EP2649219B1 - Metallvorbehandlungszusammensetzung mit zirkonium, kupfer und metallchelatbildner sowie deren beschichtungen auf metallsubstraten - Google Patents

Metallvorbehandlungszusammensetzung mit zirkonium, kupfer und metallchelatbildner sowie deren beschichtungen auf metallsubstraten Download PDF

Info

Publication number
EP2649219B1
EP2649219B1 EP11847810.6A EP11847810A EP2649219B1 EP 2649219 B1 EP2649219 B1 EP 2649219B1 EP 11847810 A EP11847810 A EP 11847810A EP 2649219 B1 EP2649219 B1 EP 2649219B1
Authority
EP
European Patent Office
Prior art keywords
coating
metal
zirconium
pretreatment
ppm
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
EP11847810.6A
Other languages
English (en)
French (fr)
Other versions
EP2649219A2 (de
EP2649219A4 (de
Inventor
Donald R. Vonk
Edis Kapic
Michael L. Sienkowski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=46207721&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2649219(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2649219A2 publication Critical patent/EP2649219A2/de
Publication of EP2649219A4 publication Critical patent/EP2649219A4/de
Application granted granted Critical
Publication of EP2649219B1 publication Critical patent/EP2649219B1/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
    • C23C22/34—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
    • 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
    • C23C22/73—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 characterised by the process
    • 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
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • This invention relates generally to coating compositions, in particular, coating compositions that can be applied to metal substrates to enhance paint adhesion even after extended coating times.
  • the invention also relates to the coatings obtained from the coating composition, methods of applying these coatings and the coated substrate.
  • a pretreatment coating is often applied to metal substrates, especially metal substrates that contain iron such as steel, prior to the application of a protective or decorative coating.
  • the pretreatment coating minimizes the amount of corrosion to the metal substrate.
  • the pretreatment coating can affect the adhesion of subsequently applied decorative coatings such as paints and clear coats.
  • Many of the present pretreatment coating compositions are based on metal phosphates, and/or rely on a chrome-containing rinse.
  • the metal phosphates and chrome rinse solutions produce waste streams that are detrimental to the environment. As a result, there is the ever-increasing cost associated with their disposal.
  • these pretreatment coating compositions be effective in minimizing corrosion and enhancing decorative coating adhesion on a variety of metal substrates because many objects of commercial interest contain more than one type of metal substrate. For example, the automobile industry often relies on metal components that contain more than one type of metal substrate. The use of a coating composition effective for more than one metal substrate would provide a more streamlined manufacturing process.
  • the coating compositions of the present invention are called pretreatment coatings because they are typically applied after the substrate has been cleaned and before the various primer and decorative coatings have been applied.
  • coatings often comprise the following layers in order from the substrate out: a pretreatment coating for corrosion resistance, an electrodeposited electrocoat, then a primer layer, a base coat paint, and then a top clear coat.
  • all coatings after the pretreatment coating are considered as paints unless otherwise noted.
  • One known pretreatment coating is Bonderite® 958 available from Henkel Adhesive Technologies.
  • the Bonderite® 958 provides a zinc-phosphate based conversion coating composition that includes zinc, nickel, manganese and phosphate.
  • Bonderite® 958 is a standard conversion coating used extensively in the automotive industry.
  • the new class of coatings generally comprises a zirconium-based conversion coating deposited on a metal substrate by contact with a working bath containing dissolved zirconium in the coating compositions.
  • These conversion coating compositions which are based on a zirconium coating technology, typically have no phosphates and no nickel or manganese.
  • Zirconium-based coatings are finding increasing use in the automotive industry as a pretreatment coating EP 1 433 875 A1 , WO 2010/001861 A1 , EP 1 433 878 A1 , US 5 584 946 A , US 2007/272900 A1 disclose each zirconium-based conversion treatment compositions for metal surfaces to provide chemical conversion coatings having good corrosion resistance and coating film adhesion.
  • Manufacturing plants' metal coating assembly lines are part of an overall process that is highly coordinated and carefully timed. Metal workpieces are cut to size, formed, cleaned, coated with a pretreatment coating, and then coated with several over layers. Several different types of metal may pass separately through parts of the process to be joined to each other in one step and then proceed through the remaining process steps as an assembly of dissimilar metals. These processes are carried out on hundreds of pieces per hour and the system requires precise movement of a metal workpiece through the process. From time to time, the processing line may be halted, sometimes unexpectedly due to a problem in one of the processes in the assembly line. When line stoppage occurs, workpieces are held in the various stages of the line for far longer than is desirable.
