EP0391442A1 - Oberflächenbehandlung für zinkhaltige Oberflächen - Google Patents

Oberflächenbehandlung für zinkhaltige Oberflächen Download PDF

Info

Publication number
EP0391442A1
EP0391442A1 EP19900106675 EP90106675A EP0391442A1 EP 0391442 A1 EP0391442 A1 EP 0391442A1 EP 19900106675 EP19900106675 EP 19900106675 EP 90106675 A EP90106675 A EP 90106675A EP 0391442 A1 EP0391442 A1 EP 0391442A1
Authority
EP
European Patent Office
Prior art keywords
acid
group
process according
component
mixtures
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.)
Granted
Application number
EP19900106675
Other languages
English (en)
French (fr)
Other versions
EP0391442B1 (de
Inventor
Noriaki Yoshitake
Kenshi Saeki
Takumi Nihon Parker Hiratsuka Dormitory Honda
Takao Ogino
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 EP0391442A1 publication Critical patent/EP0391442A1/de
Application granted granted Critical
Publication of EP0391442B1 publication Critical patent/EP0391442B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23C22/37—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 hexavalent chromium compounds
    • C23C22/38—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 hexavalent chromium compounds 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
    • C23C22/24—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 hexavalent chromium compounds
    • C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
    • 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 treatment method which is capable of developing a chromium containing film that pro­vides an excellent base for paint, by having both good paint adherence and good corrosion resistance after paint­ing, as well as excellent corrosion resistance, alkali resistance, and ease of welding, because of relatively low electrical resistance, when left unpainted.
  • Treatment ac­cording to the invention is applied to surfaces containing zinc as a predominant constituent, particularly to surfaces of electrogalvanized steel sheet, zinc-alloy electroplated steel sheet, and galvannealed steel sheet (collectively denoted as "zinc-plated steel sheet” below).
  • the invention of Japanese Patent Application Laid Open [Kokai] Number 50-158535 [158,535/75] concerns a method for the formation of solution resistant chromate films on the surface of zinc-plated steel sheet.
  • the chromate solution contains chromic anhydride, phosphoric acid, and water-soluble or water-dispersible polymer, and the Cr6+ in this treatment bath is at least 70 % reduced to Cr3+ by a reductant such as ethylene glycol.
  • a reductant such as ethylene glycol
  • the chromate bath taught in Japanese Patent Publica­tion Number 61-58522 [58,522/86] contains specified amounts of chromic acid, reduced chromic acid, and silica sol components.
  • a surface-treated steel sheet carrying the chromate film formed by the method of this invention is processed for painting, most of the hexavalent chromium in the chromate film is easily eluted by the al­kali rinse prior to painting.
  • the corrosion resist­ance of the film is then lowered due to its poor alkali resistance.
  • the film contains silica its weldability, for example, its spot weldability, is poor.
  • Japanese Patent Application Laid Open Numbers 58-22383 [22,383/83] and 62-83478 [83,478/87] are examples of the disclosure of the use of silane coupling agents as reduct­ants for the hexavalent chromium in chromate treatment solutions. While the films formed by the methods of these references provide excellent paint bondability, the chrom­ate film formed by the method of the former reference has a poor alkali resistance because it does not contain silica or organic polymer. In the latter reference, the spot weldability is unsatisfactory because colloidal silica is present.
  • One embodiment of the present invention is a process for treating objects with a zinciferous surface, preferably sheets of zinc-plated steel, by contact between the surface of the treated object and a liquid solution composition that comprises, or preferably consists essentially of, water and the following components:
  • composition of the aqueous solution used by the method of the present invention is discussed in more detail below.
