US20030209293A1 - Metal surface treatment agent - Google Patents

Metal surface treatment agent Download PDF

Info

Publication number
US20030209293A1
US20030209293A1 US10/275,660 US27566003A US2003209293A1 US 20030209293 A1 US20030209293 A1 US 20030209293A1 US 27566003 A US27566003 A US 27566003A US 2003209293 A1 US2003209293 A1 US 2003209293A1
Authority
US
United States
Prior art keywords
metal
surface treatment
treatment agent
vanadium
compound
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.)
Abandoned
Application number
US10/275,660
Inventor
Ryousuke Sako
Keiichi Ueno
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 AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2000137985 priority Critical
Priority to JP2000-137985 priority
Priority to JP2001137985A priority patent/JP2002302208A/en
Priority to JP2001-137985 priority
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to US10/275,660 priority patent/US20030209293A1/en
Priority to PCT/US2001/015468 priority patent/WO2001086016A2/en
Assigned to HENKEL KOMMANDI GESELLSCHAFT AUF AKTIEN reassignment HENKEL KOMMANDI GESELLSCHAFT AUF AKTIEN ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAKO, RYOUSUKE, UENO, KEIICHI, YAMAMOTO, MAYUMI
Publication of US20030209293A1 publication Critical patent/US20030209293A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/40Chemical 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
    • C23C22/44Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/34Chemical 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
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/40Chemical 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

