EP3935205A1 - Composition et processus de protection de substrats en métal précieux par une nanocouche organique - Google Patents

Composition et processus de protection de substrats en métal précieux par une nanocouche organique

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Publication number
EP3935205A1
EP3935205A1 EP20707301.6A EP20707301A EP3935205A1 EP 3935205 A1 EP3935205 A1 EP 3935205A1 EP 20707301 A EP20707301 A EP 20707301A EP 3935205 A1 EP3935205 A1 EP 3935205A1
Authority
EP
European Patent Office
Prior art keywords
composition
group
precious metal
thiol
combinations
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.)
Withdrawn
Application number
EP20707301.6A
Other languages
German (de)
English (en)
Inventor
Coline Nelias
Marianna Bartoletti
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 EP3935205A1 publication Critical patent/EP3935205A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/58—Treatment of other metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/165—Heterocyclic compounds containing sulfur as hetero atom
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated

Definitions

  • the present invention refers to a composition for the protection of precious metal substrates as well as a process for obtaining an organic protective nanolayer on precious metal substrates. Moreover, the present invention refers to a precious metal substrate having an Organic Protective nanolayer and a product comprising a precious metal substrate and a leather part.
  • the purpose of the invention is to protect precious metal surfaces against interactions with leather causing a transfer of its color or other additives. As regards products in the leather goods industry, a good resistance of metallic parts against interactions with leather is required to provide a final product with long life durability. These transfer problems have become an issue as a consequence of the introduction of nickel free sequences in metal plating which are less resistant to the contact with leather.
  • the affinity of thiols RSH for the coinage metals silver and gold (M) is based on the high polarizability of both the sulfur and the metal atoms which qualify as soft donors and acceptors (S->M) according to the concept of Hard and Soft Acids and Bases (HSAB).
  • S->M soft donors and acceptors
  • HSAB Hard and Soft Acids and Bases
  • US 9,914,838 B2 discloses a composition containing a cationic polymer obtained from as a reaction product from nitrogen-containing heterocyclic compounds, epihalohydrines and a phosphorus compound.
  • the composition can be used as a surface treatment for gold or gold alloys.
  • the drawback of such a composition is that it only provides resistance to corrosion due to pinholes on the surface of the gold or gold alloy and does not offer protection against other corrosion mechanisms.
  • WO 2013/028309 A1 discloses an aqueous tarnish inhibiting solution comprising a mercapto carboxylic acid and a corrosion inhibitor to produce an anti tarnish layer on metal surfaces, such as silver plated copper leadframes, and a method of using the same is provided.
  • the drawbacks of such compositions is that it only provides silver and copper protection and that the use of carbox ylic acid is mandatory.
  • WO 2005/021836 A2 discloses an aqueous, antitarnish and adhesion promot ing treatment composition, comprising zinc ions along with metal ions selected from the group consisting of tungsten, molybdenum, cobalt, nickel, zirconium, titanium, manganese, vanadium, iron, tin, indium, silver, and combinations thereof; and optionally, an electrolyte that does not contain potassium or sodium ions; wherein the composition is substantially free of chromium, and where the treatment composition forms a coating on a substrate or material that enhances adhesion of a polymer to the material.
  • WO 2005/021836 A2 also discloses materials coated with the above treat ment composition, and methods of coating materials using the above composition. The drawback of such a composition is that its use is limited to copper.
  • US 2017/0002211 A1 discloses a composition containing a cationic polymer obtained from a reaction product of nitrogen-containing heterocyclic com pounds, an epihalohydrin and a phosphorus compound.
  • the composition can be used as a surface treatment for gold or gold alloy.
  • the composition can seal pinholes on the surface of the gold or gold alloy. The drawback of such a composition is that it seals only pinholes.
  • WO 2009/067446 A1 discloses a method comprising depositing a metallic surface layer comprising a precious metal on a surface of a copper or copper alloy substrate by immersion displacement plating and exposing the electronic device to an aqueous composition comprising a first organic molecule comprising at least one functional group that interacts with and protects precious metal surfaces and a second organic molecule comprising at least one functional group that interacts with and protects copper surfaces. This method does not prevent color transfer from leather.
  • the composition for the protection of precious metal substrates selected from the group consisting of gold, palla dium, silver, platinum, rhodium, ruthenium and alloys thereof with each other and other alloy formers against the transfer of color and other additives from leather is provided, wherein the composition is an aqueous solution comprising a) at least one compound of the general formula I:
