EP0015021B1 - Process for the pretreatment of metal surfaces for electrophoretic dip painting - Google Patents
Process for the pretreatment of metal surfaces for electrophoretic dip painting Download PDFInfo
- Publication number
- EP0015021B1 EP0015021B1 EP80200097A EP80200097A EP0015021B1 EP 0015021 B1 EP0015021 B1 EP 0015021B1 EP 80200097 A EP80200097 A EP 80200097A EP 80200097 A EP80200097 A EP 80200097A EP 0015021 B1 EP0015021 B1 EP 0015021B1
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- European Patent Office
- Prior art keywords
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- metal surfaces
- ions
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- Prior art date
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- 238000000034 method Methods 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 title claims description 13
- 239000002184 metal Substances 0.000 title claims description 13
- 238000010422 painting Methods 0.000 title claims description 5
- 238000000576 coating method Methods 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 12
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 4
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000003682 vanadium compounds Chemical class 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 229910001447 ferric ion Inorganic materials 0.000 claims 1
- 229910001448 ferrous ion Inorganic materials 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- -1 ferrous metals Chemical class 0.000 description 10
- 239000003973 paint Substances 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AWUCVROLDVIAJX-UHFFFAOYSA-N alpha-glycerophosphate Natural products OCC(O)COP(O)(O)=O AWUCVROLDVIAJX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- AWUCVROLDVIAJX-GSVOUGTGSA-N sn-glycerol 3-phosphate Chemical compound OC[C@@H](O)COP(O)(O)=O AWUCVROLDVIAJX-GSVOUGTGSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/362—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also zinc cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
Definitions
- aqueous phosphating solutions are used for the treatment of surfaces made of ferrous metals and zinc, the essential constituents of which contain phosphate ions, zinc ions, cobalt, copper or nickel ions, magnesium ions, nitrite ions, fluorine and / or chlorine ions and optionally nitrate ions (DE -OS 2 049 350).
- the solutions have contents of 3 to 20 g phosphate ions, 0.5 to 3 g zinc ions, 0.003 to 0.7 g cobalt ions or 0.003 to 0.04 g copper ions or preferably 0.05 to 3 g nickel ions, 1 to 8 g magnesium ions, 0.01 to 0.25 g of nitrite ions and 0.1 to 3 g of fluorine ions and / or 2 to 30 g of chlorine ions and optionally up to about 40 g of nitrate ions.
- One of the ways of introducing the fluorine ions can be in the form of fluorosilicate or fluoroborate ions.
- Paint or other fast-drying organic coatings can then be applied to the phosphate layers produced in this way.
- a disadvantage of the coatings produced with the known solutions based on zinc phosphate or magnesium and / or calcium phosphate as the basis for the subsequent electrodeposition coating is in particular that a considerable part of the phosphate coating is separated off during the coating process, passes into the coating film and adversely affects it .
- Essentially free of ferroions means that the treatment of non-ferrous metals does not involve the use of bath solutions that contain substantial amounts of ferroions, and the preferred treatment of steel surfaces brings them into contact with solutions that contain accelerators that oxidize ferroions.
- Treatment solutions containing chlorate and / or nitrite are particularly suitable. It is sufficient to use as much chlorate and / or nitrite as is necessary to remove excess ferroions by oxidation. The amounts are thus dependent on the throughput and do not need to be specifically matched to the amount of zinc ions and phosphoric acid or to phosphoric acid, as is required in known processes. However, it has been found that the chlorate content should be set to at least 0.1 g / l. Larger quantities are advisable for high throughputs.
- Solutions are advantageously used which contain vanadium compounds, preferably in amounts of 0.1 to 10 mg / l vanadium, which has proven to be particularly advantageous at high throughputs.
- Other polyvalent cations such as Ni, Mn or Ca ions, the amount of which, however, should not exceed 0.5 gll, bring about a further improvement.
- alkali metal ions Na, NH 4 etc.
- the content of P0 4 is in the usual range and is about 5 to 20 g / l .