Abstract

The present invention relates to a metal surface treatment agent that characteristically contains (A) at least 1 vanadium compound and (B) at least one metal compound containing at least 1 metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium. The present invention also relates to a metal surface treatment method using the foregoing treatment agent and the corresponding surface-treated metals.
The present invention provides a metal surface treatment agent that does not contain chromium and that can be used to impart an excellent corrosion resistance and alkali resistance to metals. The present invention provides a metal surface treatment method that uses the foregoing treatment agent and also provides the corresponding surface-treated metals.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0001]
  • This invention relates to a metal surface treatment agent and method that can be used to form a chromium-free coating on the surface of metal sheet coil and metal formed articles and that impart to such surfaces an excellent corrosion resistance and excellent alkali resistance. The invention also relates to the corresponding surface-treated metals. [0002]
  • More particularly, this invention relates to a metal surface treatment agent and method that can be used to form a chromium-free coating that imparts an excellent corrosion resistance and excellent alkali resistance to formed articles, castings, and sheet coil (for example, automotive body elements and other automotive parts, construction materials, parts for household electrical appliances) of zinciferous-plated steel sheet, steel sheet, or aluminiferous metal. The invention additionally relates to the corresponding surface-treated metals. [0003]
  • 2. Background Art [0004]
  • Metals such as zinciferous-plated steel sheet, steel sheet, and aluminiferous metals are susceptible to oxidation and corrosion by atmospheric oxygen, moisture, and the ions present in moisture. One known method for inhibiting this corrosion comprises forming a chromate coating on the metal surface by bringing the metal into contact with a chromium-containing treatment bath, for example, a chromic acid chromate or phosphoric acid chromate bath. [0005]
  • While the coatings generated by these chromate treatments do tend to exhibit excellent corrosion resistance and excellent paint adherence, the treatment baths used in these treatments typically contain toxic hexavalent chromium, which can impose substantial time, labor, and cost burdens on wastewater treatment. Moreover, hexavalent chromium is also present in the coatings produced by these treatments, which has led based on environmental and safety considerations to an ever increasing tendency to avoid the use of these coatings. [0006]
  • Methods that employ non-chromate (chromium-free) treatments baths are known. For example, Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 7-278410 (278,410/1995) teaches a polymer composition and a method for treating metal surfaces wherein the polymer composition contains an acidic compound and a phenolic resin-type polymer with a specific structure. An agent and method for treating metal surfaces are also disclosed in Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 8-73775 (73,775/1996). This agent and method provide an excellent fingerprint resistance. The agent contains at least 2 silane coupling agents having reactive functional groups with specific structures; these reactive functional groups are different from each other but are capable of reacting with one other. Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 9-241576 (241,576/1997) discloses a method and agent for treating metal surfaces wherein the agent contains a silane coupling agent with a specific structure and a phenolic resin-type polymer with a specific structure. Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 10-1789 (1,789/1998) teaches an agent and method for treating metal surfaces and metal surfaces thereby treated. This agent contains a specific polyvalent anion and an organic polymer, such as an epoxy resin, acrylic resin, or urethane resin, that contains at least 1 nitrogen atom. Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 10-60233 (60,233/1998) teaches a treatment method that uses two rust preventives (1) and (2) and metals thereby treated. Rust preventive (1) contains a bisphenol A epoxy resin with a specific structure, while rust preventive (2) contains phenolic resin and a specific non-phenolic resin (e.g., polyester) in quantities that provide a solids ratio of 4:1 to 1:4 upon mixing. [0007]
  • None of the metal surface treatments taught in these laid open patent applications uses chromium, and, while they do offer the advantage of a treatment bath free of hexavalent chromium, in each case they produce coatings that exhibit a corrosion resistance inferior to the corrosion resistance from chromate treatment. The coatings produced by these chromium-free treatments also suffer from an unacceptable fingerprint resistance and lubricity. [0008]
  • Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 10-1789 teaches vanadic acid among the therein specified polyvalent anions. However, vanadic acid, which is an oxyacid of pentavalent vanadium, has a poor resistance to water and alkali. As a result, when the treated metal is rinsed, and particularly when it is rinsed with alkali, the vanadic acid is eluted from the coating, which results in a major reduction in corrosion resistance. This laid open patent application also teaches the post-treatment execution of a water rinse and drying. Thus, while the problem of a chromium-containing wastewater is not present, the organics create the problem of a COD-containing wastewater. [0009]
  • Inventions that use vanadium compounds as rust preventives are also known. Japanese Laid Open (Kokai or Unexamined) Patent Application Number Hei 1-9229 (9,229/1990) teaches an antirust paint that contains a film-forming resin, a phosphate ion source that releases phosphate ion in an ambient containing water and oxygen, and a vanadate ion source that releases vanadate ion in an ambient containing water and oxygen. Japanese Granted Patent 2,795,710 teaches an antirust composition in which specific compounds are blended in specific proportions; the specific compounds include (A) a vanadate ion source that releases vanadate ion in specific concentrations in a water-based dispersion and (B) an organophosphonic acid capable of dissolution in specific concentrations in a water-based dispersion. The vanadate ion source is added to function as the antirusting pigment of these antirust paints, and when baked at high temperatures (600° C. and above) is converted to a pigment with an average particle size of several μm. The particles of this pigment do manifest an anticorrosion activity when present in paint films having a certain film thickness (several times the particle size of the pigment), but exhibit no anticorrosion activity at all in the thin films (no greater than several μm) encountered in the field of metal treatment. Another problem with these treatment agents is that settling occurs due to aggregation of the particles therein when the treatment agent is allowed to stand. [0010]
  • Thus, no extant non-chromate metal surface treatment agent has the ability to form a coating that can simultaneously impart an excellent corrosion resistance, an excellent alkali resistance, and an excellent fingerprint resistance to metal surfaces. [0011]
  • SUMMARY OF THE INVENTION
  • The present invention remedies the herein above described problems associated with the prior art. An object of the present invention is to provide a metal surface treatment agent that does not contain chromium and that can impart an excellent corrosion resistance and excellent alkali resistance to metals. Additional objects of the present invention are to provide a metal surface treatment method that uses this agent and metals whose surface has been treated using the inventive agent and method. [0012]
  • The present inventors have discovered that highly corrosion-resistant, highly alkali-resistant coatings can be obtained by treating metal surfaces with a surface treatment agent whose essential components are a vanadium compound and a particular type of metal compound. This invention was achieved based on this discovery. [0013]
  • In specific terms, this invention relates to a metal surface treatment agent that characteristically contains: (A) at least 1 vanadium compound and (B) a metal compound or compounds containing at least 1 metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium. [0014]
  • In an embodiment preferred in order to obtain a better stability by the vanadium compound in the treatment agent and an improved corrosion resistance and alkali resistance by the produced film, the ratio in vanadium compound (A) of vanadium ion in the trivalent and tetravalent oxidation states to the total vanadium (V[0015] 3++V4+)/V is in the range of 0.1 to 1.0.
  • In another preferred embodiment, the inventive metal surface treatment agent additionally contains (C) an organic compound that contains at least 1 functional group selected from the group consisting of hydroxyl groups, carbonyl groups, carboxyl groups, primary to tertiary amino groups, amide groups, phosphoric acid groups, and phosphonic acid groups. The purpose of this embodiment is to reduce the pentavalent vanadium compound, when used, to the tetravalent or trivalent oxidation state and/or to improve the stability of the vanadium compound in the inventive treatment bath. [0016]
  • In another embodiment preferred in order to improve the adherence of the obtained coating, the inventive metal surface treatment agent additionally contains (D) at least 1 etchant selected from the group consisting of inorganic acids, organic acids, and fluorine compounds. [0017]
  • The invention additionally relates to a method for treating metal surfaces comprising treating a metal surface with any of the inventive metal surface treatment agents described above, and drying by heating so the temperature of the metal reaches 50 to 250° C. [0018]
  • The invention further relates to surface-treated metals that bear a coating produced using the aforementioned inventive surface treatment method. [0019]
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
  • The vanadium compound present in the metal surface treatment agent of the present invention comprises at least 1 selection from vanadium compounds in which the vanadium has a pentavalent, tetravalent, or trivalent oxidation state. Examples of suitable vanadium compounds include, but are not necessarily limited to, pentavalent vanadium compounds such as vanadium pentoxide (V[0020] 2O5), metavanadic acid (HVO3), ammonium metavanadate, sodium metavanadate, and vanadium oxytrichloride (VOCl3), and trivalent and tetravalent vanadium compounds such as vanadium trioxide (V2O3), vanadium dioxide (VO2), vanadium oxysulfate (VOSO4), vanadium oxyacetylacetonate (VO(OC(CH3)═CHCOCH3)2), vanadium acetylacetonate (V(OC(CH3)═CHCOCH3)3), vanadium trichloride (VCl3), and phosphovanadomolybdic acid {H15—X(PV12—xMoxO40)·nH2O(6<×<12, n<30)}.
  • Preferably, the treatment agent of the present invention contains a trivalent or tetravalent vanadium compound as the vanadium compound (A). More preferably, the ratio of vanadium ions in the trivalent and tetravalent oxidation states to the total vanadium (V[0021] 3++V4+)/V (V3+ refers to the mass of the vanadium in the trivalent oxidation state, V4+ refers to the mass of the vanadium in the tetravalent oxidation state, and V refers to the total mass of the vanadium) is in the range of 0.1 to 1.0, even more preferably in the range of 0.2 to 1.0, and most preferably in the range of 0.4 to 1.0. When this ratio is below 0.1, the stability of the vanadium in the treatment agent can be poor and the ultimately formed coating may have reduced corrosion resistance and alkali resistance.
  • Preferably, the ratio of vanadium ions in the pentavalent oxidation state (V[0022] 5+) to the total vanadium is in the range of 0 to 0.9, even more preferably in the range of 0 to 0.8, and most preferably in the range of 0 to 0.6.
  • One process for introducing a trivalent or tetravalent vanadium compound into the treatment agent of the present invention comprises using at least one of the trivalent or tetravalent vanadium compounds described above. Another suitable process comprises effecting a preliminary reduction of a pentavalent vanadium compound to a trivalent or tetravalent vanadium compound using a reducing agent. The reducing agent used for this purpose may be inorganic or organic but preferably is organic. The use of the above-described compound (C) is particularly preferred. [0023]
