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
  • C25D3/56—Electroplating: Baths therefor from solutions of alloys
  • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C9/00—Alloys based on copper
  • C22C9/02—Alloys based on copper with tin as the next major constituent
• • 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
  • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
• • 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
  • C25D5/60—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
  • 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 invention provides an electroplating bath for electrochemical deposition of a novel Cu-Sn-Zn-Pd alloy on a substrate.
• the novel alloy is characterized by exceptional corrosion resistance.
• the commonly used precious metal intermediate layer e.g. a Pd-layer
• the novel alloy can be provided free of toxic metals (e.g. free of nickel) which makes it hypoallergenic and not prone to cause skin irritation.
• the plating of the inventive alloy between a substrate and its finishing layer prevents discolouration or colour fading of the finishing layer over time. All these advantages render the novel alloy particularly suitable for plating it on items of the fashion industry.
• Nickel has been highlighted as an allergenic metal and its use in consumer products is strongly restricted. Prior to these restrictions, a decorative galvanic layer sequence comprised a nickel layer to reach the bright aspect of the final article, but also to optimize the corrosion resistance properties and to function as a copper diffusion barrier. A high robustness is required for the final object in order to resist the aggressive media created by environmental pollution. A specific nickel-phosphorus alloy was also proposed in order to protect articles produced for the Asian market, where the atmosphere tends to contain high nitrogen and sulphur oxide concentrations.
• bronze as a protective under-layer does not provide the provision of a corrosion resistance like the one previously achieved with nickel. These copper alloys are also less efficient as copper diffusion barriers.
• a nickel layer with a bronze layer most variants require the use of a precious metal under-layer like palladium which is commonly applied between the bronze layer and the final decorative finishing layer. This additional under-layer considerably increases the production costs and can lead to a lack of adhesion of the finishing layer due to palladium passivity.
• Tin and other tin alloys as barrier layers with high tin content have also been developed, but are not really efficient regarding the high brightness required by the fashion market or the high resistance necessary to pass pertinent corrosion tests.
• EP 1 930 478 B1 presents a quaternary bronze alloy where the fourth metal is gallium, indium or thallium.
• Thallium was introduced into the decorative market as a grain refining agent to substitute lead previously present in typical cyanide bronze electrolytes.
• the use of thallium does not raise the bronzes corrosion resistance i.e. the alloy is still highly sensitive to acidity generated by nitrogen and sulphur oxides present ubiquitously in polluted atmospheres.
• thallium is highly toxic.
• Gallium and indium alloys have the disadvantage that they are poorly resistant to aggressive media such as synthetic sweat or saline humidity.
• EP 2 035 602 B1 proposes the introduction of a palladium, ruthenium, rhodium or cobalt layer between the copper-tin layer and the finishing layer. These metals raise considerably the production costs of the final article. Moreover, the passivity of these electroplated layers results in poor adhesion of the final layer and in poor performance regarding corrosion resistance.
• EP 2 757 180 A1 recommends the use of tin alloys with a precious metal, ruthenium in this particular case.
• the ruthenium content needs to be high and this does not allow reducing the production costs due to the high price of ruthenium.
• the process does not yield products with the bright aspect required by the decorative and fashion industries.
• CN 1 175 287 A discloses the deposition of white ornamental surfaces built on a base material covered with copper with a thickness of 1 micron as an under-layer. Said layer is followed by a layer of a Sn-Cu-Pd alloy in a thickness of 0.2 microns or higher, comprising 10-20 wt.-% Sn, 10-80 wt.-% Cu and 10-50 wt.-% Pd as the essential components. Owing to the lack of zinc in this alloy, it does not give the required performance regarding the efficiency as a copper migration barrier.
• This ternary copper-tin-palladium alloy is not suitable as a nickel substitute since the deposit is not bright and shows only poor corrosion resistance.
• JP 2 977503 B2 discloses an alkaline copper-palladium alloy plating liquid comprising a soluble zinc compound, an alkaline salt, a soluble copper compound, a soluble palladium component and a soluble stannic alkaline compound, wherein the concentration of the palladium component is 5 to 20 g/L.