  • the coated workpiece does not perform up to required standards.
  • the coated workpieces may not exhibit the desired corrosion resistance or paint adhesion characteristics. This can lead to increased scrap rates and potential recalls, which can drive up costs of manufacturing.
  • zirconium-based conversion coating baths contain copper, either as an additive to improve features of the pretreatment coating and/or process or as a trace element from water or metal workpieces being coated. Regardless of its source, the present inventors have discovered that copper from the zirconium-based coating bath that is deposited in the pretreatment coating at too high an amount relative to other coating components can negatively affect performance of the coated metal substrate. Accordingly, it is desirable to develop zirconium-based coating baths that overcome this deficiency.
  • this invention provides a metal pretreatment coating that is zirconium-based and that provides a longer pot life and enhanced paint adhesion without decreasing the corrosion resistance.
  • the invention also relates to the coatings and coated substrate obtained from the coating composition.
  • a zirconium-based metal pretreatment coating composition according to claim 1 is provided.
  • the zirconium-based metal pretreatment coating composition said copper chelating agent is capable of reducing amounts of copper deposited in a zirconium based coating on a metal substrate by contact with the zirconium based metal pretreatment coating composition, said copper chelating agent present in an amount sufficient to thereby produce an average total ratio of atomic % of Cu to atomic % of Zr in said coating deposited on the metal substrate that is from 0.3 to 0.1.
  • the zirconium-based metal pretreatment coating composition comprises: water and
  • the zirconium-based metal pretreatment coating composition described above has a copper chelating agent comprising tartaric acid and/or salts thereof.
  • Another aspect of the invention is a method for improving paint adhesion to a metal substrate comprising the steps of:
  • a method for improving paint adhesion to a metal substrate that is subjected to a pretreatment with a zirconium-based pretreatment coating composition comprising the steps of:
  • the copper chelating agent is present in an amount of at least 10 ppm and at most 2000 ppm.
  • Another aspect of the invention is an article of manufacture comprising a coated metal substrate comprising: a metal substrate; and deposited on said metal substrate, a pretreatment coating comprising metal from said substrate, zirconium, oxygen, copper, and optional elements fluorine and carbon; wherein the pretreatment coating on the metal substrate has an average total ratio of atomic % of Cu to atomic % of Zr that from 0.3 to 0.1
  • the article of manufacture is provided wherein atomic % of Cu in said pretreatment coating measured at a series of depths from an outer surface of the pretreatment coating to the metal substrate does not exceed 33 atomic % Cu at any of said depths.
  • the article of manufacture is provided further comprising at least one paint applied to the pretreatment coating resulting in a painted coated substrate that achieves at least 95% paint remaining when tested according to ASTM 3330M (Revised Oct. 1, 2004).
  • the article of manufacture is provided further comprising at least one paint applied to the pretreatment coating resulting in a painted coated substrate that achieves 1.9 mm or less average corrosion creep when tested according to ASTM B117 (Revised Dec. 15, 2007) for 500 hours.
  • the invention is directed to a method for improving paint adhesion to a metal substrate comprising the steps of: providing a metal substrate; applying to the metal substrate an aqueous, zirconium-based metal pretreatment coating composition as defined in claim 1 and applying a paint to the metal pretreatment coated metal substrate.
  • the pretreatment coating can be used on a variety of metal substrates including cold rolled steel (CRS), hot-rolled steel, stainless steel, steel coated with zinc metal, zinc alloys such as electrogalvanized steel (EG), 55% Aluminum-Zinc alloy coated sheet steel, such as Galvalume®, galvanneal (steel sheet with a fully alloyed iron-zinc coating) (HIA), and hot-dipped galvanized steel (HDG), aluminum alloys such as AL6111 and aluminum plated steel substrates.
  • CRS cold rolled steel
  • hot-rolled steel stainless steel
  • steel coated with zinc metal zinc alloys
  • zinc alloys such as electrogalvanized steel (EG), 55%
  • Aluminum-Zinc alloy coated sheet steel such as Galvalume®, galvanneal (steel sheet with a fully alloyed iron-zinc coating) (HIA), and hot-dipped galvanized steel (HDG)
  • AL6111 and aluminum plated steel substrates aluminum alloys such as AL6111 and aluminum plated steel substrates.
  • the invention is directed to a coated substrate comprising a metal substrate having deposited on said metal a pretreatment coating comprising metal from the substrate, zirconium, oxygen, copper and optional elements fluorine and carbon; wherein average total ratio of atomic % of Cu to atomic % of Zr in the pretreatment coating on the metal substrate that is from 0.3 to 0.1.
  • the coated substrate further comprises at least one paint applied to the pretreatment coating wherein the painted coated substrate achieves at least 95% paint remaining when tested according to ASTM 3330M (Revised Oct. 1, 2004).