- the phosphate layers achieved with the method according to the invention provide such a high level of corrosion protection (higher sub-walls protection) that a subsequent treatment with the known rinse agents, for. B. Cr (VI) - or Cr (III) ion-containing, practically no additional improvement.
- the phosphate layers produced with the invention are of a quality that is otherwise only achieved by using additional rinsing agents.
- the sheets were then rinsed with water and deionized water and then dried.
- the layer weight achieved was 1.8 g / m 2 .
- a modified epoxy resin varnish was then cathodically deposited on the steel sheet pretreated in this way.
- the electrodeposition bath had room temperature, the deposition voltage and duration were 180 volts or 2 minutes.
- the varnish was then baked at an object temperature of 190 ° C for 25 minutes.
- the paint film thickness obtained was 15 ⁇ m, the paint layer was uniform and shiny.
- the paint infiltration determined after the salt spray test was only less than 1 mm.
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)
Description
Die Erfindung betrifft ein Verfahren zur Vorbereitung von Metalloberflächen, insbesondere aus Stahl, für die elektrophoretische Tauchlackierung durch Aufbringen von Phosphatschichten mittels Lösungen auf Basis Zinkphosphat mit einem Zusatz von Alkaliionen, in denen das Gewichtsverhältnis von Zn : P04 = I : (12 bis 110), vorzugsweise = 1 : ( 20 bis 100) ist.The invention relates to a method for preparing metal surfaces, in particular steel, for electrophoretic dip coating by applying phosphate layers by means of solutions based on zinc phosphate with the addition of alkali ions, in which the weight ratio of Zn: P0 4 = I: (12 to 110) , preferably = 1: (20 to 100).
Es ist seit langem üblich, Metalloberflächen durch Aufbringung eines Phosphatüberzuges für die anschliessende Lackierung vorzubereiten, um eine Verbesserung des Korrosionsschutzes und eine Erhöhung der Lackhaftung zu erzielen. Als Grundlage für die Elektrotauchlackierung dienen hauptsächlich Zinkphosphatüberzüge. Zu deren Erzeugung werden üblicherweise wässrige saure Überzugslösungen auf Basis Monozinkphosphat verwendet, denen Chlorat, Nitrit, Nitrat, organische Nitroverbindungen oder Gemische hiervon als Beschleuniger zugesetzt werden. Die erhaltenen Überzüge sind jedoch häufig für die anschliessende Lackierung wegen ihrer Dicke und Grobkristallinität unbefriedigend. Da zur Vorbehandlung vor der Elektrotauchlackierung dünne und feinkörnige Überzüge erwünscht sind, werden deshalb den Lösungen ausserdem häufig verschiedene organische oder anorganische Chelatierungsmittel, wie Zitronensäure, Weinsäure, Malonsäure, Polyphosphorsäure, Glycerophosphorsäure, Äthylendiamintetraessigsäure, Nitrilotriessigsäure oder deren Salze zugesetzt. Hierdurch ergeben sich jedoch häufig schwierigkeiten, die Lösungen zu kontrollieren; auch genügt die Schichtausbildung oft nicht den gestellten Anforderungen.It has long been customary to prepare metal surfaces by applying a phosphate coating for the subsequent painting in order to improve corrosion protection and increase paint adhesion. Mainly zinc phosphate coatings serve as the basis for electrocoating. To produce them, aqueous acidic coating solutions based on monozinc phosphate are usually used, to which chlorate, nitrite, nitrate, organic nitro compounds or mixtures thereof are added as accelerators. However, the coatings obtained are often unsatisfactory for the subsequent coating because of their thickness and coarse crystallinity. Since thin and fine-grained coatings are desired for the pretreatment before electrocoating, various organic or inorganic chelating agents, such as citric acid, tartaric acid, malonic acid, polyphosphoric acid, glycerophosphoric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid or salts thereof, are therefore often added to the solutions. However, this often creates difficulties in controlling the solutions; the layer formation also often does not meet the requirements.
