EP2798098B1 - Zusammensetzung zur vorbehandlung einer aluminiumoberfläche, verfahren zur herstellung und verwendung der zusammensetzung, verwendung der zusammensetzung und produkt - Google Patents

Zusammensetzung zur vorbehandlung einer aluminiumoberfläche, verfahren zur herstellung und verwendung der zusammensetzung, verwendung der zusammensetzung und produkt Download PDF

Info

Publication number
EP2798098B1
EP2798098B1 EP12710647.4A EP12710647A EP2798098B1 EP 2798098 B1 EP2798098 B1 EP 2798098B1 EP 12710647 A EP12710647 A EP 12710647A EP 2798098 B1 EP2798098 B1 EP 2798098B1
Authority
EP
European Patent Office
Prior art keywords
acid
fluoro
composition
solution
aluminum
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
EP12710647.4A
Other languages
English (en)
French (fr)
Other versions
EP2798098A1 (de
EP2798098B8 (de
Inventor
Adeval Antonioa Meneghesso
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP2798098A1 publication Critical patent/EP2798098A1/de
Application granted granted Critical
Publication of EP2798098B1 publication Critical patent/EP2798098B1/de
Publication of EP2798098B8 publication Critical patent/EP2798098B8/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—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
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • the present invention relates to an aqueous solution used in the pre-treatment of aluminum and alloys thereof, in order to make their surface suitable for receiving the application of a selected painting system.
  • the present invention describes a composition free from chrome and toxic derivatives, as well as a method for preparing said composition, and still a method for applying it to an aluminum surface during the chemical treatment step.
  • the present invention relates also to the use of said composition and to a product the surface of which is treated with the composition described before.
  • Aluminum and alloys thereof have been used since 1886 and, although aluminum is the third most abundant chemical element on the earth's crust, its present-day production exceeds the sum of all the other nonferrous metals. Additionally, the techniques of manufacturing it enable the manufacture of the finished product at competitive prices, the main and most economical raw material for industrial use being the ore bauxite.
  • Products that use aluminum and alloys thereof incorporate the advantages inherent in this metal, such as lightness, electrical conductibility and thermal conductivity, impermeability and opacity, high strength/weigh relationship, beauty, durability, moldability and weldability, corrosion resistance and hardness, recyclability and possibility of a number of finishes.
  • Various segments use aluminum and alloys thereof in a form that is the most suitable for their purposes, taking advantage of the properties of this metal in receiving various types of treatment on its surface.
  • aluminum and products thereof can be applied in the segments of packages, transport, electricity, civil engineering, consumption goods, machines and equipment, among others.
  • aluminum and alloys thereof can be used with or without finishing processes, that is, for some applications the natural finish of aluminum is totally satisfactory, in both appearance and durability.
  • applications such as metallic sashes (doors, windows, façades, grids, shower boxes, etc.), furniture (kitchen cabinets, closets, bathroom closets, etc), consumption goods (ice-boxes, kitchen ranges, microwave apparatus, washing machines etc.), transport (open and closed bodyworks, van-type bodyworks, accessories, etc.), decoration articles (chandeliers, lamp-holders, mirrors, knobs, etc), among other applications, the aluminum surfaced requires adequate finish for protection and decoration.
  • the properties of aluminum do not enable adherence of paints directly on its surface.
  • an aluminum surface has to undergo a pre-treatment so that a conversion layer can be created, by means of a chemical treatment, in order to prepare the aluminum for paint adherence. If the pre-treatment is adequate, the paint will have good adherence without the risk of peeling upon cutting the aluminum borders.
  • said conversion layer is capable of providing high corrosion resistance.
  • the durability of the paint on an aluminum surface depends especially on the paint adherence and on the metal resistance to corrosion, and these properties can be imparted by the conversion layer formed during the pre-treatment.
  • the painting of an aluminum surface is carried out in the step of finishing the pre-treatment and it is very important for coating some products, mainly for the cases in which the metal is used for decoration and protection purposes.
  • the process of finishing an aluminum surface can be carried out in more than one way.
  • mechanical abrasion is considered a relevant process.
  • a special configuration of the parts to be treated creates difficulty for this technique. More specifically, with these types of parts there are dead angles, "shadows" that do not allow uniform access of the abrasion jet to all the points of the surface of a metallic piece. So, mechanical abrasion fails to achieve satisfactory homogeneity for subsequent application of a paint film onto the aluminum surface.
  • Another example consists in carrying out the abrasion by hand.