  • Figures 1A, 1B, 1C, and 1D are scanning electron microscope (SEM) images of pretreatment coatings on cold rolled steel;
  • Figure 2A is an SEM image of the sample shown in Figure 1A with several circled areas of interest
  • Figure 2B is a graph of the chemical composition of the areas circled in Figure 2A ;
  • Figure 3A is an SEM image of the sample shown in Figure 1B with several circled areas of interest
  • Figure 3B is a graph of the chemical composition of the areas circled in Figure 3A ;
  • Figure 4 is a graph of an X-ray photoelectron spectroscopy analysis of a pretreatment coating composition of Figure 1A according to the invention.
  • Figure 5 is a graph of an X-ray photoelectron spectroscopy analysis of the pretreatment coating composition of Figure 1B .
  • the present invention is directed to a metal pretreatment coating composition, and a method for applying the same, as well as to articles of manufacture comprising coatings according to the invention.
  • the invention provides surprising improvements in performance in zirconium-based conversion coating pretreatments such as, by way of non-limiting example, zirconium-based conversion coatings deposited on a metal substrate by contact with a working bath containing dissolved zirconium in the coating compositions.
  • zirconium-based conversion coatings such as, by way of non-limiting example, zirconium-based conversion coatings deposited on a metal substrate by contact with a working bath containing dissolved zirconium in the coating compositions.
  • These conversion coating compositions are exemplified by aqueous coating baths comprising dissolved zirconium and free fluoride that form coatings comprising zirconium and oxygen.
  • the baths are typically aqueous, neutral to acidic, and comprise dissolved zirconium, dissolved copper, either as an additive or as a trace element from water or metal substrates, and a source of fluoride.
  • Optional components may be present including materials comprising one or more of silicon (e.g. silica, silicates, silanes), boron, yttrium, particular embodiments of which have no phosphates and no zinc, nickel, cobalt, manganese, and chromium.
  • zirconium-based coating baths contain copper, either as an additive or as a trace element from water or from metal workpieces being coated. Regardless of its source, the present inventors have discovered that copper from the zirconium-based coating bath that is deposited in the coating can negatively affect performance of the coated metal substrate, if present in amounts such that undesirable morphologies in the coating arise and/or in amounts above desirable levels.
  • the coating baths typically are aqueous, neutral to acidic, and comprise dissolved zirconium, dissolved copper, a source of fluoride and counter ions for the dissolved metals, for example sulfates and/or nitrates.
  • Optional components may be present including materials comprising one or more of silicon (e.g. silica, silicates, silanes), boron, yttrium.
  • the zirconium-based pretreatment coating compositions may contain acid, generally a mineral acid, but optionally organic acids; and/or an alkaline source. The acid and/or alkali may be a source of other components in the composition, may be used to control pH or both.
  • the zirconium-based pretreatment coating compositions according to the invention may likewise, consist essentially of or consist of the materials described herein.
  • the coating composition according to the invention provides zirconium-based coatings having improved paint adhesion and maintained corrosion resistance. These and other benefits are achieved by adding to a zirconium-based coating composition, either a bath or the concentrate, a copper metal chelating agent, to control the amount of copper deposited onto the metal substrate by the zirconium-based pretreatment coating composition.
  • This chelating agent can be added to the zirconium-based pretreatment coating composition even where no copper is present in the unused zirconium-based pretreatment coating composition, as a protective agent to prevent later copper deposition as the bath ages and copper is incorporated into the bath as a trace element from water, such as from prior cleaning or rinse steps, and/or from metal workpieces being coated.
  • the inclusion of the chelating agent also extends the pot life of the pretreatment coating bath because is allows for a wider range of immersion times without negative effects on paint adhesion or corrosion protection.
  • the chelating agent comprising tartaric acid and/or salts thereof is capable of reducing the amount of copper deposited in the zirconium based coating.
  • chelating agents may be utilized according to the following methods: they may be incorporated into a pre-rinse applied prior to contacting the metal substrate with a zirconium-based pretreatment coating composition; the chelating agents may be incorporated into a zirconium-based pretreatment coating composition as discussed above; the chelating agents may also be applied as a post-rinse applied after the metal substrate has been contacted with a zirconium-based pretreatment coating composition.
  • the chelating agents are used at a level sufficient to ensure that in the deposited pretreatment coating the average total ratio of the atomic % of Cu to the atomic % of Zr in the pretreatment coating on the metal substrate is from 0.30 to 0.10.
  • the amount of chelating agent in the coating composition may range from 10ppm to 2000ppm.
  • the amount required is affected by, for example, the amount of copper present in the coating composition, the temperature of the coating bath, the substrate being coated, whether the composition is a concentrate or the working bath.
  • the chelating agent is present in an amount ranging from 25-100 ppm in the coating bath. More chelating agent may be added provided the concentration does not adversely affect bath performance.
  • the amount of chelating agent in the pretreatment coating composition is an amount sufficient to achieve a desired Cu:Zr ratio in the deposited coating and preferably the chelating agent amount is at least, in increasing order of preference 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70 or 75 ppm and is at most, in increasing order of preference, 2000, 1500, 1000, 900, 800, 700, 600, 500, 400, 300, 200, 100 ppm.
  • the average total ratio of atomic % of Cu to atomic % of Zr may range downward from 0.3 to 0.1.
  • Zirconium-based pretreatment coatings of the invention may have a variety of components in the coating provided that the amount of copper in the coating is not such that undesirable coating morphology and performance failures result.
  • the immersion bath time for a pretreatment coating step is about 120 seconds, but during an assembly line stoppage this time can be 10 minutes or longer.
  • an alternative protocol was developed by the present inventors. The process used in the experiments described in the present specification is as shown in TABLE 1 below.
  • the standard pretreatment process for all of the data is as described below in TABLE 1.
  • the Parco® Cleaner 1533R is an alkaline cleaner available from Henkel Adhesive Technologies.
  • the Ridosol 1270 is a basic nonionic surfactant and is available from Henkel Adhesive Technologies.
  • the weight ratio of Parco to Ridosol used was 8.33 to 1.
  • Aging of the cleaner was simulated by adding the oil Tirroil 906 available from Tirreno Industries, to age the cleaner at 4 grams/liter.
  • the base pretreatment composition was a zirconium-based pretreatment.
  • the electrodeposited paint coating used in all of the paint adhesion tests was BASF Cathoguard 310X available from BASF.
  • the zirconium-based pretreatment bath used for Example 1 included 180 parts per million (ppm) of zirconium, 30 ppm of copper, 35 ppm of free and 400 ppm of total fluoride, 42 ppm of SiO 2 ; the zirconium-based pretreatment bath pH was set at 4.2 Two different batches of commercially available, cold rolled steel (CRS 1 and CRS 2), as is typically used in automobile manufacture, were processed according to Table 1. The zirconium coating weight in milligrams Zr per square meter was determined for each sample.
  • the paint adhesion of the BASF Cathoguard 310 X was determined using the following protocol. A sample area was cross hatched down to the level of the substrate with a razor using a line spacing of 1 millimeter and 6 lines for each direction. Then a 75 millimeter long strip of adhesive tape 20 millimeters wide was applied to the cross hatched area. The tape adhesively bonds to steel according to ASTM 3330M (Revised Oct. 1, 2004) with a 180 degree peel strength value of 430 N/m. After 5 to 10 seconds of adhesion, the tail end of the tape was grasped and pulled upward with a rapid jerking motion perpendicular to the paint.
  • Example 1 The percent paint remaining attached to the substrate (indicative of paint adhesion) was determined as a percentage of the area covered by the tape. The results of Example 1 are reported below in TABLE 2. In Table 2, the bake temperature is 176.7°C (350°F) or 190.6° (375°F). TABLE 2 Sample No.
  • Figures 1A and 1C are scanning electron microscope (SEM) photographs of CRS 1 coated with a pretreatment coating composition according to Example 1, using fresh 1533/1270, a Zr coating weight of 143 mg/m 2 and a bake temperature of 190.6°C (375°F) as described above (Sample 3).
  • Figure 1A and 1B are at a magnification of 10,000x and 1C and 1D are a magnification of 30,000x.
  • Figures 1B and 1D are SEM photographs of CRS 2 coated with a pretreatment coating according to Example 1, using fresh 1533/1270, a Zr coating weight of 165 mg/m 2 and a bake temperature of 190.6°C (375°F) as described above (Sample 7).
  • Sample 7 the CRS 2 sample exhibited poor paint adhesion.
  • the photographs show that the deposited pretreatment coating of Sample 3 in Figures 1A and 1C was composed of much smaller substructures than that found in the pretreatment coating surface of Sample 7 in Figures 1B and 1D .
  • the surface in Figures 1B and 1D had larger and more clumped looking substructures.
  • Figures 2A and 2B are a further analysis of the Sample 3 surface shown in Figures 1A and 1C .
  • Figure 2A shows an SEM photograph of the pretreatment coating at a magnification of 15,000x and also shows three circles labeled 1, 2, and 3. Each of these areas was subjected to Auger Emission Spectroscopy (AES) to identify the elements and their levels found in each area of analysis. The results were evaluated by looking at the deviation from the baseline for each area, to make comparison possible the baselines were offset as can be seen.
  • the units on the y-axis in Figure 2B are (counts/second) X 10 5 , that is, the y-axis amounts were increased by a factor of 100,000. The results show differences in the levels of copper between the three areas.
  • Figures 3A and 3B show a further analysis of the surface shown in Figures 1B and 1D (Sample 7).
  • Figure 3A shows an SEM photograph of the pretreatment coating at a magnification of 15,000x and also shows two circles labeled 4 and 5. Each of these areas was subjected to AES to identify the elements and their levels found in each spot of analysis. The results were evaluated by looking at the deviation from the baseline for each area, to make comparison possible the baselines were offset as can be seen.
  • the units on the y-axis of Figure 3B are (counts/second) X 10 4 , that is, the y-axis amounts were increased by a factor of 10,000, therefore 1 unit in Figure 3B is equal to 10 units in Figure 2B .
  • Area 4 is of a large substructure and the AES analysis showed that it had a very high level of copper, much higher than that found in the large substructure shown in Figures 2A and 2B , area 1.
  • area 5 a small substructure showed lower levels of copper than area 4, but much higher than even area 1 of Figures 2A and 2B considering the differences in the units.
  • the actual values for Sample 7, Figure 3B were as follows: area 4 had a copper level of 31 atomic percent and area 5 had a copper level of 25 atomic percent, much higher on average than those of Sample 3, which had good paint adhesion.
  • Figures 4 and 5 are graphical representations of the results from X-ray photoelectron spectroscopy (XPS) depth analysis of the two sample pretreatment coatings described in Figures 2 and 3 , respectively.
  • XPS X-ray photoelectron spectroscopy
  • Figure 5 showing a graph of Sample 7, the sample exhibiting poor paint adhesion, showed that the copper levels in the deposited pretreatment coating were much higher than in Sample 3, the pretreatment coating exhibiting good paint adhesion, whose graph is shown in Figure 4 .
  • Both the atomic percentage and the area under the curve for the copper were much greater in Figure 5 (Sample 7) compared to Figure 4 (Sample 3).
  • the peak atomic % Cu in Figure 4 was 33 atomic %.
  • the peak atomic % Cu in Figure 5 at any depth was 42.73 atomic %.
  • control pretreatment coating composition was a zirconium-based coating bath, wherein the Zr level was 180 ppm , Cu was 30 ppm, total Fluoride was 400 ppm and free Fluoride was 35 ppm, the level of SiO 2 was 42 ppm.
  • the test pretreatment coating composition was the same as the control and further comprising a chelating agent, tartrate introduced as tartaric acid at 50 ppm.
  • the pH of the pretreatment coating compositions was adjusted to 4.0.
  • the substrate was CRS that had been pre-cleaned with fresh Parco ® 1533 and rinsed as described in TABLE 1 above.
  • the immersion time in the control and the test zirconium-based coating baths was either 4 minutes or 10 minutes, simulating a shorter and a longer line stoppage.
  • a portion of each set of samples were then further coated with BASF Cathoguard 310X as described above and baked at 190.6°C (375°F). The baked samples were then tested for paint adhesion as described above.
  • the coating weights of Zr in mg/m 2 were determined for the samples.
  • the average atomic percentage of Zr and Cu in the pretreatment coatings was determined for each sample. The results are present below in TABLE 3.
  • TABLE 3 Example Pretreatment coating bath Immersion time minutes Zr coating wt.
  • Samples were then scribed to the CRS substrate and subjected to one of two corrosion performance tests.
  • the first test was according to ASTM B117 (Revised Dec. 15, 2007) for 500 hours.
  • a second test a 31 cycle test, the sample panels were subjected to 31 cycles of a 24 hour testing protocol using a salt misting spray.
  • the salt misting spray comprised 0.9% by weight sodium chloride, 0.1% by weight calcium chloride, and 0.075% by weight sodium bicarbonate at pH 6 to 9.
  • the first 8 hours the panels were kept at 25° C and 45% Relative Humidity (RH) and misted 4 times during the 8 hours at time 0, 1.5 hours, 3 hours and 4.5 hours.
  • RH Relative Humidity
  • the panels were then put at 49° C and 100% RH for the next 8 hours with a ramp up from 25° C to 49° C and 100% RH over the first hour.
  • the final 8 hours were at 60° C and less than 30% RH with a ramp to the new conditions of 3 hours.
  • the cycle was carried out for a total of 31 times.
  • the panels were then evaluated for average creep and maximum creep in millimeters from the scribe line.
  • the results for the ASTM B117 test are presented in TABLE 5.
  • the results for the 31 cycle corrosion test are presented in TABLE 6.
  • the results of using the tartrate were at least as good as the standard zirconium-based coating bath and were slightly better for extended dwell time of the CRS in the bath evidencing the improved pot life from the chelator. The longer immersion times did not reduce the corrosion protection and may even increase it.
  • the benefit of using a pretreatment coating was shown, in the clean only sample there was much more corrosion than in any of the pretreatment coating examples.
  • the presence or absence of the tartrate did not seem to affect the corrosion protection ability of the pretreatment coating.
  • TABLE 7 triethanolamine (TEA)
  • the substrate was CRS and the pretreatment coating and BASF Cathoguard were applied as described below in TABLE 7.
  • the zirconium-based coating bath included 180 ppm of Zr, 30 ppm of Cu, 35 ppm of free and 400 ppm total Fluoride and 42 ppm of SiO 2 .
  • Samples were then tested for Zr coating weight in mg/m 2 , paint adhesion, and corrosion protection under ASTM B117 for 500 hours.
  • As a control samples were also prepared with a pretreatment coating of Bonderite® 958 and Parcolene® 91 as described in Example 3. The results are presented below in TABLE 8.

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)
  • Paints Or Removers (AREA)

Claims (6)

  1. Metallvorbehandlungsbeschichtungszusammensetzung auf Zirkoniumbasis, umfassend Wasser und 50 bis 300 ppm in Lösung gehendes Zr, bis zu 50 ppm in Lösung gehendes Cu, 0 bis 100 ppm SiO2, 150 bis 2000 ppm Gesamtfluorid, 10 bis 100 ppm freies Fluorid, mindestens 10 ppm eines Kupferchelatbildners, umfassend Weinsäure und/oder Salze davon.
  2. Metallvorbehandlungsbeschichtungszusammensetzung auf Zirkoniumbasis nach Anspruch 1, wobei der Kupferchelatbildner in einer Menge von 25 bis 1500 ppm vorliegt.
  3. Verfahren zum Verbessern einer Haftung eines Anstrichstoffs auf einem Metallsubstrat, umfassend die Schritte:
    Auftragen einer Metallvorbehandlungsbeschichtungszusammensetzung auf Zirkoniumbasis nach einem der vorhergehenden Ansprüche auf das Metallsubstrat, wobei dadurch eine Vorbehandlungsbeschichtung auf dem Metallsubstrat ausgebildet wird; und
    Auftragen eines Anstrichstoffes auf das mit der Metallvorbehandlung beschichtete Metallsubstrat.
  4. Verfahren nach Anspruch 3, wobei der Kupferchelatbildner in einer Menge von höchstens 2000 ppm vorliegt.
  5. Herstellungserzeugnis, umfassend ein beschichtetes Metallsubstrat, umfassend:
    ein Metallsubstrat; und,
    abgeschieden auf dem Metallsubstrat, eine Vorbehandlungsbeschichtung, umfassend Metall aus dem Substrat, Zirkonium, Sauerstoff, Kupfer;
    wobei die Vorbehandlungsbeschichtung auf dem Metallsubstrat ein durchschnittliches Gesamtverhältnis von Atom-% Cu zu Atom-% Zr aufweist, das von 0,3 bis 0,1 beträgt.
  6. Erzeugnis nach Anspruch 5, wobei Atom-% Cu in der Vorbehandlungsbeschichtung, gemessen in einer Reihe von Tiefen von einer Außenoberfläche der Vorbehandlungsbeschichtung zu dem Metallsubstrat, 33 Atom-% Cu in keiner der Tiefen überschreitet.
EP11847810.6A 2010-12-07 2011-12-07 Metallvorbehandlungszusammensetzung mit zirkonium, kupfer und metallchelatbildner sowie deren beschichtungen auf metallsubstraten Active EP2649219B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42050910P 2010-12-07 2010-12-07
PCT/US2011/063789 WO2012078788A2 (en) 2010-12-07 2011-12-07 Metal pretreatment composition containing zirconium, copper, and metal chelating agents and related coatings on metal substrates

Publications (3)

Publication Number Publication Date
EP2649219A2 EP2649219A2 (de) 2013-10-16
EP2649219A4 EP2649219A4 (de) 2017-12-06
EP2649219B1 true EP2649219B1 (de) 2021-04-14

Family

ID=46207721

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11847810.6A Active EP2649219B1 (de) 2010-12-07 2011-12-07 Metallvorbehandlungszusammensetzung mit zirkonium, kupfer und metallchelatbildner sowie deren beschichtungen auf metallsubstraten

Country Status (9)

Country Link
EP (1) EP2649219B1 (de)
JP (1) JP2014504333A (de)
KR (1) KR20130126658A (de)
CN (1) CN103249867B (de)
BR (1) BR112013016613B1 (de)
CA (1) CA2819524A1 (de)
ES (1) ES2872342T3 (de)
MX (1) MX2013006286A (de)
WO (1) WO2012078788A2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023275270A3 (de) * 2021-07-02 2023-03-09 Henkel Ag & Co. Kgaa Verfahren für den sequenziellen aufbau einer konversionsschicht auf bauteilen umfassend stahloberflächen

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102181792B1 (ko) 2012-08-29 2020-11-24 피피지 인더스트리즈 오하이오 인코포레이티드 리튬을 함유하는 지르코늄 전처리 조성물, 관련된 금속 기판 처리 방법 및 관련된 코팅된 금속 기판
EP2890830B1 (de) 2012-08-29 2018-06-27 PPG Industries Ohio, Inc. Mit zirkonium vorbehandelte molybdänhaltige zusammensetzungen, entsprechende verfahren zur behandlung von metallsubstraten und entsprechende beschichtete metallsubstrate
CN104846359B (zh) * 2014-02-17 2017-12-29 广州中国科学院工业技术研究院 用于金属表面预处理的复合处理剂及其制备方法和应用
US20150315718A1 (en) * 2014-05-05 2015-11-05 Ppg Industries Ohio, Inc. Metal pretreatment modification for improved throwpower
JP6961492B2 (ja) 2015-04-15 2021-11-05 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA ポリアミドアミンポリマーを用いる薄い腐食保護コーティング
KR20190043155A (ko) 2016-08-24 2019-04-25 피피지 인더스트리즈 오하이오 인코포레이티드 금속 기판을 처리하기 위한 알칼리성 조성물
EP3336219B1 (de) * 2016-12-19 2019-04-17 Henkel AG & Co. KGaA Verfahren zur korrosionsschützenden und reinigenden vorbehandlung von metallischen bauteilen

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5584946A (en) 1993-05-24 1996-12-17 Henkel Kommanditgesellschaft Auf Aktien Chromium-free conversion coating treatment of aluminum
WO2001083850A1 (en) 2000-05-02 2001-11-08 Henkel Corporation Process and composition for conversion coating with improved heat stability
US6558480B1 (en) 1998-10-08 2003-05-06 Henkel Corporation Process and composition for conversion coating with improved heat stability
US20040163736A1 (en) 2002-12-24 2004-08-26 Nippon Paint Co., Ltd. Pretreatment method for coating
US20050103229A1 (en) 2002-01-11 2005-05-19 Kazuya Tanaka Aqueous agent for treating substrate, method for treating substrated and treated substrate
WO2007065645A1 (de) 2005-12-09 2007-06-14 Henkel Ag & Co. Kgaa Nass in nass verfahren und chromfreie saure lösung zur korrosionsschutzbehandlung von stahloberflächen
US20070272900A1 (en) 2004-12-08 2007-11-29 Masayuki Yoshida Composition for Metal Surface Treatment, Treating Liquid for Surface Treatment, Method of Surface Treatment, and Surface-Treated Metal Material
US20080254315A1 (en) 2007-01-19 2008-10-16 Nihon Hyomen Kagaku Kabushiki Kaisha Chromium-free solution for treating metal surfaces
US20090032144A1 (en) 2007-08-03 2009-02-05 Mcmillen Mark W Pretreatment compositions and methods for coating a metal substrate
WO2009115504A1 (de) 2008-03-17 2009-09-24 Henkel Ag & Co. Kgaa Optimierte passivierung auf ti-/zr-basis für metalloberflächen
US7749368B2 (en) 2006-12-13 2010-07-06 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated substrates
EP2280094A1 (de) 2008-02-27 2011-02-02 Henkel AG & Co. KGaA Metallwerkstoff und herstellungsverfahren dafür
WO2011090691A2 (en) 2009-12-28 2011-07-28 Henkel Ag & Co. Kgaa Metal pretreatment composition containing zirconium, copper, zinc, and nitrate and related coatings on metal substrates

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals
US5964928A (en) * 1998-03-12 1999-10-12 Natural Coating Systems, Llc Protective coatings for metals and other surfaces
US20030096893A1 (en) * 2001-09-28 2003-05-22 Boomgaard Ritse Eltjo Oxidatively drying coating composition
JP2004068069A (ja) * 2002-08-05 2004-03-04 Nippon Parkerizing Co Ltd 燒結材製品、及びその製造方法
DE60324379D1 (de) * 2002-12-24 2008-12-11 Chemetall Gmbh Chemisches Konversionsbeschichtungsmittel und beschichtete Metalloberflächen
TW200417419A (en) * 2002-12-24 2004-09-16 Nippon Paint Co Ltd Chemical conversion coating agent and surface-treated metal
CN101400826B (zh) * 2006-03-15 2012-06-20 日本帕卡濑精株式会社 铜材料用表面处理液、铜材料的表面处理方法、带表面处理被膜的铜材料和层合构件
AU2007317650B2 (en) * 2006-11-07 2012-06-14 H.C. Starck Surface Technology and Ceramic Powders GmbH Method for coating a substrate and coated product
JP2008174832A (ja) * 2006-12-20 2008-07-31 Nippon Paint Co Ltd カチオン電着塗装用金属表面処理液
JP2010013677A (ja) * 2008-07-01 2010-01-21 Nippon Parkerizing Co Ltd 金属構造物用化成処理液および表面処理方法
US9213979B2 (en) * 2008-12-17 2015-12-15 Oracle International Corporation Array attribute configurator

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5584946A (en) 1993-05-24 1996-12-17 Henkel Kommanditgesellschaft Auf Aktien Chromium-free conversion coating treatment of aluminum
US6558480B1 (en) 1998-10-08 2003-05-06 Henkel Corporation Process and composition for conversion coating with improved heat stability
WO2001083850A1 (en) 2000-05-02 2001-11-08 Henkel Corporation Process and composition for conversion coating with improved heat stability
US20050103229A1 (en) 2002-01-11 2005-05-19 Kazuya Tanaka Aqueous agent for treating substrate, method for treating substrated and treated substrate
US20040163736A1 (en) 2002-12-24 2004-08-26 Nippon Paint Co., Ltd. Pretreatment method for coating
US20070272900A1 (en) 2004-12-08 2007-11-29 Masayuki Yoshida Composition for Metal Surface Treatment, Treating Liquid for Surface Treatment, Method of Surface Treatment, and Surface-Treated Metal Material
WO2007065645A1 (de) 2005-12-09 2007-06-14 Henkel Ag & Co. Kgaa Nass in nass verfahren und chromfreie saure lösung zur korrosionsschutzbehandlung von stahloberflächen
US7749368B2 (en) 2006-12-13 2010-07-06 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated substrates
US20080254315A1 (en) 2007-01-19 2008-10-16 Nihon Hyomen Kagaku Kabushiki Kaisha Chromium-free solution for treating metal surfaces
US20090032144A1 (en) 2007-08-03 2009-02-05 Mcmillen Mark W Pretreatment compositions and methods for coating a metal substrate
EP2280094A1 (de) 2008-02-27 2011-02-02 Henkel AG & Co. KGaA Metallwerkstoff und herstellungsverfahren dafür
WO2009115504A1 (de) 2008-03-17 2009-09-24 Henkel Ag & Co. Kgaa Optimierte passivierung auf ti-/zr-basis für metalloberflächen
WO2011090691A2 (en) 2009-12-28 2011-07-28 Henkel Ag & Co. Kgaa Metal pretreatment composition containing zirconium, copper, zinc, and nitrate and related coatings on metal substrates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023275270A3 (de) * 2021-07-02 2023-03-09 Henkel Ag & Co. Kgaa Verfahren für den sequenziellen aufbau einer konversionsschicht auf bauteilen umfassend stahloberflächen

