US20190177859A1 - A water-based composition for post-treatment of metal surfaces - Google Patents
A water-based composition for post-treatment of metal surfaces Download PDFInfo
- Publication number
- US20190177859A1 US20190177859A1 US16/310,836 US201716310836A US2019177859A1 US 20190177859 A1 US20190177859 A1 US 20190177859A1 US 201716310836 A US201716310836 A US 201716310836A US 2019177859 A1 US2019177859 A1 US 2019177859A1
- Authority
- US
- United States
- Prior art keywords
- water
- based composition
- composition according
- range
- silver
- 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.)
- Abandoned
Links
- 0 C.C.C.C.[1*]OCC([2*])(CC#CC([2*])(C[1*]O)CC(C)C)CC(C)C Chemical compound C.C.C.C.[1*]OCC([2*])(CC#CC([2*])(C[1*]O)CC(C)C)CC(C)C 0.000 description 3
- BGHCVCJVXZWKCC-UHFFFAOYSA-N CCCCCCCCCCCCCC Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 1
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, dialkyl sulfide or dialkyl disulfide and at least one of an amphoteric, nonionic or cationic surfactant in a concentration that is effective to solubilise the treatment agent.
- a treatment agent selected from an alkanethiol, alkyl thioglycollate, dialkyl sulfide or dialkyl 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.
- 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/lead frame 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:
- water-based composition further contains a compound of the general formula I:
- R 1 is —H, —CH 3 , —C 2 H 5 , —(C 2 H 4 O) p —H, —(C 2 H 4 O) p —CH 3 , —(C 2 H 4 O) p —CH(CH 3 ) 2 , —(C 2 H 4 O) 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, R2 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 “gemini 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 1 is independently selected from the group consisting of R 1 is —H, —CH 3 , —C 2 H 5 and —(C 2 H 4 O) 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, 2,5,8,11-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:
- 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 7-11.
- the surfactant is a polyethylene glycol, more preferably PEG-11 C10-11 Oxo alcohol ethoxylate (CAS Nr: 78330-20-8).
- the water-based composition may comprise a co-emulsifier, which can also be called a “second surfactant”.
- the co-emulsifier may have the general formula III
- 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-emulsifier is preferably polyalkylene glycol ether.
- the co-emulsifier 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. decanethiol, undecanethiol, dodecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, eicosanethiol, most preferably heptadecanethiol, octadecanethiol, nonadecanethiol, eicosanethiol.
- alkanethiol is octadecanethiol.
- 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-emulsifier: 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:
- the water-based composition was made by dissolving the following components in water:
- 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.
- the post-treatment was performed on silver plated copper panels. These panels, having a copper surface, may be provided from the following steps:
- 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 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 decorative silver layer (Silverlume ® Plus) Compound of 0 g/L 2 g/L 3 g/L 4 g/L formula I (comparative (c1-c3) (c1) (c1) example) Residues Very poor Excellent Excellent Excellent (many (none) (none) (none) residues) Anti-tarnish Very poor Improved Strongly Excellent (after 5 min into (dark (yellow improved (no discoloration) K 2 S 2%) discoloration) discoloration) (Yellow to no discoloration)
- Test material bright silver plated surface (Argalux NCTM mod), cyanide free
- Water-based composition conditions pH 2.5—Temperature 55° C.—Agitation 200 RPM—1 min immersion process, rinse & dry.
- Test material bright silver cyanide free (Argalux NC TM mod.) Compound (c1) 0 g/L 3 g/L 4 g/L of formula I (comparative example) Residues Poor (many) Excellent (none) Excellent (none) Anti-tarnish Very poor Strongly improved Excellent (no (after 5 min (dark colored) (yellow colored) discoloration) into K 2 S 2%)
- Test material technical silver plated surface (AgO-56TM)
- 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)
- Test material technical silver (AgO-56 TM) Compound 0 g/L 3 g/L (c1) of (comparative example) formula I Process Immersion Cathodic Immersion Cathodic Residues Poor (many) Poor (many) Excellent (none) Excellent (none) Anti-tarnish 5 min 10 min 5 min 10 min (dipping time Very poor Strongly Good (yellow to no Excellent (no into K 2 S 2%) (dark colored) improved discoloration) discoloration)
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 Treatment Of Metals (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
-
- 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:
-
- R1 is —H, —CH3, —C2H5, —(C2H4O)p—H, —(C2H4O)p—CH3, —(C2H4O)p—CH(CH3)2, —(C2H4)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
- 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, dialkyl sulfide or dialkyl 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.
- 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/lead frame 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
R1 is —H, —CH3, —C2H5, —(C2H4O)p—H, —(C2H4O)p—CH3, —(C2H4O)p—CH(CH3)2, —(C2H4O)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:
- 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 R1 is independently selected from the group consisting of R1 is —H, —CH3, —C2H5 and —(C2H4O)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, 2,5,8,11-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:
-
R3O(CH2CH2O)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 7-11. - Preferably the surfactant is a polyethylene glycol, more preferably PEG-11 C10-11 Oxo alcohol ethoxylate (CAS Nr: 78330-20-8).
