EP3704286B1 - Verfahren und zusammensetzung zur behandlung von metalloberflächen unter verwendung dreiwertiger chromverbindungen - Google Patents

Verfahren und zusammensetzung zur behandlung von metalloberflächen unter verwendung dreiwertiger chromverbindungen Download PDF

Info

Publication number
EP3704286B1
EP3704286B1 EP18804756.7A EP18804756A EP3704286B1 EP 3704286 B1 EP3704286 B1 EP 3704286B1 EP 18804756 A EP18804756 A EP 18804756A EP 3704286 B1 EP3704286 B1 EP 3704286B1
Authority
EP
European Patent Office
Prior art keywords
composition
metal surface
panels
pretreatment composition
trivalent chromium
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.)
Active
Application number
EP18804756.7A
Other languages
English (en)
French (fr)
Other versions
EP3704286A1 (de
Inventor
Jose B. Rivera
Cody HANNA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bulk Chemicals Inc
Original Assignee
Bulk Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bulk Chemicals Inc filed Critical Bulk Chemicals Inc
Publication of EP3704286A1 publication Critical patent/EP3704286A1/de
Application granted granted Critical
Publication of EP3704286B1 publication Critical patent/EP3704286B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also 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
    • 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
    • C23C22/10—Orthophosphates containing oxidants
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • This invention relates generally to compositions and the use of such compositions for passivating and improving the paint adhesion of metal surfaces.
  • the composition may be used as a pre-paint treatment and is intended to be used to treat a range of metals including copper, brass, magnesium, aluminum, iron, zinc, cadmium, or alloys thereof. More particularly, this invention relates to an aqueous composition, suitable for use as a dried-in-place coating for metal, that comprises trivalent chromium, phosphate, silica, and hydrogen peroxide and methods for using that composition. The process and seal coat have been found to demonstrate good paint adhesion results.
  • Known methods of treating metal surfaces to improve paint adhesion and corrosion resistance of painted metal surfaces include two general classes of chemistries.
  • the first class is based on traditional conversion coating types of chemistries, such as zinc phosphate, iron phosphate, chromium chromate, chromium phosphate, etc.
  • the second class is based on more recent developments in the metal pretreatment industry and is characterized by what is now referred to as "dried-in-place" technology.
  • Traditional conversion coating chemistries require rinsing of the metal substrate to remove applied pretreatment solution. Dried-in-place chemistries allow for the applied solutions to be dried on the metal substrate to which they are applied, without rinsing prior to the application of a paint.
  • chromate conversion coatings aqueous hexavalent chromium solutions which contain chemicals that dissolve the surface of the metal and form insoluble films.
  • chromate conversion coatings which contain hexavalent chromium, are corrosion resistant and protect the metal from various elements which cause corrosion.
  • hexavalent chromate conversion coatings generally have good paint bonding characteristics and, therefore, provide an excellent base for paint or other finishes.
  • Hexavalent chromium shows toxicological effects and has been determined by the Environmental Protection Agency as a risk to the environment and by the Occupational Safety and Health Agency as a health risk. Moreover, chemistries based on hexavalent chromium are classified as carcinogens by these agencies.
  • aqueous compositions for treating metal surfaces comprising silica and Cr(H 2 PO 4 ) 3 are disclosed in GB2201157 A , JP 54935432 A , EP 2060660 A1 , EP 0532779 A1 , JP H01123081 A EP 1484432 A , and EP 1712524 A1 .
  • the present invention relates to a composition for treating a metal surface to improve paint adhesion and corrosion resistance and/or maintain low electrical contact resistance.
  • a composition consisting of water, a trivalent chromium compound with the formula Cr(H x PO 4 ) 3 , where x is 2, a silica compound, and optionally hydrogen peroxide.
  • composition consisting of water, a trivalent chromium compound with the formula Cr(H x PO4) 2 where x is 1.5, a silica compound, and optionally hydrogen peroxide.
  • the trivalent chromium compound is present in an amount of between: about 10% wt. % to about 5% wt. %; about 10% wt. % to about 2.5% wt. %, about 10% wt. % to about 1% wt. %, or about 10% wt. % to about 0.5% wt. %..
  • the silica is present in an amount of less than 2% wt. %; less than 1.75% wt. %; or less than 1.5% wt. %.
  • a process for treating a metal surface includes the step of contacting the metal surface with a composition of claims 1 or 5.
  • the process for treating a metal surface comprises the steps of: (1) cleaning the metal surface to form a cleaned metal surface; (2) rinsing the cleaned metal surface with water to form a rinsed metal surface; and (3) contacting the rinsed metal surface with a composition of claims 1 or 5.
  • the process additionally comprises, after contacting the rinsed metal surface with the composition, again rinsing the metal surface with water and then sealing the metal surface.
