EP0478648B1 - Process for producing zinc phosphate coatings containing manganese and magnesium - Google Patents
Process for producing zinc phosphate coatings containing manganese and magnesium Download PDFInfo
- Publication number
- EP0478648B1 EP0478648B1 EP90909688A EP90909688A EP0478648B1 EP 0478648 B1 EP0478648 B1 EP 0478648B1 EP 90909688 A EP90909688 A EP 90909688A EP 90909688 A EP90909688 A EP 90909688A EP 0478648 B1 EP0478648 B1 EP 0478648B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- zinc
- magnesium
- nickel
- steel
- 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
- 238000000034 method Methods 0.000 title claims description 29
- 238000000576 coating method Methods 0.000 title claims description 22
- 230000008569 process Effects 0.000 title claims description 22
- 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 title claims description 8
- 229910000165 zinc phosphate Inorganic materials 0.000 title claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 title abstract description 14
- 239000011777 magnesium Substances 0.000 title abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title description 9
- 229910052748 manganese Inorganic materials 0.000 title description 9
- 239000011572 manganese Substances 0.000 title description 9
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- -1 magnesium(II) ions Chemical class 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 5
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- 238000003618 dip coating Methods 0.000 claims 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 238000007654 immersion Methods 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 41
- 229910052759 nickel Inorganic materials 0.000 description 20
- 239000010410 layer Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000009189 diving Effects 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001076195 Lampsilis ovata Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241001499740 Plantago alpina Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- LKCUKVWRIAZXDU-UHFFFAOYSA-L zinc;hydron;phosphate Chemical compound [Zn+2].OP([O-])([O-])=O LKCUKVWRIAZXDU-UHFFFAOYSA-L 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
- C23C22/368—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 magnesium 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
- C23C22/07—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
- C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
Definitions
- the present invention relates to a method for phosphating metal surfaces, in particular a method for producing zinc phosphate coatings containing manganese and magnesium on steel, zinc, aluminum and / or their alloys. These zinc phosphate layers containing manganese and magnesium are applied by spraying, splash-dipping and dipping with aqueous solutions.
- Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components.
- the pH of such solutions is usually in the range between 2.8 and 3.4.
- the process consists essentially of two reactions: the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
- manganese-modified zinc phosphate coatings are known as a basis of liability for modern coatings.
- the use of manganese ions in addition to zinc and nickel ions in Low-zinc phosphating processes have been proven to improve corrosion protection, especially when using surface-coated thin sheets.
- the incorporation of manganese into the zinc phosphate coatings leads to smaller and more compact crystals with increased stability to alkali.
- the working range of phosphating baths is increased; Aluminum can also be phosphated in combination with steel and electrolytically or hot-dip galvanized steel, whereby the generally achieved quality standard is guaranteed.
- EP-A-0 261 704 discloses a method for producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, by spraying or splash-dipping to form uniform phosphate layers with a high degree of coverage a phosphating solution is being worked which, in addition to zinc, phosphate and fluoride, can also contain other cations from the group nickel, manganese, magnesium and calcium.
- a high nickel zinc phosphating process is known from WO 85/03089.
- extraordinarily high nickel concentrations are used for phosphating.
- part of the nickel can in principle be replaced by a series of monovalent or divalent cations. These are selected, for example, from cobalt, manganese and magnesium.
- the nickel content of the solution to be used must be at least 1.0 g / l.
- the ratio to be used between low zinc and high nickel content is an essential part of technical teaching.
- the object of the present invention was to provide a phosphating process which is nickel-free or has a lower nickel content compared to the prior art, since nickel is an extremely expensive bath component and is also ecologically unsafe. Since the discharge of nickel-containing wastewater is subject to a charge, the task continued to be to achieve the layer-refining effect of nickel by means of ions that are less harmful to the environment.
- An advantage of the present invention is that extremely low area-related masses of the phosphate layers could be obtained without loss of corrosion protection behavior. This applies in particular to steel surfaces.
- fluoride ions are not absolutely necessary when phosphating steel or zinc surfaces.
- the use of fluoride ions leads to a uniform one Degree of coverage of the phosphate layers on the aluminum.
- Pure aluminum, AlMg and AlMgSi kneading materials may be mentioned as examples of aluminum surfaces and their alloys. A detailed description of the aluminum materials can be found, for example, in the aluminum pocket book, 14th edition, Aluminum-Verlag, Düsseldorf, 1988.
- the term steel is understood to mean unalloyed to low-alloy steel, as it e.g. in the form of sheets for body construction.
- galvanized steel includes e.g. Galvanizing on the electrolytic and on the hot-dip route and refers to zinc and zinc alloys, e.g. Z, ZE, ZNE, ZF, ZA, AZ.
- the phosphating in the sense of the present invention takes place in spraying, splash immersion and immersion.
- the metal surfaces to be phosphated must be free from disturbing deposits of oils, lubricants, oxides and the like.
- the surfaces are cleaned in a suitable manner and, if necessary, with activating agents known per se, e.g. activated aqueous titanium suspensions.
- the activating agent can usually be introduced in the cleaning bath or as a separate process step.
- the substances generally used in phosphating technology can be used as accelerators.
- aqueous phosphating solution which contains chlorate, nitrate, nitrite, peroxide and / or organic oxidizing agents, in particular organic nitro compounds, as accelerators.
- phosphating solutions known in phosphating technology can be used to modify the procedure and of the layer properties included.
- examples include: surfactants, polyhydroxycarboxylic acids, polyphosphates, ammonium, alkali, copper, cobalt ions and indifferent anions such as chloride and / or sulfate.
- the above object is achieved according to claim 1 by a process for the preparation of manganese and magnesium-containing zinc phosphate coatings on steel, zinc, aluminum and / or their alloys by spraying, spray-immersing and / or containing with an aqueous solution 0.4 to 0.6 g / l zinc (II) ions, 0.9 to 1.1 g / l manganese (II) ions, 1.4 to 1.6 g / l magnesium (II) ions, 12.0 to 16.0 g / l phosphate ions, 0.4 to 0.6 g / l fluoride ions, 1.0 to 5.0 g / l nitrate ions and optionally 0.2 to 0.8 g / l Nickel (II) ions and as accelerators: 0.02 to 0.2 g / l nitrite ions and / or 0.4 to 1 g / l chlorate ions and / or 0.2 to 1.0 g / l of an organic
- a low-zinc process in which nickel is replaced by magnesium is thus described in a first embodiment.
- the present invention is therefore a zinc phosphating process, which in particular Low zinc range can be used.
- phosphate layers are generated which contain manganese as well as zinc and magnesium.
- the addition of Ni ions can be advantageous.
