EP0717787B1 - Nickelfreies phosphatierverfahren - Google Patents
Nickelfreies phosphatierverfahren Download PDFInfo
- Publication number
- EP0717787B1 EP0717787B1 EP94925483A EP94925483A EP0717787B1 EP 0717787 B1 EP0717787 B1 EP 0717787B1 EP 94925483 A EP94925483 A EP 94925483A EP 94925483 A EP94925483 A EP 94925483A EP 0717787 B1 EP0717787 B1 EP 0717787B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- hydroxylamine
- free
- phosphating solution
- ions
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations 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
- C23C22/364—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 manganese cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
Definitions
- the invention relates to methods for phosphating metal surfaces with aqueous, acid phosphating solutions, the zinc, manganese and phosphate ions and hydroxylamine in free or bound form and / or m-nitrobenzenesulfonic acid or contain their water-soluble salts, and their Application as pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting.
- the procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized alloy Steel, aluminum, aluminized or alloy aluminized Steel, in particular for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
- the phosphating of metals pursues the goal on the metal surface to produce firmly grown metal phosphate layers that are in themselves improve the corrosion resistance and in connection with paints and other organic coatings to significantly increase the Paint adhesion and resistance to infiltration when exposed to corrosion contribute.
- Such phosphating processes have long been known.
- For pretreatment before painting is particularly suitable for low-zinc phosphating processes, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l.
- An essential parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually is in the range> 8 and can take values up to 30.
- the high content of nickel ions in the phosphating solutions of the trication processes and of nickel and nickel compounds in the phosphate layers formed however, has disadvantages in that nickel and nickel compounds from the point of view of environmental protection and workplace hygiene as be critically classified.
- low-zinc phosphating processes have been becoming increasingly common described without sharing from nickel to high-quality phosphate layers similar to that lead nickel-containing processes.
- nitrite and Nitrates are increasingly raised concerns about possible formation of nitrous gases.
- DE-A-39 20 296 describes a phosphating process which dispenses with nickel and uses magnesium ions in addition to zinc and manganese ions.
- the phosphating baths described here contain from 0.2 to 10 g / l nitrate ions other oxidizing agents acting as accelerators, selected from nitrite, chlorate or an organic oxidizing agent.
- EP-A-60 716 discloses low zinc phosphating baths which are considered essential Cations contain zinc and manganese and that as an optional ingredient May contain nickel.
- the necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- EP-A-228 151 also describes phosphating baths which are essential Cations contain zinc and manganese.
- the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzenesulfonate, m-nitrobenzoate or p-nitrophenol.
- the nitrate content to 5 to about 15 g / l and an optional nickel content specified between 0.4 and 4 g / l.
- the exemplary embodiments contain this all nickel and nitrate.
- the main focus of this application is due to the fact that chlorate-free phosphating processes are provided will.
- EP-A-544 650 teaches something similar.
- the phosphating process disclosed in WO-A-86/04931 works without nitrates.
- the accelerator system is based on a combination of 0.5 - 1 g / l Bromate and 0.2-0.5 g / l m-nitrobenzenesulfonate.
- the phosphating solutions preferably contain in addition to zinc, at least 2 of these optional metals.
- EP-A-36689 teaches the use of preferably 0.03-0.2% by weight of nitrobenzenesulfonate in Combination with preferably 0.1-0.5% by weight chlorate in phosphating baths, whose manganese content is 5-33% by weight of the zinc content.
- DE-A-40 13 483 discloses phosphating processes with which similarly good ones Corrosion protection properties as achieved with the trication process can. These processes do without nickel and use instead Copper in low concentrations, 0.001 to 0.03 g / l.
- Oxygen and / or other equivalent functions serve in the trivalent stage Oxidizing agent. As such are nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds, such as nitrobenzenesulfonate, specified.
- German patent application with the file number P 42 10 513.7 modifies this process in that as a modifying agent for the Morphology of the phosphate crystals formed hydroxylamine, its salts or complexes are added in an amount of 0.5 to 5 g / l hydroxylamine.