  • the processes may additionally comprise, before the first contacting step, the step of cleaning the metal surface with an alkaline cleaner and rinsing.
  • the processes may further comprise, after contacting the metal surface with the pretreatment composition, the steps of rinsing the metal surface with water and then painting the surface of the metal.
  • the pH of the aqueous pretreatment composition is preferably acidic and more preferably has a pH of between about 1 and about 4.
  • compositions according to the present invention consist of water, a trivalent chromium compound with the formula Cr(H x PO 4 ) 3 , where x is 2, or with the formula Cr(H x PO 4 ) 2 , where x is 1.5, a silica compound, and optionally hydrogen peroxide.
  • Processes according to the present invention include contacting a metal surface with the above compositions.
  • compositions of the present invention are applied to a metal surface after cleaning but before some final coat is applied to the metal surface, contributing to at least one of the following: (1) improving the paint adhesion of the metal surface; (2) improving the corrosion resistance of the metal surface; and (3) maintaining or reducing the resistivity of the metal surface.
  • Compositions of the present invention include compositions which significantly improve one or two of these characteristics, even though at least one of the others is worsened to a lesser extent. The improvement could be due to the compositions alone or the compositions in combination other process steps. Such compositions are referred to herein or in the metal treatment industry as pretreatment compositions, conversion coatings, or working compositions. "Resistivity" is defined as resistance per unit surface area.
  • hexavalent chromium compound means compounds, namely salts, of chromium in which the chromium has a valence of plus 6.
  • anions could be used, and more than one hexavalent chromium compound could be used.
  • the hexavalent chromium compound is anhydrous chromic acid (CrO 3 ), chromic acid (H 2 CrO 4 ), or chromium chromate (Cr 5 O 12 ).
  • metal used for example in the phrase “metal surface,” includes copper, brass, magnesium, aluminum, iron, zinc, cadmium, or alloys thereof. Each metal listed includes both the elemental metal and alloys thereof; for example, the term “aluminum” means aluminum and aluminum alloys.
  • alloy is a metal in which the primary element has a higher content than every other element or a content equal to the highest content of every other element (e.g., an aluminum alloy being a metal in which aluminum is present in an amount at least equal to that of any other element).
  • Iron alloys include cold rolled steel, electro-galvanized steel, and hot-dipped galvanized steel.
  • compositions of the present invention are used to treat a range of metals including alloys of copper, brass, magnesium, aluminum, and iron.
  • pretreatment composition means any composition which improves the paint adhesion and corrosion resistance of a metal surface.
  • Aqueous pretreatment compositions are used as a pretreatment before painting and may be used as a passivation treatment to reduce the formation of corrosion in the uncoated (unpainted) condition.
  • the composition may be called a pretreatment composition for convenience, it is a composition used for pretreatment (i.e., improving the adhesion of subsequently applied paint) and passivation (i.e., resisting corrosion of the unpainted surface).
  • the term "treating” shall mean applying a treatment or cleaning, rinsing, and applying a pretreatment.
  • the pretreatment also functions as a sealant to seal the metal surface, so the term “treating” shall optionally include the step of sealing the metal surface.
  • “treating” optionally can include process steps up through and including painting.
  • treatment steps may also include a step of applying a decorative coating, such as painting.
  • the pretreatment may be rinsed first or dried-in-place before application of the paint. Each of these steps play a role in a final product's ability to resist corrosion and minimize paint loss.
  • the treatment composition can be used as a pre-paint treatment.
  • trivalent chromium compound means compounds, namely salts, of chromium in which the chromium has a valence of plus 3. No hexavalent chromium is present in such compounds.
  • the trivalent chromium compound is a compound with the formula Cr(H x PO 4 ) 3 , where x is 2 or a compound with the formula Cr(H x PO 4)2 , where x is 1.5.
  • the trivalent chromium compound is present in an amount of between: about 10% wt. % to about 5% wt. %; about 10% wt. % to about 2.5% wt. %, about 10% wt. % to about 1% wt. %, or about 10% wt. % to about 0.5% wt. %..
  • the silica is present in an amount of less than 2% wt. %; less than 1.75% wt. %; or less than 1.5% wt. %.
  • the precursor hexavalent chromium compound is anhydrous chromic acid (CrO 3 )
  • the chromic acid is first reduced in the presence of phosphoric acid to create a trivalent chromium compound, chromium dihydrogen phosphate (Cr(H 2 PO 4 ) 3 ). Hydrogen peroxide is the reducing agent. After the chromium is reduced, silica is added.
  • pH range has been found to be preferred given certain other conditions: 1 to 4.
  • compositions given above are of the working bath. It is desirable, of course, to transport the product in the form of a concentrate, namely up to a 10 to 100 fold increase in concentration of the above working bath concentrations.