- surfaces containing zinc (Z, ZE) and in the alloys ZNE, ZF, ZA and AZ the presence of nickel results in improved phosphating results, while a positive effect was not observed on steel surfaces.
- the solutions to be used can contain small amounts of nickel (II) ions. In this sense, preference is therefore given to solutions which contain 0.2 to 0.8 g / l, in particular 0.25 to 0.5 g / l, of nickel (II) ions.
- 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
- the sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic oxidizing agent.
- the phosphating is carried out at a temperature in the range from 40 to 70 ° C.
- the surfaces of steel are preferably phosphated in the course of 1 to 5 minutes to form a layer.
- the surface layers produced with the aid of the method according to the invention can be used well in all fields in which phosphate coatings are used.
- a particularly advantageous application is the preparation of the metal surfaces for painting, in particular electrocoating.
- Typical layer analysis (determination quantitatively by atomic absorption spectroscopy, AAS) of the method on: a) Steel Application type element Diving Syringes B2 B1 (nickel free) A2 A1 (nickel free) iron 6.0% 5.4% 2.3% 1.9% manganese 4.3% 4.9% 5.9% 6.1% nickel 0.8% 0.0% 0.8% 0.0% magnesium 0.7% 0.9% 1.1% 1.0% zinc 24.6% 29.5% 30.7% 31.9% Average mass per unit area according to DIN 50942: 1.0 gm ⁇ 2 1.7 gm ⁇ 2 b) Electrolytically galvanized steel Application type element Diving Syringes B2 B1 (nickel free) A2 A1 (nickel free) manganese 4.6% 5.7% 5.3% 5.7% nickel 0.8% 0.0% 0.7% 0.0% magnesium 1.2% 1.2% 1.2% 1.2% 1.2% 1.2% 1.4% zinc 34.4% 34.4% 34.1% 33.8% 33.8% Average mass per unit area according to DIN 50942: 2.5 gm ⁇ 2 2.2 gm ⁇ 2
- Procedure B2 (diving) 5 rounds (35 days) 10 rounds (70 days) CRS 1) Z 2) ZE 3) CRS Z.
- ZE Area according to DIN 53209 mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO mO / gO Cut according to DIN 53167 in mm 0.2 1.2 1.4 0.3 1.7 1.9 Rockfall according to VW norm K 2 K 1 K 2 K 3 K 2 K 2 Procedure C (spray-immersion) 5 rounds (35 days) 10 rounds (70 days) CRS 1) Z 2) ZE 3) CRS Z.
- blistering that occurs in paints is defined by specifying the degree of blistering.
- the degree of bubbles according to this standard is a measure of the formation of bubbles on a coating according to the frequency of the bubbles per unit area and the size of the bubbles.
- the degree of bubbles is indicated by a code letter and a code number for the frequency of the bubbles per unit area as well as a code letter and a code number for the size of the bubbles.
- the code letter and the code mO means no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the degree of bubbles according to DIN 53 209.
- the size of the bubbles is given the code letter g and the code number in the range from 0 to 5.
- Code letter and code number GO has the meaning - no bubbles - while g5 is shown in accordance with the size of the bubbles in accordance with the degree of bubbles in DIN 53 209.
- the degree of blistering is determined, the image of which is most similar to the appearance of the coating.
- the salt spray test according to this standard is used to determine the behavior of paints, coatings and similar coatings when exposed to sprayed sodium chloride solution. If the coating has weak points, pores or injuries, the coating preferably infiltrates from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic surface.
- the salt spray test is used so that such errors can be recognized and the infiltration can be determined.
- the VW standard P 1210 is an alternating test that consists of a combination of different standardized test methods. So in Over the course of 60 days in the present case, a test cycle that consists of 4 h salt spray test according to DIN 50 021, 4 h rest at room temperature and 16 h condensation constant climate according to DIN 50 017.
- the test bone is bombarded with a defined amount of steel shot with a certain grain size distribution.
- a key figure is assigned to the degree of corrosion.
- the key figure 1 denotes an invisible corrosion, while with a key figure 10 practically the entire surface is corroded.
- One round (7 days) of the VDA alternating climate test consists of 24 h salt spray test according to DIN 50021, 96 h condensation water change climate according to DIN 50017 48 h rest at room temperature.
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Phosphatierung von Metalloberflächen, insbesondere ein Verfahren zur Herstellung von mangan- und magnesiumhaltigen Zinkphosphatüberzügen auf Stahl, Zink, Aluminium und/oder deren Legierungen. Diese mangan- und magnesiumhaltigen Zinkphosphatschichten werden durch Spritzen, Spritztauchen und Tauchen mit wäßrigen Lösungen aufgebracht.The present invention relates to a method for phosphating metal surfaces, in particular a method for producing zinc phosphate coatings containing manganese and magnesium on steel, zinc, aluminum and / or their alloys. These zinc phosphate layers containing manganese and magnesium are applied by spraying, splash-dipping and dipping with aqueous solutions.
Verfahren zum Phosphatieren von Oberflächen aus Eisen, Stahl, Zink und deren Legierungen sowie Aluminium sind seit langem Stand der Technik (Ullmanns Encyklopädie der technischen Chemie, 4. Auflage, Band 15, Seiten 686 und 687). Das Phosphatieren der genannten Oberflächen dient zur Erhöhung der Haftfestigkeit von Lackschichten und zur Verbesserung des Korrosionsschutzes.Processes for phosphating surfaces made of iron, steel, zinc and their alloys as well as aluminum have long been state of the art (Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 15, pages 686 and 687). The phosphating of the surfaces mentioned serves to increase the adhesive strength of paint layers and to improve corrosion protection.
Die größte Bedeutung als Phosphatierverfahren besitzen saure Zink- und Alkaliphosphatlösungen. Zinkphosphatierbäder können beispielsweise Monozinkphosphat, freie Phosphorsäure, Zinknitrat und Oxidationsmittel als Hauptkomponenten enthalten. Der pH-Wert solcher Lösungen liegt üblicherweise im Bereich zwischen 2,8 und 3,4. Der Verfahrensablauf besteht aus im wesentlichen zwei Reaktionen: der Beizreaktion und der Bildung einer Zinkphosphatschicht auf der zu phosphatierenden Oberfläche.Acidic zinc and alkali phosphate solutions are of the greatest importance as phosphating processes. Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components. The pH of such solutions is usually in the range between 2.8 and 3.4. The process consists essentially of two reactions: the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
Aus W.A. Roland und K.-H. Gottwald, "Metalloberfläche", 42. Jahrgang 1988/6 sind manganmodifizierte Zinkphosphatüberzüge als Haftungsgrund für moderne Lackierungen bekannt. Hier wird ausgeführt, daß der Einsatz von Manganionen neben Zink- und Nickelionen in Niedrig-Zink-Phosphatierverfahren den Korrosionsschutz nachweislich verbessert, insbesondere bei der Verwendung oberflächenveredelter Feinbleche. Der Einbau von Mangan in die Zinkphosphatüberzüge führt zu kleineren und kompakteren Kristallen mit erhöhter Alkalistabilität. Gleichzeitig wird die Arbeitsbreite von Phosphatierbädern erhöht; auch Aluminium kann im Verbund mit Stahl und elektrolytisch- oder schmelztauchverzinktem Stahl schichtbildend phosphatiert werden, wobei der allgemein erreichte Qualitätsstandard gewährleistet ist.From WA Roland and K.-H. Gottwald, "Metallfläche", 42nd year 1988/6, manganese-modified zinc phosphate coatings are known as a basis of liability for modern coatings. Here it is stated that the use of manganese ions in addition to zinc and nickel ions in Low-zinc phosphating processes have been proven to improve corrosion protection, especially when using surface-coated thin sheets. The incorporation of manganese into the zinc phosphate coatings leads to smaller and more compact crystals with increased stability to alkali. At the same time, the working range of phosphating baths is increased; Aluminum can also be phosphated in combination with steel and electrolytically or hot-dip galvanized steel, whereby the generally achieved quality standard is guaranteed.
Aus EP-A-0 261 704 ist ein Verfahren zum Erzeugen von Phosphatüberzügen auf Oberflächen bekannt, die aus Aluminium oder dessen Legierungen sowie mindestens einem der Werkstoffe Stahl oder verzinktem Stahl gebildet werden, wobei durch Spritzen oder Spritztauchen zwecks Bildung gleichmäßiger Phosphatschichten mit hohem Deckungsgrad mit einer Phosphatierlösung gearbeitet wird, die neben Zink, Phosphat und Fluorid auch weitere Kationen aus der Gruppe Nickel, Mangan, Magnesium und Calcium enthalten kann.EP-A-0 261 704 discloses a method for producing phosphate coatings on surfaces which are formed from aluminum or its alloys and at least one of the materials steel or galvanized steel, by spraying or splash-dipping to form uniform phosphate layers with a high degree of coverage a phosphating solution is being worked which, in addition to zinc, phosphate and fluoride, can also contain other cations from the group nickel, manganese, magnesium and calcium.
Aus WO 85/03089 ist ein Hochnickel-Zinkphosphatierverfahren bekannt. Hierbei werden außerordentlich hohe Nickel-Konzentrationen zur Phosphatierung eingesetzt. Es wird allgemein darauf hingewiesen, daß ein Teil des Nickels prinzipiell durch eine Reihe einwertiger oder zweiwertiger Kationen ersetzt werden kann. Diese sind beispielsweise ausgewählt aus Cobalt, Mangan und Magnesium. Weiterhin wird ausgeführt, daß der Nickel-Gehalt der einzusetzenden Lösung wenigstens 1,0 g/l betragen muß. Das einzusetzende Verhältnis zwischen geringem Zink- und hohem Nickelgehalt ist ein wesentlicher Bestandteil der technischen Lehre.A high nickel zinc phosphating process is known from WO 85/03089. Here extraordinarily high nickel concentrations are used for phosphating. It is generally pointed out that part of the nickel can in principle be replaced by a series of monovalent or divalent cations. These are selected, for example, from cobalt, manganese and magnesium. Furthermore, it is stated that the nickel content of the solution to be used must be at least 1.0 g / l. The ratio to be used between low zinc and high nickel content is an essential part of technical teaching.
Die Aufgabe der vorliegenden Erfindung bestand darin, ein Phosphatierungsverfahren zur Verfügung zu stellen, das Nickel-frei ist oder gegenüber dem Stand der Technik einen niedrigeren Nickelgehalt aufweist, da Nickel einen außerordentlich teuren Badbestandteil darstellt und außerdem ökologisch bedenklich ist. Da das Ablassen nickelhaltiger Abwässer kostenpflichtig ist, bestand die Aufgabe weiterhin darin, die schichtverfeinernde Wirkung von Nickel durch ökologisch unbedenklichere Ionen zu erzielen.The object of the present invention was to provide a phosphating process which is nickel-free or has a lower nickel content compared to the prior art, since nickel is an extremely expensive bath component and is also ecologically unsafe. Since the discharge of nickel-containing wastewater is subject to a charge, the task continued to be to achieve the layer-refining effect of nickel by means of ions that are less harmful to the environment.
Ein Vorteil der vorliegenden Erfindung besteht darin, daß außerordentlich geringe flächenbezogene Massen der Phospatschichten ohne Einbuße im Korrosionsschutzverhalten erhalten werden konnten. Dies gilt insbesondere für Oberflächen von Stahl.An advantage of the present invention is that extremely low area-related masses of the phosphate layers could be obtained without loss of corrosion protection behavior. This applies in particular to steel surfaces.
Durch separate Aktivierung und den Zusatz von Magnesium zu den erfindungsgemäßen Badzusammensetzungen konnten in der Phosphatierung sehr kleine Kristalle mit einer Kantenlänge von etwa 0,5 bis 1,5 µm im Tauchverfahren und etwa 1 bis 2 um beim Spritzverfahren erhalten werden. Mit Hilfe der vorliegenden Erfindung konnte in den Phosphatschichten ein sehr geringer Hopeitanteil, insbesondere auf Stahl erreicht werden. Die Ursache ist insbesondere in dem Einbau eines zusätzlichen Kations zu sehen und darin, daß erfindungsgemäß mit niedrigem Zinkgehalt gearbeitet wird.Through separate activation and the addition of magnesium to the bath compositions according to the invention, very small crystals with an edge length of approximately 0.5 to 1.5 μm in the immersion process and approximately 1 to 2 μm in the spray process could be obtained in the phosphating. With the help of the present invention, a very small amount of hopite, in particular on steel, could be achieved in the phosphate layers. The cause can be seen in particular in the incorporation of an additional cation and in the fact that the invention works with a low zinc content.
Gute Korrosionstestwerte konnten sowohl ohne die Verwendung von Nickel als auch bei Substitution von Teilen des Nickelgehaltes durch Magnesium bezüglich der Unterwanderung am Schnitt als auch im Lackhaftungsergebnis auf Stahl erhalten werden. Die Substitution von Nickel durch Magnesium zeigte sehr gute Korrosionstestwerte.Good corrosion test values could be obtained both without the use of nickel and with the substitution of parts of the nickel content by magnesium with regard to the infiltration at the cut and in the paint adhesion result on steel. The substitution of nickel with magnesium showed very good corrosion test values.
