[go: up one dir, main page]

EP3084035B1 - Procédé de fabrication de surfaces en acier inoxydable colorées - Google Patents

Procédé de fabrication de surfaces en acier inoxydable colorées Download PDF

Info

Publication number
EP3084035B1
EP3084035B1 EP14780490.0A EP14780490A EP3084035B1 EP 3084035 B1 EP3084035 B1 EP 3084035B1 EP 14780490 A EP14780490 A EP 14780490A EP 3084035 B1 EP3084035 B1 EP 3084035B1
Authority
EP
European Patent Office
Prior art keywords
stainless steel
coating
sol
colored
transparent
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
EP14780490.0A
Other languages
German (de)
English (en)
Other versions
EP3084035A1 (fr
Inventor
Olaf Boehme
Siegfried Piesslinger-Schweiger
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.)
Sepies GmbH
Original Assignee
Sepies GmbH
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 Sepies GmbH filed Critical Sepies GmbH
Priority to EP14780490.0A priority Critical patent/EP3084035B1/fr
Publication of EP3084035A1 publication Critical patent/EP3084035A1/fr
Application granted granted Critical
Publication of EP3084035B1 publication Critical patent/EP3084035B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007—After-treatment

Definitions

  • the present invention relates to a process for producing colored stainless steel surfaces having high durability and a wide range of uses, as well as articles or stainless steel having such surfaces.
  • stainless steels are widely used in both technical and decorative applications.
  • decorative applications such as architecture, interior design, furniture, paneling, kitchen equipment and automotive and railway construction is increasingly the desire loud colored stainless steel surfaces. These should not appear "painted or enamelled", but preserve their stainless steel character and have at least equivalent performance and corrosion resistance compared to non-colored surfaces.
  • Stainless steel which is often referred to as stainless steel, is an iron alloy which, in addition to iron, may contain a number of other alloying elements such as chromium, nickel, molybdenum copper and others.
  • An essential component of the stainless steel alloys is the element chromium, which is present in a minimum concentration of about 13 wt .-%, to ensure increased corrosion resistance of the steel.
  • the chromium that is present in the alloy reacts with oxygen from the environment and forms a dense oxide layer on the surface, which protects the surface from corrosion (so-called passive layer).
  • passive layer The quality and thus the corrosion resistance of passive layers depend on their structure and their content of chromium oxides and iron oxides. This is controlled classically by the concentration of alloying elements in the stainless steel.
  • WO 2008/107082 It is also possible to subsequently optimize passive layers by treatment in an aqueous solution containing a special combination of chelating agents and complexing agents with regard to their resistance to corrosion and thermal discoloration.
  • the WO 02/50330 A2 discloses a method for refining metallic surfaces to avoid thermal tarnish colors. This goal can be achieved, for example, by first mechanically and / or chemically roughening a metallic surface to be coated and then carrying out a so-called sol-gel process.
  • the WO 2008/107082 relates to a method for improving the temperature and corrosion resistance of stainless steel by a special passivation process.
  • the stainless steel is treated with an aqueous solution comprising a complexing agent combination and at least one oxidizing agent.
  • the EP 2 182 095 A1 describes a process for surface treatment of stainless steel. In this process, thermal oxide layers on the stainless steel are contacted with a composition which causes iron ions to be dissolved out of the oxide layer.
  • Coating layers consist of an organic matrix enriched with pigments as desired.
  • Paints consist either of resins which are thinned with solvent and thus rendered paintable or sprayable. After application, the solvents evaporate, which solidifies the paint layers.
  • Two-component paints consist of synthetic resins, which are mixed with a reactive substance (hardener) shortly before application, resulting in a polymerization process that solidifies the paints.
  • Powder coatings consist of plastic powders which are electrostatically applied to the metal surfaces to be painted and then thermally baked.
  • the powder layers are heated to temperatures in the range of 200 ° C to 250 ° C, whereby they melt and form a dense, smooth and closed layer on cooling.
  • Coating layers are not very well suited for the production of colored stainless steel surfaces for several reasons: Due to the chromium oxide layer on stainless steel surfaces, the necessary adhesion of the paint layers on the surfaces is generally not given, so that they tend to peel off again. When used outdoors, with the surfaces exposed to sunlight, the organic paints and pigments are attacked and destroyed by the UV rays in sunlight. The paints become brittle and cracked and the pigments fade. Coating layers have a significantly greater thickness compared to the layers according to the invention. They level the surfaces, and the metallic character and texture of stainless steel surfaces are lost. The gloss of lacquer layers is caused and determined by the gloss of the surfaces of the lacquers and not by the metal surfaces. Metallic paints contain metal particles that create the metallic effect.
  • lacquers are not advantageous in the production of colored stainless steel surfaces and are therefore not used.
  • a chemical reaction of the metal with the chemicals in the bath over time forms a transparent chromium oxide layer of increasing thickness.
  • the respective thickness of the layer determines the color effect. This is due to interference of the incident and reflected light on the surface similar to an oil film on water.
  • the colors essentially correspond to the spectral colors and change with the viewing angle, so that large surfaces can be perceived uniformly only from a sufficiently large distance.
  • Chemically colored stainless steel surfaces do not show a metallic sheen, but absorb up to 80% of the incident light and convert it into heat, so they look dark inside rooms and heat up significantly in the sunshine.
  • the temperature resistance is limited to approx. 180 ° C. At higher temperatures, the color effect is lost.
  • the rate of layer growth can not be actively controlled and is determined by the exact composition of the alloy and microstructure, the surface condition of the stainless steel and the temperature and composition of the dip bath. Smallest local deviations lead to differently rapid layer growth and thus to color deviations within the surfaces.
  • Components consisting of two or more components are not uniformly colored by this method, as are deformed surfaces. Due to this, the method is only suitable for the treatment of semi-finished products such as sheets before further processing. Neither the exact colors that are created, nor the color depth or repeatability in the series are to control. In addition, the required chromium content in the alloy and the required homogeneity of the surface state of the dyeing ability set clear limits.