  • the upper limit of such concentrates is the solubility limit of the first constituent to meet or exceed its solubility limit.
  • the pH of the compositions is preferably, when the composition is used to treat cold rolled steel, between 1 to 4. More preferably, the pH is about 1.75.
  • compositions according to the invention may be made by mixing the ingredients in any of a number of sequences.
  • a hexavalent chromium compound is a precursor material
  • the hexavalent chromium compound is first reduced in the presence of phosphoric acid to create a trivalent chromium compound, chromium dihydrogen phosphate (Cr(H 2 PO 4 ) 3 ). Hydrogen peroxide is the reducing agent. After the chromium is reduced, silica is added.
  • hexavalent chromium compound is a precursor material
  • the hexavalent chromium compound is metered into a solution containing phosphoric acid and hydrogen peroxide until the hexavalent chromium compound is fully reduced. After the chromium is reduced, silica is added.
  • the hydrogen peroxide upon completion of the reaction some residual hydrogen peroxide may remain. Conversely, in another non-limiting embodiment, the hydrogen peroxide is fully utilized. Preferably, upon completion of the reaction the hydrogen peroxide concentration is within the following range: from 0 to about 0.85 grams H 2 O 2 (35%) per gram of Cr(H 2 PO 4 ) 3 .
  • a metal surface is coated with a pretreatment composition of the present invention.
  • the composition may contact the metal surface by any number of techniques known in the art.
  • One such method is immersion coating in which the metal is immersed in the bath of pretreatment.
  • Other techniques known in the art including spraying, roll coating, or reverse roll coating, as well as manual application (e.g., brushing).
  • the coating step is done for a time sufficient to achieve the desired coating weight on the metal surface, which can be determined empirically. This desired coating weight will depend on a number of factors well-known in the art.
  • 1 milligram per square foot is equal to 10.7639 milligrams per square meter.
  • the amount of coating is sufficient to leave from about 0.1 to about 30 milligrams of chromium and phosphate per each square foot of dried metal surface as determined by the weight-strip-weight method. In another embodiment, the amount of coating is sufficient to leave from about 1 to about 10 milligrams of chromium per each square foot of dried metal surface as determined by x-ray fluorescence, and most preferably about 2.5 to about 3.5 milligrams of chromium per each square foot of dried metal surface as determined by x-ray fluorescence.
  • a process for treating a metal surface to improve corrosion resistance, improve paint adhesion, and/or maintain low electrical contact resistance comprises: (1) cleaning the metal surface to form a cleaned metal surface; (2) rinsing the cleaned metal surface with water to form a rinsed metal surface; and (3) contacting the rinsed metal surface with a composition disclosed herein.
  • the cleaning step may be carried out in any manner known in the art.
  • the types of cleaners suitable for use in the present invention will vary with a number of factors, including the metal being treated, the desired application, and the amount and type of impurities and soils on the metal surface. As such, the preferred cleaners can be determined empirically based on these factors.
  • an alkaline cleaner is used.
  • An exemplary alkaline cleaning agent which can be used in connection with the present invention is Bulk Kleen ® 841MC cleaner, an alkaline liquid cleaner sold by Bulk Chemicals, Incorporated of Reading, Pa.
  • a phosphoric acid cleaner is used.
  • the cleaning step may be accomplished by contacting the metal surface with a bath of an alkaline cleaning solution to form a cleaned metal surface.
  • the alkaline cleaning solution may be an aqueous solution of an alkaline cleaning agent.
  • the cleaning bath cleans the metal surface by removing oil and other contaminants from the metal surface.
  • the cleaning bath is effective to remove the loose impurities and surface soils.
  • the cleaning bath removes soils and certain impurities from the surfaces of the metal surface. If the metal surface is heavily soiled, a detergent cleaner additive may be included in the cleaning step.
  • a metal surface which has been contacted by an alkaline cleaning solution is referred to herein as a "cleaned metal surface.” It is cleaned in the sense that it has been exposed to a cleaning bath. It may not be completely cleaned, however, in the sense that substantially all of the impurities have been removed such that it is ready to be exposed to a pretreatment composition. In some cases, it may be adequately cleaned, but in other cases, it should first be rinsed with water before being contacted with a pretreatment composition (i.e., substantially all of the impurities are removed by that point).
  • the rinsing step is well-known in the art, and deionized water is preferably used.
  • deionized water avoids the introduction of any deleterious ions, such as chloride ions, into the system.
  • the rinsing step can be two-fold, with a first rinsing step done using tap water and then rinsing with deionized water.