Bei der Phosphatierung von Oberflächen von Stahl oder Zink ist der Einsatz von Fluoridionen nicht unbedingt erforderlich. Im Falle der Phosphatierung von Aluminiumoberflächen oder dessen Legierungen führt der Einsatz von Fluoridionen zu einem gleichmäßigen Deckungsgrad der Phosphatschichten auf dem Aluminium. Als Beispiele für Aluminium-Oberflächen und deren Legierungen seien Reinaluminium-, AlMg und AlMgSi-Knetwerkstoffe genannt. Eine ausführliche Darstellung der Aluminiumwerkstoffe findet sich z.B. im Aluminiumtaschenbuch, 14. Auflage, Aluminium-Verlag, Düsseldorf, 1988.The use of fluoride ions is not absolutely necessary when phosphating steel or zinc surfaces. In the case of phosphating aluminum surfaces or their alloys, the use of fluoride ions leads to a uniform one Degree of coverage of the phosphate layers on the aluminum. Pure aluminum, AlMg and AlMgSi kneading materials may be mentioned as examples of aluminum surfaces and their alloys. A detailed description of the aluminum materials can be found, for example, in the aluminum pocket book, 14th edition, Aluminum-Verlag, Düsseldorf, 1988.
Unter dem Begriff Stahl wird un- bis niedrig-legierter Stahl verstanden, wie er z.B. in Form von Blechen für den Karosseriebau Verwendung findet. Der Begriff verzinkter Stahl umfaßt z.B. Verzinkungen auf elektrolytischem und auf dem Schmelz-Tauch-Wege und bezieht sich auf Zink und Zinklegierungen, z.B. Z, ZE, ZNE, ZF, ZA, AZ.The term steel is understood to mean unalloyed to low-alloy steel, as it e.g. in the form of sheets for body construction. The term galvanized steel includes e.g. Galvanizing on the electrolytic and on the hot-dip route and refers to zinc and zinc alloys, e.g. Z, ZE, ZNE, ZF, ZA, AZ.
Die Phosphatierung im Sinne der vorliegenden Erfindung erfolgt im Spritzen, Spritztauchen und Tauchen. Die zu phosphatierenden Metalloberflächen müssen frei von störenden Belägen aus Ölen, Schmierstoffen, Oxiden und dergleichen sein. Vor der Phosphatierung werden die Oberflächen in geeigneter Weise gereinigt und gegebenenfalls mit an sich bekannten Aktivierungsmitteln, z.B. titansalzhaltigen wäßrigen Suspensionen aktiviert. Üblicherweise kann das Aktivierungsmittel im Reinigerbad oder als getrennte Verfahrensstufe eingebracht werden.The phosphating in the sense of the present invention takes place in spraying, splash immersion and immersion. The metal surfaces to be phosphated must be free from disturbing deposits of oils, lubricants, oxides and the like. Before phosphating, the surfaces are cleaned in a suitable manner and, if necessary, with activating agents known per se, e.g. activated aqueous titanium suspensions. The activating agent can usually be introduced in the cleaning bath or as a separate process step.
Als Beschleuniger können die in der Phosphatierungstechnik generell üblichen Substanzen eingesetzt werden.The substances generally used in phosphating technology can be used as accelerators.
Von besonderem Vorteil ist es, die Oberfläche mit einer wäßrigen Phosphatierungslösung in Kontakt zu bringen, die als Beschleuniger Chlorat, Nitrat, Nitrit, Peroxid und/oder organische Oxidationsmittel, insbesondere organische Nitroverbindungen, enthält.It is particularly advantageous to bring the surface into contact with an aqueous phosphating solution which contains chlorate, nitrate, nitrite, peroxide and / or organic oxidizing agents, in particular organic nitro compounds, as accelerators.
Weiterhin können die Phosphatierungslösungen in der Phosphatiertechnik bekannte Zusätze zur Modifizierung der Verfahrensweise und der Schichteigenschaften enthalten. Als Beispiele seien genannt: Tenside, Polyhydroxycarbonsäuren, Polyphosphate, Ammonium-, Alkali-, Kupfer-, Cobaltionen und indifferente Anionen, wie Chlorid und/oder Sulfat.Furthermore, the phosphating solutions known in phosphating technology can be used to modify the procedure and of the layer properties included. Examples include: surfactants, polyhydroxycarboxylic acids, polyphosphates, ammonium, alkali, copper, cobalt ions and indifferent anions such as chloride and / or sulfate.
Die vorstehend genannte Aufgabe wird gemäß Anspruch 1 gelöst durch ein Verfahren zur Herstellung von mangan- und magnesiumhaltigen Zinkphosphatüberzügen auf Stahl, Zink, Aluminium und/oder deren Legierungen durch Spritzen, Spritztauchen und/oder Tauchen mit einer wäßrigen Lösung enthaltend
0,4 bis 0,6 g/l Zink(II)-Ionen,
0,9 bis 1,1 g/l Mangan(II)-Ionen,
1,4 bis 1,6 g/l Magnesium(II)-Ionen,
12,0 bis 16,0 g/l Phosphat-Ionen,
0,4 bis 0,6 g/l Fluorid-Ionen,
1,0 bis 5,0 g/l Nitrat-Ionen und gegebenenfalls 0,2 bis 0,8 g/l
Nickel(II)-Ionen, sowie als Beschleuniger:
0,02 bis 0,2 g/l Nitrit-Ionen und/oder
0,4 bis 1 g/l Chlorat-Ionen und/oder
0,2 bis 1,0 g/l eines organischen Oxidationsmittels,
wobei die wäßrige Lösung einen Gehalt an freier Säure von 0,6 bis 1,8 Punkten und einen Gesamtsäuregehalt von 15 bis 30 Punkten aufweist und Na⁺ in der zur Einstellung der freien Säure notwendigen Menge vorhanden ist.
Die Anwesenheit der Nitrationen ist bedingt durch die Verwendung von Metallnitraten, beispielsweise Zn(NO₃)₂, zur Herstellung der zugrundeliegenden Konzentrate und daher Folge der ausgewählten (preiswerten) Rohstoffe.The above object is achieved according to claim 1 by a process for the preparation of manganese and magnesium-containing zinc phosphate coatings on steel, zinc, aluminum and / or their alloys by spraying, spray-immersing and / or containing with an aqueous solution
0.4 to 0.6 g / l zinc (II) ions,
0.9 to 1.1 g / l manganese (II) ions,
1.4 to 1.6 g / l magnesium (II) ions,
12.0 to 16.0 g / l phosphate ions,
0.4 to 0.6 g / l fluoride ions,
1.0 to 5.0 g / l nitrate ions and optionally 0.2 to 0.8 g / l
Nickel (II) ions and as accelerators:
0.02 to 0.2 g / l nitrite ions and / or
0.4 to 1 g / l chlorate ions and / or
0.2 to 1.0 g / l of an organic oxidizing agent,
wherein the aqueous solution has a free acid content of 0.6 to 1.8 points and a total acid content of 15 to 30 points and Na⁺ is present in the amount necessary to adjust the free acid.