  • Ri or R 2 independently selected from the group consisting of
  • nitrogen-functional groups selected from the group consisting of amino, mono- and dialkylamino, aminoalkyl, monoalkylami- noalkyl, dial ky I a m i n oa I ky I and the corresponding ammonium functions at linear or branched alkyl groups wherein each of them are C 1 -C 12 , and
  • the composition also has a protective anti tarnish effect for precious metal substrates.
  • the nanolayer is generated selectively on the precious metal surfaces of wafers owing to the high affinity of the thiolate function for late transition elements.
  • the aqueous medium is buffered to secure long-term stability of the solutions of the thiol agent and to regulate the growth of the nanolayers.
  • an organic protective nanolayer is applied on top of a precious metal finishing to prevent transfer of organic dyes from the leather to the metallic surface. This is achieved by slightly changing the polarity of the positively charged metallic surface to create an additional barrier against interactions with leather.
  • the organic protective nanolayer is deposited on the precious metal surface and this nanolayer is produced using a solution that contains a five-membered heterocycles bearing at least one thiol or thiolate function and a buffering agent.
  • 1,3,4-thiadiazoles have been introduced which bear (a) thiol/thiolate group(s) in the 2 and/or 5 positions of the heterocycle. These thiol function are the anchoring groups for the metal surface. Where only one thiol/thiolate group is present (as Ri), the remaining position (R 2 ) may be occupied by a choice of functional groups to regulate the solubility in the aqueous medium and the deposition process.
  • Ri and R 2 are independently from each other selected from the group consisting of
  • Ri and R 2 are independently from each other selected from the group consisting of
  • the compound is of the general formula II
  • R selected from the group consisting of
  • nitrogen-functional groups selected from the group consisting of amino, mono- and dialkylamino, aminoalkyl, monoalkylami- noalkyl, dial ky I a m i n oa I ky I and the corresponding ammonium functions at linear or branched alkyl groups wherein each of them are C -C , and
  • the compound is of the general formula II
  • R selected from the group consisting of
  • the concentration of the compound of general formula I or II in the composition is from 5 to 500 mmol/L, more preferably from 10 to 250 mmol/L and most preferably from 15 to 100 mmol/L.
  • the buffering agent is selected from the group consisting of citric acid and its salts, phosphoric acid and its salts, boric acid and its salts, mono-, di- and tri-carboxylic acids and their salts, preferably selected from the group consisting of formic acid and its salts, acetic acid and its salts, and Rochelle salt, and combinations thereof, wherein the concentration of the buffering agent in the composition is preferably from 1 to 100 g/L, more preferably from 5 to 70 g/L, and most preferably from 10 to 50 g/L.
  • the composition has preferably a pH from 2 to 10, more preferably from 4 to 8, most preferably from 5 to 7.
  • the aqueous solution comprises only water a solvent.
  • the solution comprises additional solvents, e g. alcohols.
  • the substrate is exposed to the composition by immersion.
  • the substrate is exposed to the composition for at least 5 minutes, preferably 10 to 30 min, more preferably 15 to 20 min.
  • the substrate is exposed to the composition under cathodic and/or anodic polarization, preferably with pulsed current.
  • the substrate after exposing a substrate to the composi tion, the substrate is exposed to water for cleaning, preferably by immersion.
  • the precious metal substrate comprises or consists of a precious metal selected from the group consisting of gold, palladium, silver, platinum, rhodium, ruthenium and alloys thereof with each other and other alloy formers, preferably selected from the group consisting of gold, palla dium, ruthenium and alloys combinations thereof.
  • a precious metal substrate having an organic protective nanolayer as protective layer wherein the protective layer is obtainable with a process as described above.
  • a product comprising a precious metal substrate and a leather part, wherein the precious metal substrate has an organic protective nanolayer as protective layer obtainable with the process as described above.
  • presious metal substrate and the leather part of the product are in direct contact to each other or are joined together.
  • the type of product is generally not limited as far as the product comprises a precious metal substrate and a leather part, preferably in direct contact to eacg other.
  • the product may be selected from the group consist ing of bags, shoes, jewelleries, perennial and combinations thereof.
  • Fig. 1 shows the Raman spectrum of molecule 1 in solution
  • Fig. 2 shows the Raman spectrum of molecule 2 in solution
  • Fig. 3 shows STM image obtained after modification by molecule 1 and rinsing with water
  • Fig. 4 shows the STM-TERS spectrum obtained on a flat gold surface, previ ously immerged into Molecule 1 solution
  • Fig. 5 shows the STM-TERS spectrum obtained on a cluster present on Gold surface, previously immerged into Molecule 1 solution
  • Fig. 6 shows the TERS spectrum on flat gold surface treated with Molecule 2 solution