  • the metal surface may be rinsed with water once again, as is well-known in the art.
  • the rinsed metal surface can then be sealed. Any chemical sealing composition well-known in the industry can be used.
  • an intervening rinsing step is preferably applied.
  • the metal surface may be dried, or rinsed and dried, and then a decorative coating may be applied to it.
  • the metal surface may be painted or lacquered, or first primed and then painted.
  • finishing steps are known in the art as "finishing steps," and any known and suitable finishing steps may be used.
  • Suitable paints include acrylic paints and fluorocarbon paints, among others.
  • the metal surface can be dried and then a decorative coating (a paint layer) is applied, without an intervening rinsing step between these steps.
  • a decorative coating a paint layer
  • This alternative process is known as a "dried-in-place" pretreatment. Regardless of whether the pretreatment is “dried-in-place" or there is an intermediate rinsing step, any known method of drying may be employed.
  • the coating may be dried by, for example, using an oven, forced air, etc.
  • Determining the times of treatments of the metal surfaces with the baths of the various steps is well-known in the art. They need only be long enough to permit a sufficient time for cleaning (in the case of the cleaning step) or reaction (in the case of the pretreatment or sealing steps). They can be very short or as long as thirty minutes and depend on the stage of treatment, the type of application (e.g., immersion, spray), the type of metal surface, and the desired coating weight, among other factors.
  • the immersion time of a substrate into the composition solution will vary with the stage, and generally varies between approximately 1 minute up to about 10 minutes. The times for immersion are typically longer than when spray is used as the method of contact. Rinse times in general can be fairly short, e.g., 30 seconds to one minute.
  • the specific times of treatment may vary over wide ranges and can be readily determined by one of ordinary skill in the art.
  • the desirable performance characteristics of the present invention can be achieved by the processing steps described above to produce a pretreated metal surface with good paint adhesion and corrosion resistance. These characteristics are obtained on the metal surface without a decorative coating. Accordingly, the treated metal surface can be used as unpainted products and will exhibit corrosion resistance even if there is a delay between the treatment steps and any subsequent painting.
  • compositions and processes of the present invention provide the stated benefits without the use of additional components which affect the basic and novel characteristics of the invention.
  • other components may affect the novel characteristics.
  • certain components may make the compositions unstable. Such components may affect the shelf-life of the treatment.
  • Other components may degrade the performance of the compositions and processes of the present invention.
  • the present invention provides environmentally friendly compositions and processes for treating metal, while still maintaining excellent paint adhesion and corrosion resistance. More particularly, the present invention avoids the use of hexavalent chromium, and its associated health hazards and disposal problems.
  • Figs. 1-4 illustrate the improved results obtained by employing aqueous compositions of this invention. These examples are exemplary, not restrictive, of the invention.
  • Cold rolled steel panels were treated via the following spray process.
  • Bulk Kleen ® 841MC is an alkaline cleaner designed to clean steel, zinc, and aluminum parts.
  • the panels were rinsed with deionized water at ambient temperature for 30 seconds.
  • Fifth, Composition 1 was applied to the panels using a roll coater.
  • Seventh, all panels were painted using a high reflectance white, single coat polyester at a dry film thickness of 0.018-0.02 mm.
  • Cold rolled steel panels were treated via the following spray process.
  • Composition 2 was applied to the panels using a roll coater.
  • the panels were rinsed with deionized water. Sixth, the panels were dried using hot air. Seventh, the control panels were then sealed with Bulk Bond ® NP250 35% v/v using a roll coater. Bulk Bond ® NP250 is a liquid chrome/silica product designed to be mill applied as a passivation/pretreatment for multi-metal surfaces. Eighth, all panels were dried and painted using a high reflectance white, single coat polyester at a dry film thickness of 0.018-0.02 mm.
  • Cold rolled steel panels were treated via the following spray process.
  • Fifth, the composition outlined in Example 1 of the Rausch et al. patent was applied to the panels using a roll coater.
  • composition 1 and Composition 2 provided comparable protection to the control formula (i.e., Bulk Bond ® 780) and outperformed the Rausch et al. formula. Specifically, Composition 1 and Composition 2 exhibited similar corrosion and pitting as the control formula, whereas the Rausch et al. formula exhibited increased corrosion and pitting.
  • Composition 1 and Composition 2 outperformed the Rausch et al. formula because of the additional ions other than chromium, phosphate, and silica present in the Rausch et al. formula.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Paints Or Removers (AREA)

