[go: up one dir, main page]

EP3765658B1 - Produits galvanisés et bain électrolytique approprié pour fournir de tels produits - Google Patents

Produits galvanisés et bain électrolytique approprié pour fournir de tels produits Download PDF

Info

Publication number
EP3765658B1
EP3765658B1 EP19709513.6A EP19709513A EP3765658B1 EP 3765658 B1 EP3765658 B1 EP 3765658B1 EP 19709513 A EP19709513 A EP 19709513A EP 3765658 B1 EP3765658 B1 EP 3765658B1
Authority
EP
European Patent Office
Prior art keywords
indium
gold
copper
electroplated product
group
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
EP19709513.6A
Other languages
German (de)
English (en)
Other versions
EP3765658A1 (fr
Inventor
Coline Nelias
Jean-Jacques Duprat
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.)
Coventya SpA
Original Assignee
Coventya SpA
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 Coventya SpA filed Critical Coventya SpA
Publication of EP3765658A1 publication Critical patent/EP3765658A1/fr
Application granted granted Critical
Publication of EP3765658B1 publication Critical patent/EP3765658B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • the present invention relates to electroplated products having a combination of layers used to provide a diffusion barrier layer which prevents the interdi-fussion between the underlayer and the top layer under a precious metal top layer on a substrate comprising a copper based material and/or a copper based underlayer, such that the layer or combination of layers prevents or retards the migration of copper into the precious metal layer or the opposite.
  • the diffusion barrier layer is an indium alloy according to claim 8.
  • the present invention refers a method for preparing such an electroplated product.
  • the common electroplating sequence comprises electroplating on the substrate a first layer of acid copper to ensure a proper levelling of the substrate roughness followed by a white bronze layer of 2 to 5 ⁇ m and by a thin palladium based layer of a thickness from 0.2 to 0.5 ⁇ m to stop the diffusion of the top precious metal layer, mainly gold or a gold alloy, into the copper or copper alloy underlayer, and most importantly to prevent the diffusion of copper into the precious metal layer.
  • the present bronze technology mainly uses cyanide as a complexing agent to enable the co-deposition of a ternary alloy of copper, tin and zinc which is also efficient as a copper diffusion barrier.
  • WO2016/166330 A1 describes an electroplated product with a precious metal finishing layer that has an improved corrosion and abrasion resistance.
  • the electroplated product comprises two electroplated copper alloy layers having a different copper concentration (e.g. white bronze and yellow bronze). Another advantage of the electroplated product is that the use of allergenic nickel or expensive palladium intermediate layers against copper migration can be dispensed with.
  • WO2017/055553 A1 describes an electroplating bath for electrochemical deposition of a novel Cu-Sn-Zn-Pd alloy on a substrate.
  • the novel alloy is characterized by improved corrosion resistance but is based on cyanide media.
  • the metal indium is nowadays used mainly for photovoltaic applications due to its high thermal conductivity ( ⁇ 82 W/mK). It also has other unique physical properties which make it very useful in numerous industries. For example, it is sufficiently soft such that it is readily deformed and fills microstructures between two mating parts, has a low melting temperature (156° C). Such properties recommend indium for various uses in the electronics and related industries.
  • WO2015/000010 A1 describes a bath for the cathodic deposition of ternary bronze alloys.
  • the electrolyte composition comprises indium as a third metallic alloying constituent.
  • a ternary copper-tin-indium alloy is deposited directly on an optional copper layer.
  • EP 1 930 478 A1 teaches an electrolyte composition as well as a method for the deposition of another quaternary copper alloy on a substrate.
  • the electrolyte composition comprises besides the alloying metals copper, tin and zinc, at least one metal from the group consisting of indium and gallium providing white bronze layers free of noxious heavy metals.
  • the previously mentioned documents are based on baths containing cyanide. Cyanide based solutions have several disadvantages associated with the high toxicity of the electrolyte, difficulties associated with storage and transportation of the cyanide salts and solutions, and costs associated with the wastewater treatments.
  • Several attempts have been made to formulate cyanide free ternary bronze to substitute the dangerous complexing agent but none of them fulfils the market requirements to prevent the gold and copper inter diffusion as well as to maintain a bright and shiny aspect of the electroplated layers.
