[go: up one dir, main page]

EP1230422A1 - Procede et composition de traitement pour des metaux - Google Patents

Procede et composition de traitement pour des metaux

Info

Publication number
EP1230422A1
EP1230422A1 EP00955557A EP00955557A EP1230422A1 EP 1230422 A1 EP1230422 A1 EP 1230422A1 EP 00955557 A EP00955557 A EP 00955557A EP 00955557 A EP00955557 A EP 00955557A EP 1230422 A1 EP1230422 A1 EP 1230422A1
Authority
EP
European Patent Office
Prior art keywords
component
treatment composition
acid
surface treatment
molecules
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00955557A
Other languages
German (de)
English (en)
Inventor
Yasuhiro Kinoshita
Kensuke Mizuno
Katsuyuki Kawakami
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of EP1230422A1 publication Critical patent/EP1230422A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C23C22/34—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 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
    • 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
    • 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
    • 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
    • C23C22/34—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 fluorides or complex fluorides
    • C23C22/36—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 fluorides or complex fluorides 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
    • C23C22/06—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
    • C23C22/42—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 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
    • C23C22/06—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
    • C23C22/46—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
    • 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
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • This invention relates to a surface treatment agent that can form a highly corrosion-resistant, strongly paint-adherent film on the surface of a metal, e.g., steel sheet, zinciferous-plated steel sheet, and aluminum sheet.
  • the invention also relates to a process for treating metal surfaces using this surface treatment agent.
  • Zinciferous-plated steel sheet is used in a variety of fields, for example, in automotive applications, for household electrical appliances, and as a building material. Since zinciferous-plated steel sheet corrodes upon exposure to the atmosphere with the production of a corrosion product known as white rust, it has heretofore typically been treated with a treatment composition containing an aqueous chromic acid solution in order to improve its corrosion resistance. This treatment, known as a chromate treatment, forms a coating layer that contains hexavalent chromium and trivalent chromium on the surface of zinciferous-plated steel sheet.
  • An object of this invention is to solve the problems described above for the prior art by providing a liquid surface treatment composition for application to metals that can form a highly corrosion-resistant, strongly paint-adherent coating on metal surfaces and particularly on the surface of zinciferous-plated steel sheet.
  • An alternative and/or concurrent object of this invention is to provide a process for treating metal surfaces that uses this surface treatment composition.
  • a highly corrosion-resistant, strongly paint-adherent coating can be formed on metal surfaces by treating such surfaces with an aqueous liquid that, in addition to water, comprises, preferably consists essentially of, or more preferably consists of:
  • each molecule contains at least two moieties that conform to general formula (I):
  • each of R ⁇ R 2 , and R 3 is independently selected from the group consisting of hydrogen atoms and alkyl moieties containing from 1 to 4 carbon atoms; and (A.2) for all of the molecules considered together, the weight average value for the molecular weight divided by the average number per molecule of moieties conforming to formula (I) as given above yields a quotient that is within a range from 100 to 30,000; and
  • organic acids phosphoric acid, hydrofluoric acid, tetrafluoroboric acid, hexafluorosilicic acid, hexafluorotitanic acid, hexafluorozirconic acid, and hexafluorohafnic acid.
  • a liquid treatment composition according to the invention also contains a component (C) selected from the group consisting of resins each of the molecules of which contains at least one tertiary amino moiety or quaternary ammonium moiety but does not qualify to be part of component (A).
  • component (C) selected from the group consisting of resins each of the molecules of which contains at least one tertiary amino moiety or quaternary ammonium moiety but does not qualify to be part of component (A).
  • the weight of component (A) preferably has a ratio to the weight of component (C) in the same composition that is from 1.0:9 to 9:1.0, the weights of components (A) and (C) being measured in the same units.
  • a liquid treatment composition according to the invention also contains a component (D) selected from the water soluble salts of the metals cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium, and molybdenum, exclusive of any such salts that could be part of any of components (A), (B), and (C) as described above but inclusive of salts in which the metals are part of oxycations as well as salts in which the metals are cations.
  • a component (D) selected from the water soluble salts of the metals cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium, and molybdenum, exclusive of any such salts that could be part of any of components (A), (B), and (C) as described above but inclusive of salts in which the metals are part of oxycations as well as salts in which the metals are cations.
  • component (D) When component (D) is present in a composition according to the invention, its weight preferably has a ratio to the weight of component (A) in the same composition that is from 0.00010:1.0 to 1.0:1.0, the weights of components (A) and (D) being measured in the same units.
  • component (E) is present in a composition according to the invention, its weight preferably has a ratio the weight of component (A) in the same composition that is from 0.0010:1.0 to 1.0:1.0, the weights of components (A) and (E) being measured in the same units.
  • a process according to this invention for treating metal surfaces is characterized by the formation of a liquid coating of a composition according to the invention on the surface of a metal substrate, and later, or preferably immediately, drying said surface treatment composition into place on said metal surface, without removing, e.g., by rinsing away, any of the non-volatiles content of the liquid coating before the coating is dried.
  • the coating film so formed should have a mass per unit area, often called
  • coating weight' that is from 0.1 to 3.0 grams of dried coating per square meter of metal surface coated, a unit of coating weight that is hereinafter usually abbreviated as "g/m 2 ",
  • Components (A) and (B) are the necessary active ingredients in a liquid surface treatment composition according to the invention.
  • the weight average value for the molecular weight of component (A) divided by the average number per molecule of moieties conforming to formula (I) as given above in component (A) preferably has a value that is at least, with increasing preference in the order given, 120, 130, 140, 150, or 160 and independently preferably is not more than, with increasing preference in the order given, 10,000, 5000, 2000, 1500, 1000, or 800. Synthesis of a compound in which the molecular weight per functional group is below 100 is highly problematic. Adherence to the metal surface, which is a characteristic function of this functional group, declines when the value of the molecular weight per functional group exceeds 30,000.
  • component (A) While the process for synthesizing component (A) is not critical, this component can be synthesized, for example, by reacting chlorosilane with a compound bearing at least two active hydrogen-containing functional groups, by reacting two or more different silane coupling agents with each other, by reacting a reactive functional group-containing compound with the organofunctional groups in a silane coupling agent, and by copolymerizing a vinyl-functional silane coupling agent with other copolymerizable vinyl compound(s).
  • the use, as part of component (A), of molecules containing only one moiety conforming to general formula (I) in each molecule is undesirable because the presence of such molecules gives a diminished adherence to metal surfaces.
  • Organic acids which are preferred over their salts, are advantageous constituents of component (B) as described above when treating zinc-coated steel, because organic acids do not strongly etch the zinc-coated steel sheet and nevertheless remove the very thin oxide film present on the surface of the plating. Strong acids such as sulfuric acid, hydrochloric acid, and nitric acid reduce the corrosion resistance because they remove too much of the zinc coating.
  • the subject organic acid can be exemplified by formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, L-ascorbic acid, tartar ic acid, citric acid, DL-malic acid, malonic acid, maleic acid, and phthalic acid.
  • Phosphoric acid is believed to increase the corrosion resistance by forming a zinc phosphate conversion coating — albeit in very small amounts — on the surface of a zinciferous coating.
  • Usable as this phosphoric acid are, for example, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, and tetraphosphoric acid and the ammonium, aluminum, and magnesium salts of these acids.
  • Fluoride when present as part of component (B) is believed to improve the corrosion resistance through a controlled etching activity and ability to chelate metal cations.
  • component (B) has somewhat different preferred concentrations relative to component (A).
  • organic acids when organic acids are used, their concentration preferably is at least, with increasing preference in the order given, 0.01 , 0.05, 0.10, 0.50, 1 .0, 3.0, or 4.0 and independently preferably is not more than, with increasing preference in the order given, 300, 200, 100, 75, 50, 25, 20, 10, or 6 parts by weight;
  • phosphoric acid when phosphoric acid is used, its concentration preferably is at least, with increasing preference in the order given, 0.05, 0.10, 0.50, 1.0, 3.0, or 4.0 and independently preferably is not more than, with increasing preference in the order given, 200, 100, 75, 50, 25, 20, 10, or 6 parts by weight;
  • complex fluorides when complex fluorides are used, their concentration preferably is at least 0.01 , 0.05, 0.10, 0.50, 1.0, 3.0, 6.0, or 9.0 and independently preferably is not more than
  • component (C) a resin whose molecules contain at least one tertiary amino moiety or quaternary ammonium moiety. While the type of resin is not critical, a general-purpose predominantly polyacrylic, epoxy, polyurethane, or polyester resin is preferred. The technique for introducing tertiary amino and/or quaternary ammonium moieties is also not critical.
  • Component (C) when used preferably has a concentration that will result in a ratio by weight of component (A) to component (C) that is at least, with increasing preference in the order given, 1.00:9.0, 1.00:7.0, 1.00:6.0, or 1.00:5.0 and independently preferably is not more than, with increasing preference in the order given, 9.0:1.00, 7.0:1.00, 6.0:1.00, or 5.0:1.00.
  • the corrosion resistance is diminished when this ratio of (A)/(C) is below 1.0:9.
  • only a weak effect is generated by the addition of component (C) when (A)/(C) is above 9:1.0, making such a use of component (C) uneconomical.
  • component (D) preferably is present in an amount such that its ratio by weight to component (A) in the same treatment composition is at least, with increasing preference in the order given, 0.00010:1.0, 0.0005:1.00, 0.0010:1.00, 0.0050:1.00, 0.0100:1.00, 0.050:1.00, 0.070:1.00, 0.090:1.00, or 0.10:1.00 and independently preferably is not more than, with increasing preference in the order given, 1.00:1.00, 0.80:1.00, 0.70:1.00, 0.60:1.00, or 0.50:1.00. Little or no improvement in corrosion resistance is seen from a component (D) addition below 0.00010:1.0, while a component (D) addition above 1.0:1.0 is uneconomical since no additional benefit results from such an addition.
  • component (E) When component (E) is present, it preferably is present in an amount such that the ratio by weight of component (E) to component (A) in the same composition is at least, with increasing preference in the order given, 0.0010:1.0, 0.0050:1.00, 0.010:1.00, 0.030:1.00, 0.050:1.00, 0.070:1 .00, 0.080:1.00, 0.090:1.00, or 0.097:1.00 and independently preferably is not more than, with increasing preference in the order given, 1.00:1.00, 0.50:1.00, 0.40:1 .00, 0.30:1.00, 0.20:1.00, or 0.12:1.00. Little or no improve- ment in corrosion resistance is obtained from a component (E) ratio below 0.0010:1.0, while the paint adherence is reduced when the (E)/(A) ratio is more than 1.0:1.0.
  • the surface treatment composition of this invention may also contain: additives such as thickeners and surfactants (the latter also known as wetting agents) for the purpose of generating a uniform coating on the substrate surface; electrical conductivity im- provers in order to improve the welding behavior; colored pigments in order to improve the aesthetics, and film-forming auxiliaries in order to improve the film-forming performance.
  • additives such as thickeners and surfactants (the latter also known as wetting agents) for the purpose of generating a uniform coating on the substrate surface
  • electrical conductivity im- provers in order to improve the welding behavior
  • colored pigments in order to improve the aesthetics
  • film-forming auxiliaries in order to improve the film-forming performance.
  • the surface treatment composition of this invention is preferably applied, for example, to: aluminum sheet; steel sheet, e.g., cold-rolled steel sheet and hot-rolled steel sheet; and, most preferably, zinciferous-plated steel sheet, e.g., electrogalvanized steel sheet, hot-dipped galvanized steel sheet, galvannealed steel sheet, steel sheet plated with aluminum-containing zinc, Zn/Ni-plated steel sheet, Zn/Co-plated steel sheet, and vapor-deposition zinc-plated steel sheet.
  • zinciferous-plated steel sheet e.g., electrogalvanized steel sheet, hot-dipped galvanized steel sheet, galvannealed steel sheet, steel sheet plated with aluminum-containing zinc, Zn/Ni-plated steel sheet, Zn/Co-plated steel sheet, and vapor-deposition zinc-plated steel sheet.
  • a coating with a weight after drying of 0.1 to 3.0 g/m 2 is preferably formed by application of a surface treatment composition according to the invention to the metal surface by, for example, roll coating, dipping, or electrostatic coating, followed by drying by induction heating or with a hot gas current to an attained sheet temperature of 60 to 250 °C and preferably 80 to 220 °C.
  • the performance of the resulting coating may often be unsatisfactory when the attained sheet temperature does not reach 60 °C, while an attained sheet temperature in excess of 250 °C can result in pyrolysis of the coating.
  • the performance of the coating may often be unsatisfactory when the coating weight is less than 0.1 g/m 2 , while no additional increments in coating performance are obtained at above 3.0 g/m 2 , making such weights uneconomical.
  • the solids concentration in the surface treatment composition of the invention is preferably in the range from 1 to 50 %. Since the surface treatment composition is an aqueous system, a solids concentration below 1 % is undesirable because such concentrations result in long drying times. At the other end of the range, a solids concentration in excess of 50 % is undesirable because concentrations at this level cause such problems as a reduced dispersion stability and an increased viscosity of the treatment agent. Because a composition according to the invention is dried into place on the surface being treated in a process according to the invention, the concentration of the surface treatment composition has little or no technical effect on the results obtained, provided that a preferred coating weight as described above is obtained.
  • a preferred coating weight can be obtained with either a thick coating of a dilute surface treatment liquid or a thin coating of a concentrated surface treatment liquid.
  • This invention is illustrated in more specific terms in the following through working and comparative examples, but the scope of the invention is not limited by the working examples that follow. Described immediately below are the test specimens, degreasing treatment, and process for applying the metal surface treatment composition that were used in the working and comparative examples. 1. Preparation of the test specimens (1 -1 ) Materials tested
  • coating weight 20 grams of electroplated zinc per square meter of steel sheet on both major surfaces, the unit of grams per square meter being hereinafter usually abbreviated as “g/m2” and coating on both major surfaces being hereinafter indicated by numbers with a virgule between them, so that the abbreviated description of this coating would be "20/20 g/m2";
  • G galvannealed (Zn-Fe) hot-dip zinc-coated steel sheet
  • A-1100 aluminum sheet hereinafter usually abbreviated as "AL"
  • the metal surface treatment composition (see below for details) was applied with a bar coater. This was followed by drying at an ambient temperature of 300 °C. 2. Painted sheet performance testing
  • + + rust produced over at least 3 % but less than 10 % of the total surface area
  • + rust produced over at least 10 % but less than 30 % of the total surface area
  • x rust produced over at least 30 % of the total surface area
  • + + rust produced over at least 10 % but less than 20 % of the total surface area
  • TREATMENT COMPOSITION A An amount of 5 parts by weight of ammonium dihydrogen phosphate as component (B) was added to 100 parts by weight of the compound afforded by the reaction in ethanol of 1.0 mole of hexamethylenediamine and 2.0 moles of ⁇ -glycidoxypropyltrime- thoxysilane as component (A). The resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • Component (A) in this instance had 2 moieties conforming to formula (I) per molecule, and its ratio of gram molecular weight to the number of such moieties per molecule was approximately 294.
  • component (B) An amount of 5.0 parts by weight of oxalic acid as component (B) was added to 100 parts by weight of the compound(s) afforded by the reaction in N-methyl-2-pyrroli- done of 1.0 mole of bisphenol-A epoxy resin (EPONTM 828 type, hereinafter usually abbreviated as "#828 type") and 2.0 moles of ⁇ -aminopropyltriethoxysilane as component (A). The resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • Component (A) in this instance had 2 moieties conforming to formula (I) per molecule, and its ratio of gram molecular weight to the number of such moieties per molecule was approximately 411 .
  • composition A as described above was added 20 parts by weight, per 100 parts by weight of component (A), of the polymer(s) afforded by the emulsion polymerization in deionized water of 1 .0 mole of acrylic acid, 5.0 moles of methyl methacrylate, 3.0 moles of 2-hydroxyethyl methacrylate, and 2.0 moles of dimethylaminoethyl methacrylate as component (C).
  • the resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • the component (A)/component (C) weight ratio was 5:1.0.
  • TREATMENT COMPOSITION F To Treatment Composition C as described above was added 500 parts (solids) by weight, per 100 parts by weight of component (A), of a water-based urethane resin containing tertiary amino and quaternary ammonium moieties (Adeka BontiterTM HUX 670, registered trademark of Asahi Denka Kogyo Kabushiki Kaisha) as component (C). The resulting mixture was diluted with deionized water to a solids concentration of 5 %. The component (A)/component (C) weight ratio was 1.0:5.0. TREATMENT COMPOSITION G
  • composition A As described above was added 10 parts by weight, per 100 parts by weight of component (A), of anhydrous magnesium acetate as component (D). The resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • composition C As described above was added 30 parts by weight, per 100 parts by weight of component (A), of aluminum phosphate (AIPO 3 ) as component (D). The resulting mixture was diluted with deionized water to give a solids concentration of 5%.
  • TREATMENT COMPOSITION J To Treatment Composition A as described above was added 10 parts by weight, per 100 parts by weight of component (A), of 2-butyn-1 ,4-diol (HOCH 2 C ⁇ CCH 2 OH) as component (E). The resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • TREATMENT COMPOSITION K To Treatment Composition A as described above was added 10 parts by weight, per 100 parts by weight of component (A), of 2-butyn-1 ,4-diol (HOCH 2 C ⁇ CCH 2 OH) as component (E). The resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • Amounts of 5 parts by weight, per 100 parts by weight of component (A), of ammonium dihydrogen phosphate as part of component (B) and 10 parts by weight, per 100 parts by weight of component (A), of ammonium fluorosilicate as the remainder of component (B) were added to 100 parts by weight of the compound(s) afforded by the reaction in ethanol of 1 mole hexamethylenediamine and 2 moles of ⁇ -glycidoxypropyltri- methoxysilane as component (A).
  • the resulting mixture was diluted with deionized water to give a solids concentration of 5 %.
  • Component (A) in this instance had 2 moieties conforming to formula (I) per molecule, and its ratio of gram molecular weight to number of such moieties per molecule was approximately 294.
  • component (A) in this instance had 2 moieties conforming to formula (I) per molecule, and its ratio of gram molecular weight to number of such moieties per molecule was approximately 171.
  • the ratio by weight of component (A) to component (C) was 1.0:2.0.
  • COMPARATIVE TREATMENT COMPOSITION Q An amount of 10 parts by weight of ammonium fluosilicate, which in itself would be suitable to constitute component (B) of a composition according to this invention, was added to 100 parts by weight of the compound(s), with an average molecular weight of approximately 40,000, afforded by the emulsion polymerization in deionized water of 50 moles of acrylic acid, 100 moles of butyl acrylate, 100 moles of methyl methacrylate, 100 moles of 2-hydroxyethyl methacrylate, and 1.0 mole ⁇ -methacryloxypropyltriethoxysilane as the closest to a proper component (A) as described above.
  • component (A) was diluted with deionized water to give a solids concentration of 5 %.
  • What might otherwise be component (A) in this instance had an average of only 1 moiety conforming to formula (I) per molecule, and its ratio of gram molecular weight to number of such moieties per molecule was approximately 40,000 — a value outside the range specified for component (A) according to the present invention.
  • This treatment composition was produced by the suitable dilution of Zinchrom® 3360H chromate treatment agent, a product commercially available from Nihon Parkerizing Co., Ltd. and intended for imparting temporary corrosion resistance to zinc- coated steel sheet.
  • This treatment composition was produced by the suitable dilution of Zinchrom® 3383 chromate treatment agent, a product commercially available from Nihon Parkerizing Co., Ltd. and intended for imparting intermediate corrosion resistance to zinc-coated steel sheet. 4. Test results
  • Table 1 reports the Example and Comparative Example numbers associated with the metal surface treatment compositions identified by letters above, while Table 2 reports the results of painted sheet performance testing using the metal surface treatment compositions.
  • Numbers 1 through 25 in Table 2 refer to experiments in which coatings were formed by application of a metal surface treatment composition according to the invention. Good values were obtained in all performance categories (flat region corrosion resistance, worked region corrosion resistance, overcoated paint adherence) in all of these experiments.
  • Numbers 27 to 31 in Table 2 refer to experiments that used the treatment agents of Comparative Examples 1 through 5 in Table 1 — treatment agents that fell outside the scope of the present invention. These latter experiments gave relatively poor results for at least one, and often all, of the flat region corrosion resistance, worked region corrosion resistance, and overcoated paint adherence.
  • Table 1 reports the Example and Comparative Example numbers associated with the metal surface treatment compositions identified by letters above, while Table 2 reports the results of painted sheet performance testing using the metal surface treatment compositions.
  • Numbers 1 through 25 in Table 2 refer to experiments in which coatings were formed by application of a metal

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)

Abstract

Composition de traitement de surface aqueuse et liquide renfermant: (i) des molécules qui contiennent chacune au moins deux fractions qui sont conformes à la formule (I) dans laquelle chaque R?1, R2, et R3¿ est indépendamment sélectionné dans le groupe constitué par des atomes d'hydrogène et des fractions alkyle contenant de 1 à 4 atomes de carbone, toutes ces molécules ayant ensemble une valeur du poids moléculaire moyen divisée par le nombre moyen des fractions par molécule correspondant à la formule (I) qui se situe dans la fourchette comprise entre 100 et 30 000, et (ii) une ou plusieurs substances sélectionnées dans le groupe formé par les acides organiques, l'acide phosphorique, l'acide fluorhydrique, l'acide tétrafluoroborique, l'acide hexafluorosilicilique, l'acide hexafluorotitanique, l'acide hexafluorozirconique, l'acide hexafluorohafnique, et les sels d'ammonium des acides organiques, de l'acide phosphorique, de l'acide fluorhydrique, de l'acide tétrafluoroborique, de l'acide hexafluorosilicilique, de l'acide hexafluorotitanique, de l'acide hexafluorozirconique, et de l'acide hexafluorohafnique. Cette composition forme, sur des surfaces métalliques, un film qui résiste fortement à la corrosion et qui adhère très bien à la peinture sans qu'il soit nécessaire d'utiliser une composition contenant du chrome.
EP00955557A 1999-08-16 2000-08-14 Procede et composition de traitement pour des metaux Withdrawn EP1230422A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP23009499 1999-08-16
JP23009499A JP4113309B2 (ja) 1999-08-16 1999-08-16 耐食性に優れた金属材料用表面処理剤および金属材料の表面処理方法
PCT/US2000/022363 WO2001012876A1 (fr) 1999-08-16 2000-08-14 Procede et composition de traitement pour des metaux

Publications (1)

Publication Number Publication Date
EP1230422A1 true EP1230422A1 (fr) 2002-08-14

Family

ID=16902466

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00955557A Withdrawn EP1230422A1 (fr) 1999-08-16 2000-08-14 Procede et composition de traitement pour des metaux

Country Status (6)

Country Link
EP (1) EP1230422A1 (fr)
JP (1) JP4113309B2 (fr)
KR (1) KR100676602B1 (fr)
CA (1) CA2383485A1 (fr)
MX (1) MXPA02001637A (fr)
WO (1) WO2001012876A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4634650B2 (ja) * 2001-06-06 2011-02-16 日新製鋼株式会社 耐食性に優れた溶接鋼管
ES2316706T3 (es) * 2002-12-24 2009-04-16 Chemetall Gmbh Metodo de pre-tratamiento para revestir.
JP4989842B2 (ja) * 2002-12-24 2012-08-01 日本ペイント株式会社 塗装前処理方法
JP2008184690A (ja) * 2002-12-24 2008-08-14 Nippon Paint Co Ltd 塗装前処理方法
JP4351926B2 (ja) * 2003-02-17 2009-10-28 日本ペイント株式会社 防錆処理剤及び防錆処理方法
US6867318B1 (en) 2004-06-30 2005-03-15 Nalco Company Composition for coating of aluminum
JP4683581B2 (ja) * 2005-02-02 2011-05-18 日本パーカライジング株式会社 水系金属材料表面処理剤、表面処理方法及び表面処理金属材料
KR100945709B1 (ko) * 2005-02-02 2010-03-05 니혼 파커라이징 가부시키가이샤 수계 금속 재료 표면 처리제, 표면 처리 방법 및 표면 처리금속 재료
JP5313432B2 (ja) * 2005-12-28 2013-10-09 日本ペイント株式会社 金属表面処理用組成物、金属表面処理方法及び表面処理された亜鉛めっき鋼板
US7862862B2 (en) 2006-01-18 2011-01-04 Nalco Company Water dispersible silanes as corrosion-protection coatings and paint primers for metal pretreatment
KR101122814B1 (ko) 2006-11-15 2012-03-22 신닛뽄세이테쯔 카부시키카이샤 표면 처리 금속재 및 그 제조 방법
JP4907315B2 (ja) * 2006-11-28 2012-03-28 新日本製鐵株式会社 表面処理金属材
JP4616854B2 (ja) * 2007-03-13 2011-01-19 新日本製鐵株式会社 熱間プレス用Ａｌめっき鋼板
JP5259168B2 (ja) * 2007-12-06 2013-08-07 朝日化学工業株式会社 表面処理剤および鋼板
CA2722413C (fr) * 2008-04-25 2016-10-04 Henkel Ag & Co. Kgaa Trichrome passivant le traitement d'acier galvanise
JP5314547B2 (ja) * 2009-09-15 2013-10-16 日本パーカライジング株式会社 金属材料用表面処理剤、表面処理方法、および表面処理金属材料
JP5712980B2 (ja) * 2012-08-06 2015-05-07 信越化学工業株式会社 金属表面処理剤、表面処理鋼材及びその表面処理方法、並びに塗装鋼材及びその製造方法
CN104233252B (zh) * 2014-09-16 2016-08-24 南京华锐化工有限公司 一种常温无磷皮膜剂
US11965249B2 (en) 2019-03-19 2024-04-23 Nippon Steel Corporation Surface-treated metal material