  • Colored sol-gel layers have the following disadvantages according to the prior art: Sol-gel layers must be baked after application to ceramicize. The temperatures used for baking are in the range of 220 ° C to 400 ° C for a period of at least 30 minutes. Under these conditions, yellow or brownish discolorations of the surfaces occur in stainless steel. Transparent sol-gel layers on stainless steel can not be produced without discoloration of the surfaces according to the prior art without special pretreatment of the surfaces. Opaque colored layers are possible. They have a relatively high layer thickness, cover the discoloration of the stainless steel surfaces and look similar in appearance to enamel. A corresponding procedure is in the DE 197 15 940 described. Such surfaces do not meet the requirements of the market and are therefore not accepted.
  • the present invention relates to a process for producing colored stainless steel surfaces having high durability and a wide range of uses, as well as articles having such stainless steel surfaces.
  • the term "colored” here means that the color of the surface differs from the color of untreated stainless steel, for example, the surfaces in all achievable by inorganic pigments and their mixtures colors such as blue, brown, red, green, yellow, white, gray or black, wherein the metallic luster and structure is created by the stainless steel surface with its passive layer underlying the colored layer.
  • the colored stainless steel surfaces produced according to the invention have, on a chemically optimized passive layer, a transparent, glass-ceramic coating which contains inorganic (usually non-transparent) colored pigments and was produced by thermal curing of a sol-gel coating.
  • the first step is to treat the natural stainless steel surface on the stainless steel surface with an aqueous solution containing a special combination of chelating and chelating agents to give the surfaces the necessary resistance to thermal discoloration.
  • the next step for example, by spraying, spraying or rolling a transparent silica-based sol-gel coating applied and then thermally cured, wherein the layer thickness of the sol-gel coating during application is selected so that the finished sol-gel coating after thermal curing has a layer thickness of preferably 1 to 3 microns.
  • the coating contains inorganic color pigments, which are deliberately introduced and distributed in arrangement and number in a manner that causes special color and gloss effects.
  • the diameter of the color pigments is preferably less than 1 ⁇ m and thus regularly below the thickness of the sol-gel layer.
  • the usual diameters of the color pigments are in a range of 500 to 1500 nm.
  • the number and distribution of the pigments per coated unit area is variable and is chosen so that the underlying stainless steel surfaces are not completely covered by the pigments and in substantial proportions by the transparent Coating remain visible. On the one hand this gives the surfaces colors with selectable color depth combined with the original metallic luster and the surface structure of the stainless steel surfaces.
  • the surfaces according to the invention are colored, transparent reflective, inorganic, resistant to UV radiation and temperatures up to 400 ° C and corrosion. They are food-safe, water and dirt repellent and have anti-graffiti and anti-fingerprint properties.
  • the invention relates to colored stainless steel surfaces, which overcome the disadvantages of the previous colored stainless steel surfaces and have significantly improved properties in terms of color design and usability, and a method for producing such colored stainless steel surfaces and objects with these colored stainless steel surfaces.
  • articles of stainless steel can be completely or partially dyed.
  • the entire surfaces or only certain areas of the surfaces can be colored.
  • reference to a "surface to be colored” is therefore always to be understood in such a way that the surface to be colored can be arranged on different surfaces of the stainless steel article or can only represent specific locations of one or more surfaces thereof.
  • the colored stainless steel surfaces according to the invention are first conditioned by pretreatment in such a way that they are insensitive to thermal discoloration by temperatures up to 300 ° C.
  • This pretreatment is carried out in an aqueous solution containing the multidentate complexing agents, preferably a mixture of chelating agents and complexing agents, to remove iron oxides and iron atoms from the passive layer on the stainless steel surface, as exemplified in the patent application WO 2008/107082 A1 , Reference is made in particular to the in WO 2008/107082 A1 described aqueous solutions with complexing agents and the method for their use, which are also suitable for the inventive method.
  • the conditioned surfaces i. the treated passive layer, a transparent silica sol-gel coating applied with a layer thickness of preferably 0.5 to 5.0 microns, preferably from 1 to 3 microns.
  • the type of coating is chosen so that it is transparent and has a baking temperature below 300 ° C, preferably from 200 ° C to 250 ° C, so that the stainless steel surface does not discolour during baking.
  • the selected sol-gel coating must have sufficient resistance to chemicals, temperature and corrosion. It must be permanently resistant to temperatures up to 400 ° C and in the salt spray test to withstand at least 200 hours load without damage.
  • the sol-gel coating contains inorganic pigments, with a diameter of 500 to 1500 nm, whereby the colors are freely selectable.
  • An essential property of the pigments is the size of the pigment grains. It should preferably be smaller than 1 ⁇ m in diameter.
  • the size of the pigments can be adjusted by prior comminution, for example by a ball mill, and secured by filtration. This can ensure that later all the pigment particles are trapped in the sol-gel layer and sufficiently covered to protect it from corrosive attack. Furthermore, this ensures that the properties of the colored glass-ceramic coating are determined exclusively by the cured sol-gel itself and the pigments have no influence on the performance characteristics of the colored coatings.
  • the defined size of the pigment granules allows a uniform distribution of the pigments on the surfaces to be coated in the coating process and improves the scattering of the incident light and the light reflected from the underlying stainless steel surface and increases the optical intensity of the colors.
  • the amount and distribution of the pigment grains during application of the sol-gel layers are chosen such that they do not completely cover but completely cover the underlying stainless steel surfaces and the latter are still partially uncovered and visible with their own luster and their structure. This preserves the metallic character of the coated surfaces.