- EP-A-321 059 teaches zinc phosphating baths which contain 0.1 to 2.0 g / l zinc and an accelerator also 0.01 to 20 g / l tungsten in the form of a soluble tungsten compound, preferably alkali metal or ammonium tungstate or silicotungstate, alkaline earth metal silicotungstate or boro- or silicotungstic acid.
- the accelerator is selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- nickel in quantities of 0.1 - 4 g / l and nitrate in quantities 0.1 - 15 g / l.
- DE-C-27 39 006 describes a phosphating process for surfaces Zinc or zinc alloys that are free of nitrate and ammonium ions.
- an essential content of zinc in amounts between 0.1 and 5 g / l are 1 to 10 parts by weight of nickel and / or cobalt per part by weight of zinc required.
- Hydrogen peroxide is used as an accelerator. From the From the point of view of workplace hygiene and environmental protection, cobalt is not one Alternative to nickel.
- the object of the invention is to provide phosphating baths positions that are free from environmental and workplace hygiene Reasonably questionable nickel or the similarly questionable cobalt, no Contain nitrite and at the same time a greatly reduced nitrate content have and are preferably free of nitrate. Furthermore, the Phosphating baths should be free of copper, the dosage of which according to DE-A-40 13 483 effective concentration range of 1 - 30 ppm is problematic.
- phosphating baths are free of nickel, copper, nitrite and oxo anions Halogens mean that these elements or ions not deliberately added to the phosphating baths. However, it is in the Practice does not rule out that such components are beyond what is to be treated Material, the preparation water or the ambient air in traces in the Phosphating baths are entered. In particular, it cannot be ruled out that in the phosphating of coated with zinc-nickel alloys Steel nickel ions are introduced into the phosphating solution. However, the expectation is placed on the phosphating baths according to the invention that that under technical conditions the nickel concentration in the Baths is below 0.01 g / l, in particular below 0.0001 g / l.
- baths Preferably no nitrate is added to the baths.
- the baths contain the nitrate content of the locally available drinking water (according to Drinking water regulation in Germany maximum 50 mg / l) or by evaporation have higher nitrate levels due to The invention
- baths should have a maximum nitrate content of 0.5 g / l and preferably contain less than 0.1 g / l nitrate.
- Hydroxylamine can be used as a free base, as a hydroxylamine complex or in the form of Hydroxylammonium salts are used. If you add free hydroxylamine Phosphating bath or a phosphating bath concentrate too, it is due of the acidic character of these solutions largely as a hydroxylammonium cation available.
- Sulfates and the phosphates are particularly suitable. In the case of the phosphates the acidic salts are preferred because of their better solubility.
- Hydroxylamine or its compounds in the phosphating bath in such Amounts added that the calculated concentration of free hydroxylamine is between 0.1 and 5 g / l, in particular between 0.4 and 2 g / l. It has proven to be beneficial to choose the hydroxylamine concentration so that the ratio of the sum of the concentrations of zinc and manganese for the concentration of the hydroxylamine, in each case in g / l, 1.0 to 6.0, preferably Is 2.0 to 4.0.
- the inventive Phosphating baths containing hydroxylamine or hydroxylamine compounds the presence of soluble compounds of hexavalent tungsten Advantages in terms of corrosion resistance and paint adhesion, although with the Phosphating method according to the invention, in contrast to the teaching of EP-A-321 059, without the accelerators nitrite or hydrogen peroxide can be.
- Phosphating solutions are used that additionally 20 to 800 mg / l, preferably 50 to 600 mg / l tungsten in the form of water-soluble tungstates, Silicotungstates and / or borotungstates contain.
- the mentioned anions in the form of their acids and / or their ammonium, Alkali metal and / or alkaline earth metal salts are used.
- m-Nitrobenzenesulfonate can be used as a free acid or in the form of water-soluble Salts are used.
- Such salts become "water-soluble” referred to, which dissolve in the phosphating baths so far that the required concentrations of 0.2 to 2 g / l m-nitrobenzenesulfonate can be achieved.
- the alkali metal salts are particularly suitable for this the sodium salts.
- the phosphating baths preferably contain 0.4 to 1 g / l m-nitrobenzenesulfonate.