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6022067B2 (ja) * 1982-09-30 1985-05-30 日本パ−カライジング株式会社 金属表面の皮膜形成方法
JPS60197773A (ja) * 1984-03-21 1985-10-07 Kansai Paint Co Ltd 金属表面処理組成物及びこのものを用いた金属の表面処理方法
US4689085A (en) * 1986-06-30 1987-08-25 Dow Corning Corporation Coupling agent compositions
US5846342A (en) * 1994-02-03 1998-12-08 Henkel Corporation Surface treatment agent for zinciferous-plated steel
JPH0873775A (ja) * 1994-09-02 1996-03-19 Nippon Parkerizing Co Ltd 耐指紋性、耐食性、塗装密着性にすぐれた皮膜形成用金属表面処理剤および処理方法
US5711996A (en) * 1995-09-28 1998-01-27 Man-Gill Chemical Company Aqueous coating compositions and coated metal surfaces
US5750197A (en) * 1997-01-09 1998-05-12 The University Of Cincinnati Method of preventing corrosion of metals using silanes
JP3898302B2 (ja) * 1997-10-03 2007-03-28 日本パーカライジング株式会社 金属材料用表面処理剤組成物および処理方法
US6132808A (en) * 1999-02-05 2000-10-17 Brent International Plc Method of treating metals using amino silanes and multi-silyl-functional silanes in admixture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0112876A1 *

Also Published As

Publication number Publication date
KR100676602B1 (ko) 2007-01-30
WO2001012876A1 (fr) 2001-02-22
JP2001049453A (ja) 2001-02-20
KR20010021220A (ko) 2001-03-15
CA2383485A1 (fr) 2001-02-22
JP4113309B2 (ja) 2008-07-09
MXPA02001637A (es) 2002-08-06

Similar Documents

Publication Publication Date Title
EP1230422A1 (fr) Procede et composition de traitement pour des metaux
US5801217A (en) Chromium-free conversation coating and methods of use
EP1163297B1 (fr) Procede de traitement des metaux a l'aide de silanes d'aminos et de silanes a fonction multi-silyl melanges
US9200165B2 (en) Surface treatment liquid for zinc or zinc alloy coated steel sheet, zinc or zinc alloy-coated steel sheet, and method for manufacturing the same
EP1433877B1 (fr) Procédé de prétraitement avant revêtement
US6475300B2 (en) Non-chromate metallic surface-treating agent, method for surface treatment, and treated steel material
US7250193B2 (en) Pretreatment method for coating
US7510612B2 (en) Chemical conversion coating agent and surface-treated metal
US6361833B1 (en) Composition and process for treating metal surfaces
JPWO2006082951A1 (ja) 水系金属材料表面処理剤、表面処理方法及び表面処理金属材料
JP7169409B1 (ja) ６価クロムフリー水性表面処理液、表面処理金属および表面処理方法
US6149735A (en) Chromate treatment bath composition and process for application to metals
US6485580B1 (en) Composition and process for treating surfaces or light metals and their alloys
JP7063298B2 (ja) 溶融亜鉛系めっき鋼板用の表面処理液ならびに亜鉛系めっき鋼板およびその製造方法
KR102872150B1 (ko) 유기 수지 피복용 표면 처리 강판 및 그의 제조 방법, 그리고 유기 수지 피복 강판 및 그의 제조 방법
JP2002105358A (ja) 無機膜形成用塗布剤、その無機膜形成方法、そのものを用いて得られる無機膜被覆アルミニウム材及び無機膜被覆鋼材
US20050072495A1 (en) Passivation composition and process for zinciferous and aluminiferous surfaces
US5908892A (en) N, N-alkyl polyacrylamide metal treatment
JP2002167553A (ja) 無機膜形成用塗布剤、その無機膜形成方法、そのものを用いて得られる無機膜被覆アルミニウム材及び無機膜被覆鋼材
JPH01225780A (ja) 高耐食性クロメート処理鋼板およびその製造方法ならびにクロメート処理液
JPH07300683A (ja) 低温焼付性に優れたクロメート処理方法
JP2945046B2 (ja) 亜鉛系めつき鋼板のクロメート処理方法
JP2004197179A (ja) 非クロム型処理亜鉛系めっき鋼板の製造方法
WO1999060186A1 (fr) Composition et procede permettant de traiter les surfaces des metaux legers et de leurs alliages
JPH09228067A (ja) 耐環境汚染性、耐食性に優れた表面処理鋼板

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020222

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RBV Designated contracting states (corrected)

Designated state(s): AT BE DE ES FR GB

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20040302