  • WO2004/035875 A3 refers to a method for bronze galvanic coating which consists of metallizing a substrate to be coated by its immersion into an acidic electrolyte which contains at least tin and copper ions.
  • the acidic electrolyte used for bronze coating is also disclosed.
  • WO2013/092314 cites an aqueous alkaline electrolyte, which is cyanide-free, pyrophosphate-free and phosphonic acid-free for depositing a ternary alloy comprising copper and tin present in dissolved form and zinc present as a zinc salt.
  • KR1168215 B1 teaches a copper-tin alloy plating film, a non-cyanide-based copper-tin alloy plating bath, and a plating method using the same. However, the deposit was not a barrier to copper diffusion.
  • EP2139012 A1 relates to a silver-coated material for a movable contact component and a method for manufacturing such a silver-coated material.
  • the US 2,458,839 A teaches a bath which comprises at least 20 g/L of indium. However, with such high concentrations that no thin bright layers can be provided.
  • WO2009/097360 A1 describes an electroplating solution for the deposition of a pure indium film on a conductive surface useful in fabricating electronic devices.
  • the indium electroplating solutions are used to deposit indium films which are compositionally pure, uniform, substantially free of defects and smooth. Such films can be plated with almost 100% plating efficiency.
  • sub-micron thick indium layers are described. Such indium layers are used in fabrication of electronic devices such as thin film solar cells.
  • EP 2 123 799 B1 teaches a method to prevent silver from tarnishing by electroplating a thin indium metal layer onto a silver substrate.
  • the indium and silver composite has high electrical conductivity.
  • WO2017/060216 A1 teaches a process for indium or indium alloy deposition and for the formation of very smooth and glossy indium or indium alloy layers and their use in electronic and semiconductor devices, in particular interconnections used in electronic and semiconductor industries such as flip chips, tape automated bonding and the like.
  • a method for preparing an electroplated product by electroplating a substrate according to claim 1 is provided.
  • indium has been found to be an efficient copper diffusion barrier, able with very low thickness to prevent copper migration to the top gold layer and thus preventing the article from undesirable change of colour.
  • the indium in the diffusion barrier layer which is deposited between the copper or copper alloy underlayer and the precious metal or precious metal alloy top layer, can migrate into the precious metal top layer, but prevents the interdiffusion between the underlayer and the top layer.
  • an underlayer consisting of copper or a copper alloy is obtained by electrodeposition from a copper electroplating solution.
  • This copper electroplating solution is generally very acidic as it contains up to 60 g/L of 98% sulfuric acid. It produces a bright deposit with high levelling characteristics. The deposits are free of pits even at high thicknesses.
  • the electroplated copper thicknesses can vary from 5 to 60 ⁇ m depending on the substrate and the targeted properties.
  • the function of the top layer consisting of a precious metal selected from the group consisting of Au, Ag, Ru and its alloys is highly decorative, it must be of a constant colour and give a very uniform and generally bright aspect to the final item.
  • the thickness is generally low due to the cost of the precious metals used. It typically varies between 0.05 ⁇ m up to 5 ⁇ m preferably between 0.1 and 1 ⁇ m. It is absolutely necessary that the top layer colour and aspects are not affected by the copper underlayer. In the absence of a proper diffusion barrier, the interdiffusion of the copper or copper rich underlayer and the top finishing layer will lead to a non-acceptable finish of the part upon ageing or storage. That is why it is so important to provide an intermediate layer that prevents the interdiffusion of the copper rich underlayer and the precious metal top layer.
  • the electroplating bath of step b) preferably has a pH in the range of 1 to 14, more preferably of 2 to 11, and most preferably of 4 to 10.
  • the at least one source of indium ion in the electroplating bath of step b) is preferably selected from the group consisting of indium sulfate, indium chloride, indium acetate, indium sulfamate and its combinations or mixtures. Considering the cost of this valuable metal, the source of indium ion should be affordable.
  • the bath has a concentration of indium as a metal of 0.1 to 20 g/L, preferably 0.2 to 15 g/L, more preferably 0.3 to 10 g/L, most preferably 0.5 to 7 g/L.
  • a concentration in these ranges is sufficient to obtain the suitable aspect of the indium thin layer.
  • a concentration of indium above 20 g/L was found to be detrimental to maintain brightness and thickness distribution.
  • the electroplating bath contains conductive salts in order to spread the indium distribution throughout the required current density range.
  • the conductive salts are selected and balanced to not only act as a conductive salt but also as a buffering agent.
  • the conductive salts/buffering agents are preferably selected from the group consisting of citrates (e.g. sodium or potassium citrate or their corresponding acidic version), formiates (e.g. sodium formiate or the corresponding acidic version), pyrophosphates (e.g. tetrapotassium pyrophosphate) and gluconates (e.g. sodium or potassium gluconate) and combinations or mixtures thereof.
  • the at least one conductive salt has a concentration of 30 to 500 g/L, more preferably 50 to 300 g/L, and most preferably 100 to 200 g/L.
  • a concentration in this range is suitable for keeping the pH of the inventive electroplating solution constant for many turnovers (TOs) of the electroplating solution.
  • the brightness of the indium deposit is controlled by the introduction of a surfactant.
  • the surfactant acts as a wetting agent and reduces the surface tension to allow indium electroplating.
  • the surfactants may belong to the amphoteric family and are selected from the group consisting of propionic amino acids, propionic imino acids, quaternary alkyl betaines or sulfo-betains.
  • the surfactant is preferably selected from the group of betain, aminobetain, imidazoline, cocoamidopropyl betaine, N,N-dimethyl-N-(3-cocoamidopropyl)-N-(2-hydroxy-3-sulfopropyl) ammonium betain, N,N-dimethyl-N-octadecyl-N-(3-sulfopropyl)ammonium betaine, N,N-dimethyl-N-dodecyl-N-(3-sulfopropyl)ammonium betaine and combinations or mixtures thereof.
  • the surfactant concentration according to the invention is preferably from 0.1 to 5 g/L, more preferably from 0.5 to 1.5 g/L.
  • the indium ions may be complexed in solution by a complexing agent.
  • the complexing agent is preferably selected from the group consisting of carbohydrates, amino acids, imino acids, sulfur compounds, sugar alcohols, and combinations or mixtures thereof. More preferably, the complexing agent is selected from the group consisting of sorbitol, mannitol, gluconate, erithrytol, xylitol, nitrilotriacetic acid, cysteine, iminodiacetic acid, triethanolamine and combinations or mixtures thereof. Said complexing agents were found to be perfectly suited for complexing indium ions.
  • the concentration of the complexing agent in the bath is preferably from 0.5 to 100 g/L, preferably from 1 to 75 g/L, most preferably from 2.5 to 50 g/L, and in particular from 5 to 35 g/L. A concentration in these ranges is sufficient for complexing the indium ions which are comprised in the inventive electroplating solution. A concentration of complexing agent under 0.5 g/L was found to be detrimental and not able to stabilize the bath at the required pH.
  • the diffusion barrier layer consists of an alloy of indium with the material of the top layer, i.e. a precious metal selected from the group consisting of Au, Ag and Ru.
  • a precious metal selected from the group consisting of Au, Ag and Ru.
  • An alloy of indium and gold is particularly preferred.
  • An alloy of indium with the mentioned precious metals is very easy to process and shows improved diffusion barrier properties compared to other metals as alloy former.
  • a diffusion barrier layer of gold and indium allows to strongly reduce copper migration.
  • it is preferred to select an indium alloy with the proviso that this indium alloy is not a ternary alloy of indium, copper and tin.
  • the electroplating bath comprises at least one source of gold ions, preferably selected from the group consisting of potassium gold (I) cyanide , sodium gold(I) sulphite, potassium gold(III) cyanide , gold (III) chloride and tetrachloroaurates(III), gold(I) thioglycerol and gold(I) and gold(III) hydantoin complexes, and combinations or mixtures thereof.
  • a source of gold ions preferably selected from the group consisting of potassium gold (I) cyanide , sodium gold(I) sulphite, potassium gold(III) cyanide , gold (III) chloride and tetrachloroaurates(III), gold(I) thioglycerol and gold(I) and gold(III) hydantoin complexes, and combinations or mixtures thereof.
  • the concentration of the at least one source of gold is preferably from 0.5 to 10 g/L, more preferably from 1 to 5 g/L and most preferably from 2.5 to 3.5 g/L.
  • the concentration of indium in the electroplating bath is preferably from 0.1 to 20 g/L, more preferably from 0.2 to 15 g/L and most preferably from 0.25 to 0.75 g/L.
  • steps a) to c) is not interrupted by further deposition steps with the consequence that the layers electroplated in step a) to c) abut to each other.
  • an electroplated product according to claim 8 is provided.
  • the precious metal is selected from the group consisting of Au, Ag and its alloys.
  • the underlayer and the top layer are separated by a diffusion barrier layer consisting of an alloy of indium with the material of the top layer.