- a ratio of 1:10 to 10: 1 between the more reductive Hydroxylamine and the more oxidative m-nitrobenzenesulfonate can lead to special advantages with regard to layer formation, in particular regarding the shape of the crystals formed.
- the phosphating baths contain either hydroxylamine or m-nitrobenzenesulfonic acid.
- the weight ratio of phosphate ions to zinc ions in the phosphating baths can fluctuate within wide limits, provided it is in the range between 3.7 and 30 lies. A weight ratio between 10 and 20 is particularly preferred.
- Those skilled in the art are further parameters for controlling phosphating baths the free acid and total acid contents are known. The one in this Font used determination method of this parameter is in the example part specified. Free acid values between 0.3 and 1.5 points for partial phosphating, with band phosphating up to 2.5 points and the total acidity between about 15 and about 25 points are in the usual technical range Range and are suitable in the context of this invention.
- the manganese content of the phosphating bath should be between 0.3 and 4 g / l, since the lower the manganese content, the positive influence on the corrosion behavior the phosphate layers no longer exist and at higher ones Manganese content no further positive effect occurs. Keep between 0.3 and 2 g / l and in particular between 0.5 and 1.5 g / l are preferred.
- the zinc content is set in phosphating baths, which only act as accelerators Contain hydroxylamine, according to EP-A-315 059 preferably to values between 0.45 and 1.1 g / l, for phosphating baths, which only accelerate m-nitrobenzenesulfonate contain, preferably to values between 0.6 and 1.4 g / l a.
- the current zinc content of the worker Bath increases up to 2 g / l. It is important to ensure that the manganese content is at least 50% of the zinc content, otherwise it is insufficient Corrosion protection properties result.
- the Zinc and manganese ions are introduced into the phosphating baths basically irrelevant. In order to meet the conditions according to the invention, however, are the nitrites, nitrates, and salts with oxo anions of halogens these cations cannot be used. It is particularly useful as Zinc and / or manganese source to use the oxides and / or carbonates. In addition to the divalent cations mentioned, they contain phosphating baths usually sodium, potassium and / or ammonium ions to adjust the parameters free acid and total acid are used. Ammonium ions can also be formed by degradation of the hydroxylamine.
- iron goes in the form of iron (II) ions in solution. Since the phosphating baths according to the invention do not contain substances that are strong compared to iron (II) have an oxidizing effect, the divalent iron mainly goes off in succession Air oxidation into the trivalent state, so that it is called ferric phosphate can fail. Therefore, in the phosphating baths according to the invention Build up iron (II) levels that are well above the levels which contain baths containing oxidizing agents. With that in mind Iron (II) concentrations up to 50 ppm normal, with short-term in the production process Values up to 500 ppm can also occur. For the invention Phosphating processes are such iron (II) concentrations not harmful.
- the phosphating baths can be used in hard water also the hardness cations Mg (II) and Ca (II) in a total concentration up to 7 mmol / l.
- the method according to the invention is suitable for phosphating surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminized steel.
- Baths containing hydroxylamine are especially designed for the treatment of galvanized on one or both sides, preferably electrolytically galvanized steel.
- the materials mentioned can - as is increasingly common in automotive engineering will also exist side by side.
- the procedure is for the application suitable in immersion, spray or spray / immersion processes. It can be used in particular in the automotive industry, where treatment times between 1 and 8 minutes are common. Use in tape phosphating in the steel mill, with treatment times between 5 and 12 seconds, is also possible.
- Suitable bath temperatures are also common in the prior art between 30 and 70 ° C, the temperature range between 40 and 60 ° C is preferred.
- the phosphating process according to the invention is used to produce a sliding layer for forming and in particular for treating the metal surfaces mentioned before painting, for example before a cathodic one Electro-dip coating thought as it is common in automotive engineering.
- the phosphating process is part of the technically usual pretreatment chain to see. In this chain, phosphating is common the steps cleaning / degreasing, rinsing and activating upstream, the activation usually with titanium phosphate-containing Activating agents are carried out.
- the phosphating according to the invention can if necessary after an intermediate rinse, a passivating after-treatment consequences. Chromic acid-containing ones are used for such a passivating aftertreatment Treatment baths widely used.
- the mass per unit area (“layer weight”) was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942, Table 6. Corrosion tests were carried out according to the VDA alternating climate test 621-415 with KTL primer (KTL-light gray from BASF, FT 85- 7042); partly also with a complete paint structure (top coat: alpine white, VW).
- KTL primer KTL-light gray from BASF, FT 85- 7042
- top coat alpine white, VW.
- Layer weights were determined by dissolving in 5% chromic acid solution. Corrosion tests were carried out according to the VDA alternating climate test 621-415 both with KTL primer (ED 12 MB from PPG) and with a complete paint system (KTL as above, filler: 1-component high-solid PU filler gray, top coat: DB 744 metallic basecoat and clearcoat). The paint infiltration (mm) was evaluated after every 10 week test cycles. In addition, a shot put test was carried out according to the Mercedes-Benz standard analogous to DIN 53 230 (6 bar corresponding to 250 km / h), evaluation at substrate temperature -20 ° C. The damage area was assessed in mm 2 (Mercedes-Benz standard: max.
Description
Unter der Punktzahl der freien Säure wird der Verbrauch in ml an 0,1-normaler Natronlauge verstanden, um 10 ml Badlösung bis zu einem pH-Wert von 3,6 zu titrieren. Analog gibt die Punktzahl der Gesamtsäure den Verbrauch in ml bis zu einem pH-Wert von 8,2 an.
Phosphatierbäder | |||
Parameter | Beispiel 8 | Vergleich 3 | Vergleich 4 |
Zn(II) (g/l) | 1,0 | 1,0 | 1,0 |
Mn(II) (g/l) | 0,8 | 1,0 | 0,8 |
Ni(II) (g/l) | - | 0,9 | 0,8 |
PO4 3- (g/l) | 14,5 | 14,6 | 13,5 |
Gesamt-F- (g/l) | 0,8 | 0,8 | 0,8 |
Freie Säure (Punkte) | 1,0 | 1,0 | 1,0 |
Gesamtsäure (Punkte) | 22 | 23 | 24,0 |
Hydroxylammoniumsulfat (g/l) | 2 | - | 2 |
Nitrit (mg/l) | - | 100 | - |
Nitrat (g/l) | - | 2 | 2 |
Unter der Punktzahl der freien Säure wird der Verbrauch in ml an 0,1-normaler Natronlauge verstanden, um 10 ml Badlösung bis zu einem pH-Wert von 3,6 zu titrieren. Analog gibt die Punktzahl der Gesamtsäure den Verbrauch in ml bis zu einem pH-Wert von 8,5 an.
Claims (16)
- Verfahren zur Phosphatierung von Metalloberflächen mit wäßrigen. sauren Phosphatierlösungen, die Zink-, Mangan- und Phosphationen und als Beschleuniger Hydroxylamin oder eine Hydroxylaminverbindung und/oder m-Nitrobenzosulfonsäure oder deren wasserlösliche Salze enthalten, dadurch gekennzeichnet, daß man die Metalloberflächen mit einer Phosphatierlösung in Berührung bringt, die frei von Nickel, Kobalt, Kupfer, Nitrit und Oxo-Anionen von Halogenen in dem Sinne ist, daß diese Elemente beziehungsweise Ionen dem Bad nicht bewußt zugesetzt werden und die Nickelkonzentration unter 0,01 g/l liegt, und die0,3 bis 2 g/l Zn(II)0,3 bis 4 g/l Mn(II)5 bis 40 g/l Phosphationen0,1 bis 5 g/l Hydroxylamin in freier oder gebundener Form und/oder0,2 bis 2 g/l m-Nitrobenzolsulfonatund höchstens 0,5 g/l Nitrationen
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Phosphatierlösung weniger als 0,1 g/l Nitrat enthält.
- Verfahren nach einem oder beiden der Ansprüche 1 und 2, dadurch gekennzeichnet, daß die Phosphatierlösung zusätzlich Fluorid in freier und/oder komplex gebundener Form in Mengen bis zu 2,5 g/l Gesamtfluorid, davon bis zu 800 mg/l freies Fluorid enthält.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Phosphatierlösung ein Gewichtsverhältnis Phosphationen zu Zinkionen zwischen 3,7 und 30, vorzugsweise zwischen 10 und 20 aufweist.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Phosphatierlösung einen Mn(II)-Gehalt zwischen 0,3 und 2 g/l, vorzugsweise zwischen 0,5 und 1,5 g/l aufweist.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Phosphatierlösung m-Nitrobenzolsulfonat als freie Säure oder als wasserlösliches Salz, insbesondere als Natriumsalz, enthält und die Konzentration an m-Nitrobenzolsulfonat vorzugsweise 0,4 bis 1 g/l beträgt.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Wert der Gesamtsäure zwischen 15 und 25 Punkten und der Wert der freien Säure bei Teilephosphatierung zwischen 0,3 und 1,5 Punkte, bei Bandphosphatierung zwischen 0,3 und 2,5 Punkten betragen.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Phosphatierlösung Hydroxylamin in freier oder in komplex gebundener Form oder in Form seiner Salze, insbesondere in Form der Sulfate oder der Phosphate enthält.
- Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Phosphatierlösung einen Gehalt an Hydroxylamin in freier Form, in Form von Salzen oder in komplex gebundener Form zwischen 0,4 und 2 g/l, berechnet als Hydroxylamin, aufweist.
- Verfahren nach einem oder beiden der Ansprüche 8 und 9, dadurch gekennzeichnet, daß das Verhältnis der Summe der Konzentrationen von Zink und Mangan zur Konzentration des Hydroxylamins, jeweils in g/l, 1,0 bis 6,0, vorzugsweise 2,0 bis 4,0 beträgt.
- Verfahren nach einem oder mehreren der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß die Phosphatierlösung zusätzlich 20 bis 800 mg/l, vorzugsweise 50 bis 600 mg/l Wolfram in Form wasserlöslicher Wolframate, Silicowolframate und/oder Borowolframate in Form ihrer Säuren und/oder ihrer Ammonium-, Alkalimetall- und/oder Erdalkalimetallsalze enthält.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die Phosphatierlösung entweder Hydroxylamin oder m-Nitrobenzolsulfonsäure enthält.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 12 zur Behandlung von Oberflächen aus Stahl, verzinktem oder legierungsverzinktem Stahl, Aluminium, aluminiertem oder legierungsaluminiertem Stahl.
- Verfahren nach Anspruch 13, dadurch gekennzeichnet, daß man die Metalloberfläche mit der Phosphatierlösung durch Spritzen, Tauchen oder Spritztauchen für Behandlungszeiten zwischen 5 Sekunden und 8 Minuten in Kontakt bringt.
- Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß die Temperatur der Phosphatierlösung zwischen 30 und 70 °C, beträgt.
- Verfahren nach Anspruch 15 zur Behandlung von Metalloberflächen vor einer Lackierung, insbesondere vor einer kathodischen Elektrotauchlackierung.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4330104 | 1993-09-06 | ||
DE4330104A DE4330104A1 (de) | 1993-09-06 | 1993-09-06 | Nickel- und Kupfer-freies Phosphatierverfahren |
DE19934341041 DE4341041A1 (de) | 1993-12-02 | 1993-12-02 | Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat |
DE4341041 | 1993-12-02 | ||
PCT/EP1994/002848 WO1995007370A1 (de) | 1993-09-06 | 1994-08-29 | Nickelfreies phosphatierverfahren |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0717787A1 EP0717787A1 (de) | 1996-06-26 |
EP0717787B1 true EP0717787B1 (de) | 1998-01-14 |
Family
ID=25929280
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94925483A Expired - Lifetime EP0717787B1 (de) | 1993-09-06 | 1994-08-29 | Nickelfreies phosphatierverfahren |
Country Status (13)
Country | Link |
---|---|
US (1) | US5792283A (de) |
EP (1) | EP0717787B1 (de) |
JP (1) | JP3348856B2 (de) |
KR (1) | KR100327287B1 (de) |
CN (1) | CN1041001C (de) |
AT (1) | ATE162233T1 (de) |
AU (1) | AU678284B2 (de) |
BR (1) | BR9407485A (de) |
CA (1) | CA2171180A1 (de) |
CZ (1) | CZ286514B6 (de) |
DE (1) | DE59405046D1 (de) |
ES (1) | ES2111949T3 (de) |
WO (1) | WO1995007370A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103184444A (zh) * | 2013-03-29 | 2013-07-03 | 柳州煜华科技有限公司 | 一种适用于金属紧固件的磷化液 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5653790A (en) * | 1994-11-23 | 1997-08-05 | Ppg Industries, Inc. | Zinc phosphate tungsten-containing coating compositions using accelerators |
DE19511573A1 (de) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Verfahren zur Phosphatierung mit metallhaltiger Nachspülung |
DE19639596A1 (de) * | 1996-09-26 | 1998-04-02 | Henkel Kgaa | Verfahren zur Phosphatierung von Stahlband |
DE19756735A1 (de) * | 1997-12-19 | 1999-06-24 | Henkel Kgaa | Phosphatierung von einseitig verzinktem Stahlband |
DE19808440C2 (de) * | 1998-02-27 | 2000-08-24 | Metallgesellschaft Ag | Wässrige Lösung und Verfahren zur Phosphatierung metallischer Oberflächen sowie eine Verwendung der Lösung und des Verfahrens |
DE19808755A1 (de) * | 1998-03-02 | 1999-09-09 | Henkel Kgaa | Schichtgewichtsteuerung bei Bandphosphatierung |
DE19834796A1 (de) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung |
AU2348500A (en) * | 1998-12-23 | 2000-07-31 | Henkel Corporation | Composition and process for heavy zinc phosphating |
JP2001342575A (ja) * | 2000-05-31 | 2001-12-14 | Nippon Dacro Shamrock Co Ltd | 水性金属表面処理剤 |
DE10110833B4 (de) * | 2001-03-06 | 2005-03-24 | Chemetall Gmbh | Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile |
DE10155666A1 (de) * | 2001-11-13 | 2003-05-22 | Henkel Kgaa | Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren |
KR100554740B1 (ko) * | 2001-12-17 | 2006-02-24 | 주식회사 포스코 | 인산피막이 형성된 전기아연 도금강판 제조방법 |
US20080314479A1 (en) * | 2007-06-07 | 2008-12-25 | Henkel Ag & Co. Kgaa | High manganese cobalt-modified zinc phosphate conversion coating |
DE102010001686A1 (de) | 2010-02-09 | 2011-08-11 | Henkel AG & Co. KGaA, 40589 | Zusammensetzung für die alkalische Passivierung von Zinkoberflächen |
PL2503025T3 (pl) | 2011-03-22 | 2013-12-31 | Henkel Ag & Co Kgaa | Chroniąca przed korozją, wielostopniowa obróbka metalowych elementów konstrukcyjnych o powierzchniach cynkowych |
CN102703889B (zh) * | 2012-05-28 | 2014-06-04 | 武汉永正科技发展有限公司 | 低温单组份锌系磷化液及其制备方法 |
CN104651820A (zh) * | 2015-02-16 | 2015-05-27 | 天津大学 | 一种碳钢超声磷化液及制备方法以及采用磷化液对碳钢磷化的方法 |
WO2016162423A1 (de) * | 2015-04-07 | 2016-10-13 | Chemetall Gmbh | Verfahren zur nickelfreien phosphatierung von metallischen oberflächen |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5339945A (en) * | 1976-09-25 | 1978-04-12 | Nippon Packaging Kk | Surface treatment of zinc or zinc alloy |
GB2072225B (en) * | 1980-03-21 | 1983-11-02 | Pyrene Chemical Services Ltd | Process and composition for coating metal surfaces |
JPS57152472A (en) * | 1981-03-16 | 1982-09-20 | Nippon Paint Co Ltd | Phosphating method for metallic surface for cation type electrodeposition painting |
ES8606528A1 (es) * | 1985-02-22 | 1986-04-01 | Henkel Iberica | Procedimiento para el fosfatado de superficies metalicas, especialmente ferreas |
ATE160592T1 (de) * | 1985-08-27 | 1997-12-15 | Henkel Corp | Verfahren zur phosphatierung von metalloberflächen |
US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
NL8703050A (nl) * | 1987-12-16 | 1989-07-17 | Johannes Schuitemaker | Invoermechanisme voor een opraapwagen. |
AU610313B2 (en) * | 1987-12-18 | 1991-05-16 | Nippon Paint Co., Ltd. | Process for phosphating metal surfaces |
JP2636919B2 (ja) * | 1989-01-26 | 1997-08-06 | 日本パーカライジング株式会社 | 鉄鋼の冷間塑性加工用潤滑処理方法 |
US5232523A (en) * | 1989-03-02 | 1993-08-03 | Nippon Paint Co., Ltd. | Phosphate coatings for metal surfaces |
DE3913089A1 (de) * | 1989-04-21 | 1990-10-25 | Henkel Kgaa | Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten |
JPH0696773B2 (ja) * | 1989-06-15 | 1994-11-30 | 日本ペイント株式会社 | 金属表面のリン酸亜鉛皮膜形成方法 |
DE3920296A1 (de) * | 1989-06-21 | 1991-01-10 | Henkel Kgaa | Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatueberzuegen |
DE4013483A1 (de) * | 1990-04-27 | 1991-10-31 | Metallgesellschaft Ag | Verfahren zur phosphatierung von metalloberflaechen |
US5268041A (en) * | 1990-04-27 | 1993-12-07 | Metallgesellschaft Ag | Process for phosphating metal surfaces |
DE4210513A1 (de) * | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-freie Phosphatierverfahren |
-
1994
- 1994-08-29 CA CA002171180A patent/CA2171180A1/en not_active Abandoned
- 1994-08-29 EP EP94925483A patent/EP0717787B1/de not_active Expired - Lifetime
- 1994-08-29 DE DE59405046T patent/DE59405046D1/de not_active Expired - Lifetime
- 1994-08-29 CZ CZ1996673A patent/CZ286514B6/cs not_active IP Right Cessation
- 1994-08-29 WO PCT/EP1994/002848 patent/WO1995007370A1/de active IP Right Grant
- 1994-08-29 CN CN94193230A patent/CN1041001C/zh not_active Expired - Fee Related
- 1994-08-29 ES ES94925483T patent/ES2111949T3/es not_active Expired - Lifetime
- 1994-08-29 KR KR1019960701115A patent/KR100327287B1/ko not_active IP Right Cessation
- 1994-08-29 AU AU75373/94A patent/AU678284B2/en not_active Ceased
- 1994-08-29 JP JP50842695A patent/JP3348856B2/ja not_active Expired - Fee Related
- 1994-08-29 US US08/612,925 patent/US5792283A/en not_active Expired - Lifetime
- 1994-08-29 BR BR9407485A patent/BR9407485A/pt not_active IP Right Cessation
- 1994-08-29 AT AT94925483T patent/ATE162233T1/de not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103184444A (zh) * | 2013-03-29 | 2013-07-03 | 柳州煜华科技有限公司 | 一种适用于金属紧固件的磷化液 |
CN103184444B (zh) * | 2013-03-29 | 2016-08-03 | 柳州煜华科技有限公司 | 一种适用于金属紧固件的磷化液 |
Also Published As
Publication number | Publication date |
---|---|
AU678284B2 (en) | 1997-05-22 |
CZ286514B6 (cs) | 2000-05-17 |
JP3348856B2 (ja) | 2002-11-20 |
ES2111949T3 (es) | 1998-03-16 |
CN1129961A (zh) | 1996-08-28 |
ATE162233T1 (de) | 1998-01-15 |
JPH09502224A (ja) | 1997-03-04 |
KR960705076A (ko) | 1996-10-09 |
EP0717787A1 (de) | 1996-06-26 |
BR9407485A (pt) | 1996-06-25 |
WO1995007370A1 (de) | 1995-03-16 |
CZ67396A3 (en) | 1996-12-11 |
KR100327287B1 (ko) | 2002-11-22 |
AU7537394A (en) | 1995-03-27 |
US5792283A (en) | 1998-08-11 |
CA2171180A1 (en) | 1995-03-16 |
DE59405046D1 (de) | 1998-02-19 |
CN1041001C (zh) | 1998-12-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0717787B1 (de) | Nickelfreies phosphatierverfahren | |
EP0817872B1 (de) | Verfahren zur phosphatierung mit metallhaltiger nachspülung | |
EP1114202A1 (de) | Verfahren zur phosphatierung, nachspülung und kathodischer elektrotauchlackierung | |
DE3920296A1 (de) | Verfahren zur herstellung von mangan- und magnesiumhaltigen zinkphosphatueberzuegen | |
EP0931179B1 (de) | Verfahren zur phosphatierung von stahlband | |
DE19705701A1 (de) | Verfahren zur Niedrig-Nickel-Phosphatierung mit metallhaltiger Nachspülung | |
EP0889977B1 (de) | Zinkphosphatierung mit geringen gehalten an kupfer und mangan | |
EP1005578B1 (de) | Mit n-oxiden beschleunigtes phosphatierverfahren | |
DE4330104A1 (de) | Nickel- und Kupfer-freies Phosphatierverfahren | |
DE4341041A1 (de) | Nickelfreies Phosphatierverfahren mit m-Nitrobenzolsulfonat | |
EP1090160B1 (de) | Schichtgewichtsteuerung bei bandphosphatierung | |
DE19606018A1 (de) | Zinkphosphatierung mit geringen Gehalten an Nickel- und/oder Cobalt | |
WO1999014397A1 (de) | Verfahren zur phosphatierung von stahlband | |
WO1997014821A1 (de) | Schichtgewichtssteuerung bei hydroxylamin-beschleunigten phosphatiersystemen | |
EP0866888B1 (de) | Verfahren zur phosphatierung von metalloberflächen | |
DE19958192A1 (de) | Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung | |
WO1997016581A2 (de) | Nitratarme, manganfreie zinkphosphatierung | |
DE19500927A1 (de) | Lithiumhaltige Zinkphosphatierlösung | |
WO1998009000A1 (de) | Rutheniumhaltige zinkphosphatierung | |
DE10310680A1 (de) | Verfahren zur Phosphatierung mit einer Kombination von Beschleunigern | |
DE19940619A1 (de) | Zinkphosphatierung mit Epoxiden | |
DE19939519A1 (de) | Beschleuniger für die Phosphatierung von Metalloberflächen | |
DE19716075A1 (de) | Mit Hydroxylamin und Chlorat beschleunigtes Phosphatierverfahren | |
DE19750301A1 (de) | Mit N-Oxiden und Clorat beschleunigtes Phosphatierverfahren |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19960226 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES FR GB IT NL PT SE |
|
17Q | First examination report despatched |
Effective date: 19960712 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE DE ES FR GB IT NL PT SE |
|
REF | Corresponds to: |
Ref document number: 162233 Country of ref document: AT Date of ref document: 19980115 Kind code of ref document: T |
|
ET | Fr: translation filed | ||
REF | Corresponds to: |
Ref document number: 59405046 Country of ref document: DE Date of ref document: 19980219 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2111949 Country of ref document: ES Kind code of ref document: T3 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19980225 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN P. & C. S.N.C. |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 19980211 |
|
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 | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20010807 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20010813 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20010814 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010830 Year of fee payment: 8 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20020826 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020829 |
|
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: 20020830 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20021018 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030301 |
|
EUG | Se: european patent has lapsed | ||
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030301 |
|
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: 20030830 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030831 |
|
BERE | Be: lapsed |
Owner name: *HENKEL K.G.A.A. Effective date: 20030831 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20030830 |
|
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: 20050829 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20130821 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20130808 Year of fee payment: 20 Ref country code: GB Payment date: 20130828 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59405046 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20140828 |
|
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 EXPIRATION OF PROTECTION Effective date: 20140830 |
|
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 EXPIRATION OF PROTECTION Effective date: 20140828 |