WO2017220790A1 - A water-based composition for post-treatment of metal surfaces - Google Patents

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

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Publication number
WO2017220790A1
WO2017220790A1 PCT/EP2017/065564 EP2017065564W WO2017220790A1 WO 2017220790 A1 WO2017220790 A1 WO 2017220790A1 EP 2017065564 W EP2017065564 W EP 2017065564W WO 2017220790 A1 WO2017220790 A1 WO 2017220790A1
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Prior art keywords
water
based composition
silver
composition according
range
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PCT/EP2017/065564
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French (fr)
Inventor
Chiho ARAI
Florence Lagorce-Broc
Dr. Robert RÜTHER
Olaf Kurtz
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Atotech Deutschland Gmbh
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Application filed by Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Priority to CN201780038677.6A priority Critical patent/CN109477226A/en
Priority to US16/310,836 priority patent/US20190177859A1/en
Priority to EP17731183.4A priority patent/EP3475466B1/en
Priority to KR1020197001189A priority patent/KR102351460B1/en
Priority to JP2018567197A priority patent/JP6931010B2/en
Priority to ES17731183T priority patent/ES2781310T3/en
Publication of WO2017220790A1 publication Critical patent/WO2017220790A1/en

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    • 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.

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  • 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 Treatment Of Metals (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

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, a compound of the general formula (I) wherein R1 is -H, -CH3, -C2H5, -(C2H4O)p-H, -(C2H4O)p-CH3, -(C2H4O)p-CH(CH3)2, -(C2H4O)p-C(CH3)3, wherein p is 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 to 2.

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:
Figure imgf000003_0001
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
Figure imgf000005_0001
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.
Figure imgf000011_0001
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.
Figure imgf000011_0002
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.
Figure imgf000012_0001
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
Figure imgf000012_0002
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 :
Figure imgf000013_0001
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.
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