  • the diffusion barrier layer has preferably a thickness of 10 to 200 nm, more preferably 25 to 150 nm and most preferably 50 to 100 nm. It has been determined that a thickness of the indium intermediate layer of less than 50 nm does not prevent the diffusion of copper into the gold. A thickness above 200 nm leads to poor brightness and presents a powdering aspect.
  • the diffusion barrier layer comprises an gold indium alloy, preferably with 90 to 95 % by weight of gold and 5 to 10 % by weight of indium.
  • the electroplated products are preferably selected from the group consisting of jewelry, leather goods, spectacle frame, fashion, watch, trinkets and/or lock industry.
  • the copper plated panels were then plated with various subsequent layers using different electrolytes.
  • Table 1 Determination of optimum thickness to obtain copper migration barrier Indium thickness 0 ⁇ m 0.05 ⁇ m 0.1 ⁇ m 0.25 ⁇ m 0.5 ⁇ m 1 ⁇ m 3 ⁇ m Gold thickness 0.5 ⁇ m 0.5 ⁇ m 0.5 ⁇ m 0.5 ⁇ m 0.5 ⁇ m 0.5 ⁇ m 0.5 ⁇ m 0.5 ⁇ m ⁇ L* -44 -2,7 -1,5 -2,8 -2,9 0 -4,8 ⁇ a* 6,1 0,7 -2,3 -7,8 -9,6 -9,8 -10,7 ⁇ b* -38,2 1,4 3,8 -19,1 -22,1 -25,1 -26,4
  • GDOES low discharge optical emission spectrometry
  • the sample forms the cathode and a thin (4 mm diameter) copper tube forms the anode.
  • a small O-ring separates the anode from the cathode.
  • High-purity argon is pumped into the anode chamber.
  • a high voltage (DC or RF) between sample and anode ionizes the argon to produce a glow discharge plasma.
  • the excited argon ions bombard the electroplated product sample and cause uniform sputtering of the sample surface. Atoms ejected are then excited by the argon plasma, and finally relax to their fundamental energy level, emitting a characteristic X-ray photon.
  • Emitted photons whose energy is characteristic of the energy level of a chemical element, are then collected by photomultipliers.
  • the intensity of each emission depends on the concentration of the element in the sample.
  • the recorded signals are processed to obtain the distribution of the elements according to the erosion time.
  • GDOES provides a depth profiling analysis of solids like metals, powders, polymers, glasses and ceramics (in the present case: depth profiling of electroplated substrates).
  • GDOES GDOES-like e.g . C, N and O.
  • the spectrum obtained represents the qualitative intensity of the metallic signal variation depending on time of sputtering in s.
  • Figs. 4 to 9 give the GDOES depth profiles for the different electroplated products of Examples 1 to 6 before and after the heat treatment at 180°C for 24 hours.
  • concentration of each chemical element Au, Cu, In and optionally Sn and Zn for reference is shown (y-axis for intensity) as a function of the distance from the surface of the finishing layer towards the base material of the electroplated product (x-axis for erosion time).
  • Table 2 Samples analyzed by GDOES analysis Copper thickness 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m Layer 1 GOLD White bronze Indium Indium Gold-Indium alloy %Au 95 %In 5 Gold-Indium alloy %Au 90 %In 10 Thickness layer 1 0,5 ⁇ m 3 ⁇ m 100 nm 100 nm 0,5 ⁇ m 0,5 ⁇ m Layer 2 - GOLD GOLD GOLD - - Thickness layer 2 - 0,5 ⁇ m 0,5 ⁇ m 0,5 ⁇ m - - REF example Comparative EX 1 Comparative EX 2 EX 3 EX 4 EX 5 EX 6 REF Figure (without thermal treatment) 4a 5a 6a 7a 8a 9a REF Figure (with thermal treatment) 4b 5b 6b 7b 8b 9b
  • Fig. 5a is the profile of a sample reported in Example 2 before heat treatment. We can see that each layer is well-defined, and no copper is present in the gold layer.
  • Example 3 the following sequence was used on the reference brass panels:
  • Example 3 From Example 3, it can be seen from Fig. 6a that the thin intermediate layer of indium is located between the copper and the top gold top layer.
  • the resulting top layer is an alloy of gold and indium that contains only very little if any copper. Obviously, copper migration to the surface was inhibited.
  • the top layer is composed of an Au-In alloy as a cover layer for the Cu under layer (and the substrate). It appears, therefore, that In can be employed as a copper diffusion barrier between a copper or copper alloy substrate and a gold surface layer in a way similar to the action of a nickel or palladium barrier commonly used until recently.
  • Example 5 according to the present invention the following sequence was used on the reference brass panels:
  • Example 5 according to the present invention the following sequence was used on the reference brass panels:
  • the gold-indium alloy (Au 90-95 % : In 5-10 %) layer can strongly reduce the copper migration during the thermal treatment procedure.
  • the interface between the copper layer and the gold-indium alloys is well defined in both cases and no copper migration is observed from the bottom copper layer.
  • Example 8 the following sequence was used on the reference brass panels:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (13)

  1. Procédé de préparation d'un produit électroplaqué par électroplaquage d'un substrat comprenant les étapes suivantes :
    a) l'électroplaquage d'un substrat avec une sous-couche constituée de cuivre ou d'un alliage de cuivre avec un électrolyte comprenant au moins une source d'ions de cuivre, au moins un sel conducteur et, éventuellement, au moins une source d'ions d'un formateur d'alliage pour le cuivre,
    b) l'électroplaquage d'une couche barrière de diffusion qui empêche l'interdiffusion entre la sous-couche et la couche supérieure sur la sous-couche avec un bain aqueux comprenant au moins une source d'ions d'indium et au moins un sel conducteur,
    c) l'électroplaquage d'une couche supérieure constituée d'un métal précieux choisi dans le groupe constitué par Au, Ag, Ru et leurs alliages avec un électrolyte comprenant au moins une source d'ions pour le métal précieux et au moins un sel conducteur,
    caractérisé en ce que le bain d'électroplaquage de l'étape b) comprend au moins une source d'ions du métal précieux de la couche supérieure.
  2. Procédé de préparation d'un produit électroplaqué selon la revendication 1, caractérisé en ce que le bain d'électroplaquage à l'étape b) a un pH compris entre 1 et 14, de préférence entre 2 et 11, et plus préférentiellement entre 4 et 10.
  3. Procédé de préparation d'un produit électroplaqué selon la revendication 1 ou 2, caractérisé en ce que dans le bain d'électroplaquage de l'étape b), au moins une source d'ions indium est choisie dans le groupe constitué par le sulfate d'indium, le chlorure d'indium, l'acétate d'indium, le sulfamate d'indium et des combinaisons ou des mélanges de ceux-ci,
    dans lequel la concentration d'indium dans le bain d'électroplaquage est de préférence comprise entre 0,2 et 15 g/L, encore plus préférentiellement entre 0,3 et 10 g/L, et de manière préférée entre toutes entre 0,5 et 7 g/L.
  4. Procédé de préparation d'un produit électroplaqué selon l'une quelconque des revendications précédentes,
    caractérisé en ce que pour le bain d'électroplaquage de l'étape b), l'au moins un sel conducteur est choisi dans le groupe constitué par les citrates, les formiates, les pyrophosphates, les gluconates et leurs combinaisons ou mélanges, de préférence choisi dans le groupe constitué par le citrate de sodium, le formiate de sodium, le pyrophosphate tétrapotassique, le gluconate de sodium, le gluconate de potassium et leurs combinaisons ou mélanges, dans lequel la concentration de l'au moins un sel conducteur est de préférence de 30 à 500 g/L, plus préférentiellement de 50 à 300 g/L, et de manière préférée entre toutes de 100 à 200 g/L.
  5. Procédé de préparation d'un produit électroplaqué selon l'une quelconque des revendications précédentes,
    caractérisé en ce que le bain d'électroplaquage de l'étape b) comprend au moins un agent tensioactif, de préférence choisi dans le groupe constitué par les acides aminés propioniques, les iminoacides propioniques, les bétaïnes ou les sulfo-bétaïnes d'alkyle quaternaire, plus préférentiellement choisi dans le groupe de la bétaïne, de l'aminobétaïne, de l'imidazoline, de la cocamidopropylbétaïne, de la bétaïne de N,N-Diméthyl-N-(3-cocoamidopropyl)-N-(2-hydroxy-3-sulfopropyl)ammonium, de la bétaïne de N,N-Diméthyl-N-octadécyl-N-(3-sulfopropyl)ammonium, de la bétaïne de N,N-Diméthyl-N-dodécyl-N-(3-sulfopropyl)ammonium, et des combinaisons ou mélanges de ceux-ci,
    dans lequel la concentration de l'au moins un agent tensioactif est de préférence comprise entre 0,1 et 5 g/L, plus préférentiellement entre 0,5 et 1,5 g/L.
  6. Procédé de préparation d'un produit électroplaqué selon l'une quelconque des revendications précédentes,