  • This solution uses water as its solvent, and it con­tains 3.0 to 50 g/L of Cr6+ and 2.0 to 40 g/L of Cr3+ as essential components.
  • the formation of a satisfactorily corrosion-resistant chromium containing film becomes prob­lematic when the Cr6+ falls below 3.0 g/L or the Cr3+ falls below 2.0 g/L.
  • the chromate bath will have a high viscosity and a poor stability, and it becomes diffi­cult to control the quantity of chromium deposited in the surface coating formed.
  • a crucial element of the composition is the ratio between Cr6+ and Cr3+. It is essential that the chromium ratio (Cr3+/Cr6+) fall within the range of 0.25 to 1.5. When the chromium ratio falls below 0.25, the oxidiz­ing tendency of the Cr6+ content in the chromate bath is increased. As a result, when the silane coupling agent is added to such a bath, reduction of the Cr6+ in the chromate bath by the silane coupling agent tends to develop rather readily, and the chromate bath is heated by this. As a consequence, the rate of the Cr6+ reduction reaction by the solvent in the chromate bath and solvent volatilization are both increased, causing a decline in the quality of the chromate bath.
  • the chromium ratio can be controlled by the addition as necessary of a reductant such as ethanol, methanol, oxalic acid, starch, sucrose, and the like.
  • PO43 ⁇ is preferably added as orthophosphoric acid (H3PO4).
  • H3PO4 orthophosphoric acid
  • the corrosion re­sistance and alkali resistance of the surface coating formed on the zinciferous surfaces treated are reduced.
  • exceeding 100 g/L promotes the rapid reduction of the Cr6+ in the solution by the silane coupling agent, and the quality of the solution is degraded as a result.
  • a particularly important aspect of the PO43 ⁇ content is its ratio relative to the quantity of total chromium (Cr6+ + Cr3+) in the solution, and a PO43 ⁇ /total Cr ratio within the range of 0.1 to 1.2 is preferred.
  • this ratio falls below 0.1, the alkali resistance and corrosion resistance of the surface film formed during a process according to the invention tend to decline.
  • reduction of the Cr6+ in the chromate bath by the silane coupling agent proceeds very easily, with the result that the Cr6+ in the chromate bath is substantially or almost completely reduced to Cr3+ prior to application. As a consequence, the quality of the chromate bath is reduced, and it becomes difficult to form a coating which satisfies the object of the present invention.
  • the solution used contains 3 to 50 g/L of another component which functions as a wettability im­prover: one compound or, if desired, a mixture of com­pounds selected from C4 - C8 tertiary alcohols and aceto­nitrile.
  • a wettability im­prover one compound or, if desired, a mixture of com­pounds selected from C4 - C8 tertiary alcohols and aceto­nitrile.
  • Each of these compounds has a relatively high stability with regard to the Cr+6 present in the chromate bath at bath temperatures below approximately 35 degrees Centigrade, while none adversely affects the quality of the treatment film formed to any significant degree.
  • each can function to increase the wettability of the chromate bath on the plated surface. Accordingly, each can contribute to increasing the uniformity of chromium coating weight on the treated surface during high-speed operations.
  • this organic component is added in greater amounts, the greater the total chromium concen­tration in the treatment solution, and the greater the application speed.
  • the organic component is preferably selected from tert-butyl alcohol and/or tert-amyl alcohol.
  • the alkali resistance of the treated surface can be increased by the optional addition of 0.2 to 10 g/L of zinc ions to the aqueous treatment bath.
  • the improvement is vanishingly small at a zinc ion quantity below 0.2 g/L, while exceeding 10 g/L tends to precipitate the Cr3+ in the treatment bath.
  • the Zn+2 ions are preferably added to the treatment bath in the form of zinc oxide, zinc carbonate, zinc phosphate, or zinc hydroxide.
  • complex fluoride may optionally be added to the treatment bath, either by itself or together with zinc. It is preferably added in the range of 0.2 to 8 g/L based on F.