- The water-based composition may comprise a co-emulsifier, which can also be called a “second surfactant”.
- The co-emulsifier may have the general formula III
-
R4O(CH2CH2O)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-emulsifier is preferably polyalkylene glycol ether. Preferably the co-emulsifier 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. decanethiol, undecanethiol, dodecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, eicosanethiol, most preferably heptadecanethiol, octadecanethiol, nonadecanethiol, eicosanethiol. In one preferred embodiment alkanethiol is octadecanethiol.
- 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-emulsifier: 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.
- Hereinafter, the invention is illustrated by working examples.
- 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: octadecanethiol. (CAS Nr. 2885-00-9) amount: 2.5 g/L
- b. surfactant: PEG-11 C10-11 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. 169117-72-0) in an amount: 2, 3 or 4 g/l
- d. co-emulsifier: Alcohol C16-18 polyalkylene glycol ether, (CAS Nr. 68002-96-0) amount: 2,5 g/L.
- 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: octadecanethiol. (CAS Nr. 2885-00-9) amount: 2.5 g/L
- b. surfactant: PEG-11 C10-11 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-emulsifier: Alcohol C16-18 polyalkylene glycol ether, (CAS Nr. 68002-96-0) amount: 2.5 g/L.
- 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.
- 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. (cyanide-free bright silver deposition solution) cathodic 0.8 ASD/RT/5 min
wherein RT is room temperature between 22±2° C.; DI water is deionized water; ASD is Ampere per square decimeter A/dm2 and V is volt/voltage.
- Providing Copper Panels
- 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 DI water rinse,
- Cold DI 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
- Optical evaluation after post-treatment with the inventive and comparative composition and subsequent sulphide test due to:
- 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
- Sulphide 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.
- 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 decorative silver layer (Silverlume ® Plus) Compound of 0 g/L 2 g/L 3 g/L 4 g/L formula I (comparative (c1-c3) (c1) (c1) example) Residues Very poor Excellent Excellent Excellent (many (none) (none) (none) residues) Anti-tarnish Very poor Improved Strongly Excellent (after 5 min into (dark (yellow improved (no discoloration) K2S 2%) discoloration) discoloration) (Yellow to no discoloration) - Test material: bright silver plated surface (Argalux NC™ mod), cyanide free
- Water-based composition conditions: pH 2.5—Temperature 55° C.—Agitation 200 RPM—1 min immersion process, rinse & dry.
-
Test material: bright silver cyanide free (Argalux NC ™ mod.) Compound (c1) 0 g/L 3 g/L 4 g/L of formula I (comparative example) Residues Poor (many) Excellent (none) Excellent (none) Anti-tarnish Very poor Strongly improved Excellent (no (after 5 min (dark colored) (yellow colored) discoloration) into K2S 2%) - 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 (AgO-56 ™) Compound (c1) 0 g/L 3 g/L 4 g/L of formula I (comparative example) Residues Poor (many) Excellent (none) Excellent (none) Anti-tarnish Very poor Strongly improved Excellent (no (after 5 min (dark colored) (yellow to no discoloration) into K2S 2%) discoloration) - 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
-
Test material: technical silver (AgO-56 ™) Compound 0 g/L 3 g/L (c1) of (comparative example) formula I Process Immersion Cathodic Immersion Cathodic Residues Poor (many) Poor (many) Excellent (none) Excellent (none) Anti-tarnish 5 min 10 min 5 min 10 min (dipping time Very poor Strongly Good (yellow to no Excellent (no into K2S 2%) (dark colored) improved discoloration) discoloration) -
-
- 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.