• WO2017/021916 A2 with publication date 09-02-2017 discloses an electroplating bath for electrochemical deposition of a Cu-Sn-Zn-Pd alloy on a substrate, comprising water, a source of copper ions, a source of tin ions, a source of zinc ions and a palladium complex.
• an electroplating bath for electrochemical deposition of a Cu-Sn-Zn-Pd alloy (preferably a quaternary Cu-Sn-Zn-Pd alloy) on a substrate is provided, the bath comprising or consisting of
• the inventive electroplating bath allows the provision of a substrate having an alloy layer which comprises the precious metal palladium.
• the novel alloy resists aggressive atmospheric and other environmental conditions and considerably increases the shelf and usage life of substrates (plated articles). Even without an intermediate precious metal under-layer (e.g. a palladium under-layer) between the substrate and the finishing layer, excellent corrosion protection is provided (pertinent standardized corrosion tests are successfully passed). Furthermore, without disadvantages related to corrosion protection, the use of the inventive alloy allows a substantial reduction of the production costs compared to the use of a pure precious metal underlayer.
• the final article can be provided free of toxic metals (e.g. free of nickel) which renders it hypoallergenic and not prone to cause skin irritation.
• the new alloy provides a smooth coating to the article and prevents diffusion of metallic components from the lower layers to the finishing layer and vice versa. Thus, a colour fading or discolouration of the final aspect is prevented.
• the new bronze alloy layer has lower production costs, very high brightness, very high corrosion resistance and excellent ageing behaviour.
• the final colour (yellow or white bronze) may be adjusted.
• a concentration range of 1 to 20 % wt.-% zinc in the final alloy is sufficient.
• the palladium content of ⁇ 0.25 wt.-% in the alloy was found sufficient for providing the required corrosion resistance.
• Production costs can be minimized by keeping the palladium concentration ⁇ 5 wt.-% in the final alloy while corrosion protection performance is maintained. It was found that a palladium content higher than 5 wt.-% in the alloy considerably raises the production costs without significantly improving corrosion resistance.
• the electroplating bath does not comprise a source of nickel ions, preferably no source of nickel and silver ions, optionally no source of nickel, silver and indium ions.
• the electroplating bath may further comprise
• the electroplating bath comprises an organic brightening agent, preferably selected from the group consisting of reaction product of an amine and epihalohydrine derivatives.
• the electroplating bath comprises a complexing agent and a surfactant, preferably a complexing agent, a surfactant and a brightening agent (inorganic and/or organic), more preferably a complexing agent, a surfactant, a brightening agent and a base.
• a complexing agent preferably a complexing agent, a surfactant and a brightening agent (inorganic and/or organic), more preferably a complexing agent, a surfactant, a brightening agent and a base.
• a method for the electrochemical deposition of a Cu-Sn-Zn-Pd alloy on a substrate comprising the steps
• the method may be characterized in that a substrate is used that comprises or consists of a metal or an alloy selected from the group consisting of bronze, brass, Zamack, alpaca, copper alloy, tin alloy, steel and mixtures thereof and/or the substrate used is a metal-plated object of plastic and/or an alloy-plated object of plastic.
• a positive electrode may be used that comprises or consists of an insoluble anode material, preferably graphite, mixed metal oxides, platinated titanium and/or stainless steel.
• the applied voltage is adjusted to provide a current density of 0.05 to 5 A/dm 2 , preferably 0.2 to 3 A/dm 2 .
• the temperature of the electroplating bath may be kept at between 20 and 80 °C, preferably at between 40 to 70 °C. At temperatures below 20 °C, the coating is less bright, not homogeneous and not uniform in its colour. Above 80 °C, the electroplating results in too many break-down products which results in a quick build-up of potassium carbonate as well as a rapid ageing of the electrolyte. The optimum temperature range was discovered to be between 40 to 70°C.
• a substrate comprising an electrochemically deposited Cu-Sn-Zn-Pd alloy layer
• the alloy layer comprising or consisting of
• the Cu-Sn-Zn-Pd alloy layer electrochemically deposited on the inventive substrate is free of cracks, bright and provides the substrate with excellent corrosion resistance. Moreover, the inventive substrate is characterized by an excellent ageing behaviour i.e. it does not show discolouration or colour fading over time.