Bei einem weiteren Verfahren kommen wässrige Phosphatierungslösungen zur Behandlung von Oberflächen aus Eisenmetallen und Zink zur Anwendung, die als wesentliche Bestandteile Phosphationen, Zinkionen, Kobalt-, Kupfer- oder Nickelionen, Magnesiumionen, Nitritionen, Fluor-und/oder Chlorionen sowie gegebenenfalls Nitrationen enthalten (DE-OS 2 049 350). Die Lösungen weisen Gehalte von 3 bis 20 g Phosphationen, 0,5 bis 3 g Zinkionen, 0,003 bis 0,7 g Kobaltionen oder 0,003 bis 0,04 g Kupferionen oder vorzugsweise 0,05 bis 3 g Nickelionen, 1 bis 8 g Magnesiumionen, 0,01 bis 0,25 g Nitritionen und 0,1 bis 3 g Fluorionen und/oder 2 bis 30 g Chlorionen sowie gegebenenfalls bis etwa 40 g Nitrationen auf. Eine der Möglichkeiten der Einbringung der Fluorionen kann in Form von Fluorosilikat- oder Fluoroborationen erfolgen.In a further process, aqueous phosphating solutions are used for the treatment of surfaces made of ferrous metals and zinc, the essential constituents of which contain phosphate ions, zinc ions, cobalt, copper or nickel ions, magnesium ions, nitrite ions, fluorine and / or chlorine ions and optionally nitrate ions (DE -OS 2 049 350). The solutions have contents of 3 to 20 g phosphate ions, 0.5 to 3 g zinc ions, 0.003 to 0.7 g cobalt ions or 0.003 to 0.04 g copper ions or preferably 0.05 to 3 g nickel ions, 1 to 8 g magnesium ions, 0.01 to 0.25 g of nitrite ions and 0.1 to 3 g of fluorine ions and / or 2 to 30 g of chlorine ions and optionally up to about 40 g of nitrate ions. One of the ways of introducing the fluorine ions can be in the form of fluorosilicate or fluoroborate ions.
Auf diese so erzeugten Phosphatschichten können anschliessend Anstrichfarben oder andere schnelltrocknende organische Überzüge aufgebracht werden.Paint or other fast-drying organic coatings can then be applied to the phosphate layers produced in this way.
Ein Nachteil der mit den bekannten Lösungen auf Basis Zinkphosphat bzw. Magnesium- und/ oder Kalziumphosphat erzeugten Überzüge als Grundlage für die anschliessende Elektrotauchlackierung besteht insbesondere darin, dass ein beachtlicher Teil des Phosphatüberzuges bei der Lackierung abgetrennt wird, in den Lackfilm übergeht und diesen nachteilig beeinflusst.A disadvantage of the coatings produced with the known solutions based on zinc phosphate or magnesium and / or calcium phosphate as the basis for the subsequent electrodeposition coating is in particular that a considerable part of the phosphate coating is separated off during the coating process, passes into the coating film and adversely affects it .
Zwar ist es bekannt, diese Nachteile weitgehend zu vermeiden, indem man Behandlungslösungen zum Einsatz bringt, in denen der Zinkanteil in Bezug auf die Phosphationen gegenüber den üblichen Lösungen auf Basis Monozinkphosphat erheblich erniedrigt ist (DE-OS 2232067). Die Behandlung führt zu verbesserten dünnen und gleichmässigen Phosphatüberzügen auf Metalloberflächen, insbesondere Stahl, die sehr haftfest und beständig und als Grundlage für die anschliessende Elektrotauchlackierung geeignet sind. Die Phosphatschichten vermitteln einen hohen Korrosionsschutz und werden bei der Lackierung zu einem wesentlich geringeren Anteil abgetrennt als die bei Verwendung der bisher üblichen Lösungen erzeugten Überzüge.It is known to largely avoid these disadvantages by using treatment solutions in which the zinc content in relation to the phosphate ions is considerably reduced compared to the conventional solutions based on monozinc phosphate (DE-OS 2232067). The treatment leads to improved thin and uniform phosphate coatings on metal surfaces, especially steel, which are very adhesive and resistant and are suitable as a basis for the subsequent electrocoating. The phosphate layers provide a high level of protection against corrosion and are removed to a much lesser extent during painting than the coatings produced when using the solutions customary hitherto.
Es wurde nun gefunden, dass die mit dem Verfahren gemäss DE-OS 2 232 067 erzielten Vorteile noch vermehrt werden können, wenn man das eingangs genannte Verfahren entsprechend der Erfindung derart ausstattet, dass die Metalloberflächen mit Lösungen in Berührung gebracht werden, die zusätzlich einen Gehalt an Fluoborat, vorzugsweise in Mengen von 0,3 bis 2,0 g/I, aufweisen und im wesentlichen ferroionenfrei sind.It has now been found that the advantages achieved with the method according to DE-OS 2 232 067 can be increased further if the method mentioned at the outset according to the invention is equipped in such a way that the metal surfaces are brought into contact with solutions which additionally contain of fluoborate, preferably in amounts of 0.3 to 2.0 g / l, and are essentially free of ferroions.
Im wesentlichen Ferroionenfrei bedeutet, dass man bei der Behandlung von Nichteisenmetallen von der Verwendung von Badlösungen absieht, die wesentliche Ferroionenmengen enthalten und bei der vorzugsweise vorgesehenen Behandlung von Stahloberflächen, diese mit Lösungen in Berührung bringt, die Ferro- zu Ferriionen oxydierende Beschleuniger enthalten.Essentially free of ferroions means that the treatment of non-ferrous metals does not involve the use of bath solutions that contain substantial amounts of ferroions, and the preferred treatment of steel surfaces brings them into contact with solutions that contain accelerators that oxidize ferroions.
Besonders geeignet sind Behandlungslösungen, die Chlorat und/oder Nitrit enthalten. Dabei ist es ausreichend, soviel Chlorat und/oder Nitrit zu verwenden, als zur Entfernung von überschüssigen Ferroionen durch Oxidation notwendig sind. Die Mengen sind also vom Durchsatz abhängig und brauchen nicht besonders auf die Menge an Zinkionen und Phosphorsäure oder auf Phosphorsäure abgestimmt zu werden, wie dies bei bekannten Verfahren vorgeschrieben ist. Es hat sich jedoch erwiesen, dass der Gehalt an Chlorat auf mindestens 0,1 g/I eingestellt werden sollte. Bei hohen Durchsätzen sind grössere Mengen zweckmässig.Treatment solutions containing chlorate and / or nitrite are particularly suitable. It is sufficient to use as much chlorate and / or nitrite as is necessary to remove excess ferroions by oxidation. The amounts are thus dependent on the throughput and do not need to be specifically matched to the amount of zinc ions and phosphoric acid or to phosphoric acid, as is required in known processes. However, it has been found that the chlorate content should be set to at least 0.1 g / l. Larger quantities are advisable for high throughputs.
Vorteilhafterweise gelangen Lösungen zum Einsatz, die Vanadin-Verbindungen, vorzugsweise in Mengen von 0,1 bis 10 mg/I Vanadin, enthalten, was sich besonders bei hohen Durchsätzen als vorteilhaft erwiesen hat. Weitere mehrwertige Kationen, wie Ni-, Mn- oder Ca-Ionen, deren Menge jedoch höchstens 0,5 gll betragen soll, bewirken eine weitere Verbesserung.Solutions are advantageously used which contain vanadium compounds, preferably in amounts of 0.1 to 10 mg / l vanadium, which has proven to be particularly advantageous at high throughputs. Other polyvalent cations, such as Ni, Mn or Ca ions, the amount of which, however, should not exceed 0.5 gll, bring about a further improvement.
Um den Anteil an PO" der den erforderlichen Grad freier Säure übersteigt, zu binden, ist ein Zusatz von Alkalimetallionen (Na, NH4 usw.) erforderlich. Der Gehalt an P04 liegt im üblichen Bereich und beträgt etwa 5 bis 20 g/I.In order to bind the proportion of PO "which exceeds the required degree of free acid, an addition of alkali metal ions (Na, NH 4 etc.) is required. The content of P0 4 is in the usual range and is about 5 to 20 g / l .
Die mit dem erfindungsgemässen Verfahren erzielten Phosphatschichten vermitteln einen so hohen Korrosionsschutz (höherer Unterwanderungsschutz), dass eine Folgebehandlung mit den bekannten Nachspülmitteln, z. B. Cr(VI)- oder Cr(III)-lonen-haltig, praktisch keine zusätzliche Verbesserung bewirkt. Das heisst, die mit der Erfindung erzeugten Phosphatschichten sind von einer Qualität, die sonst nur durch Verwendung zusätzlicher Nachspülmittel erzielt wird.The phosphate layers achieved with the method according to the invention provide such a high level of corrosion protection (higher sub-walls protection) that a subsequent treatment with the known rinse agents, for. B. Cr (VI) - or Cr (III) ion-containing, practically no additional improvement. This means that the phosphate layers produced with the invention are of a quality that is otherwise only achieved by using additional rinsing agents.
a) Entfettete Stahlbleche werden innerhalb von 2 Minuten durch Spritzen mit einer Phosphatierungslösung von 58°C behandelt, die
Die Bleche wurden dann mit Wasser und mit vollentsalztem Wasser gespült und anschliessend getrocknet.The sheets were then rinsed with water and deionized water and then dried.
Das erzielte Schichtgewicht betrug 1,8 g/m2.The layer weight achieved was 1.8 g / m 2 .
Anschliessend wurde auf dem so vorbehandelten Stahlblech ein modifizierter Epoxyharzlack kathodisch abgeschieden. Das Bad für die Elektrotauchlackierung besass Raumtemperatur, Abscheidespannung und -dauer lagen bei 180 Volt bzw. 2 Minuten. Danach wurde der Lack bei einer Objekttemperatur von 190°C während 25 Minuten eingebrannt. Die dabei erhaltene Lackfilmdicke war 15 µm, die Lackschicht gleichmässig und glänzend.A modified epoxy resin varnish was then cathodically deposited on the steel sheet pretreated in this way. The electrodeposition bath had room temperature, the deposition voltage and duration were 180 volts or 2 minutes. The varnish was then baked at an object temperature of 190 ° C for 25 minutes. The paint film thickness obtained was 15 μm, the paint layer was uniform and shiny.
Der Korrosionsschutz der mit dem Lack versehenen und kreuzweise eingeritzten Blechs wurde im Salzsprühtest (1000 Std.) geprüft. Die danach ermittelte Lackunterwanderung betrug 1 bis 2 mm.The corrosion protection of the sheet, which had been lacquered and scratched crosswise, was tested in a salt spray test (1000 hours). The paint infiltration determined after this was 1 to 2 mm.
b) Der vorstehend skizzierte Verfahrensgang wurde in allen Einzelheiten wiederholt. Es kam jedoch eine Phosphatierungslösung zur Anwendung, die neben den unter a) aufgeführten Bestandteilen zusätzlich
Die nach dem Salzsprühtest ermittelte Lackunterwanderung lag nur bei kleiner 1 mm.The paint infiltration determined after the salt spray test was only less than 1 mm.
c) Der Behandlungsgang gemäss b) wurde dahingehend variiert, dass anstelle der Spülung mit Wasser einmal mit Chrom(III)-acetat-Lösung (150 mg/I Cr(III)) und einmal mit Chromsäure/ Chrom(III)-acetat-Lösung (150 mg/1 Cr(VI), 40 mg/I Cr(III)) gespült wurde.c) The course of treatment according to b) was varied such that instead of rinsing with water once with chromium (III) acetate solution (150 mg / l Cr (III)) and once with chromic acid / chromium (III) acetate solution (150 mg / 1 Cr (VI), 40 mg / I Cr (III)) was rinsed.
Der nach der Lackierung etc. vorgenommene Salzsprühtest brachte die gleichen Ergebnisse wie unter b).The salt spray test carried out after painting, etc. gave the same results as under b).
Ein Vergleich der Ergebnisse zeigt, dass der Korrosionsschutz, speziell der Lackunterwanderungsschutz, der mit Fluoborat modifizierten Phosphatierungslösung erheblich besser ist als der, der bei Verwendung einer Fluoboratfreien Phosphatierungslösung erhalten wird. Ausserdem ist erkennbar, dass auch ohne Nachspülung mit Cr(III)-bzw. Cr(VI)-Lösungen ein Korrosionsschutz erzielt wird, der dem mit Verwendung der genannten Lösung praktisch gleich ist.A comparison of the results shows that the corrosion protection, in particular the paint infiltration protection, of the phosphating solution modified with fluoroborate is considerably better than that which is obtained when using a fluoroborate-free phosphating solution. In addition, it can be seen that even without rinsing with Cr (III) or. Cor (VI) solutions a corrosion protection is achieved, which is practically the same as using the solution mentioned.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2907094 | 1979-02-23 | ||
| DE19792907094 DE2907094A1 (en) | 1979-02-23 | 1979-02-23 | PHOSPHATION SOLUTIONS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0015021A1 EP0015021A1 (en) | 1980-09-03 |
| EP0015021B1 true EP0015021B1 (en) | 1984-10-03 |
Family
ID=6063755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80200097A Expired EP0015021B1 (en) | 1979-02-23 | 1980-02-05 | Process for the pretreatment of metal surfaces for electrophoretic dip painting |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4265677A (en) |
| EP (1) | EP0015021B1 (en) |
| JP (1) | JPS5914113B2 (en) |
| AU (1) | AU531900B2 (en) |
| CA (1) | CA1134246A (en) |
| DE (2) | DE2907094A1 (en) |
| ES (1) | ES8200408A2 (en) |
| GB (1) | GB2046312A (en) |
| IT (1) | IT1141231B (en) |
| ZA (1) | ZA80915B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5811514B2 (en) * | 1979-05-02 | 1983-03-03 | 日本ペイント株式会社 | How to protect metal surfaces |
| JPS5811515B2 (en) * | 1979-05-11 | 1983-03-03 | 日本ペイント株式会社 | Composition for forming a zinc phosphate film on metal surfaces |
| US4330345A (en) * | 1980-12-08 | 1982-05-18 | Chemfil Corporation | Phosphate coating process and composition |
| DE3101866A1 (en) * | 1981-01-22 | 1982-08-26 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
| DE3118375A1 (en) * | 1981-05-09 | 1982-11-25 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS AND ITS APPLICATION FOR PRE-TREATMENT FOR ELECTRO DIP PAINTING |
| JPS58224172A (en) * | 1982-06-24 | 1983-12-26 | Nippon Parkerizing Co Ltd | Pretreatment for coating by cationic electrodeposition |
| US4681641A (en) * | 1982-07-12 | 1987-07-21 | Ford Motor Company | Alkaline resistant phosphate conversion coatings |
| DE3244715A1 (en) * | 1982-12-03 | 1984-06-07 | Gerhard Collardin GmbH, 5000 Köln | METHOD FOR PHOSPHATING METAL SURFACES, AND BATH SOLUTIONS SUITABLE FOR THIS |
| JPS59133375A (en) * | 1983-12-03 | 1984-07-31 | Nippon Paint Co Ltd | Composition for forming zinc phosphate film on metallic surface |
| DE3408577A1 (en) * | 1984-03-09 | 1985-09-12 | Metallgesellschaft Ag, 6000 Frankfurt | METHOD FOR PHOSPHATING METALS |
| DE3541997A1 (en) * | 1985-11-28 | 1987-06-04 | Collardin Gmbh Gerhard | IMPROVED METHOD FOR ACTIVATING METAL SURFACES BEFORE ZINC PHOSPHATION |
| JPS63100185A (en) * | 1986-10-16 | 1988-05-02 | Nippon Parkerizing Co Ltd | Phosphating method |
| DE3636390A1 (en) * | 1986-10-25 | 1988-04-28 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS |
| DE58905074D1 (en) * | 1988-02-03 | 1993-09-09 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METALS. |
| DE3814287A1 (en) * | 1988-04-28 | 1989-11-09 | Henkel Kgaa | POLYMERS TITANIUM PHOSPHATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR ACTIVATING METAL SURFACES BEFORE ZINC PHOSPHATION |
| KR100197145B1 (en) * | 1989-12-19 | 1999-06-15 | 후지이 히로시 | Method for phosphating metal surface with zinc phosphate |
| DE4409306A1 (en) * | 1994-03-18 | 1995-09-21 | Basf Ag | Process for modifying metal surfaces |
| DE4443882A1 (en) * | 1994-12-09 | 1996-06-13 | Metallgesellschaft Ag | Process for applying phosphate coatings on metal surfaces |
| US6193815B1 (en) * | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1585660A (en) * | 1967-10-18 | 1970-01-30 | ||
| GB1235293A (en) * | 1967-12-12 | 1971-06-09 | Canadian Ind | Cationic electrodeposition systems |
| US3617393A (en) * | 1969-10-08 | 1971-11-02 | Dainippon Toryo Kk | Pretreatment before electrophoretic painting |
| US3597283A (en) * | 1969-10-08 | 1971-08-03 | Lubrizol Corp | Phosphating solutions for use on ferrous metal and zinc surfaces |
| US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
| JPS506418B1 (en) * | 1971-07-06 | 1975-03-13 | ||
| DE2143957A1 (en) * | 1971-09-02 | 1973-03-08 | Metallgesellschaft Ag | METHOD OF APPLYING A PHOSPHATUE COATING TO IRON AND STEEL |
| US3850700A (en) * | 1971-10-18 | 1974-11-26 | Amchem Prod | Method and materials for coating metal surfaces |
-
1979
- 1979-02-23 DE DE19792907094 patent/DE2907094A1/en not_active Withdrawn
-
1980
- 1980-02-05 EP EP80200097A patent/EP0015021B1/en not_active Expired
- 1980-02-05 DE DE8080200097T patent/DE3069330D1/en not_active Expired
- 1980-02-18 ZA ZA00800915A patent/ZA80915B/en unknown
- 1980-02-19 CA CA346,000A patent/CA1134246A/en not_active Expired
- 1980-02-20 GB GB8005737A patent/GB2046312A/en not_active Withdrawn
- 1980-02-22 ES ES488871A patent/ES8200408A2/en not_active Expired
- 1980-02-22 IT IT20102/80A patent/IT1141231B/en active
- 1980-02-22 AU AU55804/80A patent/AU531900B2/en not_active Ceased
- 1980-02-22 JP JP55022147A patent/JPS5914113B2/en not_active Expired
- 1980-02-25 US US06/124,504 patent/US4265677A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU5580480A (en) | 1980-08-28 |
| JPS5914113B2 (en) | 1984-04-03 |
| EP0015021A1 (en) | 1980-09-03 |
| ES488871A0 (en) | 1981-11-01 |
| JPS55131177A (en) | 1980-10-11 |
| IT1141231B (en) | 1986-10-01 |
| US4265677A (en) | 1981-05-05 |
| IT8020102A0 (en) | 1980-02-22 |
| CA1134246A (en) | 1982-10-26 |
| AU531900B2 (en) | 1983-09-08 |
| ES8200408A2 (en) | 1981-11-01 |
| DE2907094A1 (en) | 1980-09-04 |
| ZA80915B (en) | 1981-02-25 |
| DE3069330D1 (en) | 1984-11-08 |
| GB2046312A (en) | 1980-11-12 |
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