- The inventive water-based compositions do improve:
Claims (16)
R3O(CH2CH2O)xH (II)
R4O(CH2CH2O)yH (III)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16175905.5 | 2016-06-23 | ||
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 (1)
Publication Number | Publication Date |
---|---|
US20190177859A1 true US20190177859A1 (en) | 2019-06-13 |
Family
ID=56363712
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/310,836 Abandoned US20190177859A1 (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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210253896A1 (en) * | 2020-02-14 | 2021-08-19 | Evonik Operations Gmbh | Solvent-free composition based on 2,4,7,9-tetramethyl-5-decyne-4,7-diol |
Families Citing this family (2)
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4885064A (en) * | 1989-05-22 | 1989-12-05 | Mcgean-Rohco, Inc. | Additive composition, plating bath and method for electroplating tin and/or lead |
US20030078307A1 (en) * | 2001-05-30 | 2003-04-24 | Shuichiro Shinohara | Water-soluble surfactant compositions |
US20140042494A1 (en) * | 2012-08-09 | 2014-02-13 | City University Of Hong Kong | Metal nanoparticle monolayer |
Family Cites Families (20)
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 treating agent for plating on electrical contact |
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 |
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 ink-jet printing, electrodeposition liquid and color filter |
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 liquid |
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 |
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 |
-
2017
- 2017-06-23 KR KR1020197001189A patent/KR102351460B1/en active IP Right Grant
- 2017-06-23 JP JP2018567197A patent/JP6931010B2/en active Active
- 2017-06-23 US US16/310,836 patent/US20190177859A1/en not_active Abandoned
- 2017-06-23 CN CN201780038677.6A patent/CN109477226A/en active Pending
- 2017-06-23 WO PCT/EP2017/065564 patent/WO2017220790A1/en unknown
- 2017-06-23 ES ES17731183T patent/ES2781310T3/en active Active
- 2017-06-23 EP EP17731183.4A patent/EP3475466B1/en active Active
- 2017-06-23 TW TW106120995A patent/TWI746583B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4885064A (en) * | 1989-05-22 | 1989-12-05 | Mcgean-Rohco, Inc. | Additive composition, plating bath and method for electroplating tin and/or lead |
US20030078307A1 (en) * | 2001-05-30 | 2003-04-24 | Shuichiro Shinohara | Water-soluble surfactant compositions |
US20140042494A1 (en) * | 2012-08-09 | 2014-02-13 | City University Of Hong Kong | Metal nanoparticle monolayer |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210253896A1 (en) * | 2020-02-14 | 2021-08-19 | Evonik Operations Gmbh | Solvent-free composition based on 2,4,7,9-tetramethyl-5-decyne-4,7-diol |
US11851574B2 (en) * | 2020-02-14 | 2023-12-26 | Evonik Operations Gmbh | Solvent-free composition based on 2,4,7,9-tetramethyl-5-decyne-4,7-diol |
Also Published As
Publication number | Publication date |
---|---|
EP3475466B1 (en) | 2020-03-04 |
JP2019520480A (en) | 2019-07-18 |
EP3475466A1 (en) | 2019-05-01 |
WO2017220790A1 (en) | 2017-12-28 |
TWI746583B (en) | 2021-11-21 |
KR20190021326A (en) | 2019-03-05 |
KR102351460B1 (en) | 2022-01-13 |
TW201819686A (en) | 2018-06-01 |
ES2781310T3 (en) | 2020-09-01 |
CN109477226A (en) | 2019-03-15 |
JP6931010B2 (en) | 2021-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100964063B1 (en) | Aqueous antioxidant for tin or tin alloy | |
TWI688679B (en) | Tin plating bath and tin coating | |
EP3475466B1 (en) | A water-based composition for post-treatment of metal surfaces | |
US11505874B2 (en) | Methods and apparatuses for mitigating tin whisker growth on tin and tin-plated surfaces by doping tin with germanium | |
KR101286661B1 (en) | Silver-containing alloy plating bath and method for electrolytic plating using same | |
US20140098504A1 (en) | Electroplating method for printed circuit board | |
US20080187672A1 (en) | Method and Composition for Improving Adhesion of Organic Polymer Coatings with Copper Surface | |
US6555170B2 (en) | Pre-plate treating system | |
KR100802878B1 (en) | Metal surface treating agent, surface treating method and use thereof | |
KR101688756B1 (en) | Electronic component and process for producing same | |
KR20160070469A (en) | A method for plating copper alloy with tin | |
CN102282294A (en) | Solution and process for increasing the solderability and corrosion resistance of a metal or metal alloy surface | |
TWI417429B (en) | An electroplating bath using the electroplating bath, and a substrate deposited by the electrolytic plating | |
KR101510832B1 (en) | Anti-tarnishing composotion of pure copper and copper alloy | |
EP1969157B1 (en) | Passivator and lubricant for gold, silver, and copper surfaces, and method for using the same | |
KR101998605B1 (en) | Zn-Ni alloy electroplating agent, and Electroplating method using the same | |
US6331201B1 (en) | Bismuth coating protection for copper | |
JP2015067853A (en) | Electronic component and manufacturing method thereof | |
EP4249646A1 (en) | Method of inhibiting tarnish formation and corrosion | |
KR101663112B1 (en) | A composition of the corrosion inhibitors of the copper surface of the magnesium alloy is applied to the communucations rf filter and a treating method using the composition | |
WO2013147698A9 (en) | An aqueous solution for forming an alkylthiol self-assembled monolayer and a method for forming the same using the solution | |
CN116157555A (en) | Cyanide electrolytic silver alloy plating solution | |
JP6201144B2 (en) | Acid reduction type electroless bismuth plating bath and bismuth plating method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: ATOTECH DEUTSCHLAND GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ARAI, CHIHO;LAGORCE-BROC, FLORENCE;RUETHER, ROBERT;AND OTHERS;SIGNING DATES FROM 20181205 TO 20190102;REEL/FRAME:047886/0689 |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: APPLICATION DISPATCHED FROM PREEXAM, NOT YET DOCKETED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: ADVISORY ACTION MAILED |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |