[go: up one dir, main page]

EP3475466A1 - A water-based composition for post-treatment of metal surfaces - Google Patents

A water-based composition for post-treatment of metal surfaces

Info

Publication number
EP3475466A1
EP3475466A1 EP17731183.4A EP17731183A EP3475466A1 EP 3475466 A1 EP3475466 A1 EP 3475466A1 EP 17731183 A EP17731183 A EP 17731183A EP 3475466 A1 EP3475466 A1 EP 3475466A1
Authority
EP
European Patent Office
Prior art keywords
water
based composition
silver
composition according
range
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.)
Granted
Application number
EP17731183.4A
Other languages
German (de)
French (fr)
Other versions
EP3475466B1 (en
Inventor
Chiho ARAI
Florence Lagorce-Broc
Dr. Robert RÜTHER
Olaf Kurtz
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.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Atotech Deutschland GmbH and Co KG
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 Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP3475466A1 publication Critical patent/EP3475466A1/en
Application granted granted Critical
Publication of EP3475466B1 publication Critical patent/EP3475466B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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
    • C23F11/161—Mercaptans
    • 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
    • C23F11/12—Oxygen-containing compounds
    • 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/145—Amides; N-substituted amides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling

Definitions

  • the present invention relates to a water-based composition for post-treatment of metal surfaces, the use thereof and to a method for post-treatment of metal surfaces.
  • Silver and silver alloys are used in electronic devices but it is inevitable that finished articles will require further cleaning and polishing to temporarily remove undesired tarnish products. It is well-known that with exposure to everyday atmospheric conditions, silver and silver alloys develop a lustre-destroying dark film known as tarnish. Prevention of tarnishing of metals and metal alloys is a challenging problem in numerous industries. The tarnishing of metal and metal alloys has been especially problematic in the electronic materials industry where tarnishing may lead to faulty electrical contact between components in electronic devices.
  • US20070277906A1 discloses for use in treating a metal, e.g. silver or an alloy of silver, a water-based composition comprising a treatment agent selected from an alkanethiol, alkyl thioglycollate, dialkyi sulfide or dialkyi disulfide and at least one of an amphoteric, nonionic or cationic surfactant in a concentration that is effective to solubilise the treatment agent.
  • the composition comprises at least a non-ionic relatively hydrophobic surfactant e.g. cocamide DEA.
  • the composition is particularly suitable for the treatment of Ag-Cu-Ge alloys. Objectives of the Invention
  • the objective of the present invention was to provide a composition for effective post- treatment of metal surfaces, particularly silver or silver alloys, in order to prevent tarnishing of such surfaces.
  • the invention provides with a water-based composition for post-treatment of metal surfaces, preferably a silver or silver alloy surface, the use thereof and a method. Preferred embodiments are described within the dependent claims.
  • the metal surfaces are especially surfaces in the field of technical and decorative surfaces either on metal substrates or plastic materials, e.g. on connectors or IC / leadframe applications as well as surfaces on automotive, aerospace, construction, communication, furniture, sanitary and consumer goods.
  • the invention in particularly provides with a water-based composition for post-treatment of metal surfaces, preferably a silver or silver alloy surface comprising: an alkanethiol, an anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant with a HLB value of 12 to 18, preferably 15, wherein the water-based composition further contains a compound of the general formula I:
  • i is -H, -CH 3 , -C 2 H 5 , -(C 2 H 4 0)p-H, -(C 2 H 4 0) p -CH 3 , -(C 2 H 4 0) p -CH(CH 3 ) 2 , -(C 2 H 4 0) p -C(CH 3 )3, wherein p is an integer in the range of 1 to 20, preferably 1 to 10, more preferably 2 to 6, R 2 is H or CH 3 , preferably CH 3, n is an integer in the range of 0 to 3, preferably 1 to 3, even more preferably 1 or 2, m is an integer in the range of 0, 1 or 2, preferably 0.
  • HLB values were determined according to the method of W.C. Griffin.
  • the composition can be an emulsion.
  • the alkanethiol forms a self-assembled thiol monolayer onto immersed silver surfaces which prevents or retards tarnishing.
  • the compound of formula I is also called a gravisco-like surfactant" which has the more general, following structure:
  • Gemini surfactants are composed of two polar heads (hydrophilic groups) flanked by a spacer to which hydrophobic tails are linked; the spacer can be rigid or flexible, polar or apolar.
  • the invention also discloses using such general surfactants in a composition for post- treatment of metal surfaces. It has been shown that by addition of a surfactant with above structure, particularly by addition of a component of formula I, improved anti tarnishing properties of the composition can be reached.
  • n in the range of 0 to 3 preferably n in the range of 1 to 3, more preferably n is 1 or 2
  • R ⁇ is independently selected from the group consisting of R ⁇ is -H, -CH 3 , -C 2 H 5 and -(C 2 H 4 0)p-H with p in the range 2 to 6.
  • the compound of formula I is selected from the group consisting of 2,3,6,7- tetramethyl-4-octyne-3,6-diol, 2,5,8,1 1 -tetramethyl-6-dodecyn-5,8-diol ethoxylate, 2,4,7,9- tetramethyl-5-decyne-4,7-diol ethoxylate, 2,4,7, 9-tetramethyl-5-decyne-4,7-diol, 2,2'- [(2,4,7,9-tetramethyl-5-decyne-4,7-diyl) bis(oxy)] diethanol, and 2,4,7, 9-tetramethyl-5- decyne-4,7-diolbispolyoxyethylene-ether.
  • the anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant may have a hydrophobic tail that may linear or branched.
  • the anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant may be an ethoxylated or propoxylated alkyl, ethoxylated or propoxylated amine, ethoxylated or propoxylated amide, ethoxylated or propoxylated alcohol, or a mixture thereof.
  • a beneficial surfactant is 3-ethoxy- 2-methylnonane.
  • the surfactant may have the general formula II:
  • R 3 is a linear or branched alkyl group, having 6 - 15 carbon atoms, preferably 8-12 carbon atoms,
  • x is an integer in the range of 3 - 15, preferably 7 - 1 1 .
  • the surfactant is a polyethylene glycol, more preferably PEG-1 1 C10-1 1 Oxo alcohol ethoxylate (CAS Nr: 78330-20-8).
  • the water-based composition may comprise a co-emulgator, which can also be called a "second surfactant".
  • the co-emulgator may have the general formula III
  • R 4 is a linear or branched alkyl group, having 16 - 20 carbon atoms, preferably 16-18 carbon atoms,
  • the co-emulgator is preferably polyalkylene glycol ether.
  • the co-emulgator is an Alcohol C16-18 ethoxylated propoxylated, (CAS Nr. 68002-96-0).
  • the alkanethiol is preferably a branched or unbranched C 10 - to C 20 -alkanethiol, more preferred unbranched C 10 - to C 20 -alkanethiol, e.g. decanthiol, undecanthiol, dodecanthiol, hexadecanthiol, heptadecanthiol, octadecanthiol, nonadecanthiol, eicosanthiol, most preferably heptadecanthiol, octadecanthiol, nonadecanthiol, eicosanthiol.
  • alkanethiol is octadecanthiol.
  • the water-based composition is free of chromate and/or free of organic solvent.
  • the water-based composition may have a pH in the range of 1 to 6, preferably 2 to 4.
  • the pH may be adjusted by a buffer system. Suitable buffer systems are citric acid / citrate, acetic acid / acetate, tartaric acid / tartrate, phosphoric acid / phosphate or any suitable acid and salts combinations.
  • the water-based composition may comprise the mentioned constituents in following amounts: alkanethiol: 0.1 - 5 g/L, preferably 0.5 - 4 g/L surfactant: 2 - 30 g/L, preferably 5 - 20 g/L compound of formula I: 1 - 10 g/L, preferably 1 - 5 g/L; and optionally Co-emulgator: 0.1 - 5 g/L, preferably 0.5 - 2 g/L
  • the invention is directed to the use of the water-based composition above for post-treatment of metal surface, particularly a silver or silver alloy surface, to avoid tarnishing after metal deposition, particularly after silver or silver alloy deposition.
  • the invention is directed to a method for post-treatment of a metal surface, particularly a silver or silver alloy surface comprising, in this order, the steps:
  • Contacting can be done by any suitable method.
  • the contacting in step b. may particularly be done by immersing into the water-based composition and/or by spraying with the water- based-composition onto the surface.
  • Contacting in step b. may be done additionally under electroless conditions, i.e. without supplying a current between the metal surface and an electrode.
  • contacting in step b. takes place under applying an electrical current between the metal surface, particularly the silver or silver alloy surface, and at least one electrode when the metal surface is immersed into the water-based composition.
  • the metal surface can act as cathode and the other electrode (which is the counter electrode) can act as anode, or vice versa.
  • the metal surface is cathodic.
  • the present invention works preferably with a composition temperature in a range of room temperature (22 ⁇ 2°C) or higher, more preferably 30 °C or higher, most preferably in a range of 35 - 65 °C.
  • the water-based composition was made by dissolving the following components in water: a. alkanethiol: octadecanthiol. (CAS Nr. 2885-00-9)
  • the water-based composition was made by dissolving the following components in water: a. alkanethiol: octadecanthiol. (CAS Nr. 2885-00-9)
  • Comparative water-based compositions comprising a., b. and d. wherein the concentrations of compound of the general formula I (c1 -c3) was zero and the other concentrations were as stated above. 1 .
  • the post-treatment was performed on silver plated copper panels. These panels, having a copper surface, may be provided from the following steps:
  • Silver Silverlume Plus (bright silver deposition solution) cathodic 1 ASD / RT / 5 min
  • ArgaluxTM NC mod. cyanid-free bright silver deposition solution cathodic 0.8 ASD / RT / 5 min wherein RT is room temperature between 22 ⁇ 2°C; Dl water is deionized water; ASD is Ampere per square decimeter A/dm 2 and V is volt/voltage.
  • the post-treatment composition may work also with otherwise obtained silver plated surfaces in the field of use of technical or decorative (with or without cyanide) silver deposition solutions for silver plating to avoid tarnishing after this silver plating.
  • inventive water-based compositions according to the invention for post-treatment and the comparative water-based compositions were used under various conditions (see tests below).
  • the inventive water-based compositions showed improved rinsing capability in comparison with the comparative water-based compositions and eliminate oily residues issues completely.
  • the treatment of Silverlume Plus, AgO-56 and ArgaluxTM NC mod. plated silver surfaces with the comparative water-based compositions the surfaces showed poor rinsing capability, whereas the inventive water-based compositions show very good rinsing capability. 2.2 Anti tarnishing tests
  • the inventive water-based compositions showed improved anti-tarnish protection in comparison with the comparative water-based compositions without the compound of the general formula I (c1 -c3).
  • the not-treated silver surfaces obtained from silver plating solutions as Silverlume Plus, AgO-56 and ArgaluxTM NC mod. exhibit very poor anti-tarnish protection.
  • These plated silver surfaces treated with the comparative water-based compositions showed less discoloration after sulphide test, whereas the surfaces treated with the inventive water-based compositions show few to no discoloration.
  • Test material bright silver plated surface (Silverlume Plus)
  • Water-based composition conditions pH 2.5 - Temperature 55°C - agitation 200 RPM - immersion process for 1 min, rinse & dry.
  • Test material bright silver plated surface (Argalux NC mod), cyanide free
  • Test material technical silver plated surface (AgO-56 )
  • Water-based composition conditions pH 2.5 - Temperature 55°C - agitation 200 RPM - immersion process for 1 min, rinse & dry.
  • Test material technical silver plated surface (AgO-56TM)
  • Immersion and electrophoretic uses are suitable in avoiding tarnishing of the metal plated surfaces after metal plating.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Description

A water-based composition for post-treatment of metal surfaces Description of the Invention
Field of the Invention
The present invention relates to a water-based composition for post-treatment of metal surfaces, the use thereof and to a method for post-treatment of metal surfaces.
Background of the Invention
Silver and silver alloys are used in electronic devices but it is inevitable that finished articles will require further cleaning and polishing to temporarily remove undesired tarnish products. It is well-known that with exposure to everyday atmospheric conditions, silver and silver alloys develop a lustre-destroying dark film known as tarnish. Prevention of tarnishing of metals and metal alloys is a challenging problem in numerous industries. The tarnishing of metal and metal alloys has been especially problematic in the electronic materials industry where tarnishing may lead to faulty electrical contact between components in electronic devices.
US20070277906A1 discloses for use in treating a metal, e.g. silver or an alloy of silver, a water-based composition comprising a treatment agent selected from an alkanethiol, alkyl thioglycollate, dialkyi sulfide or dialkyi disulfide and at least one of an amphoteric, nonionic or cationic surfactant in a concentration that is effective to solubilise the treatment agent. Preferably the composition comprises at least a non-ionic relatively hydrophobic surfactant e.g. cocamide DEA. The composition is particularly suitable for the treatment of Ag-Cu-Ge alloys. Objectives of the Invention
The objective of the present invention was to provide a composition for effective post- treatment of metal surfaces, particularly silver or silver alloys, in order to prevent tarnishing of such surfaces. Summary and Detailed Description of the Invention
The invention provides with a water-based composition for post-treatment of metal surfaces, preferably a silver or silver alloy surface, the use thereof and a method. Preferred embodiments are described within the dependent claims.
The metal surfaces are especially surfaces in the field of technical and decorative surfaces either on metal substrates or plastic materials, e.g. on connectors or IC / leadframe applications as well as surfaces on automotive, aerospace, construction, communication, furniture, sanitary and consumer goods.
The invention in particularly provides with a water-based composition for post-treatment of metal surfaces, preferably a silver or silver alloy surface comprising: an alkanethiol, an anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant with a HLB value of 12 to 18, preferably 15, wherein the water-based composition further contains a compound of the general formula I:
wherein i is -H, -CH3, -C2H5, -(C2H40)p-H, -(C2H40)p-CH3, -(C2H40)p-CH(CH3)2, -(C2H40)p-C(CH3)3, wherein p is an integer in the range of 1 to 20, preferably 1 to 10, more preferably 2 to 6, R2 is H or CH3, preferably CH3, n is an integer in the range of 0 to 3, preferably 1 to 3, even more preferably 1 or 2, m is an integer in the range of 0, 1 or 2, preferably 0.
HLB values were determined according to the method of W.C. Griffin.
With the present invention, in general or one of the following further embodiments, one or more of the following benefits are obtained:
- enhancing of anti-tarnish properties (particularly proven by K2S test)
- transparent protective coating provides a highly hydrophobic surface property
- repelling oxidation agents
- transparent composition, prevention of negative effects on appearance of a surface treated with the composition
enhanced formation of a self-assembled thiol monolayer onto immersed silver surfaces, thereby providing with a non-polar film
- improved rinsing capability of hydrophobic alkanethiol rests after silver surfaces treatment, effective elimination of oily residues
The composition can be an emulsion.
The alkanethiol forms a self-assembled thiol monolayer onto immersed silver surfaces which prevents or retards tarnishing.
The compound of formula I is also called a„gemini surfactant" which has the more general, following structure:
spacer
hydrophilic group
hydrophobic chain
Gemini surfactants are composed of two polar heads (hydrophilic groups) flanked by a spacer to which hydrophobic tails are linked; the spacer can be rigid or flexible, polar or apolar. The invention also discloses using such general surfactants in a composition for post- treatment of metal surfaces. It has been shown that by addition of a surfactant with above structure, particularly by addition of a component of formula I, improved anti tarnishing properties of the composition can be reached.
In a preferred embodiment of the compound of formula I is m = 0, n in the range of 0 to 3, preferably n in the range of 1 to 3, more preferably n is 1 or 2, and R^ is independently selected from the group consisting of R^ is -H, -CH3, -C2H5 and -(C2H40)p-H with p in the range 2 to 6.
More preferred the compound of formula I is selected from the group consisting of 2,3,6,7- tetramethyl-4-octyne-3,6-diol, 2,5,8,1 1 -tetramethyl-6-dodecyn-5,8-diol ethoxylate, 2,4,7,9- tetramethyl-5-decyne-4,7-diol ethoxylate, 2,4,7, 9-tetramethyl-5-decyne-4,7-diol, 2,2'- [(2,4,7,9-tetramethyl-5-decyne-4,7-diyl) bis(oxy)] diethanol, and 2,4,7, 9-tetramethyl-5- decyne-4,7-diolbispolyoxyethylene-ether.
The anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant may have a hydrophobic tail that may linear or branched. The anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant may be an ethoxylated or propoxylated alkyl, ethoxylated or propoxylated amine, ethoxylated or propoxylated amide, ethoxylated or propoxylated alcohol, or a mixture thereof. A beneficial surfactant is 3-ethoxy- 2-methylnonane. The surfactant may have the general formula II:
R30(CH2CH20)xH formula II wherein
R3 is a linear or branched alkyl group, having 6 - 15 carbon atoms, preferably 8-12 carbon atoms,
x is an integer in the range of 3 - 15, preferably 7 - 1 1 . Preferably the surfactant is a polyethylene glycol, more preferably PEG-1 1 C10-1 1 Oxo alcohol ethoxylate (CAS Nr: 78330-20-8).
The water-based composition may comprise a co-emulgator, which can also be called a "second surfactant".
The co-emulgator may have the general formula III
R40(CH2CH20)yH formula III wherein
R4 is a linear or branched alkyl group, having 16 - 20 carbon atoms, preferably 16-18 carbon atoms,
y is an integer in the range of 2 - 10, preferably 3 - 6. The co-emulgator is preferably polyalkylene glycol ether. Preferably the co-emulgator is an Alcohol C16-18 ethoxylated propoxylated, (CAS Nr. 68002-96-0).
The alkanethiol is preferably a branched or unbranched C10- to C20-alkanethiol, more preferred unbranched C10- to C20-alkanethiol, e.g. decanthiol, undecanthiol, dodecanthiol, hexadecanthiol, heptadecanthiol, octadecanthiol, nonadecanthiol, eicosanthiol, most preferably heptadecanthiol, octadecanthiol, nonadecanthiol, eicosanthiol. In one preferred embodiment alkanethiol is octadecanthiol.
In a preferred embodiment, the water-based composition is free of chromate and/or free of organic solvent. The water-based composition may have a pH in the range of 1 to 6, preferably 2 to 4. The pH may be adjusted by a buffer system. Suitable buffer systems are citric acid / citrate, acetic acid / acetate, tartaric acid / tartrate, phosphoric acid / phosphate or any suitable acid and salts combinations.
The water-based composition may comprise the mentioned constituents in following amounts: alkanethiol: 0.1 - 5 g/L, preferably 0.5 - 4 g/L surfactant: 2 - 30 g/L, preferably 5 - 20 g/L compound of formula I: 1 - 10 g/L, preferably 1 - 5 g/L; and optionally Co-emulgator: 0.1 - 5 g/L, preferably 0.5 - 2 g/L
In another aspect, the invention is directed to the use of the water-based composition above for post-treatment of metal surface, particularly a silver or silver alloy surface, to avoid tarnishing after metal deposition, particularly after silver or silver alloy deposition.
In still another aspect, the invention is directed to a method for post-treatment of a metal surface, particularly a silver or silver alloy surface comprising, in this order, the steps:
a. providing a metal surface, particularly a silver or silver alloy surface,
b. contacting the metal surface, particularly the silver or silver alloy surface, with the water-based composition as described before. Any of the water-based compositions that were described before can be employed.
Contacting can be done by any suitable method. The contacting in step b. may particularly be done by immersing into the water-based composition and/or by spraying with the water- based-composition onto the surface.
Contacting in step b. may be done additionally under electroless conditions, i.e. without supplying a current between the metal surface and an electrode. In another embodiment, contacting in step b. takes place under applying an electrical current between the metal surface, particularly the silver or silver alloy surface, and at least one electrode when the metal surface is immersed into the water-based composition. The metal surface can act as cathode and the other electrode (which is the counter electrode) can act as anode, or vice versa. Preferably the metal surface is cathodic.
The present invention works preferably with a composition temperature in a range of room temperature (22±2°C) or higher, more preferably 30 °C or higher, most preferably in a range of 35 - 65 °C.
EXAMPLES Hereinafter, the invention is illustrated by working examples. Inventive Example 1 :
Water-based compositions were provided, wherein the concentrations of c.) compound of the general formula I (compound c1 )), vary while the concentrations of other components are fixed, respectively.
The water-based composition was made by dissolving the following components in water: a. alkanethiol: octadecanthiol. (CAS Nr. 2885-00-9)
amount: 2,5 g/L
b. surfactant: PEG- 11 C10-1 1 Oxo alcohol ethoxylates (CAS Nr: 78330-20-8)
amount: 17,5 g/l
c. compound of the general formula I: c1 ) 2,5,8, 11 -Tetramethyl-6-dodecyn-5,8-diol ethoxylate, (CAS Nr. 1691 17-72-0) in an amount: 2, 3 or 4 g/l
d. co-emulgator: Alcohol C16-18 polyalkylene glycol ether, (CAS Nr. 68002-96-0) amount: 2,5 g/L.
Inventive Example 2:
Water-based composition was provided wherein the following compound c2) 2,4,7,9- tetramethyl-5-decyne-4,7-diol ethoxylate (CAS Nr. 9014-85-1 ) and c3) 2,4,7, 9-tetramethyl-5- decyne-4,7-diol (CAS Nr. 126-86-3) of c.) compound of the general formula I were separately used at same concentrations:
The water-based composition was made by dissolving the following components in water: a. alkanethiol: octadecanthiol. (CAS Nr. 2885-00-9)
amount: 2,5 g/L
b surfactant: PEG- 11 C10-1 1 Oxo alcohol ethoxylates (CAS Nr: 78330-20-8)
amount: 17,5 g/l c. compound of the general formula I (c2 or c3): amount: 2 g/l
d. co-emulgator: Alcohol C16-18 polyalkylene glycol ether, (CAS Nr. 68002-96-0) amount: 2,5 g/L. Comparative Example:
Comparative water-based compositions were provided, comprising a., b. and d. wherein the concentrations of compound of the general formula I (c1 -c3) was zero and the other concentrations were as stated above. 1 . Methods
The post-treatment was performed on silver plated copper panels. These panels, having a copper surface, may be provided from the following steps:
■ Providing copper panels
1 . Degrease Uniclean™ 260 (electrophoretic alkaline cleaner) cathodic 7V / 45°C / 30 sec
2. Activate: Uniclean™ 675 (mild acidic activator)immersion / RT / 30 sec
3. Pre-silver Pre-silver (low silver concentrated solution) cathodic 3V / RT / 15 sec
4. Silver Silverlume Plus (bright silver deposition solution) cathodic 1 ASD / RT / 5 min
or AgO-56 (technical silver deposition solution) cathodic 1 ASD / RT / 5 min
or Argalux™ NC mod. (cyanid-free bright silver deposition solution) cathodic 0.8 ASD / RT / 5 min wherein RT is room temperature between 22±2°C; Dl water is deionized water; ASD is Ampere per square decimeter A/dm2 and V is volt/voltage.
In the sense of this invention the post-treatment composition may work also with otherwise obtained silver plated surfaces in the field of use of technical or decorative (with or without cyanide) silver deposition solutions for silver plating to avoid tarnishing after this silver plating. The inventive water-based compositions according to the invention for post-treatment and the comparative water-based compositions were used under various conditions (see tests below).
After post-treatment in the water-based composition all samples were rinsed with:
- Hot Dl water rinse,
- Cold Dl water rinse and
- dried with compressed air.
■ Optical evaluation after post-treatment with the inventive and comparative composition and subsequent sulphide test due to:
- Residues immediately after post-treatment and rinse
- Colorations and tarnishing after sulphide test
The observations have been carried out without any instruments by skilled person.
■ Sulphide test
■ Material: Glass beaker
■ Chemicals: Potassium Sulphide 44% K2S, 2% w/w in water
■ Temperature: 22 ± 2°C
■ Dipping time: 5 - 10 min
■ Evaluation by the skilled person
■ according to colour intensity
2. Results
2.1 Rinsing capability test
The inventive water-based compositions showed improved rinsing capability in comparison with the comparative water-based compositions and eliminate oily residues issues completely. The treatment of Silverlume Plus, AgO-56 and Argalux™ NC mod. plated silver surfaces with the comparative water-based compositions the surfaces showed poor rinsing capability, whereas the inventive water-based compositions show very good rinsing capability. 2.2 Anti tarnishing tests
The inventive water-based compositions showed improved anti-tarnish protection in comparison with the comparative water-based compositions without the compound of the general formula I (c1 -c3). The not-treated silver surfaces obtained from silver plating solutions as Silverlume Plus, AgO-56 and Argalux™ NC mod. exhibit very poor anti-tarnish protection. These plated silver surfaces treated with the comparative water-based compositions showed less discoloration after sulphide test, whereas the surfaces treated with the inventive water-based compositions show few to no discoloration. Test material: bright silver plated surface (Silverlume Plus)
Water-based composition conditions: pH 2.5 - Temperature 55°C - agitation 200 RPM - immersion process for 1 min, rinse & dry.
Test material: bright silver plated surface (Argalux NC mod), cyanide free
Water-based composition conditions: pH 2.5 - Temperature 55°C - Agitation 200
1 min immersion process, rinse & dry.
Test material: technical silver plated surface (AgO-56 )
Water-based composition conditions: pH 2.5 - Temperature 55°C - agitation 200 RPM - immersion process for 1 min, rinse & dry.
2.3 Cathodic use
Test material: technical silver plated surface (AgO-56™)
Water-based composition conditions: pH 2.5 - Temperature 55°C - Agitation 200 RPM - immersion for 1 min or cathodic 0.5 A/dm2 for 1 min, rinse & dry
3. Conclusions
■ The inventive water-based compositions do improve:
- The wettability of immersed metal surfaces, especially silver.
- The formation of a self-assembled thiol monolayer onto immersed silver surfaces, making a non-polar film and enhancing anti-tarnish properties.
- The rinsing of hydrophobic alkanethiol rests after silver surfaces treatment with water based solution of the invention.
■ Immersion and electrophoretic uses are suitable in avoiding tarnishing of the metal plated surfaces after metal plating.

Claims

Claims
1 . A water-based composition for post-treatment of metal surfaces, preferably a silver or silver alloy surface, comprising an alkanethiol, an anionic, cationic, non-ionic, amphoteric or zwitterionic surfactant with a HLB value of 1 2 to 18, characterized in that the water-based composition further contains a compound of the general formula I :
wherein
Ri is -H, -CH3, -C2H5, -(C2H40)p-H, -(C2H40)p-CH3, -(C2H40)p-CH(CH3)2,
-(C2H40)p-C(CH3)3, wherein p is an integer in the range of 1 to 20,
R2 is H or CH3, n is an integer in the range of 0 to 3, m is an integer in the range of 0, 1 or 2.
2. The water-based composition according to claim 1 , wherein in the compound of formula I is m = 0, n in the range of 0 to 3 and is independently selected from the group consisting of -H, -CH3, -C2H5 and -(C2H40)p-H wherein p in the range 2 to 6.
3. The water-based composition according to claim 1 , wherein the compound of formula I is selected from the group consisting of 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 2,5,8,1 1 -tetramethyl-6-dodecyn-5,8-diol ethoxylate, 2,4,7, 9-tetramethyl-5-decyne-4,7- diol ethoxylate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol-bispolyoxyethyleneether, and 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
4. The water-based composition according to any of the foregoing claims, wherein the surfactant is an ethoxylated or propoxylated alkyl, ethoxylated or propoxylated amine, ethoxylated or propoxylated amide, ethoxylated or propoxylated alcohol, or a mixture thereof.
5. The water-based composition according to any of the foregoing claims, wherein the surfactant has the general formula II
R30(CH2CH20)xH (II) wherein
R3 is a linear or branched alkyl group, having 6 - 15 carbon atoms, preferably 8-12 carbon atoms,
x is an integer in the range of 3 - 15, preferably 7 - 1 1 .
6. The water-based composition according to any of the foregoing claims, wherein the alkanethiol is a C10- to C20-alkanethiol.
7. The water-based composition according to any of the foregoing claims, wherein the composition comprises a co-emulgator
8. The water-based composition according to claim 7, wherein the co-emulgator has the general formula III
R40(CH2CH20)yH (I II) wherein R4 is a linear or branched alkyl group, having 16 - 20 carbon atoms, preferably 16-18 carbon atoms,
y is an integer in the range of 2 - 10, preferably 3 - 6.
9. The water-based composition according to claim 7 or 8, wherein the co-emulgator is a polyalkylene glycol ether.
10. The water-based composition according to any of the foregoing claims, wherein the composition is free of chromate and/or free of organic solvent.
1 1 . The water-based composition according to any of the foregoing claims, having a pH in the range of 1 to 10.
12. The use of the water-based composition according to one of the foregoing claims 1 - 10 for post-treatment of metal surface, particularly a silver or silver alloy surface, to avoid metal tarnishing.
13. A method for post-treatment of a metal surface, particularly a silver or silver alloy surface comprising, in this order, the steps a. providing a metal surface, particularly a silver or silver alloy surface, b. contacting the metal surface, particularly the silver or silver alloy surface, with a water-based composition according to any of claims 1 - 1 1 .
14. The method according to claim 13, wherein the contacting in step b. is applied as immersing and/or per spraying and/or per any other suitable method allowing the contact between the metal and the claim solution.
15. The method according to claim 13 or 14, wherein the contacting in step b. takes place under applying an electrical current between the metal surface, particularly the silver or silver alloy surface, and at least one electrode when the metal is immersed into the claim solution.
EP17731183.4A 2016-06-23 2017-06-23 A water-based composition for post-treatment of metal surfaces Active EP3475466B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16175905 2016-06-23
PCT/EP2017/065564 WO2017220790A1 (en) 2016-06-23 2017-06-23 A water-based composition for post-treatment of metal surfaces

Publications (2)

Publication Number Publication Date
EP3475466A1 true EP3475466A1 (en) 2019-05-01
EP3475466B1 EP3475466B1 (en) 2020-03-04

Family

ID=56363712

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17731183.4A Active EP3475466B1 (en) 2016-06-23 2017-06-23 A water-based composition for post-treatment of metal surfaces

Country Status (8)

Country Link
US (1) US20190177859A1 (en)
EP (1) EP3475466B1 (en)
JP (1) JP6931010B2 (en)
KR (1) KR102351460B1 (en)
CN (1) CN109477226A (en)
ES (1) ES2781310T3 (en)
TW (1) TWI746583B (en)
WO (1) WO2017220790A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110424030B (en) * 2019-08-30 2020-06-30 广州三孚新材料科技股份有限公司 Cyanide-free alkaline copper electroplating solution, preparation thereof and application thereof in flexible printed circuit board
JP2021042326A (en) * 2019-09-12 2021-03-18 日華化学株式会社 Electrolytic detergent and method for cleaning metal
JP7608195B2 (en) * 2020-02-14 2025-01-06 エボニック オペレーションズ ゲーエムベーハー 2,4,7,9-tetramethyl-5-decyne-4,7-diol-based solvent-free composition
CN119061398A (en) * 2023-05-30 2024-12-03 纳米铸币科技有限公司 Compositions and related methods for depositing alkanethiol monolayers on metal surfaces

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59215490A (en) * 1983-05-23 1984-12-05 Alps Electric Co Ltd Discoloration inhibitor for metal
JPS60251285A (en) * 1984-05-25 1985-12-11 Showa Denko Kk Surface treatment agent for plating electrical contacts
JPS61270382A (en) * 1985-05-23 1986-11-29 Nippon Shokubai Kagaku Kogyo Co Ltd Aqueous surface treating composition for metal capable of treating oil stuck surface
US4885064A (en) * 1989-05-22 1989-12-05 Mcgean-Rohco, Inc. Additive composition, plating bath and method for electroplating tin and/or lead
JP2905658B2 (en) * 1993-01-11 1999-06-14 信越化学工業株式会社 Underwater non-separable concrete composition and defoamer for concrete composition
US5525206A (en) * 1995-02-01 1996-06-11 Enthone-Omi, Inc. Brightening additive for tungsten alloy electroplate
JP2001276705A (en) * 2000-01-24 2001-10-09 Daikin Ind Ltd Method for coating base material, coated article and coating apparatus
JP2002356602A (en) * 2000-07-28 2002-12-13 Sekisui Chem Co Ltd Colored resin emulsion, ink for inkjet printing, electrodeposition liquid and color filter
JP4386156B2 (en) * 2001-05-30 2009-12-16 日信化学工業株式会社 Water-soluble surfactant composition
GB0307290D0 (en) * 2003-03-31 2003-05-07 Cole Paul G Enhancing silver tarnish-resistance
GB2412666B (en) * 2004-03-30 2008-10-08 Paul Gilbert Cole Water-based metal treatment composition
US7771588B2 (en) * 2005-11-17 2010-08-10 General Electric Company Separatory and emulsion breaking processes
JP2007246978A (en) * 2006-03-15 2007-09-27 Jsr Corp Electroless plating solution
CN101353800B (en) * 2007-07-26 2011-09-21 深圳市华傲创表面技术有限公司 Water-soluble silver protecting agent and preparation thereof
CN102145267A (en) * 2010-02-09 2011-08-10 天津赛菲化学科技发展有限公司 Multifunctional surfactant composition for water-based system and preparation method thereof
IT1398698B1 (en) * 2010-02-24 2013-03-08 Mesa S A S Di Malimpensa Simona E Davide E C METHOD FOR THE PROTECTION OF SILVER SURFACES AND ITS UNDERSTANDING ALLOYS.
CN101967631A (en) * 2010-11-04 2011-02-09 西北工业大学 Water-soluble silver anti-blushing agent and preparation method and using method thereof
JP5666940B2 (en) * 2011-02-21 2015-02-12 株式会社大和化成研究所 SEALING AGENT SOLUTION AND SEALING TREATMENT METHOD USING THE SAME
JP5599762B2 (en) * 2011-06-17 2014-10-01 富士フイルム株式会社 Ink composition, ink set, and image forming method
US9293571B2 (en) * 2012-08-09 2016-03-22 City University Of Hong Kong Metal nanoparticle monolayer
JP6004469B2 (en) * 2012-08-31 2016-10-05 Ｊｘ金属株式会社 Metal surface treatment agent and surface treatment method
TW201509245A (en) * 2013-03-15 2015-03-01 Omg Electronic Chemicals Llc Process for forming self-assembled monolayer on metal surface and printed circuit board comprising self-assembled monolayer
CN103726056B (en) * 2013-12-26 2015-10-21 张文博 The protectant preparation method of a kind of water soluble molecules self-assembled film shaped metal

Also Published As

Publication number Publication date
KR102351460B1 (en) 2022-01-13
WO2017220790A1 (en) 2017-12-28
TWI746583B (en) 2021-11-21
US20190177859A1 (en) 2019-06-13
JP2019520480A (en) 2019-07-18
KR20190021326A (en) 2019-03-05
ES2781310T3 (en) 2020-09-01
CN109477226A (en) 2019-03-15
TW201819686A (en) 2018-06-01
JP6931010B2 (en) 2021-09-01
EP3475466B1 (en) 2020-03-04

Similar Documents

Publication Publication Date Title
EP3475466B1 (en) A water-based composition for post-treatment of metal surfaces
KR100964063B1 (en) Aqueous Antioxidant of Tin and Tin Alloy
CN102162113A (en) Tin-silver-copper ternary alloy electroplating solution and electroplating method
TW201343980A (en) Method of preventing silver tarnishing
US11505874B2 (en) Methods and apparatuses for mitigating tin whisker growth on tin and tin-plated surfaces by doping tin with germanium
CN105378151B (en) Method and apparatus for mitigating tin whisker growth on tin and tin-plated surfaces by doping tin with gold
TWI779028B (en) Etching liquid composition and etching method
KR20140044785A (en) Processes and compositions for improving corrosion performance of zirconium oxide pretreated zinc surfaces
US20080187672A1 (en) Method and Composition for Improving Adhesion of Organic Polymer Coatings with Copper Surface
EP2878702A1 (en) Organic disulfide-containing surface treatment solution for gold or gold alloy plating and method thereof
CN102282294A (en) Solutions and methods for increasing brazeability and corrosion resistance of metal or metal alloy surfaces
JP6192181B2 (en) Electronic component and manufacturing method thereof
KR101510832B1 (en) Anti-tarnishing composotion of pure copper and copper alloy
KR20120051658A (en) Tin-containing alloy plating bath, electroplating method using same, and base having electroplated material deposited thereon
KR100802878B1 (en) Metal surface treatment agent, surface treatment method and use thereof
CN112410838A (en) Water-based electroplated nickel sealing agent and preparation method thereof
WO1998049367A1 (en) Bismuth coating protection for copper
JP2005041989A (en) Detergent composition for component made of tin-containing alloy, and washing method
EP1969157B1 (en) Passivator and lubricant for gold, silver, and copper surfaces, and method for using the same
EP3339471A1 (en) Method for electroless plating
WO2013147698A9 (en) An aqueous solution for forming an alkylthiol self-assembled monolayer and a method for forming the same using the solution
EP3889318A1 (en) Method for forming a black-passivation layer on a zinc-iron alloy and black-passivation composition
JP2015004104A (en) Acid reduction type electroless bismuth plating bath and bismuth plating method

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: 20181207

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)
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

RIC1 Information provided on ipc code assigned before grant

Ipc: C23F 11/12 20060101AFI20191107BHEP

Ipc: C23F 11/14 20060101ALI20191107BHEP

Ipc: C23F 11/16 20060101ALI20191107BHEP

INTG Intention to grant announced

Effective date: 20191209

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: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1240449

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200315

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017012651

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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: 20200304

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: 20200604

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: 20200304

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200304

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

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: 20200304

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: 20200304

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: 20200304

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: 20200605

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: 20200604

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2781310

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200901

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: 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: 20200304

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: 20200304

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: 20200304

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: 20200704

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: 20200304

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: 20200304

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: 20200304

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: 20200304

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: 20200729

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017012651

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

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

Ref country code: 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: 20200304

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: 20200304

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

26N No opposition filed

Effective date: 20201207

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: 20200304

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: 20200304

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: 20200623

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20200630

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: 20200623

Ref country code: CH

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

Effective date: 20200630

Ref country code: LI

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

Effective date: 20200630

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: 20200630

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

Effective date: 20210623

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: 20210623

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

Ref country code: TR

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

Effective date: 20200304

Ref country code: MT

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

Effective date: 20200304

Ref country code: CY

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

Effective date: 20200304

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

Ref country code: MK

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

Effective date: 20200304

Ref country code: AL

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

Effective date: 20200304

REG Reference to a national code

Ref country code: AT

Ref legal event code: UEP

Ref document number: 1240449

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200304

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

Ref country code: DE

Payment date: 20250626

Year of fee payment: 9

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

Ref country code: FR

Payment date: 20250624

Year of fee payment: 9

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

Ref country code: AT

Payment date: 20250617

Year of fee payment: 9

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

Ref country code: ES

Payment date: 20250710

Year of fee payment: 9

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

Ref country code: IT

Payment date: 20250623

Year of fee payment: 9