Claims (10)

  1. Wässrige Vorbehandlungszusammensetzung zur Behandlung einer Metalloberfläche, wobei die Zusammensetzung besteht aus:
    Wasser;
    Kieselsäure;
    eine dreiwertige Chromverbindung mit der Formel Cr(H2PO4)3, und
    optional Wasserstoffperoxid.
  2. Wässrige Vorbehandlungszusammensetzung nach Anspruch 1, wobei die Vorbehandlungszusammensetzung sauer ist.
  3. Wässrige Vorbehandlungszusammensetzung nach Anspruch 1 oder 2, wobei die Vorbehandlungszusammensetzung einen pH-Wert von 1 bis 4 aufweist.
  4. Wässrige Vorbehandlungszusammensetzung nach einem der Ansprüche 1 bis 3, wobei die wässrige Vorbehandlungszusammensetzung weniger als 1,75 Gew.-% Kieselsäure und 2,5 Gew.-% bis 10 Gew.-% der dreiwertigen Chromverbindung enthält.
  5. Wässrige Vorbehandlungszusammensetzung zur Behandlung einer Metalloberfläche, wobei die Zusammensetzung besteht aus:
    Wasser;
    Kieselsäure;
    einer dreiwertigen Chromverbindung mit der Formel Cr(H1,5PO4)2,
    und optional Wasserstoffperoxid.
  6. Wässrige Vorbehandlungszusammensetzung nach Anspruch 5, wobei die Vorbehandlungszusammensetzung sauer ist.
  7. Wässrige Vorbehandlungszusammensetzung nach Anspruch 5 oder 6, wobei die Vorbehandlungszusammensetzung einen pH-Wert von 1 bis 4 aufweist.
  8. Wässrige Vorbehandlungszusammensetzung nach einem der Ansprüche 5 bis 7, wobei die wässrige Vorbehandlungszusammensetzung weniger als 1,75 Gew.-% Kieselsäure und 2,5 Gew.-% bis 10 Gew.-% der dreiwertigen Chromverbindung enthält.
  9. Verfahren zum Beschichten einer Metalloberfläche, das folgende Schritte umfasst:
    Walzbeschichten der Metalloberfläche mit der Zusammensetzung nach Anspruch 1 oder 5;
    Besprühen der Metalloberfläche für eine Dauer von bis zu 300 Sekunden in die Zusammensetzung nach Anspruch 1 oder 5; oder
    Eintauchen der Metalloberfläche für eine Dauer von bis zu 300 Sekunden mit der Zusammensetzung nach Anspruch 1 oder 5.
  10. Verfahren nach Anspruch 9, wobei die Metalloberfläche aus der Gruppe, bestehend aus Zink, Zinklegierungen, Aluminium, Aluminiumlegierungen, Stahl, verzinktem Stahl und Zink mit Aluminiumlegierung ausgewählt ist.
EP18804756.7A 2017-10-30 2018-10-25 Verfahren und zusammensetzung zur behandlung von metalloberflächen unter verwendung dreiwertiger chromverbindungen Active EP3704286B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762578787P 2017-10-30 2017-10-30
PCT/US2018/057533 WO2019089347A1 (en) 2017-10-30 2018-10-25 Process and composition for treating metal surfaces using trivalent chromium compounds

Publications (2)

Publication Number Publication Date
EP3704286A1 EP3704286A1 (de) 2020-09-09
EP3704286B1 true EP3704286B1 (de) 2023-12-06

Family

ID=64362639

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18804756.7A Active EP3704286B1 (de) 2017-10-30 2018-10-25 Verfahren und zusammensetzung zur behandlung von metalloberflächen unter verwendung dreiwertiger chromverbindungen

Country Status (9)

Country Link
US (1) US20200325582A1 (de)
EP (1) EP3704286B1 (de)
JP (1) JP2021501263A (de)
KR (1) KR20200081415A (de)
CN (1) CN111356786A (de)
BR (1) BR112020008635A2 (de)
CA (1) CA3079516A1 (de)
MX (1) MX2020004244A (de)
WO (1) WO2019089347A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240401204A1 (en) * 2023-06-05 2024-12-05 Bulk Chemicals Method and composition for adjusting hydrophilicity of metal using a polyphenol and a silane modified nano particulate or amino acid amnd silica

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS512331B2 (de) * 1972-08-09 1976-01-24
DE2711431C2 (de) 1977-03-16 1986-12-11 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Oberflächenbehandlung von Metallen
GB2201157B (en) * 1986-12-23 1991-07-17 Albright & Wilson Processes and products for surface treatment
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
JPH07116616B2 (ja) * 1987-11-04 1995-12-13 新日本製鐵株式会社 耐スクラッチ性に優れた化成皮膜付プレコート金属板の製造方法
JPH03271379A (ja) * 1990-03-20 1991-12-03 Kawasaki Steel Corp 塗装用ステンレス鋼板および塗装鋼板
US5415702A (en) * 1993-09-02 1995-05-16 Mcgean-Rohco, Inc. Black chromium-containing conversion coatings on zinc-nickel and zinc-iron alloys
JP4145016B2 (ja) * 2001-01-31 2008-09-03 日本パーカライジング株式会社 亜鉛系メッキ鋼板用防錆処理剤および亜鉛系メッキ鋼板
JP3774415B2 (ja) * 2002-03-14 2006-05-17 ディップソール株式会社 亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成するための処理溶液及び亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成する方法。
JP4625244B2 (ja) * 2003-07-02 2011-02-02 ディップソール株式会社 ３価クロメート皮膜用仕上げ剤組成物及び３価クロメート皮膜の仕上方法
US7641721B2 (en) * 2003-12-10 2010-01-05 Nippon Chemical Industrial Co., Ltd. Aqueous solution of chromium salt and method for producing same
WO2008029953A1 (fr) * 2006-09-07 2008-03-13 Nippon Steel Corporation LIQUIDE DE TRAITEMENT AQUEUX DESTINÉ À TRAITER UNE TÔLE D'ACIER PLAQUÉE DE Sn QUI PRÉSENTE D'EXCELLENTES CARACTÉRISTIQUES DE RÉSISTANCE À LA CORROSION ET D'ADHÉSION DE REVÊTEMENT, ET PROCÉDÉ DE PRODUCTION DE LA TÔLE D&apos
CN104073074B (zh) * 2013-09-05 2016-08-24 攀钢集团攀枝花钢铁研究院有限公司 一种金属表面铬处理剂及其制备方法和热镀金属材料
CN104060249B (zh) * 2013-09-05 2016-06-29 攀钢集团攀枝花钢铁研究院有限公司 金属表面铬处理剂及其制备方法和热镀金属材料
JP6206112B2 (ja) * 2013-11-19 2017-10-04 新日鐵住金株式会社 Ｓｎ系めっき鋼板及び水系処理液