• the alloy comprises
• a concentration of zinc between 2 and 15% wt.-%.in the alloy was discovered to give the most effective copper diffusion barrier.
• the alloy layer is free of nickel, preferably free of nickel and silver, optionally free of nickel, silver and indium or free of nickel, silver, indium and mercury.
• the thickness of the electrochemically deposited Cu-Sn-Zn-Pd alloy layer may be 1 nm to 25 ⁇ m, preferably 10 nm to 20 ⁇ m, more preferably 0.1 ⁇ m to 15 ⁇ m, even more preferably 1 ⁇ m to 10 ⁇ m, most preferably 2 ⁇ m to 5 ⁇ m.
• the inventive substrate may be characterized in that it comprises additionally an electrochemically deposited layer comprising or consisting of acidic copper, wherein said layer is preferably located between the substrate and the electrochemically deposited Cu-Sn-Zn-Pd alloy layer.
• the inventive substrate is characterized in that it comprises additionally an electrochemically deposited finishing layer comprising or consisting of a noble metal.
• the electrochemically deposited Cu-Sn-Zn-Pd alloy layer is located between the substrate and the electrochemically deposited finishing layer.
• the electrochemically deposited layer comprising or consisting of acidic copper has a thickness of 1 nm to 1 mm, preferably 10 nm to 500 ⁇ m, more preferably 0.1 ⁇ m to 100 ⁇ m, even more preferably 1 ⁇ m to 50 ⁇ m, most preferably 5 ⁇ m to 20 ⁇ m or even 10 ⁇ m to 15 ⁇ m.
• the electrochemically deposited finishing layer may optionally have a thickness of 0.01 ⁇ m to 20 ⁇ m, preferably 0.02 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, most preferably 0.1 ⁇ m to 3.0 ⁇ m or even 0.2 ⁇ m to 0.5 ⁇ m.
• the substrate is producible with the inventive method.
• the inventive substrate as fashion item is suggested, preferably as an article selected from the group consisting of jewellery, fashion, leather article, watch, eyewear, trinket, lock and/or perfume packaging application.
• the inventive substrate fulfils all requirements of the fashion industry (especially the one for jewellery and leather goods articles), namely:
• the electroplating method for depositing an alloy on a substrate comprised the following plating sequence: - copper layer on substrate: 10 - 15 microns layer thickness - bronze layer on copper layer: ⁇ 2 microns layer thickness - gold finishing layer on bronze layer: 0.2 - 0.5 microns layer thickness
• Example 1 Electrodeposition of a quaternary white bronze Cu-Sn-Zn-Pd deposit
• the deposit was obtained using the following electrolyte solution: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - zinc as Zn(CN) 2 : 1 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 50 mg/L - free potassium cyanide: 50 g/L - free potassium hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
• the electrodeposition was performed at 60 °C since this temperature turned out to be the best compromise for spreading the (white) brightness range to its maximum and obtaining a homogeneous alloy throughout the current density range.
• the copper plated substrate is introduced into the electrolyte after proper cleaning and activation, with a current density of 1 A/dm 2 applied for 20 minutes in order to raise the Cu-Sn-Zn-Pd bronze layer thickness to 5 microns.
• the final aspect of the ternary Cu-Sn-Zn-Pd bronze layer is bright and presents a white colour.
• Example 2 Electrodeposition of a quaternary yellow bronze Cu-Sn-Zn-Pd deposit
• the deposit was obtained using the following electrolyte solution: - copper as CuCN: 15 g/L - tin as K 2 SnO 3 : 12 g/L - palladium as Pd(NH 3 ) 4 Cl 2 : 30 mg/L - zinc as Zn(CN) 2 : 1 g/L - free potassium cyanide: 35 g/L - free potassium hydroxide: 15 g/L - surfactant solution: 3 mL/L - brightening agent solution: 5 mL/L
• the electrodeposition was performed at 50°C since this temperature turned out to be the best compromise for spreading the (yellow) brightness range at its maximum and obtain a homogeneous alloy through the current density range.