  • Preferred examples of the complex fluoride are fluozirconic acid (H2ZrF6), fluotitanic acid (H2TiF6), fluosilicic acid (H2SiF6), and fluoboric acid (H2BF6).
  • H2ZrF6 fluozirconic acid
  • H2TiF6 fluotitanic acid
  • H2SiF6 fluosilicic acid
  • fluoboric acid H2BF6
  • This zinc or other metal complex becomes a constituent component of the chromium containing film formed, and contributes to improving the film's uniformity and corrosion resistance.
  • the effects of addition are difficult to note at fluoride quantities below 0.2 g/L, while exceeding 8 g/L lowers the corrosion resistance of the chromium containing film formed.
  • silane coupling agent is preferably first mixed with the chromate bath at a molar ratio referred to the gram-atomic concentration of Cr6+ in the chromate bath within the range of 0.05 to 0.30.
  • the silane coupling agent component is selected from the group consisting of vinyltrimethoxy­silane, vinyltriethoxysilane, gamma-mercaptopropyltrimeth­oxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-­glycidoxypropylmethyldimethoxysilane, gamma-methacryloxy­propyltrimethoxysilane, gamma-methacryloxypropylmethyldi­methoxysilane, and mixtures of any two or more of these.
  • Silane coupling agents with the above general formula are preferred because they have good solubilities in the aqueous solution used to contact zinc surfaces in a process according to this invention and make a relatively large contribution to improving the corrosion resistance of the protective film formed on the zinc surface.
  • the improvement in the chromium contain­ing film's alkali resistance is negligible.
  • the chromate bath tends to evidence a gradual decline in stability, i.e., the Cr3+ in the chromate bath increases and gelation is facilitated.
  • Use of the silane coupling agent in the molar ratio to Cr+6 range of 0.1 to 0.2 is even more preferred.
  • the treatment bath mixed with silane coupling agent as explained above, may be coated on the zinc-plated steel sheet or other zinciferous surface by, for example, a roll coater, curtain coater, or any other convenient method that establishes contact between the solution and the surface to be treated and results in a satisfactorily uniform coating of the solution over the surface before drying.
  • a film with a chromium content of 10 to 200 mg/m2 be formed by drying for 5 to 10 seconds at a temperature on the drying surface of 60 to 150 degrees Centigrade.
  • the liquid treating solution itself should be maintained at no greater than 35 degrees Centigrade and preferably at no greater than 25 degrees Centigrade after addition of the silane coupling agent to the bath.
  • Treatment solution according to this invention is satisfactorily stable for approximately 1 month at relatively low chromium concentrations, but use within 1 week after the addition of the silane component is strongly preferred for such solutions with high chromium concentra­tions.
  • the corrosion resistance of the treated object with a film as formed and the corrosion resistance after painting are both unsatisfactory with less than 10 mg/m2 of chromium uptake during a treatment according to this invention.
  • uptakes exceeding 200 mg/m2
  • it becomes difficult to control the quantity of chromium adherence in the chromate film the improvement in corrosion resistance reaches an upper limit and further benefits cannot be expected; and paint adherence is reduced because portions of the chromate film are easily removed by external forces when it is so thick.
  • pH of the aqueous chromate bath used in the present invention is not critical, values around 1.0 to 3.0 are preferable.
  • the Cr6+, Cr3+, and PO43 ⁇ components in the aqueous chromate bath are believed to react with one another and/or the treated surface, at a rate speeded by the thermal energy supplied by drying.
  • the constituent components of the resulting chromate film are believed to be the colorless materials respectively specified in (a) and (b) below, the green material specified in (c), and the gold colored material specified in (d) and (e).
  • the aforemen­tioned chromic chromate (e), for example, can undergo condensation reactions as depicted by Figure 1, while at the same time, the chromic chromate is cross linked as depicted in Figure 2 by the hydrolyzate ⁇ f ⁇ deriving from the silane coupling agent. Moreover, the hexavalent chromium in the chromic chromate is reduced by the methanol. Therefore, it is thought that a companion macromolecular network structure is formed by the development of complex cross linkages between the chromic chromate and silane coupling agent hydrolyzate.
  • each of the aforementioned compon­ents (a), (b), (c), and (d) may be present within the structure of the macromolecular, chromium containing coating represented by Figures 1 and 2, either in a chain-stopping position or bonded with said macromolecular chromium compound.
  • the chromate film having this network molecular structure exhibits a strong alkali resistance, i.e., the chromium in the film strongly resists elution due to alkali rinsing. Moreover, it is thought that this network molecular structure contributes to in­creasing both the corrosion resistance and uniformity.
  • this film does not contain silica or an organic macromolecular compound, the electrical resistance of the film is relatively low, so that it is relatively easy to weld surfaces treated according to this invention.
  • Chromate coating bath No. A as reported in Table 1 was prepared as follows: 200 grams ("g") of chromic anhydride (Cr2O6) was first dissolved in 500 g of water, 86 g of phos­phoric acid (75% aqueous solution) and 18 g of methanol were added to the aqueous solution thus obtained, and this was then heated for 1 hour at 80 to 90 degrees Centigrade to cause reduction to a Cr3+/Cr6+ weight ratio of 1.0. After cooling, 26 g of tert-butanol and sufficient water to make a total weight of 1 kg were added. This solution is denoted in the following as the aqueous base solution.
  • aqueous base solution was then diluted with water to give a total chromium concentration (Cr6+ + Cr3+) of 40 g/L, along with 10 g/L tert-butanol.
  • Silane coupling agent gamma-glycidoxypropyltrimethoxysilane from Toshiba Sili­cone Company, Limited
  • Silane coupling agent was then added with stirring, in an amount to yield a concentration of 9 g/L, to give final treating bath No. A.
  • the treated zinc coated steel was paint­ed with a bakeable melamine alkyd paint (DeliconTM 700 White from Dainippon Paint Company, Limited) and then baked for 20 minutes at 140 degrees Centigrade to give a painted sheet carrying a 25 micrometer thick coating.
  • a bakeable melamine alkyd paint (DeliconTM 700 White from Dainippon Paint Company, Limited) and then baked for 20 minutes at 140 degrees Centigrade to give a painted sheet carrying a 25 micrometer thick coating.
  • the treated sheet was alkali rinsed using the condi­tions specified below, and the quantity of adhering chrom­ium in mg/m2 was measured by X-ray fluorescence both before and after this rinse.
  • the "alkali resistance" as reported in Table 2 is defined as the percentage of the chromium originally present that is removed by this rinsing. Thus, the alkali resistance increases as the percent value declines, and a zero value indicates absolutely no loss from alkali in this test, or complete resistance.
  • the alkali rinse conditions were as follows: 2 minute spray at 60 degrees Centigrade using a 2% aqueous solution of a sodium silicate-based alkaline degreaser (Par-Clean® N364S from Nihon Parkerizing Company, Limited).
  • test specimen 70 x 150 mm
  • JIS Japanese Industrial Standard
  • the test specimen was subjected to a composite corrosion test (50 cycles) both before and after alkali rinsing. Each cycle consisted of salt spray for 4 hours, drying at 60 degrees Centigrade for 2 hours, and wetting at 50 degrees Centigrade and a relative humidity of ⁇ 95 % for 2 hours.
  • the painted test specimen (with no alkali rinse) was extruded 6 mm.
  • Conventional transparent adhesive tape was then applied and rapidly peeled off, and the degree of paint film peeling was in­spected and reported with the same symbols as for the crosscut test.
  • practice of the present invention forms a surface film which is very uniformly distributed over the surface of zinc objects, especially zinc-plated steel sheet.
  • the treated sheet is well suited to welding, resistant to alkali treatment and corrosion, and very well adapted for painting, because paint adheres very well and the painted surface is corrosion resistant.

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)
  • Manufacture And Refinement Of Metals (AREA)
  • Laminated Bodies (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
EP90106675A 1989-04-07 1990-04-06 Oberflächenbehandlung für zinkhaltige Oberflächen Expired - Lifetime EP0391442B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1089415A JPH0753911B2 (ja) 1989-04-07 1989-04-07 亜鉛系めっき鋼板のクロメート処理方法
JP89415/89 1989-04-07

Publications (2)

Publication Number Publication Date
EP0391442A1 true EP0391442A1 (de) 1990-10-10
EP0391442B1 EP0391442B1 (de) 1993-10-06

Family

ID=13970020

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90106675A Expired - Lifetime EP0391442B1 (de) 1989-04-07 1990-04-06 Oberflächenbehandlung für zinkhaltige Oberflächen

Country Status (9)

Country Link
EP (1) EP0391442B1 (de)
JP (1) JPH0753911B2 (de)
KR (1) KR930007389B1 (de)
AT (1) ATE95575T1 (de)
DE (1) DE69003716T2 (de)
DK (1) DK0391442T3 (de)
ES (1) ES2045616T3 (de)
NZ (1) NZ233236A (de)
ZA (1) ZA902660B (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991005078A1 (en) * 1989-09-27 1991-04-18 Henkel Corporation Composition and process for chromating galvanized steel and like materials
EP0479289A1 (de) * 1990-10-05 1992-04-08 Nihon Parkerizing Co., Ltd. Verfahren zur Chromatierung von einer Stahlplatte mit einer Beschichtung auf Zink-Basis
EP0485972A1 (de) * 1990-11-14 1992-05-20 Nippon Steel Corporation Verfahren zur Erzeugung eines organisch verbundbeschichteten Stahlbleches
WO1999014398A1 (de) * 1997-09-12 1999-03-25 Henkel Kommanditgesellschaft Auf Aktien CHROMATIERUNG ODER NACHPASSIVIERUNG MIT STABILISIERTEN Cr(III)/Cr(VI)-HALTIGEN LÖSUNGEN
WO1999014399A1 (en) * 1997-09-17 1999-03-25 Brent International Plc Method and compositions for preventing corrosion of metal substrates
EP1002889A2 (de) * 1998-11-18 2000-05-24 Nippon Paint Co., Ltd. Antikorrosive Beschichtungszusammensetzung für Metalle und Verfahren
EP1024905A1 (de) * 1997-08-21 2000-08-09 Henkel Corporation Verfahren zum beschichten und/oder nachbessern von beschichtungen auf metalloberflächen
WO2003054249A1 (de) * 2001-12-20 2003-07-03 Walter Hillebrand Gmbh & Co. Galvanotechnik Schwarzpassivierungsverfahren
US6749952B2 (en) * 2001-03-21 2004-06-15 Jfe Steel Corporation Tin-plated steel sheet
WO2004065642A2 (en) 2003-01-23 2004-08-05 The United States Of America, As Represented By The Secretary Of The Navy, Et Al. Pretreatment for aluminum and aluminum alloys
EP1585847A2 (de) * 2003-01-23 2005-10-19 The United States of America as Represented by The Secretary of The Navy Nachbehandlung für metallbeschichtete substrate
RU2547374C1 (ru) * 2014-01-31 2015-04-10 Закрытое акционерное общество "ФК" Хроматирующий состав для обработки оцинкованной стали

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2743220B2 (ja) * 1991-04-22 1998-04-22 新日本製鐵株式会社 ポリウレタン重防食被覆鋼材

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2180263A (en) * 1985-09-05 1987-03-25 Nihon Parkerizing Chromating solutions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2180263A (en) * 1985-09-05 1987-03-25 Nihon Parkerizing Chromating solutions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, C section, vol. 11, no. 290, September 18, 1987 THE PATENT OFFICE JAPANESE GOVERNMENT page 50 C 447 & JP - A - 62 - 83 478 ( SUMITOMO METAL IND LTD ) *
PATENT ABSTRACTS OF JAPAN, unexamined applications, C section, vol. 7, no. 97, April 23, 1983 THE PATENT OFFICE JAPANESE GOVERNMENT page 76 C 163 & JP - A - 58 - 22 383 ( N ITSUSHIN SEIKOU KK ) *