    caractérisé en ce que le bain d'électroplaquage de l'étape b) comprend au moins un agent complexant constitué d'hydrates de carbone, d'acides aminés, d'iminoacides, de composés sulfurés, d'alcools de sucre, et de combinaisons ou de mélanges de ceux-ci, de préférence choisi dans le groupe constitué du sorbitol, du mannitol, du gluconate, de l'érythrytol, du xylitol, de l'acide nitrilotriacétique, de la cystéine, de l'acide iminodiacétique, des triéthanolamines et de combinaisons ou de mélanges de ceux-ci, dans lequel la concentration de l'au moins un agent complexant est de préférence de 0,5 à 100 g/L, plus préférentiellement de 1 à 75 g/L, encore plus préférentiellement de 2,5 à 50 g/L, et de manière préférée entre toutes de 5 à 35 g/L.
  7. Procédé de préparation d'un produit électroplaqué selon l'une quelconque des revendications précédentes,
    caractérisé en ce que le bain d'électroplaquage de l'étape b) comprend au moins une source d'ions or, de préférence choisie dans le groupe constitué par le cyanure d'or (I) de potassium, le cyanure d'or (III) de potassium, le sulfite d'or (I) de sodium, le sulfite d'or (I) de potassium, le chlorure (III) et les tétrachloroaurates (III) d'or, le thioglycérol d'or (I) et les complexes d'hydantoïne d'or (I) et d'or (III), et leurs combinaisons ou mélanges, dans lequel la concentration de l'au moins une source d'ions or est de préférence comprise entre 0,5 et 10 g/L, plus préférentiellement entre 1 et 5 g/L, et de manière préférée entre toutes entre 2,5 et 3,5 g/L.
  8. Produit électroplaqué comprenant un substrat recouvert d'une sous-couche de cuivre ou d'un alliage de cuivre et d'une couche supérieure constituée d'un métal précieux choisi dans le groupe constitué par Au, Ag, Ru et leurs alliages,
    caractérisé en ce que la sous-couche et la couche supérieure sont séparées par une couche barrière de diffusion constituée d'un alliage d'indium avec le matériau de la couche supérieure qui empêche l'interdiffusion entre la sous-couche et la couche supérieure, dans lequel la couche barrière de diffusion est en contact avec la sous-couche et, du côté opposé, avec la couche supérieure.
  9. Produit électroplaqué selon la revendication 8
    caractérisé en ce que la couche barrière de diffusion a une épaisseur de 10 à 200 nm, plus préférentiellement de 25 à 150 nm et de manière préférée entre toutes de 50 à 100 nm.
  10. Produit électroplaqué selon la revendication 8 ou 9,
    caractérisé en ce que la couche barrière de diffusion comprend un alliage d'or et d'indium avec 90 à 95 % en poids d'or et 5 à 10 % en poids d'indium.
  11. Produit électroplaqué selon l'une des revendications 8 à 10,
    caractérisé en ce que la couche supérieure est constituée d'un métal précieux choisi dans le groupe constitué par Au, Ag et leurs alliages.
  12. Produit électroplaqué selon l'une des revendications 8 à 11,
    caractérisé en ce que le produit électroplaqué est choisi dans le groupe constitué par la bijouterie, la maroquinerie, les montures de lunettes, la mode, l'horlogerie, les bibelots et/ou l'industrie de la serrure.
  13. Produit électroplaqué selon l'une des revendications 8 à 12, pouvant être fabriqué selon le procédé décrit dans l'une quelconque des revendications 1 à 7.
EP19709513.6A 2018-03-13 2019-03-13 Produits galvanisés et bain électrolytique approprié pour fournir de tels produits Active EP3765658B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18161575.8A EP3540097A1 (fr) 2018-03-13 2018-03-13 Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
PCT/EP2019/056328 WO2019175270A1 (fr) 2018-03-13 2019-03-13 Produits électroplaqués et bain d'électroplacage pour obtenir lesdits produits