  • The component (B) present in the inventive metal surface treatment agent of the present invention comprises a metal compound or compounds containing at least 1 metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium. Component (B) can preferably be an oxide or hydroxide of the specified metals, a complex of these metals, or the salt of an inorganic or organic acid. Suitable examples of metal compound (B) include, but are not necessarily limited to, zirconyl nitrate ZrO(NO[0024] 3)2, zirconyl acetate, zirconyl sulfate, ammonium zirconyl carbonate (NH4)2(Zr(CO3)2(OH)2), dizirconium acetate, titanyl sulfate TiOSO4, titanium lactate, diisopropoxytitanium bisacetylacetone (C5H7O2)2Ti(OCH(CH3)2)2, the reaction product of lactic acid and titanium alkoxide, molybdic acid H2MoO4, ammonium molybdate, sodium molybdate, molybdic acid compounds such as ammonium molybdophosphate (NH4)3(PO4Mo12O36)·3H2O and sodium molybdophosphate Na3(PO4·12MoO3)·nH2O, metatungstic acid H6(H2W12O40), ammonium metatungstate (NH4)6(H2W12O40), sodium metatungstate, paratungstic acid H10(W12O46H10), ammonium paratungstate, sodium paratungstate, permanganic acid HMnO4, potassium permanganate, sodium permanganate, manganese dihydrogen phosphate Mn(H2PO4)2, manganese nitrate Mn(NO3)2, manganese sulfate, manganese fluoride, manganese carbonate MnCO3, manganese acetate, cerium acetate Ce(CH3CO2)3, cerium nitrate, and cerium chloride.
  • The organic compound (C) present on an optional basis in the metal surface treatment agent of the present invention comprises an organic compound that contains at least 1 functional group selected from the group consisting of hydroxyl groups, carbonyl groups, carboxyl groups, primary to tertiary amino groups, amide groups, phosphoric acid groups, and phosphonic acid groups. [0025]
  • Suitable examples of organic compound (C) include, but are not necessarily limited to, alcohols such as methanol, ethanol, isopropanol, and ethylene glycol; carbonyl compounds such as formaldehyde, acetaldehyde, furfural, acetylacetone, ethyl acetoacetate, dipivaloylmethane, and 3-methylpentanedione; organic acids such as formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, gluconic acid, citric acid, and malic acid; amine compounds such as triethylamine, triethanolamine, ethylenediamine, pyridine, imidazole, pyrrole, morpholine, and piperazine; acid amide compounds such as formamide, acetamide, propionamide, and N-methylpropionamide; amino acids such as glycine, alanine, proline, and glutamic acid; organophosphoric acids such as aminotri(methylenephosphonic acid), 1-hydroxyethylidene-1,1′-diphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), and phytic acid; monosaccharides such as glucose, mannose, and galactose; oligosaccharides such as maltose and sucrose; natural polysaccharides such as starch and cellulose; aromatic compounds such as tannic acid, humic acid, ligninsulfonic acid, and polyphenols; and synthetic polymers such as polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyethyleneimine, and water-soluble nylon. [0026]
  • The use of the organic compound (C) is preferred for the purposes of reducing pentavalent vanadium compound, when used, to the tetravalent or trivalent vanadium compound and/or improving the stability of the vanadium compound in the treatment bath of the present invention. [0027]
  • The organic compound (C) can be preliminarily mixed with the vanadium compound with heating (for example, at 40 to 100° C. for 5 to 120 minutes) to give a mixture in which the reduction and stabilization reactions have been thoroughly developed and the resulting mixture can then be blended into the surface treatment agent. Alternatively, the surface treatment agent in the form of a simple mixture can be coated on the metal surface and reduction can be developed during the ensuing thermal drying step. [0028]
  • The etchant (D) present on an optional basis in the metal surface treatment agent of the present invention comprises at least 1 compound selected from inorganic acids, organic acids, and fluorine compounds. [0029]
  • The optional etchant (D) is used to etch the basis metal during application of the treatment agent or during the thermal drying step. Suitable examples of etchant (D) include, but are not necessarily limited to, inorganic acids such as phosphoric acid, nitric acid, and sulfuric acid; organic acids such as formic acid and acetic acid; and fluorine compounds such as hydrofluoric acid, fluoboric acid HBF[0030] 4, fluosilicic acid H2SiF6, fluozirconic acid H2ZrF6, fluotitanic acid H2TiF6, stannous fluoride SnF2, stannic fluoride SnF4, ferrous fluoride, and ferric fluoride. Use of the etchant (D) is preferred for the purpose of improving the adherence of the ultimately obtained coating.
  • The content of the constituent component in the treatment agent of the present invention is preferably as follows: for the vanadium compound (A), preferably 1 to 100 g/L as vanadium and more preferably 2 to 70 g/L as vanadium; for the metal compound (B), preferably 1 to 100 g/L as the metal and more preferably 2 to 70 g/L as the metal. The vanadium compound (A)/metal compound (B) mass ratio is preferably 1/9 to 9/1 calculated on the metal and is more preferably 2/8 to 8/2 calculated on the metal. [0031]
  • The organic compound (C) is preferably added at from 0.05 to 10 mass parts and more preferably at from 0.1 to 5 mass parts, in each case per 1 mass part pentavalent oxidation state vanadium in the vanadium compound. An addition in excess of that required for reduction is preferred in order to stabilize the reduced material in the treatment bath. [0032]
  • The etchant (D) is present preferably at 1 to 100 g/L and more preferably at 2 to 70 g/L. [0033]
  • The treatment agent of the present invention may also contain, to help improve the adherence and corrosion resistance of the coating, a metal sol such as a water-dispersible silica sol and/or alumina sol or zirconia sol; a silane coupling agent such as an aminosilane, epoxysilane, or mercaptosilane; and/or a water-soluble or water-dispersible resin such as polyacrylic acid, polyacrylamide, or polyvinyl alcohol. When such a component is added, it is preferably added at from 5 to 40 mass % of the total nonvolatile component and more preferably at from 10 to 30 mass % of the total nonvolatile component. [0034]
  • For the purposes of this invention, the total nonvolatile component is the component remaining after the surface treatment agent has been dried by heating for 2 hours at 110° C. [0035]
  • The solvent used in the surface treatment agent of the present invention preferably comprises mainly water, but may on an optional basis also contain a water-soluble organic solvent, e.g., an alcohol, ketone, or glycol ether, in order to help improve the drying characteristics of the coating. [0036]
  • The surface treatment agent of the present invention may also contain, within a range that does not impair the essential features of the present invention or the properties of the coating of the present invention, additives such as surfactant, defoamer, leveling agent, germicide/bactericide, and colorant. [0037]
  • The surface treatment method of the present invention will now be disscussed. [0038]
  • The nature of the pretreatment for the surface treatment of the present invention is not particularly critical. As a general matter, surface treatment in accordance with the present invention will be preceded by cleaning with an alkaline or acidic degreaser, or hot water, or solvent, in order to remove any oils and contaminants present on the substrate. This can be followed on an optional basis by surface conditioning with acid or alkali. In a preferred embodiment, cleaning of the substrate surface is followed by rinsing with water so as to remove as much cleaning agent as possible from the substrate surface. [0039]
  • The treatment method of the present invention comprises application of the inventive surface treatment agent to the metal surface followed by drying by heating to 50 to 250° C.; however, the techniques used for application and drying are not particularly critical. [0040]
  • The following application techniques will typically be used: roll coating, in which the treatment agent is applied to the substrate surface by transfer from a roll; broadcasting of the treatment agent over the substrate surface using, for example, a shower ring, followed by roll squeegee; dipping the substrate in a treatment bath; or spraying the treatment agent on the substrate. While the temperature of the treatment bath again is not specifically restricted, the treatment temperature is preferably from 0 to 60° C. and is more preferably from 5 to 40° C. given that the solvent for the treatment agent of the present invention comprises mainly water. [0041]
  • The drying process does not necessarily require heating, and physical removal, for example, by air drying or air blowing, can be pursued. However, drying by the application of heat is preferred in order to improve the film-forming performance and increase the adherence. The temperature in such cases is preferably 50 to 250° C. and more preferably 60 to 220° C. [0042]
  • Coating deposition is preferably from 0.005 to 1.5 μm as the dry film thickness and more preferably from 0.01 to 1.0 μm as the dry film thickness. Acceptable corrosion resistance and overcoat adherence are not obtained at less than 0.005 μm, while deposition in excess of 1.5 μm runs the risk of producing cracks in the coating and a decline in adherence by the coating itself. [0043]
  • The formation of an organic polymer coating in a dry film thickness of 0.3 to 3.0 μm on the coating formed from the surface treatment agent of the present invention, in addition to boosting the corrosion resistance and alkali resistance of the metal workpiece, can impart thereto fingerprint resistance, solvent resistance, and surface lubricity. [0044]
  • A preferred method for establishing this organic polymer coating comprises application of an overcoating agent (Z) whose main component is water-soluble or water-dispersible organic polymer, followed by drying by heating at an attained substrate temperature of 50 to 250° C. The water-soluble or water-dispersible organic polymer used in the overcoating agent (Z) can be, for example, polymer as afforded by the polymerization of addition-polymerizable unsaturated monomer, such as acrylic resins and polyolefin resins, as well as polymer as afforded by a condensation reaction, such as epoxy resins, urethane resins, polyester resins, polyamide resins, and phenolic resins. The glass-transition temperature of the subject organic polymer is preferably from 0 to 120° C. and more preferably is from 10 to 100° C. A glass-transition temperature below 0° C. may result in a coating with poor strength and hardness, while a glass-transition temperature in excess of 120° C. may result in poor film-formability and poor adherence. [0045]
  • In addition to containing at least 1 selection from the foregoing organic polymers, the overcoating agent may preferably contain water-dispersible silica in order to improve the toughness and fingerprint resistance of the coating. The addition of a water-borne wax may also be preferred in order to improve the lubricity. The preferred contents of the foregoing components are as follows: for the organic polymer, 50 to 100 mass parts nonvolatile component per 100 mass parts total nonvolatiles in the overcoating agent; for the water-dispersible silica, 0 to 40 mass parts nonvolatile component per 100 mass parts total nonvolatiles in the overcoating agent; and for the water-borne wax, 0 to 30 mass parts nonvolatile component per 100 mass parts total nonvolatiles in the ovecoating agent. A crosslinker capable of crosslinking the organic polymer may also be present. [0046]
  • In one embodiment of the invention, one or more water-soluble or water-dispersible organic polymers of the type described herein above may be incorporated directly into the metal surface treatment agent as an additional component (E). [0047]
  • When coated on a metal substrate and dried thereon by heating, the surface treatment agent of the present invention reacts with the surface of the metal substrate and forms a fine, dense, and passive coating. [0048]