Also Published As

Publication number Publication date
CN111356786A (zh) 2020-06-30
CA3079516A1 (en) 2019-05-09
JP2021501263A (ja) 2021-01-14
US20200325582A1 (en) 2020-10-15
EP3704286A1 (de) 2020-09-09
WO2019089347A1 (en) 2019-05-09
BR112020008635A2 (pt) 2020-10-06
KR20200081415A (ko) 2020-07-07
MX2020004244A (es) 2020-07-29

Similar Documents

Publication Publication Date Title
US11248298B2 (en) Chromium-free surface-treated tinplate, production method and surface treating agent therefor
EP0713541B1 (de) Zusammensetzung und verfahren zur behandlung von phosphatierten metalloberflächen
JP3844643B2 (ja) 下地処理剤、及び下地処理方法
JP2003171778A (ja) 金属の保護皮膜形成方法及び金属の保護皮膜
EP2060660A1 (de) Wässrige behandlungsflüssigkeit für verzinntes stahlblech mit hervorragender korrosionsbeständigkeit und überzugshaftung und verfahren zur herstellung eines oberflächenbehandelten stahlblechs
CN100378246C (zh) 用于金属表面处理的组合物和方法
JP2014504333A (ja) ジルコニウム、銅、及び金属キレート化剤を含有する金属前処理用組成物、並びに金属基材の関連するコーティング
CZ20033572A3 (cs) Prostředek k ošetření kovových povrchů
CN101519775B (zh) 环保型无铬封闭电镀锌磷化钢板及其制造方法
US6733579B1 (en) Chrome free final rinse for phosphated metal surfaces
EP2673394B1 (de) Verfahren und zusammensetzungen zur verbesserung der korrosionsverhalten von zirkonoxid auf vorbehandelten zinkoberflächen
US5846342A (en) Surface treatment agent for zinciferous-plated steel
JP5827792B2 (ja) 化成処理鉄系材料
US20200325582A1 (en) Process and composition for treating metal surfaces using trivalent chromium compounds
JP5259168B2 (ja) 表面処理剤および鋼板
MX2007015827A (es) Metodo para el tratamiento de superficies galvanizadas, quimicamente pasivadas, para mejorar la adhesion de la pintura.
US20190112717A1 (en) Composition for reducing the removal of material by pickling in the pickling of metal surfaces that contain galvanized and/or ungalvanized steel
CA1197674A (en) Composition and process for the treatment of phosphatized metal surfaces
US9573162B2 (en) Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
US20040115448A1 (en) Corrosion resistant magnesium and magnesium alloy and method of producing same
US11293104B2 (en) Inorganic non-chrome aqueous treatment composition and process for coating metal surfaces
CA1261716A (en) Passivation of lead surfaces
WO2014025484A1 (en) Steel-pre-paint treatment composition
WO2024047074A1 (en) Method of pre-treating metallic substrates
WO2015023808A1 (en) Method and composition for passivating zinc, zinc-coated, silver, and silver-coated substrates

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

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

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200519

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230627

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018062295

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

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

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240307

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20231206

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

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240307

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240306

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1638474

Country of ref document: AT

Kind code of ref document: T

Effective date: 20231206

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240306

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240406

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

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240406

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240408

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240408

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018062295

Country of ref document: DE

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

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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

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

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

26N No opposition filed

Effective date: 20240909

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602018062295

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20241025

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

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231206

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: 20250501

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: 20241025

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

Ref country code: LU

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

Effective date: 20241025

Ref country code: BE

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

Effective date: 20241031

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

Ref country code: FR

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

Effective date: 20241031

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

Ref country code: CH

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

Effective date: 20241031

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20241031

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

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231207

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

Ref country code: IE

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

Effective date: 20241025

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

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20181025

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

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20181025