• the copper plated substrate is introduced into the electrolyte after proper cleaning and activation with a current density at 1.5 A/dm 2 applied for 15 minutes in order to raise the Cu-Sn-Zn-Pd bronze layer thickness to 5 microns.
• the final aspect of the quaternary Cu-Sn-Zn-Pd bronze layer is bright and presents a pale yellow colour.
• Reference example 1 Electrodeposition of a ternary white bronze Cu-Sn-Zn deposit
• a deposit was obtained using the following electrolyte solution: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - zinc as Zn(CN) 2 : 1 g/L - free potassium cyanide: 50 g/L - free potassium hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
• the electrodeposition is performed using the same conditions as in Example 1.
• the final aspect of the ternary Cu-Sn-Zn bronze layer is bright and presents a white colour.
• Reference example 2 Electrodeposition of a ternary white bronze Cu-Sn-Pd deposit
• the deposit was obtained using the following electrolyte solution: - copper as CuCN: 6 g/L - tin as K 2 SnO 3 : 30 g/L - palladium as Pd(NH 3 ) 4 SO 4 : 50 mg/L - free potassium cyanide: 50 g/L - free potassium hydroxide: 25 g/L - surfactant solution: 3 mL/L - brightening agent solution: 3 mL/L
• the electrodeposition is performed using same conditions as in Example 1.
• the final aspect of the ternary Cu-Sn-Pd bronze layer is hazy and presents a grey colour.
• the aspect of the deposit is not homogeneous.
• the deposit was obtained using the following electrolyte solution: - copper as CuCN: 15 g/L - tin as K 2 SnO 3 : 12 g/L - zinc as Zn(CN) 2 : 1 g/L - free potassium cyanide: 35 g/L - free potassium hydroxide: 15 g/L - surfactant solution: 3 mL/L - brightening agent solution 2: 5 mL/L
• the electrodeposition is performed using the same conditions as in Example 2.
• the final aspect of the ternary Cu-Sn-Zn bronze layer is bright and presents a pale yellow colour.
• the deposit was obtained using the following electrolyte solution: - copper as CuCN: 15 g/L - tin as K 2 SnO 3 : 12 g/L - palladium as Pd(NH 3 ) 4 Cl 2 : 30 mg/L - free potassium cyanide: 35 g/L - free potassium hydroxide: 15 g/L - surfactant solution: 3 mL/L - brightening agent solution: 5 mL/L
• the electrodeposition is performed using the same conditions as in Example 2.
• the final aspect of the ternary Cu-Sn-Pd bronze layer is bright and presents a yellow colour.
• This nickel layer sequence is used as a reference to highlight the comparable behaviour of the new quaternary Cu-Sn-Zn-Pd alloy regarding corrosion resistance of final articles.
• - substrate copper alloys (brass or Zamack)
• - copper 15 microns
• - bright nickel 10 microns
• nickel phosphorus 3 microns
• finishing gold
• Reference Example 6 Electrodeposition of a white ternary Cu-Sn-Zn alloy and a precious metal underlayer sequence
• the layer of ternary bronze and palladium as underlayer sequence is used as a reference to highlight the advantages of the nickel-free quaternary Cu-Sn-Zn-Pd alloy regarding corrosion resistance and the savings in production costs in comparison of the actual hypoallergenic solution.
• - substrate copper alloys (brass or Zamack)
• - copper 15 microns
• ternary Cu-Sn-Zn alloy 5 microns
• palladium alloy 0.3 microns
• gold finishing 0.5 microns
• Example 1 Copper content Tin content Zinc content Palladium content
• Example 1 49% 42% 7% 2% White Cu-Sn-Zn-Pd alloy
• Example 2 79% 16% 4.5% 0.5% Yellow Cu-Sn-Zn-Pd alloy Ref.
• Example 1 44% 46% 9% - White Cu-Sn-Zn alloy Ref.
• Example 2 48% 49% - 3% White Cu-Sn-Pd alloy Ref.
• Example 3 78% 18% 4% - Yellow Cu-Sn-Zn alloy Ref.