  • pigment grains per unit area color depth and color intensity are freely selectable in a wide range, ranging from stainless steel surfaces with a slight color glimmer to intensely colored surfaces with metallic sheen.
  • the density and / or the distribution of the inorganic color pigments make possible a uniform arrangement of these pigments in the coating.
  • the metal surface between the pigment particles still remains partially visible, so that the coated stainless steel surface still has a metallic luster.
  • the process of the invention results in extensive and spontaneous separation of pigments and coating material.
  • it may then come to a sedimentation of the pigments to the metal surface. This sedimentation takes place immediately after application of the coating material, whereby the coating solidifies at the same time or immediately thereafter by evaporation of the solvent contained in the coating material.
  • a transparent, smooth cover layer of the sol-gel material is then obtained over the pigments.
  • this sol-gel coating also exerts a protective function against the pigments, which are no longer directly vulnerable to environmental influences (including corrosion).
  • the invention thus relates to a process for producing a transparent colored coated stainless steel surface, as specified in more detail in claim 1 and the claims which follow.
  • the invention further provides a provided with a transparent colored coating stainless steel, as set forth in more detail in claim 8.
  • Passive layer refers to the oxide layer that forms on a stainless steel surface. This oxide layer is colorless, transparent and consists mainly of iron oxides and chromium oxides.
  • transparent colored Stainless steel surface means that a color impression is generated by inorganic pigments in the glass-ceramic coating, but - at locations where there are no pigments - light rays can fall through the glass-ceramic coating on the underlying stainless steel surface and are reflected by this again so that a metallic impression is created.
  • Stainless steel preferred according to the invention consists mainly of iron and contains at least 13% by weight of chromium.
  • a limitation of the chromium content upwards is not given as well as with regard to other alloying elements such as nickel, molybdenum, manganese, silicon, copper, sulfur or phosphorus.
  • Stainless steel according to the invention may have both an austenitic, ferritic or martensitic structure and also a ferritic-austenitic mixed structure (duplex structure).
  • stainless steels are materials with material numbers beginning with 1.4.
  • the stainless steel surfaces to be dyed can have different gloss levels and structures by processing before dyeing.
  • Such pre-processing methods are, for example, grinding, blasting, mechanical or electrolytic polishing, patterning or pickling.
  • the stainless steel may be used as material / starting material, e.g. as steel sheet, or product, e.g. as part of a finished structure.
  • the surface of the stainless steel to be colored should not be coated and, in particular, should be clean, free of grease and not corroded.
  • existing coatings or corrosion products may be removed mechanically or chemically prior to application of the process of the present invention.
  • the cleaning can be carried out, for example, in an alkaline decoction degreasing (for example with AK 161 from Schlötter), followed by rinsing the surface with water and drying.
  • alkaline decoction degreasing for example with AK 161 from Schlötter
  • the surfaces to be dyed are immersed in an aqueous solution containing a specific combination of organic chelating and complexing agents for a period of preferably 1-4 hours, more preferably 3-4 hours, as in the patent WO 2008/107082 A1 and described herein. If appropriate, then a rinsing step with water. By this treatment, the resistance of the stainless steel surfaces against thermal discoloration is raised so much that the subsequent thermal curing of the sol-gel layers no discoloration of the bare stainless steel surfaces occurs.
  • the type and amount of the complexing agents in the aqueous solution are preferably selected such that the ratio of chromium oxide to iron oxide in the passive layer is increased, preferably to a ratio of at least 4: 1.
  • step (ii) should not be confused with a conventional pickling process in which metal is deliberately removed from the surface of a metallic workpiece (cf. DE 92 14 890 U1 and WO 88/00252 A1 ).
  • the particular effect of the method according to the invention is attributable to the fact that a passive layer is not first produced, but rather an already existing passive layer is changed in its composition and structure by the inventive method steps in their composition and structure.
  • the aqueous solution used in the chemical treatment comprises a polydentate complexing agent, preferably at least two complexing agents, and preferably an oxidizing agent.
  • These polydentate complexing agents can remove iron from the passive layer by forming chelate complexes with the iron ions and helping to significantly increase the ratio of chromium oxide to iron oxide in the passive layer.
  • the complexing agents used are preferably hydroxycarboxylic acids, phosphonic acids and organic nitrosulfonic acids.
  • oxidizing agent Another preferred ingredient of the aqueous solution in the chemical treatment is an oxidizing agent.
  • This oxidizing agent should preferably be sufficient to ensure a normal potential of at least +300 mV in the solution.
  • Suitable oxidizing agents include, for example, nitrates, peroxo compounds, iodates and cerium (IV) compounds in the form of the respective acids or the corresponding water-soluble salts.
  • peroxo compounds are peroxides, persulfates, perborates or else percarboxylates, such as peracetate.
  • the at least one hydroxycarboxylic acid comprises citric acid, and / or the at least one phosphonic acid or hydroxyethane diphosphonic acid HEDP, and / or the at least one nitroaryl or nitroalkyl sulfonic acid m- nitrobenzenesulfonic acid, and / or the at least one alkyl glycol Ethylene glycol and / or butyl glycol, and the oxidizing agent nitrate, peroxide, persulfate and / or cerium (IV) ions, each in the weight ratios indicated above.
  • the aqueous solution preferably has a pH which is less than 7, preferably less than 4. This can be achieved by the aqueous solution containing at least one acid.
  • a preferred method is that at least one of the complexing agents and / or at least one of the oxidizing agents is at least partially added in the form of an acid to the solution.
  • the aqueous solution has a temperature of at most about 70 ° C. It is further preferred that the treatment takes place in aqueous solution at a temperature between room temperature and 60 ° C.
  • the chemical treatment in aqueous solution is preferably carried out over a period of at least 60 minutes, for example, the chemical treatment can be carried out with an aqueous solution over a period of 1-4 hours.
  • the workpiece is rinsed with water, preferably deionized water, to remove the passivating solution and dried before the glass-ceramic colored sol-gel coating occurs on the workpiece.
  • water preferably deionized water