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991005078A1 (en) * 1989-09-27 1991-04-18 Henkel Corporation Composition and process for chromating galvanized steel and like materials
US5091023A (en) * 1989-09-27 1992-02-25 Henkel Corporation Composition and process for chromating galvanized steel and like materials
EP0479289A1 (de) * 1990-10-05 1992-04-08 Nihon Parkerizing Co., Ltd. Verfahren zur Chromatierung von einer Stahlplatte mit einer Beschichtung auf Zink-Basis
US5230750A (en) * 1990-10-05 1993-07-27 Nihon Parkerizing Co., Ltd. Chromating method of zinc-based plated steel sheet
EP0485972A1 (de) * 1990-11-14 1992-05-20 Nippon Steel Corporation Verfahren zur Erzeugung eines organisch verbundbeschichteten Stahlbleches
US5304401A (en) * 1990-11-14 1994-04-19 Nippon Steel Corporation Method of producing organic composite-plated steel sheet
EP1024905A1 (de) * 1997-08-21 2000-08-09 Henkel Corporation Verfahren zum beschichten und/oder nachbessern von beschichtungen auf metalloberflächen
USRE40406E1 (en) 1997-08-21 2008-07-01 Henkel Kgaa Process for coating and/or touching up coatings on metallic surfaces
US6361622B1 (en) 1997-08-21 2002-03-26 Henkel Corporation Process for coating and/or touching up coatings on metal surfaces
EP1024905A4 (de) * 1997-08-21 2000-12-13 Henkel Corp Verfahren zum beschichten und/oder nachbessern von beschichtungen auf metalloberflächen
WO1999014398A1 (de) * 1997-09-12 1999-03-25 Henkel Kommanditgesellschaft Auf Aktien CHROMATIERUNG ODER NACHPASSIVIERUNG MIT STABILISIERTEN Cr(III)/Cr(VI)-HALTIGEN LÖSUNGEN
WO1999014399A1 (en) * 1997-09-17 1999-03-25 Brent International Plc Method and compositions for preventing corrosion of metal substrates
AU724978B2 (en) * 1997-09-17 2000-10-05 Chemetall Plc Method and compositions for preventing corrosion of metal substrates
EP1002889A3 (de) * 1998-11-18 2000-09-13 Nippon Paint Co., Ltd. Antikorrosive Beschichtungszusammensetzung für Metalle und Verfahren
EP1002889A2 (de) * 1998-11-18 2000-05-24 Nippon Paint Co., Ltd. Antikorrosive Beschichtungszusammensetzung für Metalle und Verfahren
US6749952B2 (en) * 2001-03-21 2004-06-15 Jfe Steel Corporation Tin-plated steel sheet
WO2003054249A1 (de) * 2001-12-20 2003-07-03 Walter Hillebrand Gmbh & Co. Galvanotechnik Schwarzpassivierungsverfahren
WO2004065642A2 (en) 2003-01-23 2004-08-05 The United States Of America, As Represented By The Secretary Of The Navy, Et Al. Pretreatment for aluminum and aluminum alloys
EP1585847A2 (de) * 2003-01-23 2005-10-19 The United States of America as Represented by The Secretary of The Navy Nachbehandlung für metallbeschichtete substrate
EP1585848A2 (de) * 2003-01-23 2005-10-19 The United States of America as Represented by The Secretary of The Navy Vorbehandlung für aluminium und aluminiumlegierungen
EP1585847A4 (de) * 2003-01-23 2009-05-06 Us Navy Nachbehandlung für metallbeschichtete substrate
EP1585848A4 (de) * 2003-01-23 2009-05-06 Us Navy Vorbehandlung für aluminium und aluminiumlegierungen
RU2547374C1 (ru) * 2014-01-31 2015-04-10 Закрытое акционерное общество "ФК" Хроматирующий состав для обработки оцинкованной стали

Also Published As

Publication number Publication date
ES2045616T3 (es) 1994-01-16
EP0391442B1 (de) 1993-10-06
KR900016497A (ko) 1990-11-13
DE69003716T2 (de) 1994-02-17
DE69003716D1 (de) 1993-11-11
NZ233236A (en) 1992-05-26
ZA902660B (en) 1991-01-30
ATE95575T1 (de) 1993-10-15
JPH0753911B2 (ja) 1995-06-07
KR930007389B1 (ko) 1993-08-09
JPH02267277A (ja) 1990-11-01
DK0391442T3 (da) 1993-12-20