  • this technique has disadvantages like the high cost of labor and more time spent to achieve satisfactory abrasion.
  • Anodization too is among the processes of finishing an aluminum surface, by means of which a natural oxide film is artificially produced on the aluminum, by means of an electrolyte anode.
  • the newly formed anodic film, prior to the final stage of sealing, is porous and can absorb coloring material. This is the base of most anodized colored finishes and enables printing in determined areas, clearly reproducing small details.
  • this technique presents a high manufacture cost of the film formed, so that such a disadvantage makes the present application commercially unfeasible.
  • Anodization of natural coloration too is often employed to impart additional corrosion resistance.
  • the film is uniform and hard, and internal aluminum accessories, such as door knobs, are often anodized in order to enhance its resistance to wear.
  • This property is further exploited in hard anodization, wherein a dense film with thickness of several microns is developed by means of treatment in cooled electrolyte, for use on air-entry parts on aircrafts, which are subject to abrasive effects of dust from landing-strips.
  • this technique is one that has higher corrosion resistance, the high manufacture cost of the film formed makes this application commercially unfeasible.
  • the conversion layer formed is capable of both transforming an aluminum surface into a poor conductor and isolating the metallic surface of the paint film applied later.
  • the metallic surface remains conductive under the coating layer, so that the electric current flows freely between possible electrodes existing on the surface of the metal and further enables the occurrence of corrosion.
  • the pre-treatment has the objective of removing all the impurities present in the aluminum (antioxidant oils, lubricants, grease, metal oxides, etc.), so as to make the metallic surface receptive to the coatings that will be applied later.
  • a good cleaning process ensures a total physical contact between the aluminum surface and the pre-treatment solution for the formation of a conversion layer.
  • the protocol of leaning an aluminum surface consists in a sequence comprising the steps described in the Brazilian Norm - Norma Brasileira ABNT NBR 14125 of: i) degreasing; ii) first washing; iii) deoxidizing; iv) second washing; v) conversion/chromation; vi) third washing, vii) washing with demineralized water, and viii) drying, which are described in greater detail hereinafter.
  • the degreasing step (i) may be carried out with the aid of an alkaline solution or an acidic solution.
  • Degreasing via an alkaline solution takes place when the solution used is generally composed of a mixture of alkaline salts and one or more emulsifiers solubilized in water.
  • the chosen components should diminish the surface tension of water, in order to facilitate the removal and subsequent emulsification of oils and greases present, making them easily rinsable.
  • this alkaline solution is usually carried out by immersion, but the application by means of sprays becomes more efficient because it incorporates the detergent action of the cleaning alkaline solution into the mechanical action of the directed jets.
  • this degreasing should enable saponification or emulsion of the oils and greases previously present, ensure a perfect moldability of a metallic surface and eliminate the aluminum oxide that may be present.
  • Degreasing via an acidic solution takes place when the solution used is applied at room temperature, so as to promote the cleaning of the metallic surface from oils and greases present.
  • first, second and third washings are intended to remove the excess solutions of the preceding steps that may remain on the aluminum surface, thus preventing contamination of the subsequent steps by dipping the metallic surface into a water bath. These steps have fundamental importance, and the level of contamination of the washings should be controlled by means of continuous removal of water volume.
  • the deoxidizing step (iii) consists in removing the oxides existing on the aluminum surface, since they are undesirable for subsequent treatment.
  • a method is usually applied in the production line for verifying the level of cleaning of the metallic surface. This method consists in verifying whether the metallic surface is free from "water break", that is, whether the surface, after being wetted, presents a thin and continuous film of water throughout the surface. Although this test does not indicate the presence of hydrophilic impurities, it is still a good indication that the cleaning process was satisfactory.
  • the steps of conversion / chromation (v) with amorphous chromate comprises applying aqueous solutions of chrome trioxide (CrO3), containing adequate activating agents like fluorides.
  • CrO3 chrome trioxide
  • the aluminum surface is converted into an adherent and amorphous layer of mixtures of metallic oxides of iridescent-yellow to light brown color. This layer provides corrosion resistance, paint-film adherence and durability of the aluminum surface when painted.
  • This conversion process can be carried out by immersion or application of spray, at room temperature (21-32°C) in the interval of time from 15 seconds to 5 minutes.
  • the step of conversion/chromation (v) with chromophosphate (CrPO4) comprises treating the aluminum surface with aqueous solutions of phosphoric acid (H3PO4), fluorides and chrome trioxide (CrO3) adequately balanced.
  • the aluminum surface is converted into an adherent, thin amorphous layer of lightly greenish iridescent to non-iridescent more intense green color, depending on the alloy of the aluminum surface used.
  • This conversion process can be carried out by immersion or application of spray, at a temperature ranging from 20° to 45°C, in the interval of time from 15 seconds to 5 minutes.
  • the step of washing with demineralized water (vii) is similar to the steps of first, second and third washings. However, the conductivity of water at this stage should not exceed 30 microsiemens ( ⁇ S). By demineralized water one understands a volume of water from which all the mineral salts were removed.
  • the step of drying (viii) the metallic surface is effected with dry and hot air, at a temperature ranging from 65° to 70°C, so as to eliminate all moisture present.
  • the aluminum surface is ready to receive application of the coating system (paint) selected.
  • the paint is usually applied onto a conversion layer of zinc chromate, result of a chemical treatment process for protection purpose.
  • the conversion layer of lightly iridescent yellowish to light brown color makes it easy for the consumer to identify that the metal was treated before.
  • the aluminum chromate conversion is formed by applying a solution containing chrome and toxic derivatives thereof to the aluminum surface.
  • This solution could be considered effective in the past, when the effects of toxic substances like chrome and the irreparable damages caused to the human health and to the environment were unknown.
  • extensive researches have been carried out in this segment in order to try to find an efficient substitute for hexavalent chrome, used to form said conversion layer.
  • the aluminum surface undergoes the finish process and only after about twelve hours from application of the pain is it possible to see that the metal piece did not undergo any chemical treatment to prepare for receiving the coating.
  • Another disadvantage of obtaining aluminum parts without pre-treatment is that, in the absence of a chemical treatment, the metallic surface remains conductive under the coating layer, so that the electric current can flow freely between possible electrodes existing on the metal surface. Besides, the occurrence of corrosion on the metal that did not undergo an effective chemical treatment is markedly facilitated and the coating applied onto the metal fails to be effective in the long run.
  • US 6 193 815 B1 discloses Cr-free aqueous compositions for treating the surface of aluminiferous metals containing as components a flourinated inorganice acid, such as HF, H 2 TiF 6 , H 2 SiF 6 , H 2 ZrF 6 or H 2 HfH 6 , a titanium-containing substance and a water-soluble organoperoxide.
  • a flourinated inorganice acid such as HF, H 2 TiF 6 , H 2 SiF 6 , H 2 ZrF 6 or H 2 HfH 6
  • a titanium-containing substance such as a water-soluble organoperoxide.
  • the present invention has the main objective of providing a composition for pre-treatment of an aluminum surface.
  • the present invention also has the objective of providing a method for preparing and applying the composition onto an aluminum surface.
  • the present invention has the objective of achieving the use and obtaining a product with surface treated with the composition described before.
  • composition for pre-treatment of an aluminum surface comprising:
  • the objectives of the present invention are also achieved by means of a method for applying said composition, comprising the steps of degreasing, washing, deoxidizing, chemically treating, washing and drying.
  • the objectives of the present invention can be achieved by using the composition described above for the chemical treatment of an aluminum surface, and further by a product with its surface treated with said composition.
  • the present invention has the advantage of using a solution in the chemical treatment of aluminum, prepared with a composition totally free from chrome and toxic derivatives thereof, with capability of converting the aluminum surface into a brown-colored conversion layer that is visible to the naked eye, further capable of enhancing the adherence power of the paint on the aluminum surface, and with excellent corrosion resistance, which in turn surpasses easily the present-day levels of demand of the rules that govern the quality of the painted aluminum.
  • the present invention describes an innovator and sustainable solution to the chemical treatment of a surface of aluminum and alloys thereof, which, besides having a composition free from chrome and toxic derivatives, is capable of converting the aluminum surface into an adherent, amorphous conversion layer of brown colour, with possible variations in tons from bluish and/or yellowish.
  • the pre-treatment of the aluminum surface begins with the step of degreasing in alkaline medium, by using a product capable of dissolving and removing oils, greases and lubricants resulting from the extrusion of the aluminum, like the alkaline degreasing agent LL-CLEAN M12 produced by the company Italtecno do Brasil Ltda®.
  • Said product has surfactant properties capable of dissolving easily the magnesium-oxide film that tend to form on the aluminum surface.
  • the initial degreasing step should be optionally carried out in an acidic medium, using, for example, the acidic degreasing agent LL-TEDCNOCLEAN, produced by the company Italtecno do Brasil Ltda ® .
  • Said product is composed of an acidic solution of organic salts, capable of producing a light homogeneous attack on the aluminum surface in order to remove oils, greases and lubricants.
  • the preparation of the step of degreasing in an acidic medium is similar to that of degreasing in alkaline medium, wherein the water in the tank is heated up to a temperature ranging from 35°C to 55°C, and the LL-TECNOCLEAN solution, dissolved in water, is mixed in the tank until the desired concentration (preferably from 50g/L to 70g/L) is reached.
  • the aluminum should undergo an immersion bath in the tank with the homogenized mixture for the preferred period from 1 to 3 minutes.
  • the aluminum may also go through a spray bath.
  • the aluminum is led by means of a conveyor belt as far as a sort of tunnel that sprays onto the aluminum surface jets of the alkaline solution LL-CLEAN M12 or of the acidic solution LL-TECNOCLEAN, previously homogenized, in order to promote the removal of undesired constituents.
  • pre-treating the aluminum may be carried out by means of immersion bath or spray.
  • the choice of the type of bath for the surface may vary according to the type of industrial facility.
  • the degreasing step is completed, one then carries out the first washing of the aluminum bath, either by immersion or by spray, preferably with industrial running water, in order to remove excess product used in the degreasing step.
  • the volume of water should be constantly renewed in order to control the level of contamination.
  • the deoxidizing step is preferably carried out in an acidic medium, using, for instance, the product LL-DESMUT A 30, produced by the company Italtecno do Brasil Ltda ® , for the purpose of removing the oxides existing on the aluminum surface, which in turn are undesirable for carrying out the next steps.
  • the tank water is heated up to a temperature of about 20°C to 25°C, and the solution LL-DESMUT A 30, dissolved in water, is mixed in the tank until the desired concentration (preferably from 40g/L to 50g/L) is reached.
  • the aluminum undergoes an immersion bath or spraying in the tank with the homogenized mixture for the preferred period of from 1 to 3 minutes.
  • the deoxidizing step is optional when the pre-treatment of the aluminum is carried out with acidic degreasing agent. In this case, there is no need for neutralization.
  • a second washing with industrial running water is preferably carried out, either by immersion or by spraying, in order to remove the excess product used in the deoxidizing step.
  • a third washing preferably with demineralized water, should be carried out right after the second washing.
  • the demineralized water has the purpose and the capability of removing all the ions present on the aluminum surface.
  • the aluminum is now in a position to receive the aqueous solution of the present patent application, during the next chemical treatment step, in order to form a colorful conversion layer, visible to the naked eye and free from chrome and toxic derivative thereof.
  • composition of said aqueous solution is preferably prepared in three different steps, namely:
  • the source of molybdate, titanate or zirconate of alkali metal or alkaline earth metal or ammonia is chosen from the group consisting of sodium molybdate, potassium molybdate, fluoro ammonia molybdate acid, fluoro sodium molybdate, fluoro potassium polybdate, molybdic acid, hexafluoro titanic acid, hexa fluor potassium titanate acid, hexa fluoro sodium titanate acid, hexa fluoro ammonia titanate acid, hexa fluoro zirconium acid, hexa fluoro potassium zirconate acid, hexa fluoro sodium zirconate acid and hexa fluoro ammonia zirconate acid.
  • This first solution has the objective of releasing ions, which, in the end of the preparation of the composition, will be responsible for the corrosion resistance of the metallic surface, as well as for the visible coloration expected at the end of the application of the pre-treatment solution onto the aluminum surface.
  • the alkaline solution used for adjusting the pH is an ammonium hydroxide solution.
  • the pH of the solution should be adjusted for a slightly acidic pH, since the presence of acids may generate conversion, because they react directly with the aluminum surface. Then, the volume spent is written down as percentage (%).
  • the fluorinated inorganic acid used is a fluoro silicic acid, hexa fluoro zirconic acid or hexa fluoro titanic acid.
  • the fluorinated inorganic acid is fluoro silicic acid 30% or a hexa fluoro zirconium acid 45C%. These are the preferred sources of silicon and zirconium, respectively.
  • the employ of a source of fluorine has the function of reacting with the aluminum surface, since fluorine creates the conditions necessary to form the zirconium, silicon, molybdenum and aluminum complexes.
  • the solution obtained is cooled down to room temperature, and an oxidizing agent is added.
  • the final solution is left at rest for 12 hours, so that an oxidizing medium is formed in order to complete the reactions. During this period of rest, the decantation of possible solid particles in suspension takes place.
  • the alkaline solution used to adjust the pH of the solution is an ammonium hydroxide solution.
  • the source of oxidizing agent is a hydrogen peroxide or organic peroxides.
  • an oxidizing agent has the function of making the reaction that takes place on the aluminum surface feasible, imparting stability to the compound.
  • the deficiency or excess oxidizing agent may favor an unfavorable condition for the reaction, so that an undesired complex may be formed.
  • the aqueous solution disclosed in the present application should be added in a tank at a percentage of about 45 g/L to 50 g/L and kept at a temperature ranging from 20°C to 30°C.
  • the pH of the solution should be monitored and kept between about 5.0 and 6.0. Then, the aluminum undergoes a bath, either by immersion or by spraying, for 1 to 3 minutes in the final solution previously adjusted in the operational conditions described, immediately promoting the formation of a conversion layer in the brownish colour, visible to the naked eye, totally free from chrome and toxic derivatives thereof.
  • the aluminum surface undergoes a new washing, preferably with demineralized water, in order to remove the excess aqueous solution used in the chemical treatment step, and then the pre-treatment of the aluminum is finished with the step of drying the surface with dry air at a temperature ranging from 65°C to 70°C.
  • the objective of drying is to eliminate the whole moisture present on the aluminum surface, so that the aluminum will be in an appropriate position to receive the application of the coating process (paint) selected.
  • the Brazilian rules are in conformity with the international rules like QUALICOAT - Quality Label for the Coating of Aluminum and AMMA - American Materials Manufacturing Alliance.
  • Such Brazilian rules impart quality to the application of an organic paint film onto the conversion layer formed on the aluminum surface, as follows.
  • ABNT NBR 14125 Treatment of surface - Organic coating for architectural purpose - Requirement
  • This rule specifies the requirements for organic coating for architectural purposes, by painting, for the treatment of aluminum surface and alloys thereof.
  • the pre-treatment of the aluminum should be composed by one of more of the following steps: degreasing; neutralization and conversion film (constituted by chromation/phosphocromation or anodization).
  • the pre-treated parts should not be stored for over 16 hours and, preferably, should be coated immediately after the pre-treatment, because the risk of loss of adherence increases as time passes.
  • the storage area should be kept in good atmospheric conditions, free from dust.
  • the handling of the pieces should be made with clean cloth gloves, in order to prevent contamination of the surface.
  • the final product should be within the parameters of thickness of the organic coating; brightness; impact resistance; flexibility; adherence; wet adherence; graphite hardness; resistance to artificial wearing causes; natural weathering causes; accelerated corrosion; acetic saline fog; finish and sampling.
  • ABNT NBR 15144 Aluminum and alloys thereof - Surface treatment - origanic coating of plates for architectonical purposes
  • base-plate For the purposes of this rule, by "base-plate” one understands a plate with specific finish of the lamination rollers.
  • the tests plates should meet the requirements of organic coating; resistance to corrosion by exposure to saline fog; brightness; impact resistance; adherence; graphite hardness; resistance to artificial wearing causes; bending; cure; surface aspect of the coating; sampling and marking.
  • For acceptance of the batch one measures the three test specimens. If the measurement does not meet the above-specified value, the batch should be rejected.
  • the solution of the present patent application meets the quality-parameter rules NB R 14125 and NBR 15144, as well as the requirements defined by the qualitative tests described in the following rules.
  • ABNT NBR 14901 Treatment of aluminum surfaces and aluminum alloys-determination of the accelerated corrosion resistance - Machu test of the organic coating of paints and varnishes
  • This rule prescribes the method for determining and evaluating accelerated corrosion resistance by the Machu test method, of dried organic films applied to powder and/or liquid of paints and varnishes on laminated plate products and profiles extruded from aluminum and alloys thereof, with surface pre-treatment.
  • test parameters should provide the following conditions:
  • the pH of the solution should range from 3.0 to 3.3. After 24 hours, one should add a further 5m/L of hydrogen peroxide (H 2 O 2 30%) and correct the pH with glacial acetic acid or caustic soda. For each test, it is necessary to prepare a new solution. In the results achieved, no infiltration may exceed 0.5 mm for either side of the incision.
  • H 2 O 2 30% hydrogen peroxide
  • ABNT NBR 14682 Aluminum and its alloys - surface treatment - determination of the moisture resistance of coating - pressure-cooker method
  • This rule specifies the pressure-cooker method for determining the wet adherence of electrophoretic coatings and paints to powder on aluminum and alloys thereof.
  • the test should be carried out with demineralized water at 20°C, used as a reactant, with maximum conductivity of 10 ⁇ S. Cut the tests specimen in length of 500mm ⁇ 5 mm and width larger than 25mm, as long as it fits into the pan body.
  • the test should be carried out at least 1 hour after polymerization. Pour water into the pressure cooker until it reaches the height of 25mm ⁇ 3mm of the test specimen to be tested. Place the pan lid on and heat it until water vapor begins to escape. Adjust the pressure-controlling valve so as to guarantee internal pressure at 100 fluorine ⁇ 10 fluorine. Continue to heat for 1 hour from the moment of the first vapor escape. Eliminate totally the inner pressure of the pan, remove the test specimen and allow it to cool down to room temperature. Apply the adhesive tape to the surface of the test specimen, making sure that no air will be trapped. After 1 minute, pull the tape by hand at an angle of about 45 degrees with strong and uniform traction.
  • the rule specifies methods for determining adherence to any type of paint applied to aluminum surfaces and alloys thereof through the X-cut and the grid-cut, with one or more application layers.
  • the determination of the thickness should be carried out after 1 hour from polymerization, and then one should select an area for determining the adherence (as flat as possible) free from imperfections, clean and dry. Measure the thickness of the pain of the area where the adherence will be determined, with the dry-film thickness meter, at least at five different places, making three to five individual readings at each place. The arithmetic mean of the individual reading at one measurement point is considered the thickness of the total area. For paints with thickness of up to 80 ⁇ m (inclusive), use either the X-cut method or the grid-cut method. For paint with over 80 ⁇ m up to 600 ⁇ m (inclusive), use the X-cut method.
  • the result achieved should be within the graphic parameters defined by the present rule, so that the expression of the results should be analyzed in accordance with the cut made.
  • ABNT 1490 Treatment of aluminum surface and alloys thereof - determination of the resistance to corrosion by exposure to acetic saline fog of the organic coating of paints and vanishes
  • This rule prescribes the method for determination and evaluation of the corrosion resistance, by exposure to acetic saline fog of dry organic films applied to powder and/or liquid of paints and varnishes on laminated-place products and profiles extruded from aluminum and alloys thereof, with pre-treatment of surface.
  • test should be carried out on three test specimens of plates and profiles extruded from aluminum or alloys thereof, and fixed within the test chamber with a rigid plastic material, for 1000 hours. Make a cross-incision (90 degrees), with width of 1 mm and length of 100mm, on the surface of the test specimen to be evaluated, until the metal is reached.
  • the test-specimen surface to be evaluated should be preferably parallel to the horizontal flow of fog, in order to prevent direct impact of the latter onto the surface.
  • Flat test specimens should be placed at angles of 15 degrees to 30 degrees with the vertical. In the case of pieces with complex shapes, this positioning should be made considering the region to be evaluated.
  • the result achieved by means of the infiltrations on the test specimens should not exceed 4mm for either of the incision sides and the result of the batch should be classified in accordance with the table of result classification described by the present rule.
  • composition discloses by the present invention can be better understood by means of the following non-limiting embodiment, wherein its advantages can be proven by the fact that it meets efficiently the above-cited Brazilian rules.
  • composition of said aqueous solution for pre-treatment of aluminum surface is prepared in three different steps, as described hereinafter.
  • the final solution was allowed to cool until room temperature ranging from 20°C to 25°C was reached. Then, one added 0.13% of hydrogen peroxide 130 vol. The total amount of ammonium hydroxide volume 1:1 by percentage (%) used to adjust the pH was subtracted from the percentage value (%) of the demineralized water necessary for completing 100% of the final product. The final solution obtained remained at rest for 12 hours.
  • the previously prepared aqueous solution was added to a tank at a concentration from 45 g/L to 50g/L, and kept under a temperature ranging from 20°C to 30°C with pH controlled between 5.0 and 6.0. Then, the aluminum underwent an immersion bath in said aqueous solution for 3 minutes, so that a conversion layer of brownish color, clearly visible to the naked eye was immediately formed on its surface.
  • the aluminum surface was then tested as determined by the qualitative tests described in the Brazilian rules relating to the quality of painted aluminum and alloys thereof, and the efficiency of the colored conversion layer formed by using the composition of the present application was proven, totally free from chrome and toxic derivatives thereof, with a high corrosion resistance and completely apt for receiving the coating (paint) selected.

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)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (12)

  1. Zusammensetzung zur Vorbehandlung einer Aluminiumfläche, dadurch gekennzeichnet, dass es sich um eine wässrige Lösung handelt, die folgende Bestandteile aufweist:
    a) von 2 Gew.-% bis 10 Gew.-% einer fluorierten anorganischen Säure;
    b) von 2 Gew.-% bis 10 Gew.-% eines Molybdats, Titanats oder Zirkonats eines Alkalimetalls oder Erdalkalimetalls oder Ammoniaks, optional in der Form eines Fluorsäurederivats; und
    c) von 0,02 Gew.-% bis 0,2 Gew.-% eines Wasserstoffperoxids oder organischen Peroxidoxidationsmittels;
    wobei der prozentuale Anteil der Bestandteile in wässriger Lösung an dem Gesamtgewicht im Bereich von 4,02 % bis 20,2 % liegt.
  2. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, dass die fluorierte anorganische Säure Kieselfluorsäure, Hexafluorzirkoniumsäure oder Hexafluortitansäure ist.
  3. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, dass das Molybdat, Titanat oder Zirkonat eines Alkalimetalls oder Erdalkalimetalls oder Ammoniaks ausgewählt ist aus der Gruppe bestehend aus Natriummolybdat, Kaliummolybdat, Fluorammoniummolybdatsäure, Fluornatriummolybdatsäure, Fluorokaliummolybdatsäure, Molybdänsäure, Hexafluortitansäure, Hexafluorkaliumtitanat, Hexafluornatriumtitanat, Hexafluorammoniumtitanatsäure, Hexafluorzirkoniumsäure, Hexafluorkaliumzirkonatsäure, Hexafluornatriumzirkonatsäure und Hexafluorammoniumzirkonatsäure.
  4. Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, dass sie entmineralisiertes Wasser aufweist.
  5. Verfahren zur Herstellung der Zusammensetzung, wie sie in einem der Ansprüche 1 bis 4 definiert ist, dadurch gekennzeichnet, dass es folgende Schritte aufweist:
    a) Herstellen einer Lösung Nr. 1, das das Lösen von Molybdat, Titanat oder Zirkonat eines Alkalimetalls oder Erdalkalimetalls oder Ammoniak, optional in der Form eines Fluorsäurederivats, umfasst;
    b) Herstellen einer Lösung Nr. 2, das das Neutralisieren der fluorierten anorganischen Säure umfasst, bis ein pH-Wert von 4,5 erreicht ist;
    c) Herstellen der Endlösung, das das Mischen der Lösung Nr. 1 mit der Lösung Nr. 2 und das Neutralisieren des Mediums, bis ein pH-Wert von 5,0 bis 5,8 erreicht ist, schließlich das Hinzufügen des Wasserstoffperoxids oder organischen Peroxidoxidationsmittels, umfasst.
  6. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass in Schritt (a) das Molybdat, Titanat oder Zirkonat eines Alkalimetalls oder Erdalkalimetalls oder Ammoniaks in entmineralisiertem Wasser gelöst wird.
  7. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, dass in den Schritten (b) und (c) die Neutralisierung zur Anpassung des pH-Wertes mit einer Ammoniumhydroxidlösung durchgeführt wird.
  8. Verfahren zur Anwendung der Zusammensetzung, wie sie in einem der Ansprüche 1 bis 4 definiert ist, dadurch gekennzeichnet, dass es die Schritte des Entfettens, Waschens, Desoxidierens, der chemischen Behandlung, des Waschens und Trocknens umfasst.
  9. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, dass die Zusammensetzung während des Schrittes der chemischen Behandlung angewendet wird.
  10. Verfahren gemäß Anspruch 8, dadurch gekennzeichnet, dass in sämtlichen Schritten das Baden der Aluminiumfläche durch Immersion oder Sprühen durchgeführt wird.
  11. Verwenden einer Zusammensetzung, wie sie in einem der Ansprüche 1 bis 4 definiert ist, dadurch gekennzeichnet, dass sie für eine chemische Behandlung einer Aluminiumfläche vorgesehen ist.
  12. Produkt, dadurch gekennzeichnet, dass dessen Fläche mit der Zusammensetzung behandelt ist, wie sie in einem der Ansprüche 1 bis 4 definiert ist.
EP12710647.4A 2011-12-29 2012-02-28 Zusammensetzung zur vorbehandlung einer aluminiumoberfläche, verfahren zur herstellung und verwendung der zusammensetzung, verwendung der zusammensetzung und produkt Active EP2798098B8 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI1105661-4A BRPI1105661B1 (pt) 2011-12-29 2011-12-29 Composição para o pré-tratamento de uma superfície de alumínio, método para preparar a composição e uso da composição
PCT/BR2012/000049 WO2013097002A1 (en) 2011-12-29 2012-02-28 A composition for pre-treatment of an aluminum surface, a method for preparing and applying the composition, use of the composition and a product

Publications (3)

Publication Number Publication Date
EP2798098A1 EP2798098A1 (de) 2014-11-05
EP2798098B1 true EP2798098B1 (de) 2015-10-14
EP2798098B8 EP2798098B8 (de) 2015-12-30

Family

ID=45887843

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12710647.4A Active EP2798098B8 (de) 2011-12-29 2012-02-28 Zusammensetzung zur vorbehandlung einer aluminiumoberfläche, verfahren zur herstellung und verwendung der zusammensetzung, verwendung der zusammensetzung und produkt

Country Status (4)

Country Link
EP (1) EP2798098B8 (de)
AR (1) AR085405A1 (de)
BR (1) BRPI1105661B1 (de)
WO (1) WO2013097002A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893732A (zh) * 2018-07-28 2018-11-27 广州市杰裕联环保技术有限公司 强耐腐蚀性环保薄膜钝化方法及其钝化液
CN109574292A (zh) * 2018-10-31 2019-04-05 徐州瑞马智能技术有限公司 一种助剂处理系统和方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025640A1 (en) * 1993-04-28 1994-11-10 Henkel Corporation Composition and process for imparting a bright blue color to zinc/aluminum alloy

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5603754A (en) * 1993-07-05 1997-02-18 Henkel Corporation Composition and process for treating tinplate and aluminum
US6193815B1 (en) * 1995-06-30 2001-02-27 Henkel Corporation Composition and process for treating the surface of aluminiferous metals
EP1144707B1 (de) * 1998-12-15 2006-03-01 Lynntech, Inc. Polymetallat und heteropolymetallat zur passivierungsbeschichtung metallischer oberflächen
TW567242B (en) * 2002-03-05 2003-12-21 Nihon Parkerizing Treating liquid for surface treatment of aluminum or magnesium based metal and method of surface treatment

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025640A1 (en) * 1993-04-28 1994-11-10 Henkel Corporation Composition and process for imparting a bright blue color to zinc/aluminum alloy

Also Published As

Publication number Publication date
BRPI1105661A2 (pt) 2013-10-08
EP2798098A1 (de) 2014-11-05
WO2013097002A8 (en) 2014-05-08
AR085405A1 (es) 2013-09-25
BRPI1105661B1 (pt) 2020-03-24
EP2798098B8 (de) 2015-12-30
WO2013097002A1 (en) 2013-07-04

Similar Documents

Publication Publication Date Title
CN101048277B (zh) 制成制品和在有机或无机涂层之前用陶瓷氧化物阳极氧化涂覆铝基底的方法
US3695942A (en) Zirconium rinse for phosphate coated metal surfaces
US4191596A (en) Method and compositions for coating aluminum
US4273592A (en) Coating solution for metal surfaces
CA2642365C (en) Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces
RU2421545C2 (ru) Способ получения хорошо различимого визуально нехроматного конверсионного покрытия для магния и магниевых сплавов
MXPA04008513A (es) Liquido de tratamiento para tratamiento de superficie de metal a base de aluminio o magnesio y metodo de tratamiento de superficie.
CN101429661B (zh) 连续热浸镀锌钢板用的钼酸盐钝化液
US4110129A (en) Post treatment of conversion-coated zinc surfaces
WO2014140857A2 (en) Improved trivalent chromium-containing composition for aluminum and aluminum alloys
US3850732A (en) Zirconium rinse for phosphate coated metal surfaces
JPH11335865A (ja) 金属の保護皮膜形成用処理剤と形成方法
NO873904L (no) Sjiktdannende passivering ved multimetallfremgangsmaate.
EP2798098B1 (de) Zusammensetzung zur vorbehandlung einer aluminiumoberfläche, verfahren zur herstellung und verwendung der zusammensetzung, verwendung der zusammensetzung und produkt
Ogle et al. Phosphate conversion coatings
CA2651476A1 (en) Method and composition for forming a coloured coating on a metallic surface
JP2005325401A (ja) 亜鉛又は亜鉛系合金メッキ鋼材の表面処理方法
JPH04507436A (ja) 亜鉛メッキスチールにマンガン含有燐酸亜鉛層を形成する方法
US20100181201A1 (en) Electrolytic passivated tin plated steel
CN105441927A (zh) 冷轧钢板·镀锌钢板辊涂涂装前无铬钝化剂及制备方法
JP5428105B2 (ja) マグネシウム合金用黒色化成処理液、化成処理方法及び化成処理部材
US3723162A (en) Pretreatment of metal surfaces
US3447972A (en) Process and compositions for producing aluminum surface conversion coatings
JP3737168B2 (ja) 高白色で塗装性に優れた電気亜鉛めっき鋼板の製造方法
Pereira et al. Assessment of chemical conversion coatings for the protection of aluminium alloys

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: 20140708

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

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

INTG Intention to grant announced

Effective date: 20150417

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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: AT

Ref legal event code: REF

Ref document number: 755135

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151015

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012011531

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20151014

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 755135

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151014

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: 20151014

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: 20151014

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: 20151014

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: 20151014

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: 20160214

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: 20160114

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: 20151014

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: 20151014

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: 20151014

Ref country code: BE

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

Effective date: 20160229

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: 20151014

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: 20160215

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: 20151014

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: 20151014

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012011531

Country of ref document: DE

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: 20151014

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: 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: 20151014

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: 20151014

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: 20151014

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: 20151014

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: 20151014

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602012011531

Country of ref document: DE

26N No opposition filed

Effective date: 20160715

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

Effective date: 20160228

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: 20151014

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: 20160228

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: 20160229

Ref country code: CH

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

Effective date: 20160229

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20161028

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: 20151014

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Effective date: 20151014

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: 20160229

Ref country code: DE

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

Effective date: 20160901

Ref country code: IE

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

Effective date: 20160228

Ref country code: GB

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

Effective date: 20160228

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

Ref country code: MT

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: 20151014

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: 20120228

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

Ref country code: MT

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: 20160229

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: 20151014

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: 20151014

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: 20151014

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

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: 20151014

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

Ref country code: TR

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: 20151014

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: 20151014

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

Ref country code: IT

Payment date: 20230206

Year of fee payment: 12