• Example 4 80% 19% - 1% Yellow Cu-Sn-Pd alloy
• the electroplated products obtained in Examples 1 and 2 and Reference Examples 1 to 6 were subjected to corrosion resistance tests. Salt spray tests were performed according to the ISO 9227 standard. Synthetic sweat resistance tests were conducted following NFS 80722 requirements, and leather interaction resistance was evaluated in accordance with ISO 4611 testing conditions. The resistance to a SO 2 /NO x atmosphere was tested in a close container with high SO 2 and NO x gas concentrations. The results are shown in Table 2.
• Example 1 No oxidation at 96h No alteration after 48h (upper than required) Similar aspect after 96h (upper than required) No pitting WHITE Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m
• Example 2 Oxidation visible at 72h Slight oxidation at 24h No oxidation at 48h No pitting YELLOW Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Slight oxidation at 96h Ref.
• Example 1 Oxidation visible after 48h Corrosion product after 12h Slight alteration after 48h Pitting WHITE Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Ref.
• Example 2 Corrosion products visible after 24h Oxidation visible after 6h Alteration starts at 24h Strong pitting WHITE Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Ref.
• Example 3 Oxidation visible after 24h Corrosion product after 6h Alteration after 48h Pitting YELLOW Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Ref.
• Example 4 Oxidation visible after 48h Corrosion product after 12h Alteration after 48h Slight pitting YELLOW Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Ref.
• Example 5 No oxidation at 96h No alteration after 48h (upper than required) Similar aspect after 96h (upper than required) No pitting Nickel + Nickel Phosphorus (15 microns in total) Gold finishing 0.5 ⁇ m Ref.
• Example 6 Oxidation visible at 72h Slight oxidation at 24h No oxidation at 48h Slight pitting WHITE Cu-Sn-Zn alloy 5 ⁇ m Palladium alloy 0.3 Gold finishing 0.5 ⁇ m Slight oxidation at 96h
• Example 1 Bright Bright WHITE Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Without alteration
• Example 2 Bright Bright YELLOW Cu-Sn-Zn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Without alteration Ref.
• Example 1 Bright Gold and white bronze layer mixed (white aspect) WHITE Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Ref.
• Example 2 Hazy Under-plated copper is migrating to the top of the final articles WHITE Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Ref.
• Example 3 Bright Spots due to copper migration YELLOW Cu-Sn-Zn alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Ref.
• Example 4 Bright Under-plated copper is migrating to the top of the final articles YELLOW Cu-Sn-Pd alloy 5 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Ref.
• Example 5 Bright Bright Nickel + Nickel Phosphorus (15 microns in total) Gold finishing 0.5 ⁇ m Without alteration Without alteration Ref.
• Example 6 Bright Bright WHITE Cu-Sn-Zn alloy 5 ⁇ m Palladium alloy 0.3 ⁇ m Gold finishing 0.5 ⁇ m Without alteration Without alteration
• Nitric acid resistance Example 1 Cu-Sn-Zn-Pd is not altered by nitric acid WHITE Cu-Sn-Zn-Pd alloy 5 ⁇ m
• Example 2 Nitric acid dissolves 25% of the alloy YELLOW Cu-Sn-Zn-Pd alloy 5 ⁇ m Ref.
• Example 1 Cu-Sn-Zn alloy is dissolved WHITE Cu-Sn-Zn alloy 5 ⁇ m Ref.
• Example 2 Cu-Sn-Pd alloy is dissolved WHITE Cu-Sn-Pd alloy 5 ⁇ m Ref.
• Example 3 Cu-Sn-Zn alloy is dissolved YELLOW Cu-Sn-Zn alloy 5 ⁇ m Ref.
• Example 4 Cu-Sn-Pd alloy is dissolved YELLOW Cu-Sn-Pd alloy 5 ⁇ m Ref.
• Example 5 Nickel phosphorus is not altered by nitric acid Nickel + Nickel Phosphorus (15 microns in total)

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• 2015
  • 2015-09-30 EP EP15187511.9A patent/EP3150744B1/en not_active Revoked
  • 2015-09-30 ES ES15187511T patent/ES2790583T3/es active Active
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• 2016
  • 2016-09-30 WO PCT/EP2016/073427 patent/WO2017055553A1/en unknown
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