Similar Documents

Publication Publication Date Title
US5141575A (en) Surface treatment for zinciferous surfaces
EP2112251B1 (de) Oberflächenvorbehandlungsfluid für das durch kationische elektrotauchlackierung zu beschichtende metall
EP0553164B1 (de) Verfahren zur chromatierung von mit zink beschichtetem stahl
EP0902103B1 (de) Oberflächenbehandeltes metallisches korrosionsbeständiges material und oberflächenbehandlung dafür
US6361833B1 (en) Composition and process for treating metal surfaces
JP5075321B2 (ja) 金属表面の水系処理薬剤
EP0391442B1 (de) Oberflächenbehandlung für zinkhaltige Oberflächen
WO2007011008A1 (ja) 耐食性、耐熱性、耐指紋性、導電性、塗装性および加工時の耐黒カス性に優れたクロメートフリー表面処理金属材
US5230750A (en) Chromating method of zinc-based plated steel sheet
EP1498510A2 (de) Zusammensetzung und Verfahren zur Behandlung von Metalloberflächen und galvanisierte Stahlplatte
KR102255735B1 (ko) 박막 전처리 및 밀봉 조성물을 통한 금속 기판 처리를 위한 시스템 및 방법
WO2000024948A1 (en) Composition and process for treating metal surfaces
US20230203699A1 (en) Treated substrates
EP0381190A1 (de) Phosphatierlösung für Komplexstrukturen und Verfahren zu ihrer Verwendung
EP2980272B1 (de) Mittel zur behandlung einer metalloberfläche und verfahren zur behandlung einer metalloberfläche
EP0545993A1 (de) Zusammensetzung und verfahren zur chromatierung von metallen.
US5507884A (en) Process for forming a sparingly soluble chromate coating on zinciferous metal coated steel
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
EP4209616A1 (de) Oberflächenbehandeltes stahlblech zur beschichtung mit organischem harz und herstellungsverfahren dafür, mit organischem harz beschichtetes stahlblech und herstellungsverfahren dafür
JP2003253463A (ja) 亜鉛系めっき鋼板のノンクロム処理
KR20230081132A (ko) 내식성 및 내흑변성이 우수한 삼원계 용융아연도금강판 표면처리용 조성물, 이를 이용하여 표면처리된 삼원계 용융아연도금강판 및 이의 제조방법
MXPA01004311A (en) Composition and process for treating metal surfaces

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

AK Designated contracting states

Kind code of ref document: A1

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: OGINO, TAKAO

Inventor name: HONDA, TAKUMI, NIHON PARKER HIRATSUKA DORMITORY

Inventor name: SAEKI, KENSHI

Inventor name: YOSHITAKE, NORIAKI

17P Request for examination filed

Effective date: 19901220

17Q First examination report despatched

Effective date: 19920518

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 95575

Country of ref document: AT

Date of ref document: 19931015

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: JACOBACCI CASETTA & PERANI S.P.A.

REF Corresponds to:

Ref document number: 69003716

Country of ref document: DE

Date of ref document: 19931111

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3009456

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2045616

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19940430

Ref country code: BE

Effective date: 19940430

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
BERE Be: lapsed

Owner name: HENKEL CORP.

Effective date: 19940430

EAL Se: european patent in force in sweden

Ref document number: 90106675.3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19950313

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19950323

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19950404

Year of fee payment: 6

Ref country code: AT

Payment date: 19950404

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19950427

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19950430

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Effective date: 19960406

Ref country code: AT

Effective date: 19960406

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19960408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19960430

Ref country code: CH

Effective date: 19960430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19961031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19961101

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3009456

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19961101

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19970319

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980407

EUG Se: european patent has lapsed

Ref document number: 90106675.3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990503

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010319

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010320

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010321

Year of fee payment: 12

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021231

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050406