Also Published As

Publication number Publication date
WO2012078788A3 (en) 2012-09-27
ES2872342T3 (es) 2021-11-02
WO2012078788A2 (en) 2012-06-14
BR112013016613B1 (pt) 2021-04-27
CA2819524A1 (en) 2012-06-14
EP2649219A2 (de) 2013-10-16
CN103249867B (zh) 2016-04-20
BR112013016613A2 (pt) 2017-10-10
KR20130126658A (ko) 2013-11-20
MX2013006286A (es) 2013-07-15
JP2014504333A (ja) 2014-02-20
EP2649219A4 (de) 2017-12-06
CN103249867A (zh) 2013-08-14

Similar Documents

Publication Publication Date Title
EP2649219B1 (de) Metallvorbehandlungszusammensetzung mit zirkonium, kupfer und metallchelatbildner sowie deren beschichtungen auf metallsubstraten
US10094026B2 (en) Metal pretreatment composition containing zirconium, copper, and metal chelating agents and related coatings on metal substrates
EP1433875B1 (de) Mittel zur chemischen Konversionsbeschichtung und beschichtete Metalloberflächen
US8293334B2 (en) Preliminary metallizing treatment of zinc surfaces
EP1433876B1 (de) Chemisches Mittel zur Konversionsbeschichtung und beschichtete Metalloberflächen
US9970115B2 (en) Metal pretreatment composition containing zirconium, copper, zinc, and nitrate and related coatings on metal substrates
JP4201600B2 (ja) 金属表面の被覆方法および該方法により被覆した支持体の使用
EP0713541B1 (de) Zusammensetzung und verfahren zur behandlung von phosphatierten metalloberflächen
US20110300390A1 (en) Corrosion Resistant Metallate Compostions
JP4276530B2 (ja) 化成処理剤及び表面処理金属
JP2004218070A (ja) 塗装前処理方法
JP2005501173A (ja) リン酸塩被覆の適用方法および該方法によりリン酸塩被覆した金属部材の使用
GB2420565A (en) Surface conditioner and zinc phosphate treatment agent for aluminium alloys
JP2010090407A (ja) 金属表面処理液、および金属表面処理方法
KR20180053306A (ko) 지르코늄- 및 몰리브데넘-함유 조성물로의 알루미늄 표면의 전처리
JP4187162B2 (ja) 化成処理剤及び表面処理金属
EP1900846B1 (de) Verfahren und mittel zur chemischen umwandlungsbehandlung und einer chemischen umwandlungsbehandlung unterworfene elemente
WO2006098359A1 (ja) 表面処理金属材料
JP2004501280A (ja) 化成処理溶液に加える接合剤
CA2819523C (en) Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
JP2005325401A (ja) 亜鉛又は亜鉛系合金メッキ鋼材の表面処理方法
JPH10204649A (ja) 金属表面のりん酸塩処理水溶液及び処理方法
US20170137947A1 (en) Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
CA2840117C (en) Electrolytic plating of iron on zinc surfaces
JP2007314888A (ja) 多層塗膜構造

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: 20130611

AK Designated contracting states

Kind code of ref document: A2

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

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20171108

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/78 20060101AFI20171027BHEP

Ipc: C23C 22/73 20060101ALI20171027BHEP

Ipc: C23C 22/06 20060101ALI20171027BHEP

Ipc: C23C 22/80 20060101ALI20171027BHEP

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190617

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011070712

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: C23C0022780000

Ipc: C23C0022340000

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

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 22/78 20060101ALI20201104BHEP

Ipc: C23C 22/34 20060101AFI20201104BHEP

Ipc: C23C 22/73 20060101ALI20201104BHEP

INTG Intention to grant announced

Effective date: 20201203

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: 602011070712

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: AT

Ref legal event code: REF

Ref document number: 1382451

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210515

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1382451

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210414

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210414

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: 20210414

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: 20210414

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: 20210414

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: 20210414

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: 20210414

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: 20210714

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2872342

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20211102

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

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: 20210414

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: 20210714

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: 20210816

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: 20210414

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: 20210414

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: 20210414

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: 20210814

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: 20210715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011070712

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

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

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: 20210414

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: 20210414

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: 20210414

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: 20210414

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: 20210414

26 Opposition filed

Opponent name: PPG INDUSTRIES, INC.

Effective date: 20220114

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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: 20210814

Ref country code: AL

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: 20210414

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: 20210414

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: 20211207

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211231

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: 20211207

Ref country code: IE

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

Effective date: 20211207

Ref country code: GB

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

Effective date: 20211207

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

Ref country code: BE

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

Effective date: 20211231

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

Ref country code: LI

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

Effective date: 20211231

Ref country code: CH

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

Effective date: 20211231

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: 20111207

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

Effective date: 20210414

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

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

Ref country code: IT

Payment date: 20231228

Year of fee payment: 13

Ref country code: FR

Payment date: 20231221

Year of fee payment: 13

Ref country code: DE

Payment date: 20231214

Year of fee payment: 13

Ref country code: CZ

Payment date: 20231127

Year of fee payment: 13

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

Ref country code: ES

Payment date: 20240126

Year of fee payment: 13

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

Ref country code: MK

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: 20210414