  • Sol-gel coatings usually consist of two reaction components, which are mixed in a fixed ratio shortly before processing. This mixture is last added as a third component, a dilution, usually an alcohol. Dilution sets the concentration of the reaction mixture and the viscosity of the final batch.
  • the sol-gel is first applied in the form of a liquid sol having colloidal particles suspended therein, which subsequently converts to a gel and, after thermal curing, finally forms a solid, hard topcoat. So if the "application of the sol-gel coating” or the “thermal curing of the sol-gel coating” is the expert, in which state the sol-gel system is.
  • the sol-gel is preferably a silica sol based on silanes which are dissolved in solvents, wherein the silica sol preferably also contains one or more further sol-forming elements, preferably one or more elements from the group consisting of Al, Ti, Zr, Mg, Ca and Zn, these elements replacing the Si atoms in the colloidal structures.
  • Preferred sol-gel coatings / sol-gel coatings are in EP2145980 described. Reference is made in particular to the in EP2145980 described sol-gel coatings and the method for their use.
  • the starting compounds for the formation of the preferred sols and finally the sol-gel coating are hydrolyzable silanes of the formula SiR 4 , where the 4 radicals R 2-4 comprise hydrolyzable radicals OR 'and 0-2 comprise nonhydrolyzable radicals R ".
  • the hydrolyzable radicals OR ' are hydroxy, alkoxy and / or cycloalkoxy radicals. Suitable examples thereof include, for example, hydroxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, i-butoxy, t-butoxy, pentoxy, hexoxy, cyclopentyloxy, cyclohexyloxy, in particular Ethoxy, n-propoxy and isopropoxy are preferred.
  • the hydrolyzable radicals OR ' may be identical or different from one another.
  • the non-hydrolyzable radicals R " are alkyl and / or cycloalkyl radicals, suitable examples of which include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl radicals, with particular preference being given to methyl, ethyl, n-propyl and isopropyl radicals
  • the nonhydrolyzable radicals R " may likewise be identical or different from one another.
  • the starting compounds of the preferred sols can consist of a single type of silane, but often they are mixtures of several silanes (and optionally additional sol-forming starting compounds of other elements).
  • include. It is preferred that at least one of the components of the starting compounds is a silane of the formula Si (OR ') 4-n R " n where n 0, ie Si (OR') 4
  • a preferred sol-gel lacquer may be the starting materials TEOS (tetraethoxyorthosilane) and MTES (methyltriethoxysilane) and / or DMDES (dimethyldiethoxysilane).
  • the starting compounds are partially hydrolyzed to the corresponding hydroxy compounds (such as orthosilicic acid, trihydroxyalkylsilane, etc.), which can be promoted by the addition of a catalyst such as acid. Due to the high tendency for condensation of these hydroxy compounds, these can now condense with elimination of water to form smaller siloxane networks.
  • the sol already contains colloidal particles containing siloxane bonds. Siloxane bonds are bonds of the form ⁇ Si-O-Si ⁇ , where " ⁇ " symbolizes any three independent bonds with other elements, in particular OH, OR 'and R ", thus forming a three-dimensional crosslinked structure in the colloidal particles Where OR 'and R "have the same meaning as above.
  • the sol-gel coating has a stoving temperature of below 300 ° C, preferably from 200 ° C to 250 ° C, on.
  • the sol-gel coating is colorless before the addition of the inorganic color pigments.
  • the color pigments are preferably applied as a suspension in the sol-gel.
  • the amount of color pigments is adjusted so that the coated surfaces are only partially covered by pigments, so that preferably arranged below the glass ceramic layer stainless steel surface is visible with their passive layer through the glass-ceramic layer at the points where no inorganic color pigments are present.
  • degree of coverage of inorganic color pigments ie by the proportion by weight of the inorganic color pigments in the sol-gel, color intensity and depth can be adjusted.
  • the viscosity of the sol-gel varnish can be adjusted by a person skilled in the art. It is known that the sol, with a correspondingly high dilution in its solvent, is sufficiently low-viscosity to be applied by spraying, spraying, rolling or brushing.
  • Suitable solvents for the sol are water and especially alcohols such as methanol, ethanol, n-propanol or isopropanol, with ethanol and isopropanol being preferred because of their physical properties and the low toxicity of their vapors.
  • the sol-gel used in step (iii) contains inorganic color pigments, e.g. SICOCER® Black 10901, SICOCER® Blue 2502, or SICOCER® Red 2355 from BASF.
  • inorganic color pigments e.g. SICOCER® Black 10901, SICOCER® Blue 2502, or SICOCER® Red 2355 from BASF.
  • one or more types of inorganic color pigments can be used. If different types of color pigments are used, they can be used in equal or different amounts.
  • Amounts (g / kg) of pigments are used in the range of 10 g / kg to 300 g / kg, preferably 40 g / kg to 200 g / kg, based on the amount of sol gel.
  • the amount of pigments (g / kg) is normalized by the specific gravity of the pigments so that always the same number of pigment grains per unit area (pigment density) is achieved.
  • the inorganic color pigments preferably have a maximum diameter of 1 .mu.m.
  • the desired maximum diameter is ensured by sieving or filtration processes.
  • the admixture of the pigments is carried out in the dilution, whereby the desired concentration of pigments in the final mixture is easily targeted.
  • a suspension of the pigments is prepared by intensive stirring, the homogeneity of which is crucial for the uniformity of the coated surfaces. Since the density of the dilution and the pigments differ significantly, it is necessary throughout the entire production and coating process to mix sufficiently intensively in order to keep the suspension stable.
  • the sol-gel coating prior to application, has a low viscosity similar to water and a significantly lower specific gravity than the suspended pigments. Therefore, the suspensions segregate immediately after application and the pigments attach to the stainless steel surfaces. Due to the small size of the pigment grains thus a sufficient coverage of the pigment grains is ensured by the sol-gel layer.
  • the properties of the coated stainless steel surfaces are thus determined solely by the properties of the sol-gel coating used and not by the properties of the processed pigments.
  • the sol-gel coating in step (iii) is preferably applied by spraying or rolling, spraying or painting are also possible. Preferably, however, it is done by spraying, since this allows precise control of the amount applied per unit area.
  • the surfaces can be dried until the solvent has evaporated.
  • the dried surfaces are then thermally cured.
  • the thermal curing in step (iii) is preferably carried out at a temperature of less than 300 ° C, preferably in a range of 200 ° C to 300 ° C.