Publications (2)

Publication Number Publication Date
EP3765658A1 EP3765658A1 (fr) 2021-01-20
EP3765658B1 true EP3765658B1 (fr) 2023-06-14

Family

ID=61628260

Family Applications (2)

Application Number Title Priority Date Filing Date
EP18161575.8A Withdrawn EP3540097A1 (fr) 2018-03-13 2018-03-13 Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
EP19709513.6A Active EP3765658B1 (fr) 2018-03-13 2019-03-13 Produits galvanisés et bain électrolytique approprié pour fournir de tels produits

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP18161575.8A Withdrawn EP3540097A1 (fr) 2018-03-13 2018-03-13 Produits galvanisés et bain électrolytique approprié pour fournir de tels produits

Country Status (3)

Country Link
EP (2) EP3540097A1 (fr)
ES (1) ES2970912T3 (fr)
WO (1) WO2019175270A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4001472A1 (fr) * 2020-11-16 2022-05-25 COVENTYA S.p.A. Procédé de préparation d'un produit électroplaqué par dépôt d'une sous-couche, d'une couche barrière de diffusion et d'une couche supérieure sur la surface d'un substrat et produit électroplaqué ainsi préparé
CN114525553B (zh) * 2022-03-01 2023-05-30 九牧厨卫股份有限公司 一种蓝白色复合镀层及其制备方法和蓝白色杀菌产品
CN114540895B (zh) * 2022-03-01 2023-05-30 九牧厨卫股份有限公司 一种杀菌灰色复合镀层及其制备方法和灰色杀菌产品

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2458839A (en) 1944-04-19 1949-01-11 Indium Corp America Electrodeposition of indium and its alloys
US3367754A (en) * 1965-02-03 1968-02-06 Gen Dynamics Corp Electronic transmission material and method of fabrication
EP1408141B1 (fr) 2002-10-11 2014-12-17 Enthone Inc. Methode et électrolyte pour la deposition galvanique des bronzes
EP1930478B1 (fr) 2006-12-06 2013-06-19 Enthone, Inc. Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre
JP4834022B2 (ja) * 2007-03-27 2011-12-07 古河電気工業株式会社 可動接点部品用銀被覆材およびその製造方法
US20090188808A1 (en) 2008-01-29 2009-07-30 Jiaxiong Wang Indium electroplating baths for thin layer deposition
EP2848714B1 (fr) 2008-04-22 2016-11-23 Rohm and Haas Electronic Materials LLC Procédé de régénération d'ions indium dans des compositions de dépôt électrique d'indium
EP2383244A1 (fr) * 2010-04-23 2011-11-02 Omega SA Elément céramique incrusté d'au moins un décor métallique
DE102011121798B4 (de) 2011-12-21 2013-08-29 Umicore Galvanotechnik Gmbh Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle
KR101168215B1 (ko) 2012-01-20 2012-07-25 가부시끼가이샤시미즈 동-주석 합금 도금 피막, 비시안계 동-주석 합금 도금욕 및 그것을 이용한 도금 방법
AT514427B1 (de) 2013-07-05 2015-01-15 W Garhöfer Ges M B H Ing Elektrolytbad sowie damit erhältliche Objekte bzw. Artikel
JP2015045045A (ja) * 2013-08-27 2015-03-12 Jx日鉱日石金属株式会社 電子部品用金属材料及びその製造方法、それを用いたコネクタ端子、コネクタ及び電子部品
EP3081673A1 (fr) 2015-04-16 2016-10-19 COVENTYA S.p.A. Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations
ES2790583T3 (es) 2015-09-30 2020-10-28 Coventya S P A Baño de galvanoplastia para el depósito electroquímica de una aleación de Cu-Sn-Zn-Pd, procedimiento para el depósito electroquímica de dicha aleación, sustrato que comprende dicha aleación y usos del sustrato
JP6813574B2 (ja) 2015-10-06 2021-01-13 アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ インジウムまたはインジウム合金の堆積方法および物品

Also Published As

Publication number Publication date
ES2970912T3 (es) 2024-05-31
EP3540097A1 (fr) 2019-09-18
EP3765658A1 (fr) 2021-01-20
WO2019175270A1 (fr) 2019-09-19

Similar Documents

Publication Publication Date Title
EP2855732B1 (fr) Bain de placage pour dépôt autocatalytique de couches de nickel
EP3356579B1 (fr) Bain d'électrodéposition pour le dépôt électrochimique d'un alliage cu-sn-zn-pd, procédé de dépôt électrochimique de cet alliage, substrat comprenant ledit alliage et utilisations de ce substrat
EP3765658B1 (fr) Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
CN101289756B (zh) 用于金铜合金电解沉积的电解组合物及方法
CN107771228B (zh) 具有贵金属精整层和改善的耐腐蚀性的电镀产品及其制造方法和用途
US3902977A (en) Gold plating solutions and method
EP3332044B1 (fr) Alliages d'étain et de cuivre contenant du palladium, procédé pour leur préparation, et utilisation associée
EP3312309B1 (fr) Produit plaqué présentant une couche de finition de métal précieux et une résistance à la corrosion améliorée, son procédé de production et leurs utilisations
US4617096A (en) Bath and process for the electrolytic deposition of gold-indium alloys
EP2730682B1 (fr) Solution alcaline sans cyanure pour l'électrodéposition d'alliages d'or, procédé d'électrodéposition et substrat comprenant un dépôt anticorrosion brillant d'un alliage d'or
EP1930478B1 (fr) Composition d'un électrolyte et méthode de dépôt d'alliages quaternaires de cuivre
EP0871801B1 (fr) Procedes de depot electrolytique, compositions et depots
EP4001472A1 (fr) Procédé de préparation d'un produit électroplaqué par dépôt d'une sous-couche, d'une couche barrière de diffusion et d'une couche supérieure sur la surface d'un substrat et produit électroplaqué ainsi préparé
CA1050471A (fr) Electrodeposition sur alliages de rhodium et de ruthenium
WO2021199087A1 (fr) Procédé galvanique pour l'électrodéposition d'une couche de protection, et bain associé
Bacquias Bright gold electroplating solutions: Types of brightening additives used
JPS62164893A (ja) 金色調鏡面製品
JP5888696B2 (ja) 銀系材料の変色防止方法
GB2306508A (en) Gold-iron alloy electroplating processes compositions and deposits
IT202100008084A1 (it) Soluzione elettrolitica per l’elettrodeposizione su substrato metallico di uno strato preparatore a base di rame e stagno
JPS6312954B2 (fr)
US20070012575A1 (en) Bright rhodium electrodeposition

Legal Events

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

Free format text: STATUS: UNKNOWN

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

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

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200930

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
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: 20210811

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: 20230320

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

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602019030991

Country of ref document: DE

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

Effective date: 20230607

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1579287

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230715

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20230614

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

Ref country code: SE

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

Effective date: 20230614

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: 20230914

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: 20230614

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: 20230614

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: 20230614

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: 20230614

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: 20230614

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: 20230915

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

Ref country code: FI

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

Effective date: 20230614

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: 20230614

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

Ref country code: IS

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

Effective date: 20231014

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: 20230614

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: 20230614

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: 20230614

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: 20231016

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: 20231014

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: 20230614

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: 20230614

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: 20230614

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602019030991

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1579287

Country of ref document: AT

Kind code of ref document: T

Effective date: 20230614

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: ES

Ref legal event code: PC2A

Owner name: COVENTYA S.R.L.

Effective date: 20240424

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

Ref country code: DK

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

Effective date: 20230614

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: 20230614

26N No opposition filed

Effective date: 20240315

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: 20230614

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2970912

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20240531

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: 20230614

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

Ref country code: LU

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

Effective date: 20240313

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: 20230614

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

Effective date: 20240313

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: 20230614

Ref country code: LU

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

Effective date: 20240313

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: 20230614

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20240331

REG Reference to a national code

Ref country code: AT

Ref legal event code: HC

Ref document number: 1579287

Country of ref document: AT

Kind code of ref document: T

Owner name: COVENTYA S.R.L., IT

Effective date: 20241205

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: 20240331

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: 20240313

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: 20240313

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: 20240313

Ref country code: GB

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

Effective date: 20240313

Ref country code: BE

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

Effective date: 20240331

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602019030991

Country of ref document: DE

Owner name: COVENTYA S.R.L., IT

Free format text: FORMER OWNER: COVENTYA S.P.A., CARUGO, IT

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

Ref country code: DE

Payment date: 20250218

Year of fee payment: 7

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

Ref country code: AT

Payment date: 20250220

Year of fee payment: 7

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

Ref country code: FR

Payment date: 20250218

Year of fee payment: 7

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

Ref country code: IT

Payment date: 20250218

Year of fee payment: 7

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

Ref country code: TR

Payment date: 20250224

Year of fee payment: 7

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

Ref country code: ES

Payment date: 20250401

Year of fee payment: 7

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

Ref country code: CH

Payment date: 20250401

Year of fee payment: 7

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

Ref country code: CY

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

Effective date: 20190313

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: 20190313