mentioned finishing agent, bacteria can be suppressed and it can be used for a long time without generating mold.
• an isothiazoline compound is preferable.
• the isothiazoline compound is preferably an isothiazoline compound represented by the following general formula. (In the formula, R represents an alkyl group having 1 to 8 carbon atoms, and X represents a hydrogen atom, a Cl atom, or a Br atom.)
• R represents an alkyl group having 1 to 8 carbon atoms
• X represents a hydrogen atom, a Cl atom, or a Br atom.
• the concentration of the mold inhibiting component is preferably 0.01 g / L to 50 g / L, more preferably 0.1 g / L to 5 g / L. However, even if it exceeds 50 g / L, there is no problem in performance, but it is not preferable in terms of economy.
• the finishing agent for trivalent chromium film of the present invention preferably further contains water and is in the form of an aqueous solution.
• the pH of the aqueous solution is preferably 2.5-8. More preferably, it is 3 to 7, and most preferably 4 to 6.
• an alkali agent such as alkali hydroxide, aqueous ammonia or amines is preferably used.
• the metal ion selected from the group consisting of aluminum, silicon, molybdenum, manganese, and cobalt is preferably added to the finish for a trivalent chromium film of the present invention. These metal ions can be used alone or in combination of two or more.
• the concentration is preferably from 0.1 g / L to 30 g / L, more preferably from 0.5 g / L to 5 g / L.
• the following surfactants and water-soluble resins to the finish for a trivalent chromium film of the present invention, since the uniformity of the appearance of the finished film and the gloss can be further improved.
• the surfactant to be added include ether-based nonionic surfactants, polyoxyethylene / polyoxypropylene block polymers, polyoxyethylene nonylphenyl ether, and the like.
• the concentration is preferably 0.01 g / L to 100 g / L, more preferably 1 g / L to 50 g / L.
• the water-soluble resin to be added examples include a water-soluble acrylic resin, a water-soluble urethane resin, a water-soluble melamine resin, and an emulsion type wax.
• the concentration is preferably 0.01 g / L to 100 g / L, more preferably 1 g / L to 50 g / L.
• silicone can be added in order to promote the drainage of the finish for the trivalent chromium film of the present invention and prevent dry spots.
• the concentration is preferably 1 to 1000 ppm, more preferably 10 to 100 ppm.
• the finishing agent for trivalent chromium film of the present invention preferably does not contain halogen ions, sulfate ions and sulfonate ions. Thereby, the white product generated at high temperature and high humidity is suppressed.
• the substrate used in the present invention various metals such as iron, nickel, copper, and alloys thereof, or metal or alloys such as aluminum subjected to zinc substitution treatment, rectangular parallelepipeds, cylinders, cylinders, spherical objects, etc.
• the thing of various shapes is mentioned.
• those made of zinc or zinc alloy, or those having zinc or zinc alloy plating film formed on the surface are preferable.
• the zinc or zinc alloy plating film can be easily formed by a conventional method.
• the galvanized film may be formed using any one of an acidic bath such as a sulfuric acid bath, an ammon bath, and a potassium bath, and an alkaline bath such as an alkali nocyan bath and an alkali cyan bath.
• an alkali non-cyanide plating bath such as NZ-98 bath or NZ-87 bath manufactured by Dipsol.
• the zinc alloy plating include zinc-iron alloy plating, zinc-nickel alloy plating, and zinc-cobalt alloy plating.
• the thickness of the zinc or zinc alloy plating can be arbitrary, but is preferably 1 ⁇ m or more, more preferably 5 to 25 ⁇ m.
• the substrate having a trivalent chromium conversion coating (preferably black trivalent chromium conversion coating) to be used in the present invention is obtained by rinsing the above substrate, particularly a substrate having a zinc or zinc-based alloy plating layer, with water. It can be obtained by performing a treatment to form a trivalent chromium conversion coating.
• the trivalent chromium chemical conversion coating is performed using various trivalent chromium chemical conversion treatment solutions described in US Pat. No. 5,415,702, Japanese Patent Application Laid-Open No. 2003-166074, Japanese Patent Application Laid-Open No. 2003-166075, and the like.
• Trivalent chromium exists in the form of a water-soluble complex with a chelating agent, and contains cobalt ions and / or nickel ions, and the cobalt ions and / or nickel ions form a slightly soluble metal salt with the chelating agent and precipitate. Without being present in the treatment solution, and when zinc and zinc alloy plating are brought into contact with the treatment solution, it reacts with zinc to react with zinc, chromium, cobalt and / or nickel. Preferable to use a black trivalent chromium chemical conversion treatment solution containing a chelating agent.
• a trivalent chromium chemical conversion treatment is performed by immersing a substrate having a zinc or zinc-based alloy plating layer in a trivalent chromium chemical conversion treatment solution at a liquid temperature of, for example, 10 to 80 ° C., more preferably 40 to 60 ° C. for 5 to 600 seconds. It is preferable to immerse for 30 to 120 seconds.
• the trivalent chromium conversion coating is preferably provided on the zinc or zinc-based alloy plating layer with a thickness of about 0.1 to 0.3 ⁇ m.
• the finishing agent of the present invention in the form of an aqueous solution is formed on a trivalent chromium chemical conversion film, particularly a black trivalent chromium chemical conversion film, after or without being washed with water.
• a trivalent chromium chemical conversion film particularly a black trivalent chromium chemical conversion film
• the contact temperature (preferably the immersion temperature) is preferably 10 to 80 ° C., more preferably 45 to 55 ° C.
• the contact time (preferably immersion time) is preferably 3 to 30 seconds, more preferably 3 to 5 seconds.
• the drying temperature is preferably 50 ° C to 200 ° C, more preferably 80 ° C to 120 ° C.
• the drying time is preferably 5 minutes to 60 minutes, more preferably 10 minutes to 20 minutes.
• the trivalent chromium when the total of trivalent chromium, zinc and phosphorus elements is 100 parts by weight, the trivalent chromium is 10
• a finishing layer of ⁇ 40 parts by weight, zinc of 20-75 parts by weight and phosphorus of 3-40 parts by weight can be provided.
• the optimum weight ratio of trivalent chromium / zinc / phosphorus is (20-25) / (60-50) / (20-25).
• the total of trivalent chromium, zinc and phosphorus elements in the finishing layer is preferably 30 to 75% by weight.
• the thickness of the finishing layer can be arbitrarily determined, but is preferably about 0.05 to 0.3 ⁇ m.
• an overcoat treatment can be further performed on the trivalent chromium chemical conversion film of the present invention.
• the overcoat is not only inorganic film such as silicate and phosphate, but also polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, polycarbonate, polyamide, polyacetal, fluororesin, urea resin, phenolic resin, unsaturated polyester Organic films such as resin, polyurethane, alkyd resin, epoxy resin, melamine resin, silicone oil, wax, rust preventive oil, etc. are also effective.
• the present invention provides a metal article having a metal substrate, a trivalent chromium chemical conversion coating provided thereon, and a hexavalent chromium-free corrosion-resistant coating having the finish layer provided thereon.
• This metal article can be suitably used as a metal product such as a metal member such as a screw or a bolt or an automobile part.
• Example 1 Using a NZ-87 bath made by Dipsol, zincate zinc plating with a thickness of 8 ⁇ m was applied to an M8 bolt.
• ZTB-447S123C3 type (ZTB-447S1: 50 mL / L, ZTB-447S2: 20 mL / L and ZTB-447S3: 7 mL / L) (40 seconds at 30 ° C.), then immersed in the finishing agent shown in Table 1 at 50 ° C. for 5 seconds, centrifuged and dehydrated, 120 Dried at °C.
• Cr 3+ used chromium phosphate.
• Zn 2+ used zinc oxide.
• isothiazoline ZONEN-C manufactured by Chemicrea was used.
• Si 4+ colloidal silica was used.
• Co 2+ used was cobalt carbonate (No. 5, 6, 7 and 8) or cobalt nitrate (No. 9).
• Al 3+ used aluminum phosphate.
• the concentration of the additional metal ion was 1 g / L.
• the pH was adjusted with caustic soda (No. 1, 3, 5, 6, 7, and 10) or ammonia water (No. 2, 4, 8, and 9).
• ether type nonionic surfactant “Sedran FF200” (manufactured by Sanyo Chemical Co., Ltd.) is 20 g / L, silicone is 10 ppm of L-720 manufactured by Toray Dow Corning Co., Ltd., and acrylic resin is 30 g / L of AQUALIC L series DL manufactured by Nippon Shokubai Co., Ltd. was used. The balance is water.