  • Fig. 7 shows Sample 1 AFM scanning after Dl water rinsing for 30 minutes
  • Fig. 8 shows Sample 2 AFM scanning after Dl water rinsing for 30 minutes
  • Fig. 9 shows a magnification of 20X from Fig. 8 on filaments observed on Sample 2 AFM scanning after Dl water rinsing for 30 minutes
  • Fig. 10 shows a photo of an precious metal substrate of the prior art without protective layer
  • Fig. 11 shows a photo of an precious metal substrate according to the present invention with a protective layer
  • the starting solutions were prepared by adding 100 pL of the solution containing the thiadazole compound and a conductive salt / buffer in 4.9 mL of H 0.
  • the final concentration of the active compound amounted to 50 mM (except for compound 1 and 2) and the mixture was heated to homogenize.
  • White bronze Also white bronze is a commercial product from Coventya, named Auralloy 450 LF, it is a Cu-Sn-Zn, lead-free alloy plated from a cyanide based plating solution.
  • the composition of the ternary alloy is in the following range (wt.-%):
  • the solution is composed of the following commercial products:
  • yellow bronze is a commercial product from Coventya, named Auralloy 270 LF or Auralloy 250 LF, it is a Cu-Sn-Zn, lead-free alloy plated from a cyanide based plating solution.
  • the composition of the ternary alloy is in the following range (wt.-%):
  • the gold underlayer has been prepared from a generic acidic gold bath.
  • the Coventya reference for this acidic Gold underlayer is PARADOR 9812 NF.
  • the gold substrates were flame-cured and then soaked for 15 minutes in the solutions. A first rinse with water was then performed, and subsequently the samples were left for a minimum of 30 minutes in pure water.
  • a STM (Scanning Tunneling Microscopy) image of the protected gold surface was obtained in order to screen the obtained nanolayer and find a surface area that can further be characterized.
  • Fig. 3 shows a characteristic image obtained on a 300x300 nm 2 surface (sample 1).
  • These clusters are probably small oligomers formed in solution and deposited on the substrates during the formation of the nanolayer. Notable, these clusters are still present after water rinsing which demonstrate strong bounding between the nano-layer and Gold atoms. Thanks to the TERS analysis, it is possible to identify the cluster composition as well as the presence of the nanolayers on homogeneous parts of the surface (named as homogeneous surface).
  • TERS spectra were obtained either of the clusters or of a homogeneous zone in order to highlight the presence of the organic nano-layer on both areas
  • STM scanning image was conducted, which was stopped when a cluster was identified.
  • Spectra of 20s were then recorded on the cluster and its environment, which turned out to present similar response with different intensities (see Fig. 4 and Fig. 5).
  • Substrate wafers produced with 100 nm of Au deposited by thermal evaporation under vacuum on cleaved mica
  • MOLECULE 1 deposited in citrate / citric media
  • Substrate wafers produced with 100 nm of Au deposited by thermal evaporation under vacuum on cleaved mica
  • Substrate wafers produced with 100 nm of Au deposited by thermal evaporation under vacuum on cleaved mica
  • Fig. 9 The image with increased magnification is shown in Fig. 9.
  • the nanolayer clearly forms a different structure in the presence of the buffer / conductive salt (such as filament) whereas without this component, the configuration of the SAM was in the form of clusters (white spots on Fig. 7.).
  • the reference test is following the standard conditions (ISO 4611 - 96 hours), introducing the leather below the metallic surface, in the media described below:
  • Octadecanethiol and 1-Hexadecanethiol were used as references for those tests as they are compounds from the prior art (W02009067446A1). Octadecanethiol was applied for 10 minutes without and with cathodic polarization for 1 minute at 7 V; 1-Hexadecanthiol was applied for 30 minutes.
  • a precious metal substrate of the prior art is shown without a protective nanolayer.
  • the sample shows darker areas being a result of the colour transfer from the darker leather to the substrate.
  • Fig. 11 shows a precious metal substrate according to the present invention.
  • the substrate shows a homogenous colours surface without any dark areas. Due to the protective nanolayer of the present invention a colour transfer from the leather to the precious metal substrate has been avoided completely.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne une composition pour la protection de substrats en métal précieux ainsi qu'un processus d'obtention d'une nanocouche protectrice organique sur des substrats en métal précieux. De plus, la présente invention concerne un substrat en métal précieux ayant une nanocouche de protection organique.
EP20707301.6A 2019-03-08 2020-03-06 Composition et processus de protection de substrats en métal précieux par une nanocouche organique Withdrawn EP3935205A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19161674.7A EP3705607A1 (fr) 2019-03-08 2019-03-08 Composition et procédé de protection de substrats de métal précieux par une nanocouche organique
PCT/EP2020/056080 WO2020182679A1 (fr) 2019-03-08 2020-03-06 Composition et processus de protection de substrats en métal précieux par une nanocouche organique

Publications (1)

Publication Number Publication Date
EP3935205A1 true EP3935205A1 (fr) 2022-01-12

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP19161674.7A Withdrawn EP3705607A1 (fr) 2019-03-08 2019-03-08 Composition et procédé de protection de substrats de métal précieux par une nanocouche organique
EP20707301.6A Withdrawn EP3935205A1 (fr) 2019-03-08 2020-03-06 Composition et processus de protection de substrats en métal précieux par une nanocouche organique

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP19161674.7A Withdrawn EP3705607A1 (fr) 2019-03-08 2019-03-08 Composition et procédé de protection de substrats de métal précieux par une nanocouche organique

Country Status (3)

Country Link
EP (2) EP3705607A1 (fr)
CN (1) CN113767191A (fr)
WO (1) WO2020182679A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1922844B2 (de) * 1968-05-08 1974-06-27 Eastman Kodak Co., Rochester, N.Y. (V.St.A.) Stabilisatorlösung zum Stabilisieren entwickelter photographischer Bilder
DE2021453A1 (de) * 1970-05-02 1971-12-02 Merck Patent Gmbh Antidote gegen N-Loste und N-Lost-Derivate und Mittel gegen ionisierende Strahlen
US6852427B1 (en) 2003-09-02 2005-02-08 Olin Corporation Chromium-free antitarnish adhesion promoting treatment composition
US7883738B2 (en) * 2007-04-18 2011-02-08 Enthone Inc. Metallic surface enhancement
US7972655B2 (en) 2007-11-21 2011-07-05 Enthone Inc. Anti-tarnish coatings
US20130045391A1 (en) 2011-08-19 2013-02-21 Kesheng Feng Tarnish Inhibiting Composition for Metal Leadframes
US20160168724A1 (en) * 2014-12-15 2016-06-16 The Boeing Company Polyvinylbutyral coating containing thiol corrosion inhibitors
JP6577769B2 (ja) 2015-06-30 2019-09-18 ローム・アンド・ハース電子材料株式会社 金または金合金の表面処理液
ES2805102T3 (es) * 2016-10-18 2021-02-10 Coventya S P A Producto galvanizado que tiene una capa de acabado de metal precioso y mejor resistencia a la corrosión, método para su producción y usos del mismo

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Publication number Publication date
WO2020182679A1 (fr) 2020-09-17
CN113767191A (zh) 2021-12-07
EP3705607A1 (fr) 2020-09-09

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