The presence of the nitrate ions is due to the use of metal nitrates, for example Zn (NO₃) ₂, for the production of the underlying concentrates and therefore the result of the selected (inexpensive) raw materials.
Gemäß der vorliegenden Erfindung wird somit in einer ersten Ausführungsform ein Niedrigzink-Verfahren beschrieben, bei dem Nickel durch Magnesium ersetzt ist. Bei der vorliegenden Erfindung handelt es sich somit um ein Zinkphosphatierverfahren, das insbesondere im Niedrigzink-Bereich eingesetzt werden kann. Mit Hilfe dieses Verfahrens werden Phosphatschichten erzeugt, die als Kationen neben Zink und Magnesium auch Mangan enthalten. Unter gewissen Anlagenbedingungen kann die Zugabe von Ni-Ionen vorteilhaft sein. So werden bei Zink (Z, ZE) enthaltenden Oberflächen und bei den Legierungen ZNE, ZF, ZA und AZ, durch die Anwesenheit von Nickel verbesserte Phosphatierungsergebnisse erhalten, während bei Stahloberflächen eine positive Wirkung nicht beobachtet wurde.According to the present invention, a low-zinc process in which nickel is replaced by magnesium is thus described in a first embodiment. The present invention is therefore a zinc phosphating process, which in particular Low zinc range can be used. With the help of this process, phosphate layers are generated which contain manganese as well as zinc and magnesium. Under certain system conditions, the addition of Ni ions can be advantageous. In the case of surfaces containing zinc (Z, ZE) and in the alloys ZNE, ZF, ZA and AZ, the presence of nickel results in improved phosphating results, while a positive effect was not observed on steel surfaces.
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung können die einzusetzenden Lösungen geringe Mengen an Nickel(II)-Ionen enthalten. Bevorzugt in diesem Sinne sind daher Lösungen, die 0,2 bis 0,8 g/l, insbesondere 0,25 bis 0,5 g/l Nickel(II)-Ionen enthalten.In a further preferred embodiment of the present invention, the solutions to be used can contain small amounts of nickel (II) ions. In this sense, preference is therefore given to solutions which contain 0.2 to 0.8 g / l, in particular 0.25 to 0.5 g / l, of nickel (II) ions.
Gemäß einer bevorzugten Ausführungsform der vorliegenden Erfindung wird als organisches Oxidationsmittel 3-Nitrobenzolsulfonsäure eingesetzt.According to a preferred embodiment of the present invention, 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
Als bevorzugtes organisches Oxidationsmittel wird das Natriumsalz der 3-Nitrobenzolsulfonsäure eingesetzt.The sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic oxidizing agent.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung wird die Phosphatierung bei einer Temperatur im Bereich von 40 bis 70 °C durchgeführt. In einer weiteren Ausführungsform der vorliegenden Erfindung werden vorzugsweise die Oberflächen von Stahl im Verlauf von 1 bis 5 min schichtbildend phosphatiert.In a preferred embodiment of the present invention, the phosphating is carried out at a temperature in the range from 40 to 70 ° C. In a further embodiment of the present invention, the surfaces of steel are preferably phosphated in the course of 1 to 5 minutes to form a layer.
Die mit Hilfe des erfindungsgemäßen Verfahrens erzeugten Oberflächenschichten sind auf allen Gebieten, auf denen Phosphatüberzüge angewendet werden, gut einsetzbar. Ein besonders vorteilhafter Anwendungsfall liegt in der Vorbereitung der Metalloberflächen für die Lackierung, insbesondere die Elektrotauchlackierung.The surface layers produced with the aid of the method according to the invention can be used well in all fields in which phosphate coatings are used. A particularly advantageous application is the preparation of the metal surfaces for painting, in particular electrocoating.
Innerhalb der üblichen Prozeßfolge mit den Stufen:
- 1. Reinigen und Entfetten:
Verwendung von tensidhaltigen alkalischen Reinigungsmitteln (= RIDOLINER C 1250) im Spritzen und/oder Tauchen bei 50 bis 60 °C und Behandlungszeiten von 1 bis 5 min. - 2. Spülen
- 3. Aktivieren:
Verwendung von titansalzhaltigen Mitteln (= FIXODINER C 9112) im Spritzen oder Tauchen bei 20 bis 40 °C und Behandlungszeiten von 30 bis 180 s bei separater Anwendung. Die Aktivierungsstufe kann entfallen, wenn dieses aktivierende Mittel der Reinigungsstufe zugesetzt wird. - 4. Phosphatieren:
Zusammensetzung siehe Tabelle 1. - 5. Spülen
- 6. Nachpassivieren:
Verwendung von chromhaltigen oder chromfreien Nachpassivierungsmitteln (=DEOXYLYTER 41 oder DEOXYLYTER 80) im Spritzen oder Tauchen bei 20 bis 50 °C und Behandlungszeiten von 30 bis 180 s. - 7. VE-Spülen
- 1.Cleaning and degreasing:
Use of alkaline detergents containing surfactants (= RIDOLINE R C 1250) in spraying and / or dipping at 50 to 60 ° C and treatment times of 1 to 5 min. - 2. Rinse
- 3. Activate:
Use of agents containing titanium salt (= FIXODINE R C 9112) in spraying or dipping at 20 to 40 ° C and treatment times of 30 to 180 s when used separately. The activation stage can be omitted if this activating agent is added to the cleaning stage. - 4. Phosphating:
For composition, see table 1. - 5. Rinse
- 6. Post-passivation:
Use of chrome-containing or chrome-free post-passivation agents (= DEOXYLYTE R 41 or DEOXYLYTE R 80) in spraying or dipping at 20 to 50 ° C and treatment times of 30 to 180 s. - 7. VE flushing
Mit den oben genannten Varianten wurden flächenbezogene Massen der Phosphatschicht auf Stahl von 0,6 bis 2,5 gm⁻² und auf verzinktem Stahl von 1,8 bis 4,0 gm⁻² erzeugt.With the above-mentioned variants, area-related masses of the phosphate layer on steel from 0.6 to 2.5 gm⁻² and on galvanized steel from 1.8 to 4.0 gm⁻² were generated.
Typische Schichtanalyse (Bestimmung quantitativ durch Atomabsorptionsspektroskopie, AAS) des Verfahrens auf:
Mit den mit Hilfe der Applikationsarten (A₁), (B₂) und (C) erhaltenen Blechen wurden Korrosionstests mit Wechselklima nach VW-Norm P 1210 über 60 Tage Prüfzeit und nach VDA-Norm über 5/10 Runden durchgeführt:
(Als Lackbeschichtung wurde der Standard KET-Primer FT 85 7042, Hersteller BASF Lacke und Farben AG, verwandt)With the sheets obtained with the aid of the application types (A₁), (B₂) and (C), corrosion tests with an alternating climate were carried out according to VW standard P 1210 over a test period of 60 days and according to VDA standard over 5/10 laps:
(The standard KET primer FT 85 7042, manufacturer BASF Lacke und Farben AG, was used as the coating)
Bei der Bestimmung des Blasengrades von Anstrichen gemäß DIN 53 209 wird eine bei Anstrichen auftretende Blasenbildung durch Angabe des Blasengrades definiert. Der Blasengrad nach dieser Norm ist ein Maß für eine an einem Anstrich aufgetretene Blasenbildung nach Häufigkeit der Blasen je Flächeneinheit und Größe der Blasen. Der Blasengrad wird durch einen Kennbuchstaben und eine Kennzahl für die Häufigkeit der Blasen je Flächeneinheit sowie einen Kennbuchstaben und eine Kennzahl für die Größe der Blasen angegeben. Der Kennbuchstabe und die Kennzahl mO bedeutet keine Blasen, während m5 entsprechend den Blasengradbildern gemäß der DIN 53 209 eine gewisse Häufigkeit der Blasen je Flächeneinheit definiert.When determining the degree of blistering of paints in accordance with DIN 53 209, blistering that occurs in paints is defined by specifying the degree of blistering. The degree of bubbles according to this standard is a measure of the formation of bubbles on a coating according to the frequency of the bubbles per unit area and the size of the bubbles. The degree of bubbles is indicated by a code letter and a code number for the frequency of the bubbles per unit area as well as a code letter and a code number for the size of the bubbles. The code letter and the code mO means no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the degree of bubbles according to DIN 53 209.
Die Größe der Blasen wird mit dem Kennbuchstaben g und der Kennzahl im Bereich von 0 bis 5 versehen. Kennbuchstabe und Kennzahl gO hat die Bedeutung - keine Blasen - während g5 gemäß der Größe der Blasen entsprechend den Blasengradbildern der DIN 53 209 wiedergegeben ist.The size of the bubbles is given the code letter g and the code number in the range from 0 to 5. Code letter and code number GO has the meaning - no bubbles - while g5 is shown in accordance with the size of the bubbles in accordance with the degree of bubbles in DIN 53 209.
Durch Vergleich des Anstriches mit den Blasengradbildern wird der Blasengrad ermittelt, dessen Bild dem Aussehen des Anstrichs am ähnlichsten ist.By comparing the coating with the blistering images, the degree of blistering is determined, the image of which is most similar to the appearance of the coating.
Gemäß DIN 53 167 dient die Salzsprühnebelprüfung nach dieser Norm dazu, das Verhalten von Lackierungen, Anstrichen und ähnlichen Beschichtungen bei Einwirkung versprühter Natriumchloridlösung zu ermitteln. Weist die Beschichtung Schwachstellen, Poren oder Verletzungen auf, dann findet von dort aus bevorzugt eine Unterwanderung der Beschichtung statt. Dies führt zu einer Haftungsverminderung oder zu Haftungsverlust und Korrosion des metallischen Untergrundes.According to DIN 53 167, the salt spray test according to this standard is used to determine the behavior of paints, coatings and similar coatings when exposed to sprayed sodium chloride solution. If the coating has weak points, pores or injuries, the coating preferably infiltrates from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic surface.
Die Salzsprühnebelprüfung wird angewendet, damit solche Fehler erkannt und die Unterwanderung ermittelt werden kann.The salt spray test is used so that such errors can be recognized and the infiltration can be determined.
Unterwanderung im Sinne dieser Norm ist das von einer definiert angebrachten Verletzungsstelle (Ritz) oder von vorhandenen Schwachstellen (z. B. Poren, Kanten) ausgehende Eindringen von Natriumchloridlösung in die Grenzfläche zwischen Beschichtung und Untergrund oder in die Grenzfläche zwischen einzelnen Beschichtungen. Die Breite der Zone mit verminderter oder verlorener Haftung dient als Maß für die Widerstandsfähigkeit der Beschichtung auf dem jeweiligen Untergrund gegen das Einwirken versprühter Natriumchloridlösung.Infiltration within the meaning of this standard is the penetration of sodium chloride solution into the interface between coating and substrate or into the interface between individual coatings, starting from a defined point of injury (Ritz) or from existing weak points (e.g. pores, edges). The width of the zone with reduced or lost adhesion serves as a measure of the resistance of the coating on the respective substrate to the action of sprayed sodium chloride solution.
Die VW-Norm P 1210 stellt einen Wechseltest dar, der aus einer Kombination verschieden genormter Prüfverfahren besteht. So wird im Verlauf von im vorliegenden Fall 60 Tagen ein Prüfzyklus eingehalten, der besteht aus
4 h Salzsprüh-Test gemäß DIN 50 021,
4 h Ruhezeit bei Raumtemperatur und
16 h Schwitzwasser-Konstantklima gemäß DIN 50 017.The VW standard P 1210 is an alternating test that consists of a combination of different standardized test methods. So in Over the course of 60 days in the present case, a test cycle that consists of
4 h salt spray test according to DIN 50 021,
4 h rest at room temperature and
16 h condensation constant climate according to DIN 50 017.
Zu Beginn des Tests wird das Prüfgrät mit einer definierten Menge Stahlschrot bestimmter Korngrößenverteilung beschossen. Nach Ablauf der Prüfzeit wird dem Korrosionsgrad eine Kennzahl zugeordnet. Entsprechend den Kennzahlen von 1 bis 10 bezeichnet die Kennzahl 1 eine nicht sichtbare Korrosion, während bei einer Kennzahl 10 praktisch die gesamte Oberfläche korrodiert ist.At the beginning of the test, the test bone is bombarded with a defined amount of steel shot with a certain grain size distribution. After the test period has expired, a key figure is assigned to the degree of corrosion. Corresponding to the key figures from 1 to 10, the key figure 1 denotes an invisible corrosion, while with a key figure 10 practically the entire surface is corroded.
Eine Runde (7 Tage) Prüfzyklus des VDA-Wechselklimatests besteht aus
24 h Salzsprühtest gemäß DIN 50021,
96 h Kondenswasser-Wechselklima nach DIN 50017
48 h Ruhezeit bei Raumtemperatur.One round (7 days) of the VDA alternating climate test consists of
24 h salt spray test according to DIN 50021,
96 h condensation water change climate according to DIN 50017
48 h rest at room temperature.
Zusätzlich wurde analog zum VW-Wechselklimatest eine Steinschlagprüfung nach VW-Norm durchgeführt.In addition, a rockfall test according to the VW standard was carried out analogously to the VW alternating climate test.
Claims (7)
- A process for the production of manganese- and magnesium-containing zinc phosphate coatings on steel, zinc, aluminium and/or alloys thereof by spray coating, spray/dip coating and/or dip coating with an aqueous solution containing zinc(II), manganese(II) and magnesium(II) ions and optionally nickel(II) ions, also phosphate, fluoride and nitrate ions and - as accelerators - nitrite and/or chlorate ions and/or an organic oxidizing agent, characterized in that the metal surfaces are treated with solutions containing the following components:
0.4 to 0.6 g/l zinc(II) ions,
0.9 to 1.1 g/l manganese(II) ions,
1.4 to 1.6 g/l magnesium(II) ions,
12.0 to 16.0 g/l phosphate ions,
1.0 to 5.0 g/l nitrate ions,
0.4 to 0.6 g/l fluoride ions
and, optionally,
0.2 to 0.8 g/l nickel(II) ions
and - as accelerators -
0.02 to 0.2 g/l nitrite ions and/or
0.4 to 1 g/l chlorate ions and/or
0.2 to 1.0 g/l organic oxidizing agent,
the aqueous solution having a free acid content of 0.6 to 1.8 points and a total acid content of 15 to 30 points and Na⁺ ions being present in the quantity required to establish the free acid content. - A process as claimed in claim 1, characterized in that the aqueous solution contains 0.25 to 0.5 g/l nickel(II) ions.
- A process as claimed in claim 1 or 2, characterized in that 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
- A process as claimed in claim 3, characterized in that the sodium salt of 3-nitrobenzenesulfonic acid is used.
- A process as claimed in one or more of claims 1 to 4, characterized in that phosphating is carried out at a temperature in the range from 40 to 70°C.
- A process as claimed in one or more of claims 1 to 5, characterized in that the surfaces of steel, galvanized steel, aluminium or the corresponding alloy-finished surfaces are subjected to layer-forming phosphating for 1 to 5 minutes.
- A process as claimed in one or more of claims 1 to 6 for pretreating the surfaces for painting, more particularly electrodeposition painting.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3920296 | 1989-06-21 | ||
| DE3920296A DE3920296A1 (en) | 1989-06-21 | 1989-06-21 | METHOD FOR PRODUCING ZINC PHOSPHATE CONTAINING MANGANE AND MAGNESIUM |
| PCT/EP1990/000919 WO1990015889A1 (en) | 1989-06-21 | 1990-06-12 | Process for producing zinc phosphate coatings containing manganese and magnesium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0478648A1 EP0478648A1 (en) | 1992-04-08 |
| EP0478648B1 true EP0478648B1 (en) | 1995-01-18 |
Family
ID=6383236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90909688A Expired - Lifetime EP0478648B1 (en) | 1989-06-21 | 1990-06-12 | Process for producing zinc phosphate coatings containing manganese and magnesium |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5207840A (en) |
| EP (1) | EP0478648B1 (en) |
| JP (1) | JPH04506233A (en) |
| KR (1) | KR0171219B1 (en) |
| AT (1) | ATE117381T1 (en) |
| BR (1) | BR9007437A (en) |
| CA (1) | CA2062952A1 (en) |
| DE (2) | DE3920296A1 (en) |
| ES (1) | ES2067031T3 (en) |
| PT (1) | PT94426B (en) |
| WO (1) | WO1990015889A1 (en) |
| ZA (1) | ZA904795B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4210513A1 (en) | 1992-03-31 | 1993-10-07 | Henkel Kgaa | Nickel-free phosphating process |
| CA2171180A1 (en) * | 1993-09-06 | 1995-03-16 | Wolf-Achim Roland | Nickel-free phosphating process |
| DE4440300A1 (en) * | 1994-11-11 | 1996-05-15 | Metallgesellschaft Ag | Process for applying phosphate coatings |
| DE19500927A1 (en) * | 1995-01-16 | 1996-07-18 | Henkel Kgaa | Lithium-containing zinc phosphating solution |
| DE19511573A1 (en) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Process for phosphating with metal-containing rinsing |
| US5900073A (en) * | 1996-12-04 | 1999-05-04 | Henkel Corporation | Sludge reducing zinc phosphating process and composition |
| DE19740953A1 (en) * | 1997-09-17 | 1999-03-18 | Henkel Kgaa | High speed spray or dip phosphating of steel strip |
| JP3828675B2 (en) | 1998-04-23 | 2006-10-04 | 新日本製鐵株式会社 | Surface-treated steel sheet with excellent corrosion resistance and workability and method for producing the same |
| DE19834796A1 (en) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Process for phosphating, rinsing and cathodic electrocoating |
| US6607844B1 (en) * | 1999-03-15 | 2003-08-19 | Kobe Steel, Ltd. | Zn-Mg electroplated metal sheet and fabrication process therefor |
| EP1067212A1 (en) * | 1999-07-08 | 2001-01-10 | Kawasaki Steel Corporation | Perforative corrosion resistant galvanized steel sheet |
| WO2001021853A1 (en) * | 1999-09-17 | 2001-03-29 | Kawasaki Steel Corporation | Surface treated steel sheet and method for production thereof |
| DE10109480A1 (en) * | 2001-02-28 | 2002-09-05 | Volkswagen Ag | Coating aluminum surface, e.g. of car chassis, involves forming phosphate layers on surface by spraying, in which aluminum is complexed using fluoride or other complex former before dip coating |
| CN100374620C (en) | 2002-07-10 | 2008-03-12 | 坎梅陶尔股份有限公司 | Method for coating metallic surfaces |
| DE10320313B4 (en) * | 2003-05-06 | 2005-08-11 | Chemetall Gmbh | A method of coating metallic bodies with a phosphating solution, phosphating solution and the use of the coated article |
| DE10323305B4 (en) * | 2003-05-23 | 2006-03-30 | Chemetall Gmbh | Process for coating metallic surfaces with a phosphating solution containing hydrogen peroxide, phosphating solution and use of the treated articles |
| US7815751B2 (en) * | 2005-09-28 | 2010-10-19 | Coral Chemical Company | Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings |
| DE102008004728A1 (en) | 2008-01-16 | 2009-07-23 | Henkel Ag & Co. Kgaa | Phosphated steel sheet and method for producing such a sheet |
| US10442480B2 (en) * | 2017-06-30 | 2019-10-15 | Caterpillar Inc. | Coating for seal assembly |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3676224A (en) * | 1970-10-16 | 1972-07-11 | Lubrizol Corp | Phosphating solution with scale suppressing characteristics |
| US3726720A (en) * | 1971-05-24 | 1973-04-10 | Lubrizol Corp | Metal conditioning compositions |
| US4681641A (en) * | 1982-07-12 | 1987-07-21 | Ford Motor Company | Alkaline resistant phosphate conversion coatings |
| DE3631759A1 (en) * | 1986-09-18 | 1988-03-31 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
| US4717431A (en) * | 1987-02-25 | 1988-01-05 | Amchem Products, Inc. | Nickel-free metal phosphating composition and method for use |
| DE3711931A1 (en) * | 1987-04-09 | 1988-10-20 | Metallgesellschaft Ag | METHOD FOR DETERMINING ZINC IN PHOSPHATING BATHS |
| DE3712339A1 (en) * | 1987-04-11 | 1988-10-20 | Metallgesellschaft Ag | METHOD FOR PHOSPHATIZING BEFORE ELECTROPLATING |
-
1989
- 1989-06-21 DE DE3920296A patent/DE3920296A1/en not_active Withdrawn
-
1990
- 1990-06-12 US US07/776,319 patent/US5207840A/en not_active Expired - Fee Related
- 1990-06-12 DE DE59008322T patent/DE59008322D1/en not_active Expired - Fee Related
- 1990-06-12 ES ES90909688T patent/ES2067031T3/en not_active Expired - Lifetime
- 1990-06-12 WO PCT/EP1990/000919 patent/WO1990015889A1/en active IP Right Grant
- 1990-06-12 BR BR909007437A patent/BR9007437A/en not_active Application Discontinuation
- 1990-06-12 CA CA002062952A patent/CA2062952A1/en not_active Abandoned
- 1990-06-12 KR KR1019910701931A patent/KR0171219B1/en not_active IP Right Cessation
- 1990-06-12 AT AT90909688T patent/ATE117381T1/en not_active IP Right Cessation
- 1990-06-12 JP JP2509708A patent/JPH04506233A/en active Pending
- 1990-06-12 EP EP90909688A patent/EP0478648B1/en not_active Expired - Lifetime
- 1990-06-19 PT PT94426A patent/PT94426B/en not_active IP Right Cessation
- 1990-06-20 ZA ZA904795A patent/ZA904795B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0478648A1 (en) | 1992-04-08 |
| DE3920296A1 (en) | 1991-01-10 |
| BR9007437A (en) | 1992-04-14 |
| DE59008322D1 (en) | 1995-03-02 |
| ZA904795B (en) | 1991-02-27 |
| KR0171219B1 (en) | 1999-02-18 |
| WO1990015889A1 (en) | 1990-12-27 |
| JPH04506233A (en) | 1992-10-29 |
| ES2067031T3 (en) | 1995-03-16 |
| PT94426B (en) | 1997-02-28 |
| US5207840A (en) | 1993-05-04 |
| KR920702731A (en) | 1992-10-06 |
| CA2062952A1 (en) | 1990-12-22 |
| PT94426A (en) | 1991-02-08 |
| ATE117381T1 (en) | 1995-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0478648B1 (en) | Process for producing zinc phosphate coatings containing manganese and magnesium | |
| EP0633950B1 (en) | Nickel-free phosphatization process | |
| DE2155670B2 (en) | ZINC PHOSPHATING SOLUTION FOR ALUMINUM, ZINC OR IRON | |
| EP0370535B1 (en) | Process for applying phosphate coatings | |
| WO1996017977A1 (en) | Method of applying phosphate coatings to metal surfaces | |
| EP0359296B1 (en) | Phosphating process | |
| EP0155547B1 (en) | Process for the zinc-calcium phosphatizing of metal surfaces at a low treating temperature | |
| EP0361375A1 (en) | Phosphate-coating process | |
| EP0134895B1 (en) | Process and compounds for applying accelerated and grain-refined phosphate coatings to metallic surfaces | |
| DE4326388A1 (en) | Process for the phosphating treatment of one-sided galvanized steel strip | |
| EP0486576B1 (en) | Process for producing manganese-containing zinc phosphate coatings on galvanized steel | |
| EP0469011B1 (en) | Process not using chlorate or nitrite for the production of nickel and manganese-containing zinc phosphate films | |
| EP0264811B1 (en) | Process for producing phosphate coatings | |
| WO1998013534A2 (en) | Method for phosphating a steel band | |
| EP0662164B1 (en) | Process for phosphating galvanised steel surfaces | |
| EP0215041B1 (en) | Process for the phosphating of metal surfaces | |
| WO1999014397A1 (en) | Method for phosphatizing a steel strip | |
| WO1993022474A1 (en) | Copper-containing, nickel-free phosphatizing process | |
| EP0866888B1 (en) | Method of phosphating metal surfaces | |
| EP0355525B1 (en) | Process for producing coatings on zinc | |
| WO1990015167A1 (en) | Process for producing manganese-containing phosphate coatings on metal surfaces | |
| DE19905479A1 (en) | Process for the phosphatisation of zinc or aluminum 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 |
|
| 17P | Request for examination filed |
Effective date: 19911213 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE DE ES FR GB IT NL SE |
|
| 17Q | First examination report despatched |
Effective date: 19940308 |
|
| 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 SE |
|
| REF | Corresponds to: |
Ref document number: 117381 Country of ref document: AT Date of ref document: 19950215 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 59008322 Country of ref document: DE Date of ref document: 19950302 |
|
| ET | Fr: translation filed | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2067031 Country of ref document: ES Kind code of ref document: T3 |
|
| ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950420 |
|
| 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: GB Payment date: 19980603 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980609 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19980615 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980622 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19980629 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19980813 Year of fee payment: 9 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19990414 Year of fee payment: 10 |
|
| 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: 19990612 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990612 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19990621 Year of fee payment: 10 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19990630 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990630 |
|
| BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 19990630 |
|
| 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: 20000101 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19990612 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20000101 |
|
| 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: 20000503 |
|
| 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: 20000613 Ref country code: ES Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 20000613 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| EUG | Se: european patent has lapsed |
Ref document number: 90909688.5 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20020204 |
|
| 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: 20050612 |