• Example 2 M8 bolts with iron alloy plating (Fe: 0.5% by weight) 8 ⁇ m thick are treated with black trivalent chromium chemical conversion treatment agents (ZTB-447A (200 mL / L) and ZTB- manufactured by Dipsol Co., Ltd.). 447K (8 mL / L)) (50 ° C. for 60 seconds), immersed in a finishing agent shown in Table 2 at 50 ° C. for 5 seconds, centrifuged and dehydrated, and then dried at 120 ° C.
• black trivalent chromium chemical conversion treatment agents ZTB-447A (200 mL / L) and ZTB- manufactured by Dipsol Co., Ltd.
• 447K 8 mL / L)
• Cr 3+ used chromium phosphate.
• Zn 2+ used zinc oxide.
• isothiazoline ZONEN-C manufactured by Chemicrea was used.
• Co 2+ used cobalt nitrate.
• the concentration of the additional metal ion was 1 g / L.
• the pH was adjusted with caustic soda (No. 1, 2 and 4) or aqueous ammonia (No. 3).
• As the surfactant 20 g / L of an ether-based nonionic surfactant “Cedran FF200” (manufactured by Sanyo Chemical Co., Ltd.) was used. The balance is water.
• M8 bolts plated with zinc-nickel alloy (Ni: 15% by weight) with a thickness of 8 ⁇ m are made of IZB-256 (IZB-256AY: 150 mL / L and IZB) manufactured by Dipsol Co., Ltd. -256BY: 50 mL / L) (at 25 ° C. for 45 seconds), immersed in a finishing agent shown in Table 3 at 50 ° C. for 5 seconds, centrifuged and dehydrated, and dried at 120 ° C.
• Cr 3+ used chromium phosphate.
• Zn 2+ used zinc oxide.
• isothiazoline ZONEN-C manufactured by Chemicrea was used.
• Co 2+ used cobalt nitrate.
• the concentration of the additional metal ion was 1 g / L.
• the pH was adjusted with caustic soda (No. 1, 2 and 4) or aqueous ammonia (No. 3).
• As the surfactant 20 g / L of an ether-based nonionic surfactant “Cedran FF200” (manufactured by Sanyo Chemical Co., Ltd.) was used. The balance is water.
• Comparative Example 1 As a comparative example, a black hexavalent chromate treatment (at 25 ° C. for 60 seconds) was performed on the M8 bolt, which was applied with zinc plating 8 ⁇ m in the same manner as in Example 1. As the black hexavalent chromate, ZB-535A (200 ml / L) and ZB-Black 50B (10 ml / L) manufactured by Dipsol Co., Ltd. were used.
• Example 2 As a comparative example, a black trivalent chromate treatment was performed on an M8 bolt plated with 8 ⁇ m zinc, and then No. 1 of Example 1 was applied. 1-No. Finishing treatment was carried out with the finishing agent described in Table 4 from which polyvinyl alcohol, anti-smudge agent and anti-mold component were removed from finishing agent No. 4.
• the black trivalent chromium conversion treatment used ZTB-447A (200 ml / l) and ZTB-447K (8 ml / l) manufactured by Dipsol Co., Ltd. (treatment conditions were 50 ° C. for 60 seconds).
• Cr 3+ used chromium phosphate.
• Zn 2+ used zinc oxide.
• Co 2+ used cobalt carbonate.
• the metal ion concentration was 1 g / L.
• the pH was adjusted with caustic soda (No. 1, 2 and 4) or aqueous ammonia (No. 3).
• As the surfactant 20 g / L of an ether-based nonionic surfactant “Cedran FF200” (manufactured by Sanyo Chemical Co., Ltd.) was used. The balance is water.
• Table 5 summarizes the treatment appearance of the chemical conversion coatings obtained in Examples 1 to 3 and Comparative Examples 1 and 2, the results of the salt spray test, and the occurrence of mold on the finish after standing at room temperature for 1 month.
• No. 1 of Example 1 and 3 to 10 films containing polyvinyl alcohol were No. 1 of Comparative Example 2 containing no polyvinyl alcohol.
• a glossy appearance with few scratches was obtained and the corrosion resistance was good as compared with the films of 1, 3 and 4.
• Nos. 1 to 4 of Examples 2 and 3 a glossy appearance with few scratches and accumulation spots was obtained, and the corrosion resistance was further excellent.
• the condition of mold generation in the finishing agent after standing at room temperature for 1 month is No. in Comparative Example 2 which does not contain the mold prevention component.

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