  • the curing takes place for a period of about 20 to 60, preferably 30 minutes at temperatures in the range of 160 ° C to 280 ° C, preferably 200 ° C to 250 ° C in air.
  • the sol-gel (if the color pigments are disregarded) changes to a colorless, transparent, glassy layer.
  • the thermal curing can be carried out regularly in the process according to the invention so that neither the color of the sol-gel coating nor the underlying stainless steel surface is changed. That is, the thermal stress of both the sol gel and the stainless steel surface does not cause discoloration that does not originate in the color pigments themselves.
  • the glass-ceramic coating preferably has a thickness of 0.5-5.0 ⁇ m, preferably 1.0-5.0 ⁇ m, or 0.5-3.0 ⁇ m, and most preferably 1.0-3.0 ⁇ m.
  • the glass-ceramic coating preferably has a uniform thickness with fluctuations of preferably less than 10% of the layer thickness.
  • the diameter of the inorganic color pigments / pigments is smaller than the diameter of the glass-ceramic coating which was produced from the sol-gel coating.
  • Pigments whose diameter is equal to or greater than the layer thickness of the sol-gel layer are not or not sufficiently covered and protrude from the surface of the coating. They roughen the surface and are themselves exposed to the effects of corrosion and can cause pores in the coating resulting in localized corrosion of the underlying stainless steel surface
  • the inventive method is largely independent of the alloy and the structure of stainless steel.
  • the method according to the invention is applied to a stainless steel material consisting of composite parts, which are uniformly colored by the method according to the invention.
  • the parts can be colored uniformly largely independent of their shape and shape.
  • the glass-ceramic coating according to the invention which was produced from the sol-gel coating, is transparent and not opaque. In particular, it has a metallic luster and reflects, depending on the density of the pigments, a substantial portion of the incident light. As a result, the surfaces appear much lighter in comparison to chemically colored surfaces.
  • the coating is heat-resistant, the color effect at temperatures above 180 ° C and up to 300 ° C, especially at 200 ° C or 250 ° C, is not lost.
  • the coating is also resistant to temperatures up to 400 ° C and can withstand at least 200 hours of stress in the salt spray test without damage. After cooling, the colored stainless steel surfaces are ready for use.
  • the invention also relates to stainless steel with a colored surface or objects made of stainless steel or with a surface made of stainless steel, wherein the stainless steel surface has a transparent, glass-ceramic coating containing inorganic color pigments.
  • the colored surface can be prepared according to the method described herein. All embodiments described with respect to the method of the invention are also applicable to the colored surface products. In particular, the passive layer and glass-ceramic layer described with regard to the method is present on the stainless steel with a colored surface.
  • the stainless steel surface is regularly only partially covered or optically hidden by the inorganic color pigments, so that a metallic surface arranged below the glass-ceramic layer is visible through the glass-ceramic layer at the points where no inorganic color pigments are present.
  • the gloss and structure of the colored stainless steel surface also show the gloss and structure of the underlying stainless steel surfaces.
  • the invention broadly relates to a stainless steel surface provided with a transparent colored glass-ceramic coating.
  • the color of the coating results from the selected inorganic color pigments. These color pigments regularly have a diameter of 500 to 1500 nm. Im In the case of the present invention, it has been found that, especially with these pigment diameters, a metallic luster which very probably results from the metallic surface underlying the coating is retained. This would not be possible, for example, for coatings with pigments of smaller diameter, because then the gloss is covered.
  • the invention also relates to colored stainless steel surfaces, produced or producible by the method according to the invention.
  • a stainless steel sheet of 1.0 mm thickness of quality 1.4016 with bright annealed surface (method) and the dimensions 800 x 800 mm was cleaned in an alkaline Abkochentfettung for 15 minutes by dipping and then rinsed in water. Subsequently, the sheet was immersed in an aqueous solution with complexing and chelating agents (POLINOX-Protect from POLIGRAT GmbH) for 3 hours at 55 ° C.
  • complexing and chelating agents POLINOX-Protect from POLIGRAT GmbH
  • the sheet was lying by spraying coated with a layer thickness of 2 microns.
  • a sol-gel coating based on silicon dioxide (POLIANT from POLIGRAT GmbH) was used, which was mixed with 100 g / kg of a blue pigment (SICOCER® Blue 2502). The pigment was ground into the dilution prior to admixing to a particle size below 1 ⁇ m.
  • the surface was dried for 10 minutes and then baked in the oven at 220 ° C for 30 minutes.
  • the surface After cooling, the surface showed a shiny metallic surface with intense blue, whereby a clear reflection of the environment in its natural colors was visible in the surface.
  • the surface was smooth, hydrophobic and showed no fingerprints after touching.
  • a stainless steel sheet of 1.5 mm thickness of quality 1.4301 with ground surface was pretreated as described in Example 1 and then lying coated with a sol-gel coating based on silica (POLIANT from POLIGRAT GmbH), wherein the dilution is a black Pigment (SICOCER® Black 10901) in an amount of 50.g / kg was mixed and this was then mixed with the product.
  • the particle size of the pigment was less than 1 ⁇ m in diameter. After drying for 10 minutes and baking at 200 ° C. for 30 minutes, followed by cooling, the surface showed a slightly glossy anthracite gray appearance with a clearly visible cut.
  • the surface was structured according to the microsection and felt smooth and metallic. It was hydrophobic and showed no fingerprints when touched.
  • the workpiece was passivated, rinsed and dried for a period of 3 hours.
  • the dry workpiece was coated on all sides by means of a spray gun with a sol-gel coating with a coating based on silicon dioxide (POLIANT from POLIGRAT GmbH). About the dilution, a pigment, a copper-red pigment (SICOCER® Rot 2355) in a concentration of 75 g / kg was added to the coating material.
  • a pigment a copper-red pigment (SICOCER® Rot 2355) in a concentration of 75 g / kg was added to the coating material.
  • the surfaces were baked at 220 ° C for 30 minutes. After cooling, the component showed on all sides a uniform shiny, copper-colored surface. The different materials including the welds showed uniform color and surface.
  • the surfaces were smooth, glossy, hydrophobic and fingerprint resistant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Chemically Coating (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • ing And Chemical Polishing (AREA)

Claims (10)

  1. Procédé de fabrication d'une surface en acier inoxydable à revêtement coloré transparent, le revêtement recouvrant la surface en acier inoxydable avec des pigments colorés inorganiques non transparents de telle sorte que le revêtement conserve une transparence avec laquelle la surface en acier inoxydable située sous le revêtement reste visible, les pigments colorés inorganiques ayant un diamètre de 500 à 1500 nm, le procédé comprenant les étapes suivantes :
    - traitement de la surface avec une solution aqueuse contenant des agents complexants polydentés pour éliminer les oxydes de fer et les atomes de fer de la couche passive sur la surface en acier inoxydable,
    - application sur la surface d'un revêtement sol-gel au dioxyde de silicium transparent contenant des pigments colorés inorganiques et
    - durcissement thermique du revêtement appliqué à une température inférieure à 300 °C, lors duquel est produit un revêtement vitrocéramique transparent, la surface en acier inoxydable revêtue n'étant pas entièrement recouverte par les pigments colorés.
  2. Procédé selon la revendication 1,
    dans lequel le revêtement vitrocéramique présente une épaisseur de 0,5 à 5,0 µm, de préférence de 1,0 à 5,0 µm ou de 0,5 à 3,0 µm et le plus préférentiellement de 1,0 à 3,0 µm.
  3. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que la solution aqueuse comprend, lors du traitement de la surface, un acide hydroxycarboxylique, un acide phosphonique et un acide sulfonique de nitroaryle ou de nitroalkyle ou leurs sels.
  4. Procédé selon l'une des revendications précédentes,
    caractérisé en ce que la solution aqueuse contient, lors du traitement de la surface, les agents complexants suivants :
    - au moins un acide hydroxycarboxylique ayant de 1 à 3 groupes hydroxyle et de 1 à 3 groupes carboxyle ou leur(s) sel(s),
    - au moins un acide phosphonique de structure générale R'-PO(OH)2 ou son/ses sel(s), où R' est un radical alkyle, hydroxyalkyle ou aminoalkyle monovalent, et/ou de structure générale R"[-PO(OH)2]2 ou son/ses sel(s), où R" est un radical alkyle, hydroxyalkyle ou aminoalkyle divalent, et
    - au moins un acide sulfonique de nitroaryle ou de nitroalkyle ou son/ses sel(s).
  5. Procédé selon l'une des revendications précédentes,
    dans lequel le revêtement sol-gel est appliqué par projection, pulvérisation ou laminage.
  6. Procédé selon l'une des revendications précédentes,
    dans lequel le durcissement thermique est effectué à une température comprise entre 200 °C et 300 °C.
  7. Procédé selon l'une des revendications précédentes,
    dans lequel le sol-gel est un sol de silice à base de silanes dissous dans un solvant, ledit sol de silice contenant en outre de préférence un ou plusieurs autres éléments formant un sol, de préférence un ou plusieurs autres éléments choisis dans le groupe constitué par Al, Ti, Zr, Mg, Ca et Zn, ces éléments remplaçant les atomes de Si dans les structures colloïdales.
  8. Acier inoxydable doté d'un revêtement coloré transparent,
    dans lequel la surface en acier inoxydable présente un revêtement vitrocéramique coloré transparent contenant des pigments colorés inorganiques ayant un diamètre de 500 à 1500 nm, le revêtement recouvrant la surface en acier inoxydable avec les pigments colorés inorganiques non transparents de telle sorte que le revêtement conserve une transparence avec laquelle la surface en acier inoxydable située sous le revêtement reste visible, une couche passive étant disposée sous le revêtement vitrocéramique, la couche passive présentant de l'oxyde de chrome, et le rapport de l'oxyde de chrome sur l'oxyde de fer dans la couche passive étant de préférence supérieur à 4:1.
  9. Acier inoxydable doté d'un revêtement coloré transparent selon la revendication 8,
    dans lequel le revêtement vitrocéramique présente une épaisseur de 0,5 à 5,0 µm, de préférence de 1,0 à 5,0 µm, ou de 0,5 à 3,0 µm et le plus préférentiellement de 1,0 à 3,0 µm.
  10. Acier inoxydable doté d'un revêtement coloré transparent selon la revendication 8 ou 9,
    dans lequel la surface en acier inoxydable colorée présente un lustre métallique et une structure qui sont déterminés par le lustre et la structure de la surface en acier inoxydable disposée sous le revêtement vitrocéramique coloré.
EP14780490.0A 2013-12-18 2014-10-02 Procédé de fabrication de surfaces en acier inoxydable colorées Active EP3084035B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14780490.0A EP3084035B1 (fr) 2013-12-18 2014-10-02 Procédé de fabrication de surfaces en acier inoxydable colorées

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13005900 2013-12-18
PCT/EP2014/071169 WO2015090660A1 (fr) 2013-12-18 2014-10-02 Procédé de production de surfaces colorées en acier spécial
EP14780490.0A EP3084035B1 (fr) 2013-12-18 2014-10-02 Procédé de fabrication de surfaces en acier inoxydable colorées

Publications (2)

Publication Number Publication Date
EP3084035A1 EP3084035A1 (fr) 2016-10-26
EP3084035B1 true EP3084035B1 (fr) 2018-08-15

Family

ID=49911085

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14780490.0A Active EP3084035B1 (fr) 2013-12-18 2014-10-02 Procédé de fabrication de surfaces en acier inoxydable colorées

Country Status (8)

Country Link
US (1) US20160310984A1 (fr)
EP (1) EP3084035B1 (fr)
JP (1) JP2017508066A (fr)
CN (1) CN105849312A (fr)
CA (1) CA2932979A1 (fr)
DK (1) DK3084035T3 (fr)
RU (1) RU2016127362A (fr)
WO (1) WO2015090660A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6960842B2 (ja) * 2017-12-15 2021-11-05 大阪瓦斯株式会社 金属部材の表面処理方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61205179A (ja) * 1985-03-07 1986-09-11 Hosokawa Katsupanshiyo:Kk コピ−偽造防止用紙の製造方法
DE4338360A1 (de) * 1993-11-10 1995-05-11 Inst Neue Mat Gemein Gmbh Verfahren zur Herstellung von funktionellen glasartigen Schichten
DE10064134A1 (de) * 2000-12-19 2002-06-27 Bsh Bosch Siemens Hausgeraete Verfahren zum Veredeln von metallischen Oberflächen zur Vermeidung von thermischen Anlauf-Farben
US20030138661A1 (en) * 2003-02-19 2003-07-24 Ferro Corporation Sol-gel composition and method of making same
DE102007010538A1 (de) * 2007-03-05 2008-09-11 Poligrat Gmbh Verfahren zum thermochemischen Passivieren von Edelstahl
EP2182095A1 (fr) * 2008-10-29 2010-05-05 Poligrat Gmbh Procédé destiné au traitement de surfaces en acier inoxydable
EP2206801A1 (fr) * 2008-12-24 2010-07-14 Seb Sa Ustensiles de cuisson composites comprenant un revêtement de protection vitreux
CN101914332A (zh) * 2010-09-09 2010-12-15 上海丰野表面处理剂有限公司 一种彩色耐指纹涂料、其制备方法以及其使用方法
KR20130109302A (ko) * 2012-03-27 2013-10-08 동부제철 주식회사 칼라 도장 강판 및 그 제조방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP3084035A1 (fr) 2016-10-26
WO2015090660A1 (fr) 2015-06-25
CA2932979A1 (fr) 2015-06-25
CN105849312A (zh) 2016-08-10
RU2016127362A (ru) 2018-01-23
US20160310984A1 (en) 2016-10-27
JP2017508066A (ja) 2017-03-23
DK3084035T3 (en) 2018-10-15

Similar Documents

Publication Publication Date Title
DE1519232C3 (de) Überzugsmittel zur Herstellung diffus-reflektierender Überzüge
KR20140063797A (ko) 코팅 시스템
DE3030056A1 (de) Verfahren zur herstellung von mit metalloxiden beschichteten schuppenfoermigen glimmerpigmenten
DE112013004277T5 (de) Verfahren zur Bildung eines ausgezeichneten vielschichtigen Beschichtungsfilmes
AU2009296281A1 (en) Coating compositions having improved solar reflectivity and UV protection
DE112010003357T5 (de) Passivierungsmittel für AI-Zn-schmelztauchbeschichtetes Blech und Herstellungsverfahren und Verwendung davon
DE602004001464T2 (de) Mehrschichtlackierung enthaltend farbgebende schicht
EP1506262A1 (fr) Pigments brillants goniochromatiques
DE2900530C2 (de) Verfahren zur Herstellung von Metallgegenständen mit einem halbglänzenden, perlmutterartigen Aussehen
EP3084035B1 (fr) Procédé de fabrication de surfaces en acier inoxydable colorées
EP1563016A2 (fr) Procede de recouvrement
DE1592821C3 (de) Verfahren zur Verhütung von Anlaufen und Farbänderungen der Oberfläche von Bronze- und Aluminiumpulvern
DE102013010080A1 (de) Verfahren zur Oberflächenbehandlung von Corten-Stahl
DE69511914T2 (de) Überzugszusammensetzung und Überzugsfilmszusammensetzung
EP3054033B1 (fr) Procédé de fabrication de surfaces colorées en aluminium et zinc
EP2402484B1 (fr) Procédé de fabrication d'une couche de protection sur des produits plats en zinc de titane
EP2296829A1 (fr) Substrats revêtus et procédé de fabrication de ceux-ci
EP1197325A2 (fr) Procédé de fabrication de vitrage feuilleté ayant une matage
DE102013009148B4 (de) Mischung zur Herstellung einer Schicht in einem Schichtaufbau, Verfahren zum Herstellen eines Schichtaufbaus, Schichtaufbau und Verwendung des Schichtaufbaus
JP2012061451A (ja) 複層塗膜の形成方法
EP3344470B1 (fr) Image à décalquer pour réaliser une décoration
JP2016188332A (ja) 自動車車体用クリヤー塗料組成物、自動車車体用複層塗膜の形成方法及び自動車車体用複層塗膜
WO2020156815A1 (fr) Couches protectrices de silicate alcalin dopées sur un métal
DE1719340A1 (de) UEberzug,der in Beruehrung mit anderen Substanzen nichthaftend ist,Verfahren fuer seine Anbringung und auf diese Art erhaltene Gegenstaende
DE1147344B (de) Anstrichmittel bzw. Lackfarbe

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: 20160613

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SEPIES GMBH

DAX Request for extension of the european patent (deleted)
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: 20170727

RIC1 Information provided on ipc code assigned before grant

Ipc: B05D 3/00 20060101ALN20180110BHEP

Ipc: B05D 1/28 20060101ALN20180110BHEP

Ipc: C23C 18/12 20060101AFI20180110BHEP

Ipc: B05D 1/02 20060101ALN20180110BHEP

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 18/12 20060101AFI20180124BHEP

Ipc: B05D 1/02 20060101ALN20180124BHEP

Ipc: B05D 3/00 20060101ALN20180124BHEP

Ipc: B05D 1/28 20060101ALN20180124BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20180305

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: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: AT

Ref legal event code: REF

Ref document number: 1029860

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180815

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502014009222

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20181008

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

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: 20180815

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: 20181116

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: 20180815

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: 20181115

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: 20181115

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: 20181215

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: 20180815

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

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: 20180815

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: 20180815

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: 20180815

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: 20180815

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: 20180815

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: 20180815

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: 20180815

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: 20180815

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014009222

Country of ref document: DE

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

Ref country code: SM

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

Effective date: 20180815

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: 20180815

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

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181031

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: 20180815

Ref country code: LU

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

Effective date: 20181002

26N No opposition filed

Effective date: 20190516

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 NON-PAYMENT OF DUE FEES

Effective date: 20181031

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: 20180815

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

Ref country code: IE

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

Effective date: 20181002

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: 20180815

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

Ref country code: HU

Payment date: 20190918

Year of fee payment: 6

Ref country code: SE

Payment date: 20191017

Year of fee payment: 6

Ref country code: NL

Payment date: 20191022

Year of fee payment: 6

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

Ref country code: DK

Payment date: 20191022

Year of fee payment: 6

Ref country code: IT

Payment date: 20191021

Year of fee payment: 6

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: 20180815

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

Ref country code: PT

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

Effective date: 20180815

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 NON-PAYMENT OF DUE FEES

Effective date: 20180815

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: 20180815

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

Ref country code: AT

Payment date: 20201015

Year of fee payment: 7

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20201031

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20201101

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

Ref country code: NL

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

Effective date: 20201101

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

Ref country code: SE

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

Effective date: 20201003

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

Ref country code: IT

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

Effective date: 20201002

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

Ref country code: DK

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

Effective date: 20201031

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1029860

Country of ref document: AT

Kind code of ref document: T

Effective date: 20211002

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

Ref country code: AT

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

Effective date: 20211002

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 NON-PAYMENT OF DUE FEES

Effective date: 20211003

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

Ref country code: CH

Payment date: 20221025

Year of fee payment: 9

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 NON-PAYMENT OF DUE FEES

Effective date: 20201003

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

Ref country code: GB

Payment date: 20230807

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20230807

Year of fee payment: 10

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

Ref country code: DE

Payment date: 20231026

Year of fee payment: 10

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: CH

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

Effective date: 20231031

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

Ref country code: CH

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

Effective date: 20231031

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502014009222

Country of ref document: DE

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

Effective date: 20241002

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

Ref country code: DE

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

Effective date: 20250501

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

Ref country code: GB

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

Effective date: 20241002

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

Ref country code: FR

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

Effective date: 20241031