  • The manifestation of excellent corrosion resistance by the coating produced by the surface treatment agent of the present invention, without wishing to be bound to any particular theory, is believed to be due to a delocalization of the corrosion electrons (potential leveling) and a barrier effect by the coating that checks the permeation of oxygen, moisture, and ions. With respect to the vanadium compound (A) of the present invention, it is believed that a pentavalent vanadium compound occurs with the generation of an oxygen-bonded polyvalent anion and is unable to generate an entirely acceptable performance due to its poor water resistance and alkali resistance. However, a coating having improved water resistance and alkali resistance can be formed using a treatment agent of the present invention that contains reduced tetravalent and/or trivalent vanadium compounds. The organic compound (C) is believed both to reduce the pentavalent vanadium compound and at the same time to chelate and stabilize the trivalent and/or tetravalent vanadium afforded by reduction in and present in the aqueous solution. [0049]
  • The use of an organic polymer-based overcoating on the inventive film can provide an additional and substantial boost in corrosion resistance due to a synergetic interaction with the barrier activity of the overcoating.[0050]
  • EXAMPLES
  • The present invention is explained in greater detail hereinbelow by working and comparative examples. The working examples that follow are intended only as individual examples and should not be construed as limiting the present invention. The procedures used to evaluate the treated sheet samples prepared in the working and comparative examples are also explained below. [0051]
  • 1. Substrates [0052]
  • A: electrogalvanized steel sheet (sheet thickness=0.8 mm) [0053]
  • B: hot-dip galvanized steel sheet (sheet thickness=0.8 mm) [0054]
  • C: 55% Al/Zn-plated steel sheet (sheet thickness=0.5 mm) [0055]
  • 2. Inventive treatment baths [0056]
  • (1) Treatment bath components [0057]
  • The vanadium compounds (A) used in the treatment baths were as follows. [0058]
  • A1: ammonium metavanadate [0059]
  • A2: vanadium pentoxide [0060]
  • A3: vanadium trioxide [0061]
  • A4: vanadium oxyacetylacetonate [0062]
  • The metal compounds (B) used in the treatment baths were as follows. [0063]
  • B1: ammonium molybdate [0064]
  • B2: ammonium metatungstate [0065]
  • B3: ammonium zirconium carbonate [0066]
  • B4: fluotitanic acid [0067]
  • B5: manganese carbonate [0068]
  • The organic compounds (C) used in the treatment baths were as follows. [0069]
  • C1: L-ascorbic acid [0070]
  • C2: D-glucose [0071]
  • C3: glyoxal [0072]
  • The etchants (D) used in the treatment baths were as follows. [0073]
  • D1: HF [0074]
  • D2: H[0075] 2ZrF6
  • D3: CH[0076] 3COOH
  • D4: H[0077] 2SiF6
  • (2) Preparation of the treatment baths [0078]
  • Examples 1 through 7: The vanadium compound (A), metal compound (B), etchant (D), and deionized water were mixed and heated at 50° C. for 1 hour. [0079]
  • Examples 8 through 11: The vanadium compound (A) was first mixed into the 5% aqueous solution of the organic compound (C) followed by heating for 30 minutes at 80 to 100° C. After subsequently cooling to room temperature, the metal compound (B) and then the etchant (D) were added. The bath was finally brought to its prescribed concentration by the addition of deionized water. [0080]
  • 3. Overcoating baths [0081]
  • The overcoating agents (Z) and treatment methods therewith are described below. [0082]
  • Z1: a water-borne treatment bath containing 10% nonvolatile fraction comprising 100 mass parts as solids of a water-borne polyurethane (SUPERFLEX 100 from Dai-ichi Kogyo Seiyaku Co., Ltd.), 20 mass parts as silica of a water-borne silica (SNOWTEX C from Nissan Chemical Industries, Ltd.), and 10 mass parts as solids of a water-borne wax (CHEMIPEARL W900 from Mitsui Chemicals, Inc.). [0083]
  • Z2: a water-borne treatment bath containing 20% nonvolatile fraction comprising 10 mass parts as silica of a water-dispersible silica and 100 mass parts as solids of an ammonia-neutralized water-borne polymer (ethylene-acrylic acid copolymer with ethylene/acrylic acid=80/20 and average molecular weight=approximately 20,000). [0084]
  • 4. Treatment sequence [0085]
  • (1) Degreasing [0086]
  • The substrate was degreased with an alkaline degreaser (PALKLIN 364S from Nihon Parkerizing Co., Ltd., 20 g/L bath, 60° C., 10-second spray, spray pressure=50 kPa) and was then rinsed with water by spraying for 10 seconds. [0087]
  • (2) Coating with the treatment bath of the present invention and drying [0088]
  • I: the treatment bath was applied with a #3 bar coater followed by drying at a sheet temperature of 80° C. using a convection oven. [0089]
  • II the treatment bath was applied with a #3 bar coater followed by drying at a sheet temperature of 120° C. using a convection oven. [0090]
  • (3) Coating with the overcoating treatment bath and drying [0091]
  • An overcoating bath as described above was bar-coated to a dry-film thickness of about 1 μm on the coating already formed using the treatment bath and method of the present invention. This was followed by drying by heating at a sheet temperature of 100° C. [0092]
  • 5. Evaluation procedures [0093]
  • (1) Corrosion resistance [0094]
  • The corrosion resistance was determined by salt-spray testing based on JIS Z-2371. After salt-spray exposure for 72 hours or 120 hours, the area of white rust production was scored on the following scale. [0095]
  • Evaluation scale: [0096]
  • area of white rust development [0097]
  • ++: less than 10% [0098]
  • +: less than 30% but at least 10% [0099]
  • Δ: less than 60% but at least 30% [0100]
  • x: at least 60% [0101]
  • (2) Alkali resistance [0102]
  • A bath was prepared containing 20 g/L of the alkaline degreaser PALKLIN 364S from Nihon Parkerizing Co., Ltd. The resulting aqueous degreaser solution was adjusted to 60° C. and then sprayed for 30 seconds on the already treated sheet. This was followed by rinsing with water and drying at 80° C. The sheet was subsequently evaluated for corrosion resistance using the conditions and methodology described in (1) above. [0103]
  • (3) Fingerprint resistance [0104]
  • A finger was pressed onto the surface of the treated sheet followed by evaluation by visual inspection of the status of the residual fingerprint trace. [0105]
  • Evaluation scale: [0106]
  • ++: residual fingerprint trace entirely absent [0107]
  • +: very faint residual fingerprint trace [0108]
  • Δ: residual fingerprint trace present [0109]
  • x: distinct residual fingerprint trace present [0110]
  • (4) Solvent resistance [0111]
  • An ethanol-soaked gauze was wrapped around a silicone rubber cube (1 cm) and this was rubbed back-and-forth 10 times on the test surface under 50,000 kPa. [0112]
  • Evaluation scale: [0113]
  • ++: coating exfoliation almost entirely absent [0114]
  • +: slight exfoliation of the coating occurred [0115]
  • Δ: moderate exfoliation of the coating occurred [0116]
  • x: the coating was entirely exfoliated with exposure of the substrate [0117]
  • The treatment bath compositions and treatment methods used in the working and comparative examples are reported in Tables 1 and 2, while the evaluation results for the treated sheets are reported in Tables 3 and 4. The results reported in Table 3 confirm an excellent corrosion resistance and alkali resistance for coatings produced from inventive treatment agents (Examples 1 through 11) containing the herein specified vanadium compound (A) and metal compound (B). In contrast, a poor corrosion resistance and poor alkali resistance were obtained in Comparative Examples 1 through 3, which either did not contain the vanadium compound (A) or did not contain the metal compound (B). [0118]
  • Examples 12 through 22 concerned the additional execution of a resin overcoating (Z1 or Z2) on the films produced in Examples 1 through 11. Examples 12 through 22 all gave an excellent corrosion resistance and alkali resistance as well as an excellent fingerprint resistance and solvent resistance. In contrast to this, a poor corrosion resistance and poor alkali resistance were obtained in Comparative Examples 4 through 6, which either did not contain the vanadium compound (A) or did not contain the metal compound (B). [0119]
    TABLE 1
    working and treatment bath composition in g/L
    comparative vanadium (V3+ + V4+)/ metal compound etchant treatment
    examples substrate (A)* total V (B)* (D) method
    Example 1 A A1 (7) 0.72 B1 (5) I
    A3 (18) B4 (10)
    Example 2 A A1 (7) 0.72 B1 (5) D2 (2) I
    A3 (18) B4 (10)
    Example 3 A A4 (3) 1.0 B4 (2) D2 (2) I
    Example 4 B A2 (7.2) 0.28 B3 (10) D1 (10) II
    A3 (2.8)
    A1 (3) 0.5 B2 (2) D2 (10) II
    Example 5 B A3 (1) B5 (5)
    A4 (2)
    Example 6 C A3 (5) 1.0 B4 (10) D4 (1) I
    A4 (10)
    Example 7 A A1 (7) 0 B1 (5) D1 (2) I
    B4 (10)
    Comparative A B1 (5) D1 (2) I
    Example 1 B4 (10)
    Comparative B A2 (7.2) 0.28 II
    Example 2 A3 (2.8)
  • [0120]
    TABLE 2
    working and treatment bath composition in g/L
    comparative vanadium metal compound organic compound etchant treatment
    examples substrate (A)* (B)* (C) (D) method
    Example 8 A A1 (12) B1 (5) C1 (5) D1 (2) I
    B4 (5)
    Example 9 B A (7.5) B2 (5) C2 (7.5) D3 (5) II
    Example 10 A A1 (15) B3 (15) C3 (15) D2 (5) II
    Example 11 C A1 (10) B4 (6) C1 (1) D4 (10) I
    A2 (20) B5 (4)
    Comparative A At (12) C1 (5) D1 (2) I
    Example 3
  • Example 12: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Example 1. [0121]
  • Example 13: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Example 2. [0122]
  • Example 14: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Example 3. [0123]
  • Example 15: Treatment with overcoating agent Z2 was carried out on film formed in accordance with Example 4. [0124]
  • Example 16: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Example 5. [0125]
  • Example 17: Treatment with overcoating agent Z2 was carried out on film formed in accordance with Example 6. [0126]
  • Example 18: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Example 7. [0127]
  • Example 19: Treatment with overcoating agent Z2 was carried out on film formed in accordance with Example 8. [0128]
  • Example 20: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Example 9. [0129]
  • Example 21: Treatment with overcoating agent Z2 was carried out on film formed in accordance with Example 10. [0130]
  • Example 22: Treatment with overcoating agent Z2 was carried out on film formed in accordance with Example 11. [0131]
  • Comparative Example 4: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Comparative Example 1. [0132]
  • Comparative Example 5: Treatment with overcoating agent Z1 was carried out on film formed in accordance with Comparative Example 2. [0133]
  • Comparative Example 6: Treatment with overcoating agent Z2 was carried out on film formed in accordance with Comparative Example 3. [0134]
    TABLE 3
    working and comparative corrosion resistance alkali resistance
    examples after SST for 48 hours after SST for 48 hours
    Example 1 + +
    Example 2 ++ ++
    Example 3 + +
    Example 4 ++ +
    Example 5 ++ ++
    Example 6 ++ ++
    Example 7 + Δ
    Example 8 ++ ++
    Example 9 ++ ++
    Example 10 ++ ++
    Example 11 ++ ++
    Comparative Example 1 Δ x
    Comparative Example 2 Δ x
    Comparative Example 3 Δ x
  • [0135]
    TABLE 4
    alkali
    corrosion resistance
    working and resistance after SST
    comparative after SST for 120 for 120 fingerprint solvent
    examples hours hours resistance resistance
    Example 12 +/++ +/++ + +
    Example 13 ++ ++ ++ ++
    Example 14 ++ + + ++
    Example 15 ++ ++ ++ ++
    Example 16 ++ ++ ++ ++
    Example 17 ++ ++ ++ ++
    Example 18 + +/Δ ++ ++
    Example 19 ++ ++ ++ ++
    Example 20 ++ ++ ++ ++
    Example 21 ++ ++ ++ ++
    Example 22 ++ ++ ++ ++
    Comparative Δ x + Δ
    Example 4
    Comparative Δ x + Δ
    Example 5
    Comparative Δ x + Δ
    Example 6
  • Advantageous Effects of the Invention
  • The treatment agent of the present invention is a non-chromate treatment agent that is free of toxic chromium compounds. The film or coating formed from the inventive surface treatment agent exhibits a corrosion resistance that is as good as or better than the corrosion resistance of prior-art chromate coatings. As a consequence of these features, the inventive surface treatment agent, surface treatment method, and surface-treated metals will have a very high commercial and industrial utilization value. [0136]
  • While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Moreover, the terms “a” and “an”, as used herein, mean one of more unless clearly indicated to the contrary, and the term “as the metal” means calculated based on the amount of the metal in a compound. [0137]

Claims (11)

What is claimed:
1. A metal surface treatment agent comprising:
(A) at least 1 vanadium compound; and
(B) at least one metal compound containing at least 1 metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium.
2. The metal surface treatment agent of claim 1, wherein the ratio in the vanadium compound (A) of vanadium ions in the pentavalent oxidation state to the total vanadium V5+/V is in the range of 0 to 0.6.
3. The metal surface treatment agent of claim 1 or 2, further comprising (C) an organic compound that contains at least 1 functional group selected from the group consisting of hydroxyl groups, carbonyl groups, carboxyl groups, primary to tertiary amino groups, amide groups, phosphoric acid groups, and phosphonic acid groups, wherein the organic compound (C) is present in an amount of 0.05 to 10 mass parts per 1 mass part pentavalent oxidation state vanadium in the vanadium compound.
4. The metal surface treatment agent of any of claims 1 to 3, further comprising (D) at least 1 etchant selected from the group consisting of inorganic acids, organic acids, and fluorine compounds, wherein the etchant (D) is present in an amount of 1 to 100 g/l.
5. The metal surface treatment agent of any of claims 1 to 4, wherein the vanadium compound (A) is present in an amount of 1 to 100 g/l as vanadium and the metal compound (B) is present in an amount of 1 to 100 g/l as metal.
6. The metal surface treatment agent of any of claims 1 to 5, wherein the vanadium compound (A)/metal compound (B) mass ratio is 1/9 to 9/1 calculated on the metal.
7. The metal surface treatment agent of any claims 1-6, further comprising (E) a water-dispersible or water-soluble organic polymer.
8. A method for treating a metal surface comprising:
treating the metal surface with a metal surface treatment agent according to any of claims 1 to 7; and
drying by heating so the temperature of the metal reaches 50 to 250° C.
9. A surface-treated metal that bears a coating formed using the surface treatment method of claim 8.
10. A surface-treated metal that bears a coating formed using the surface treatment agent of any of claims 1 to 7.
11. A surface-treated metal of claim 10 further comprising an organic polymer coating, wherein the organic polymer coating comprises a water-dispersible or water-soluble organic polymer having a glass transition temperature of 0 to 120° C.
US10/275,660 2000-05-11 2001-05-11 Metal surface treatment agent Abandoned US20030209293A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2000137985 2000-05-11
JP2000-137985 2000-05-11
JP2001137985A JP2002302208A (en) 2001-03-30 2001-03-30 Dust bag stopper for dust box
JP2001-137985 2001-05-01
US10/275,660 US20030209293A1 (en) 2000-05-11 2001-05-11 Metal surface treatment agent
PCT/US2001/015468 WO2001086016A2 (en) 2000-05-11 2001-05-11 Metal surface treatment agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US10/275,660 US20030209293A1 (en) 2000-05-11 2001-05-11 Metal surface treatment agent

Publications (1)

Publication Number Publication Date
US20030209293A1 true US20030209293A1 (en) 2003-11-13

Family

ID=29424226

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/275,660 Abandoned US20030209293A1 (en) 2000-05-11 2001-05-11 Metal surface treatment agent

Country Status (1)

Country Link
US (1) US20030209293A1 (en)

Cited By (70)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030168127A1 (en) * 2000-08-21 2003-09-11 Kazunari Hamamura Surface preparation agent and surface preparation method
US20050022907A1 (en) * 2002-05-22 2005-02-03 Claffey William J. Universal aqueous coating compositions for pretreating metal surfaces
US20050205165A1 (en) * 2001-10-30 2005-09-22 Kansaipaint Co., Ltd. Coating composition for forming titanium oxide film, process for forming titanium oxide film and metal substrate coated with titanium oxide film
US20070131310A1 (en) * 2005-10-13 2007-06-14 Yung Charles A Durable Coreplate For Improved Electrical Resistance In Electric Equipment And A Process Thereof
US20080254315A1 (en) * 2007-01-19 2008-10-16 Nihon Hyomen Kagaku Kabushiki Kaisha Chromium-free solution for treating metal surfaces
US20090032144A1 (en) * 2007-08-03 2009-02-05 Mcmillen Mark W Pretreatment compositions and methods for coating a metal substrate
US20090117369A1 (en) * 2007-11-02 2009-05-07 United Technologies Corporation Anodic-cathodic corrosion inhibitor-conductive polymer composite
US20090142589A1 (en) * 2005-12-06 2009-06-04 Hiromasa Shoji Composite Coated Metal Sheet, Treatment Agent and Method of Manufacturing Composite Coated Metal Sheet
US20090155456A1 (en) * 2007-12-14 2009-06-18 Validity Sensors, Inc. System and Method for Fingerprint-Resistant Surfaces for Devices Using Fingerprint Sensors
US20090224200A1 (en) * 2003-07-30 2009-09-10 Climax Engineered Materials, Llc Polishing slurries for chemical-mechanical polishing
US20100216315A1 (en) * 2005-06-24 2010-08-26 Kazuyoshi Yaguchi Etching composition for metal material and method for manufacturing semiconductor device by using same
US20100227179A1 (en) * 2006-01-09 2010-09-09 Basf Se Method for treating surfaces
CN102115880A (en) * 2009-12-31 2011-07-06 汉高股份有限及两合公司 Surface treatment compound and solution of light metal or light metal alloy and surface treatment method
US8077935B2 (en) 2004-04-23 2011-12-13 Validity Sensors, Inc. Methods and apparatus for acquiring a swiped fingerprint image
US8107212B2 (en) 2007-04-30 2012-01-31 Validity Sensors, Inc. Apparatus and method for protecting fingerprint sensing circuitry from electrostatic discharge
US8131026B2 (en) 2004-04-16 2012-03-06 Validity Sensors, Inc. Method and apparatus for fingerprint image reconstruction
US20120088122A1 (en) * 2009-03-31 2012-04-12 Jfe Steel Corporation Galvanized steel sheet
US8165355B2 (en) 2006-09-11 2012-04-24 Validity Sensors, Inc. Method and apparatus for fingerprint motion tracking using an in-line array for use in navigation applications
US8175345B2 (en) 2004-04-16 2012-05-08 Validity Sensors, Inc. Unitized ergonomic two-dimensional fingerprint motion tracking device and method
US8204281B2 (en) 2007-12-14 2012-06-19 Validity Sensors, Inc. System and method to remove artifacts from fingerprint sensor scans
US8224044B2 (en) 2004-10-04 2012-07-17 Validity Sensors, Inc. Fingerprint sensing assemblies and methods of making
US8229184B2 (en) 2004-04-16 2012-07-24 Validity Sensors, Inc. Method and algorithm for accurate finger motion tracking
US20120223064A1 (en) * 2011-03-01 2012-09-06 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel Ltd.) Stainless steel flux-cored wire
US8263232B2 (en) 2006-04-20 2012-09-11 Nippon Steel Corporation Composite coated zinc-containing plated steel material superior in corrosion resistance, blackening resistance, coating adhesion, and alkali resistance
US8276816B2 (en) 2007-12-14 2012-10-02 Validity Sensors, Inc. Smart card system with ergonomic fingerprint sensor and method of using
US8278946B2 (en) 2009-01-15 2012-10-02 Validity Sensors, Inc. Apparatus and method for detecting finger activity on a fingerprint sensor
US8290150B2 (en) 2007-05-11 2012-10-16 Validity Sensors, Inc. Method and system for electronically securing an electronic device using physically unclonable functions
US8331096B2 (en) 2010-08-20 2012-12-11 Validity Sensors, Inc. Fingerprint acquisition expansion card apparatus
US8358815B2 (en) 2004-04-16 2013-01-22 Validity Sensors, Inc. Method and apparatus for two-dimensional finger motion tracking and control
US8374407B2 (en) 2009-01-28 2013-02-12 Validity Sensors, Inc. Live finger detection
US8391568B2 (en) 2008-11-10 2013-03-05 Validity Sensors, Inc. System and method for improved scanning of fingerprint edges
CN102965656A (en) * 2012-11-27 2013-03-13 中国人民解放军国防科学技术大学 Low-temperature drying passivant and passivation method for hot-dip galvanized steel sheet
US8421890B2 (en) 2010-01-15 2013-04-16 Picofield Technologies, Inc. Electronic imager using an impedance sensor grid array and method of making
CN103046039A (en) * 2012-12-28 2013-04-17 江涛 One-step method non-phosphorus skin film agent
TWI394864B (en) * 2007-12-27 2013-05-01 Kansai Paint Co Ltd Metal surface treatment composition, and surface-treated metal material with metal surface treatment film obtained from the metal surface treatment composition
CN103103516A (en) * 2012-11-13 2013-05-15 三达奥克化学股份有限公司 Pure blue membrane treating agent for non-chromium and non-phosphorus iron and steel components and preparation method thereof
US8447077B2 (en) 2006-09-11 2013-05-21 Validity Sensors, Inc. Method and apparatus for fingerprint motion tracking using an in-line array
US8520913B2 (en) 2008-04-04 2013-08-27 Validity Sensors, Inc. Apparatus and method for reducing noise in fingerprint sensing circuits
US8538097B2 (en) 2011-01-26 2013-09-17 Validity Sensors, Inc. User input utilizing dual line scanner apparatus and method
US20130284049A1 (en) * 2010-06-09 2013-10-31 Chemetall Gmbh Inorganic chromium-free metal surface treatment agent
US8594393B2 (en) 2011-01-26 2013-11-26 Validity Sensors System for and method of image reconstruction with dual line scanner using line counts
US8600122B2 (en) 2009-01-15 2013-12-03 Validity Sensors, Inc. Apparatus and method for culling substantially redundant data in fingerprint sensing circuits
US8698594B2 (en) 2008-07-22 2014-04-15 Synaptics Incorporated System, device and method for securing a user device component by authenticating the user of a biometric sensor by performance of a replication of a portion of an authentication process performed at a remote computing device
US8716613B2 (en) 2010-03-02 2014-05-06 Synaptics Incoporated Apparatus and method for electrostatic discharge protection
US8791792B2 (en) 2010-01-15 2014-07-29 Idex Asa Electronic imager using an impedance sensor grid array mounted on or about a switch and method of making
US20140234544A1 (en) * 2011-09-30 2014-08-21 Noppon Paint Co., Ltd. Surface treatment agent for aluminum heat exchangers and surface treatment method
US8866347B2 (en) 2010-01-15 2014-10-21 Idex Asa Biometric image sensing
US9001040B2 (en) 2010-06-02 2015-04-07 Synaptics Incorporated Integrated fingerprint sensor and navigation device
US9137438B2 (en) 2012-03-27 2015-09-15 Synaptics Incorporated Biometric object sensor and method
US9152838B2 (en) 2012-03-29 2015-10-06 Synaptics Incorporated Fingerprint sensor packagings and methods
US9195877B2 (en) 2011-12-23 2015-11-24 Synaptics Incorporated Methods and devices for capacitive image sensing
US9251329B2 (en) 2012-03-27 2016-02-02 Synaptics Incorporated Button depress wakeup and wakeup strategy
US9268991B2 (en) 2012-03-27 2016-02-23 Synaptics Incorporated Method of and system for enrolling and matching biometric data
US9274553B2 (en) 2009-10-30 2016-03-01 Synaptics Incorporated Fingerprint sensor and integratable electronic display
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
US9336428B2 (en) 2009-10-30 2016-05-10 Synaptics Incorporated Integrated fingerprint sensor and display
US9400911B2 (en) 2009-10-30 2016-07-26 Synaptics Incorporated Fingerprint sensor and integratable electronic display
US9406580B2 (en) 2011-03-16 2016-08-02 Synaptics Incorporated Packaging for fingerprint sensors and methods of manufacture
US9600709B2 (en) 2012-03-28 2017-03-21 Synaptics Incorporated Methods and systems for enrolling biometric data
US9666635B2 (en) 2010-02-19 2017-05-30 Synaptics Incorporated Fingerprint sensing circuit
US9665762B2 (en) 2013-01-11 2017-05-30 Synaptics Incorporated Tiered wakeup strategy
US9739544B2 (en) 2012-03-09 2017-08-22 Nippon Paint Surf Chemicals Co., Ltd. Surface treatment method for aluminum heat exchangers
US9757811B2 (en) 2011-09-21 2017-09-12 Nippon Paint Surf Chemicals Co., Ltd. Method for treating surface of aluminum heat exchanger
US9785299B2 (en) 2012-01-03 2017-10-10 Synaptics Incorporated Structures and manufacturing methods for glass covered electronic devices
US9798917B2 (en) 2012-04-10 2017-10-24 Idex Asa Biometric sensing
US9879345B2 (en) 2012-03-09 2018-01-30 Nippon Paint Surf Chemicals Co., Ltd. Chemical conversion agent and chemical conversion coating film
US9896766B2 (en) 2013-04-03 2018-02-20 Nippon Paint Surf Chemicals Co., Ltd. Surface processing method for aluminum heat exchanger
US10043052B2 (en) 2011-10-27 2018-08-07 Synaptics Incorporated Electronic device packages and methods
US10138559B2 (en) 2013-04-03 2018-11-27 Nippon Paint Surf Chemicals Co., Ltd. Chemical conversion agent and metal surface treatment method
US10167542B2 (en) * 2012-11-27 2019-01-01 Nisshin Steel Co., Ltd. Method for producing hot-dip Zn alloy-plated steel sheet

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264378A (en) * 1979-02-14 1981-04-28 Oxy Metal Industries Corporation Chromium-free surface treatment
US4298404A (en) * 1979-09-06 1981-11-03 Richardson Chemical Company Chromium-free or low-chromium metal surface passivation
US4992115A (en) * 1988-02-15 1991-02-12 Nippon Paint Co., Ltd. Surface treatment chemical and bath for aluminum and its alloy
US5449415A (en) * 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
US5550006A (en) * 1993-01-11 1996-08-27 Macdermid, Incorporated Phosphating compositions and processes, particularly for use in fabrication of printed circuits utilizing organic resists
US5733386A (en) * 1994-04-15 1998-03-31 Henkel Corporation Polymer composition and method for treating metal surfaces
US6027579A (en) * 1997-07-07 2000-02-22 Coral Chemical Company Non-chrome rinse for phosphate coated ferrous metals
US6361833B1 (en) * 1998-10-28 2002-03-26 Henkel Corporation Composition and process for treating metal surfaces
US20030168127A1 (en) * 2000-08-21 2003-09-11 Kazunari Hamamura Surface preparation agent and surface preparation method
US6764553B2 (en) * 2001-09-14 2004-07-20 Henkel Corporation Conversion coating compositions

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264378A (en) * 1979-02-14 1981-04-28 Oxy Metal Industries Corporation Chromium-free surface treatment
US4298404A (en) * 1979-09-06 1981-11-03 Richardson Chemical Company Chromium-free or low-chromium metal surface passivation
US4992115A (en) * 1988-02-15 1991-02-12 Nippon Paint Co., Ltd. Surface treatment chemical and bath for aluminum and its alloy
US5550006A (en) * 1993-01-11 1996-08-27 Macdermid, Incorporated Phosphating compositions and processes, particularly for use in fabrication of printed circuits utilizing organic resists
US5449415A (en) * 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
US5733386A (en) * 1994-04-15 1998-03-31 Henkel Corporation Polymer composition and method for treating metal surfaces
US6027579A (en) * 1997-07-07 2000-02-22 Coral Chemical Company Non-chrome rinse for phosphate coated ferrous metals
US6361833B1 (en) * 1998-10-28 2002-03-26 Henkel Corporation Composition and process for treating metal surfaces
US20030168127A1 (en) * 2000-08-21 2003-09-11 Kazunari Hamamura Surface preparation agent and surface preparation method
US6764553B2 (en) * 2001-09-14 2004-07-20 Henkel Corporation Conversion coating compositions

Cited By (100)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030168127A1 (en) * 2000-08-21 2003-09-11 Kazunari Hamamura Surface preparation agent and surface preparation method
US20050205165A1 (en) * 2001-10-30 2005-09-22 Kansaipaint Co., Ltd. Coating composition for forming titanium oxide film, process for forming titanium oxide film and metal substrate coated with titanium oxide film
US20050022907A1 (en) * 2002-05-22 2005-02-03 Claffey William J. Universal aqueous coating compositions for pretreating metal surfaces
US20090224200A1 (en) * 2003-07-30 2009-09-10 Climax Engineered Materials, Llc Polishing slurries for chemical-mechanical polishing
US8131026B2 (en) 2004-04-16 2012-03-06 Validity Sensors, Inc. Method and apparatus for fingerprint image reconstruction
US8315444B2 (en) 2004-04-16 2012-11-20 Validity Sensors, Inc. Unitized ergonomic two-dimensional fingerprint motion tracking device and method
US8229184B2 (en) 2004-04-16 2012-07-24 Validity Sensors, Inc. Method and algorithm for accurate finger motion tracking
US8811688B2 (en) 2004-04-16 2014-08-19 Synaptics Incorporated Method and apparatus for fingerprint image reconstruction
US8358815B2 (en) 2004-04-16 2013-01-22 Validity Sensors, Inc. Method and apparatus for two-dimensional finger motion tracking and control
US8175345B2 (en) 2004-04-16 2012-05-08 Validity Sensors, Inc. Unitized ergonomic two-dimensional fingerprint motion tracking device and method
US8077935B2 (en) 2004-04-23 2011-12-13 Validity Sensors, Inc. Methods and apparatus for acquiring a swiped fingerprint image
US8224044B2 (en) 2004-10-04 2012-07-17 Validity Sensors, Inc. Fingerprint sensing assemblies and methods of making
US8867799B2 (en) 2004-10-04 2014-10-21 Synaptics Incorporated Fingerprint sensing assemblies and methods of making
US20100216315A1 (en) * 2005-06-24 2010-08-26 Kazuyoshi Yaguchi Etching composition for metal material and method for manufacturing semiconductor device by using same
US8658053B2 (en) * 2005-06-24 2014-02-25 Mitsubishi Gas Chemical Company, Inc. Etching composition for metal material and method for manufacturing semiconductor device by using same
US20070131310A1 (en) * 2005-10-13 2007-06-14 Yung Charles A Durable Coreplate For Improved Electrical Resistance In Electric Equipment And A Process Thereof
US8475930B2 (en) 2005-12-06 2013-07-02 Nippon Steel & Sumitomo Metal Corporation Composite coated metal sheet, treatment agent and method of manufacturing composite coated metal sheet
US20090142589A1 (en) * 2005-12-06 2009-06-04 Hiromasa Shoji Composite Coated Metal Sheet, Treatment Agent and Method of Manufacturing Composite Coated Metal Sheet
US20100227179A1 (en) * 2006-01-09 2010-09-09 Basf Se Method for treating surfaces
US8263232B2 (en) 2006-04-20 2012-09-11 Nippon Steel Corporation Composite coated zinc-containing plated steel material superior in corrosion resistance, blackening resistance, coating adhesion, and alkali resistance
US8447077B2 (en) 2006-09-11 2013-05-21 Validity Sensors, Inc. Method and apparatus for fingerprint motion tracking using an in-line array
US8165355B2 (en) 2006-09-11 2012-04-24 Validity Sensors, Inc. Method and apparatus for fingerprint motion tracking using an in-line array for use in navigation applications
US8693736B2 (en) 2006-09-11 2014-04-08 Synaptics Incorporated System for determining the motion of a fingerprint surface with respect to a sensor surface
US20110041958A1 (en) * 2007-01-19 2011-02-24 Nihon Hyomen Kagaku Kabushiki Kaisha Chromium-free solution for treating metal surfaces
US20080254315A1 (en) * 2007-01-19 2008-10-16 Nihon Hyomen Kagaku Kabushiki Kaisha Chromium-free solution for treating metal surfaces
US8980016B2 (en) 2007-01-19 2015-03-17 Nihon Hyomen Kagaku Kabushiki Kaisha Chromium-free solution for treating metal surfaces
US8107212B2 (en) 2007-04-30 2012-01-31 Validity Sensors, Inc. Apparatus and method for protecting fingerprint sensing circuitry from electrostatic discharge
US8290150B2 (en) 2007-05-11 2012-10-16 Validity Sensors, Inc. Method and system for electronically securing an electronic device using physically unclonable functions
WO2009020794A2 (en) * 2007-08-03 2009-02-12 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a metal substrate
WO2009020794A3 (en) * 2007-08-03 2009-03-26 Ppg Ind Ohio Inc Pretreatment compositions and methods for coating a metal substrate
US20090032144A1 (en) * 2007-08-03 2009-02-05 Mcmillen Mark W Pretreatment compositions and methods for coating a metal substrate
US8673091B2 (en) 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
US20150376419A1 (en) * 2007-11-02 2015-12-31 United Technologies Corporation Anodic-Cathodic Corrosion Inhibitor-Conductive Polymer Composite
US20090117369A1 (en) * 2007-11-02 2009-05-07 United Technologies Corporation Anodic-cathodic corrosion inhibitor-conductive polymer composite
US9738791B2 (en) * 2007-11-02 2017-08-22 United Technologies Corporation Anodic-cathodic corrosion inhibitor-conductive polymer composite
US9187650B2 (en) * 2007-11-02 2015-11-17 United Technologies Corporation Anodic-cathodic corrosion inhibitor-conductive polymer composite
US20090155456A1 (en) * 2007-12-14 2009-06-18 Validity Sensors, Inc. System and Method for Fingerprint-Resistant Surfaces for Devices Using Fingerprint Sensors
US8276816B2 (en) 2007-12-14 2012-10-02 Validity Sensors, Inc. Smart card system with ergonomic fingerprint sensor and method of using
US8204281B2 (en) 2007-12-14 2012-06-19 Validity Sensors, Inc. System and method to remove artifacts from fingerprint sensor scans
TWI394864B (en) * 2007-12-27 2013-05-01 Kansai Paint Co Ltd Metal surface treatment composition, and surface-treated metal material with metal surface treatment film obtained from the metal surface treatment composition
US8520913B2 (en) 2008-04-04 2013-08-27 Validity Sensors, Inc. Apparatus and method for reducing noise in fingerprint sensing circuits
US8787632B2 (en) 2008-04-04 2014-07-22 Synaptics Incorporated Apparatus and method for reducing noise in fingerprint sensing circuits
US8698594B2 (en) 2008-07-22 2014-04-15 Synaptics Incorporated System, device and method for securing a user device component by authenticating the user of a biometric sensor by performance of a replication of a portion of an authentication process performed at a remote computing device
US8391568B2 (en) 2008-11-10 2013-03-05 Validity Sensors, Inc. System and method for improved scanning of fingerprint edges
US8600122B2 (en) 2009-01-15 2013-12-03 Validity Sensors, Inc. Apparatus and method for culling substantially redundant data in fingerprint sensing circuits
US8278946B2 (en) 2009-01-15 2012-10-02 Validity Sensors, Inc. Apparatus and method for detecting finger activity on a fingerprint sensor
US8593160B2 (en) 2009-01-15 2013-11-26 Validity Sensors, Inc. Apparatus and method for finger activity on a fingerprint sensor
US8374407B2 (en) 2009-01-28 2013-02-12 Validity Sensors, Inc. Live finger detection
US20120088122A1 (en) * 2009-03-31 2012-04-12 Jfe Steel Corporation Galvanized steel sheet
US9400911B2 (en) 2009-10-30 2016-07-26 Synaptics Incorporated Fingerprint sensor and integratable electronic display
US9274553B2 (en) 2009-10-30 2016-03-01 Synaptics Incorporated Fingerprint sensor and integratable electronic display
US9336428B2 (en) 2009-10-30 2016-05-10 Synaptics Incorporated Integrated fingerprint sensor and display
CN102115880A (en) * 2009-12-31 2011-07-06 汉高股份有限及两合公司 Surface treatment compound and solution of light metal or light metal alloy and surface treatment method
US8421890B2 (en) 2010-01-15 2013-04-16 Picofield Technologies, Inc. Electronic imager using an impedance sensor grid array and method of making
US9659208B2 (en) 2010-01-15 2017-05-23 Idex Asa Biometric image sensing
US9600704B2 (en) 2010-01-15 2017-03-21 Idex Asa Electronic imager using an impedance sensor grid array and method of making
US10115001B2 (en) 2010-01-15 2018-10-30 Idex Asa Biometric image sensing
US9268988B2 (en) 2010-01-15 2016-02-23 Idex Asa Biometric image sensing
US8866347B2 (en) 2010-01-15 2014-10-21 Idex Asa Biometric image sensing
US8791792B2 (en) 2010-01-15 2014-07-29 Idex Asa Electronic imager using an impedance sensor grid array mounted on or about a switch and method of making
US9666635B2 (en) 2010-02-19 2017-05-30 Synaptics Incorporated Fingerprint sensing circuit
US8716613B2 (en) 2010-03-02 2014-05-06 Synaptics Incoporated Apparatus and method for electrostatic discharge protection
US9001040B2 (en) 2010-06-02 2015-04-07 Synaptics Incorporated Integrated fingerprint sensor and navigation device
US10005912B2 (en) * 2010-06-09 2018-06-26 Chemetall Gmbh Inorganic chromium-free metal surface treatment agent
EP2581471A4 (en) * 2010-06-09 2018-01-24 Chemetall GmbH Inorganic chromium-free metal surface treatment agent
KR101829483B1 (en) * 2010-06-09 2018-02-14 닛본 페인트 홀딩스 가부시키가이샤 Inorganic chromium-free metal surface treatment agent
US20130284049A1 (en) * 2010-06-09 2013-10-31 Chemetall Gmbh Inorganic chromium-free metal surface treatment agent
US8331096B2 (en) 2010-08-20 2012-12-11 Validity Sensors, Inc. Fingerprint acquisition expansion card apparatus
US8811723B2 (en) 2011-01-26 2014-08-19 Synaptics Incorporated User input utilizing dual line scanner apparatus and method
US8594393B2 (en) 2011-01-26 2013-11-26 Validity Sensors System for and method of image reconstruction with dual line scanner using line counts
US8538097B2 (en) 2011-01-26 2013-09-17 Validity Sensors, Inc. User input utilizing dual line scanner apparatus and method
US8929619B2 (en) 2011-01-26 2015-01-06 Synaptics Incorporated System and method of image reconstruction with dual line scanner using line counts
US20120223064A1 (en) * 2011-03-01 2012-09-06 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel Ltd.) Stainless steel flux-cored wire
US9406580B2 (en) 2011-03-16 2016-08-02 Synaptics Incorporated Packaging for fingerprint sensors and methods of manufacture
US9757811B2 (en) 2011-09-21 2017-09-12 Nippon Paint Surf Chemicals Co., Ltd. Method for treating surface of aluminum heat exchanger
US20140234544A1 (en) * 2011-09-30 2014-08-21 Noppon Paint Co., Ltd. Surface treatment agent for aluminum heat exchangers and surface treatment method
US10043052B2 (en) 2011-10-27 2018-08-07 Synaptics Incorporated Electronic device packages and methods
US9195877B2 (en) 2011-12-23 2015-11-24 Synaptics Incorporated Methods and devices for capacitive image sensing
US9785299B2 (en) 2012-01-03 2017-10-10 Synaptics Incorporated Structures and manufacturing methods for glass covered electronic devices
US9739544B2 (en) 2012-03-09 2017-08-22 Nippon Paint Surf Chemicals Co., Ltd. Surface treatment method for aluminum heat exchangers
US9879345B2 (en) 2012-03-09 2018-01-30 Nippon Paint Surf Chemicals Co., Ltd. Chemical conversion agent and chemical conversion coating film
US9824200B2 (en) 2012-03-27 2017-11-21 Synaptics Incorporated Wakeup strategy using a biometric sensor
US9251329B2 (en) 2012-03-27 2016-02-02 Synaptics Incorporated Button depress wakeup and wakeup strategy
US9697411B2 (en) 2012-03-27 2017-07-04 Synaptics Incorporated Biometric object sensor and method
US9268991B2 (en) 2012-03-27 2016-02-23 Synaptics Incorporated Method of and system for enrolling and matching biometric data
US9137438B2 (en) 2012-03-27 2015-09-15 Synaptics Incorporated Biometric object sensor and method
US9600709B2 (en) 2012-03-28 2017-03-21 Synaptics Incorporated Methods and systems for enrolling biometric data
US9152838B2 (en) 2012-03-29 2015-10-06 Synaptics Incorporated Fingerprint sensor packagings and methods
US10114497B2 (en) 2012-04-10 2018-10-30 Idex Asa Biometric sensing
US10101851B2 (en) 2012-04-10 2018-10-16 Idex Asa Display with integrated touch screen and fingerprint sensor
US10088939B2 (en) 2012-04-10 2018-10-02 Idex Asa Biometric sensing
US9798917B2 (en) 2012-04-10 2017-10-24 Idex Asa Biometric sensing
CN103103516A (en) * 2012-11-13 2013-05-15 三达奥克化学股份有限公司 Pure blue membrane treating agent for non-chromium and non-phosphorus iron and steel components and preparation method thereof
US10167542B2 (en) * 2012-11-27 2019-01-01 Nisshin Steel Co., Ltd. Method for producing hot-dip Zn alloy-plated steel sheet
CN102965656A (en) * 2012-11-27 2013-03-13 中国人民解放军国防科学技术大学 Low-temperature drying passivant and passivation method for hot-dip galvanized steel sheet
CN103046039A (en) * 2012-12-28 2013-04-17 江涛 One-step method non-phosphorus skin film agent
US9665762B2 (en) 2013-01-11 2017-05-30 Synaptics Incorporated Tiered wakeup strategy
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
US9896766B2 (en) 2013-04-03 2018-02-20 Nippon Paint Surf Chemicals Co., Ltd. Surface processing method for aluminum heat exchanger
US10138559B2 (en) 2013-04-03 2018-11-27 Nippon Paint Surf Chemicals Co., Ltd. Chemical conversion agent and metal surface treatment method

Similar Documents

Publication Publication Date Title
US5427632A (en) Composition and process for treating metals
KR100839744B1 (en) Treating solution for metal surface treatment and a method for surface treatment
US4921552A (en) Composition and method for non-chromate coating of aluminum
US5905105A (en) Method and composition for treating metal surfaces including dispersed silica
JP4607969B2 (en) Surface treatment agent for metal materials, surface treatment method and surface-treated metal material
US4171231A (en) Coating solutions of trivalent chromium for coating zinc surfaces
KR100729979B1 (en) Method for treating metallic surfaces
JP4105765B2 (en) Corrosion resistant surface-treated metal material and a surface treatment agent therefor
US5282905A (en) Method and composition for treatment of galvanized steel
JP4099307B2 (en) Aluminum for non-chromium anticorrosive treatment agent, rust-preventive treatment method and anticorrosive-treated aluminum product
US5451431A (en) Composition and process for treating metal surfaces
CA2454201C (en) Pretreatment method for coating
JP3860697B2 (en) Metal surface treatment agent, a surface treatment method and a surface treated metal material of the metal material
CA2632720C (en) Wet on wet method and chrome-free acidic solution for the corrosion control treatment of steel surfaces
US5242714A (en) Process for forming protective base coatings on metals
US5449415A (en) Composition and process for treating metals
US5380374A (en) Conversion coatings for metal surfaces
US6514357B1 (en) Composition for metal surface treatment and surface treated metallic material
US4992116A (en) Method and composition for coating aluminum
CA2120614C (en) Broadly applicable phosphate conversion coating composition and process
US5868872A (en) Chromium-free process for the no-rinse treatment of aluminum and its alloys and aqueous bath solutions suitable for this process
JP4154466B2 (en) Titanium oxide film-forming coating agent is coated with a titanium oxide film formation method and a titanium oxide film metal substrate
CN102257178B (en) Surface treating agent for metallic materials
US6190780B1 (en) Surface treated metal material and surface treating agent
US4263059A (en) Coating solutions of trivalent chromium for coating zinc and cadmium surfaces

Legal Events

Date Code Title Description
AS Assignment

Owner name: HENKEL KOMMANDI GESELLSCHAFT AUF AKTIEN, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SAKO, RYOUSUKE;UENO, KEIICHI;YAMAMOTO, MAYUMI;REEL/FRAME:013568/0729

Effective date: 20021121

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION