WO2005083156A1 - Non-cyanide silver plating bath composition - Google Patents
Non-cyanide silver plating bath composition Download PDFInfo
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- WO2005083156A1 WO2005083156A1 PCT/US2005/000672 US2005000672W WO2005083156A1 WO 2005083156 A1 WO2005083156 A1 WO 2005083156A1 US 2005000672 W US2005000672 W US 2005000672W WO 2005083156 A1 WO2005083156 A1 WO 2005083156A1
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- salts
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- electroplating solution
- nonprecipitating
- solution
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 34
- 239000004332 silver Substances 0.000 title claims abstract description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title description 25
- 238000007747 plating Methods 0.000 title description 24
- 239000000203 mixture Substances 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 229940091173 hydantoin Drugs 0.000 claims abstract description 31
- 238000009713 electroplating Methods 0.000 claims abstract description 27
- -1 hydantoin compound Chemical class 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims abstract description 18
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- 235000014655 lactic acid Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011149 active material Substances 0.000 claims description 9
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 8
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 8
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical class C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 150000002332 glycine derivatives Chemical class 0.000 claims description 5
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 claims description 4
- 235000001968 nicotinic acid Nutrition 0.000 claims description 4
- 239000011664 nicotinic acid Substances 0.000 claims description 4
- 229960003512 nicotinic acid Drugs 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- VFQXVTODMYMSMJ-UHFFFAOYSA-N isonicotinamide Chemical compound NC(=O)C1=CC=NC=C1 VFQXVTODMYMSMJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002659 electrodeposit Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical group CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 7
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- 150000001469 hydantoins Chemical class 0.000 description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 229960002317 succinimide Drugs 0.000 description 5
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000003222 pyridines Chemical class 0.000 description 4
- 239000004094 surface-active agent Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 235000005152 nicotinamide Nutrition 0.000 description 3
- 239000011570 nicotinamide Substances 0.000 description 3
- 229960003966 nicotinamide Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RHYBFKMFHLPQPH-UHFFFAOYSA-N N-methylhydantoin Chemical compound CN1CC(=O)NC1=O RHYBFKMFHLPQPH-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001085205 Prenanthella exigua Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- CSRCNKZJIYKJOT-UHFFFAOYSA-N formaldehyde;naphthalene;sodium Chemical compound [Na].O=C.C1=CC=CC2=CC=CC=C21 CSRCNKZJIYKJOT-UHFFFAOYSA-N 0.000 description 1
- CIUJKJGFMKSNOT-UHFFFAOYSA-N imidazolidine-2,4-dione;silver Chemical class [Ag].O=C1CNC(=O)N1 CIUJKJGFMKSNOT-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
Definitions
- Hydantoin (CAS Number 461-72-3) is a cyclic diimide possessing structural features similar to succinimide, and similarly effective as a complexing agent for silver.
- the hydantoins are soluble in moderate-to-strongly alkaline (pH > 8) solutions, are capable of forming complexes with silver and other metals, and are more resistant to hydrolysis than succinimide.
- Asakawa (4) patented non-cyanide plating solutions for silver in which silver salts are added together with a hydantoin compound and an inorganic or organic acid salt for the purpose of providing electrical conductivity.
- One preferred embodiment of the present invention is an electroplating solution for the deposition of silver; said solution comprising silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also comprising an excess (i.e., more than a stoichiometric amount based on the silver) of the hydantoin or substituted hydantoin compound, together with an effective quantity of a nonprecipitating electrolyte salt, and also an effective quantity of 2,2' dipyridyl for the purpose of obtaining a mirror-bright to brilliant deposit.
- An excess amount of the hydantoin or substituted hydantoin compound ensures the complete (or nearly complete) complexation of the silver.
- the electroplating solution further comprises an effective quantity of a pyridine or substituted pyridine compound for the purpose of improving the overall brightness of the deposit obtained.
- the electroplating solution further comprises an effective quantity of surface-active material for the purpose of further improving the overall brightness and brilliance of the deposit obtained.
- the surface-active material is selected from the group consisting of Hamposyl C, Hamposyl L, Hamposyl O, Blancol, Blancol N, Rhodacal, and Rhodacal N.
- These commercially available materials are genetically described as follows; cocoyl sarcosine, lauroyl sarcosine, oleoyl sarcosine, sulfonated naphthalene formaldehyde condensate, sodium salt of ethoxylated sulfonated naphthalene condensate, napthalene formaldehyde sulfonate, and sodium naphthalene formaldehyde sulfonate.
- the pyridine or substituted pyridine compound is selected from the group consisting of nicotinamide, isonicotinarnide, 2- amino-pyridine, 3-aminopyridine, nicotinic acid and its salts, and isonicotinic acid and its salts.
- the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
- Another preferred embodiment of the present invention is a process for the formation of a mirror-bright to brilliant electrodeposit of silver on a substrate comprising the step of: electroplating said substrate in an electroplating solution, said solution comprising silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also comprising an excess of the hydantoin or substituted hydantoin compound, together with an effective quantity of a nonprecipitating electrolyte salt, and an effective quantity of 2,2' dipyridyl for the formation of a mirror-bright to brilliant deposit.
- the electroplating solution used in the process of the invention further comprises an effective quantity of a pyridine or substituted pyridine compound for the purpose of improving the overall brightness of the deposit obtained.
- the electroplating solution used in the process of the invention further comprises an effective quantity of surface-active material for the purpose of further improving the overall brightness and brilliance of the deposit obtained.
- nonprecipitating electrolyte salts refer to salts of acids the silver salts of which are soluble.
- nonprecipitating electrolyte salts would include the sodium, potassium, or ammonium salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic and lactic acids. Such materials do not cause film formation at the anodes, and in some cases promote anode corrosion.
- the silver-hydantoin complexes of this invention arc premanufactured in that form to the plating solution, together with an excess of the hydantoin and the nonprecipitating electrolyte salt.
- 2,2'- dipyridyl to the plating solutions of this invention, usually in amounts in the range of about 0.1 to 10 grams per liter, produces bright deposits over a current density range from about 5-20 mA/cm 2 for solutions operated at room temperature.
- Addition of further quantities of various substituted pyridine compounds usually in amounts greater than that of the 2,2'-dipyridyl itself, expands the range of usable current density from about 1 to 30 mA/cm 2 , and improves the uniformity and whiteness of the entire deposit.
- Preferred substituted pyridine compounds for the purposes of this invention include nicotinamide, isonicotinamide, 2-aminopyridine, 3-aminopyridine, nicotinic acid and its salts, and isonicotinic acid and its salts. These are added in amounts from about 2.5 to 100 grams per liter, depending on other parameters of the plating solution. It should be pointed out that in the absence of 2,2 '-dipyridyl, addition of substituted pyridine compounds is generally ineffective for the purposes of this invention. It should also be pointed out that additions of 4,4'-dipyridyl and 1,10-phenanthroline arc likewise ineffective for the purposes of this invention.
- a suitable surfactant to the plating solutions of this invention containing both 2,2 , -dipyridyl and a substituted pyridine compound, produces an overall improvement of deposit brightness from mirror-bright to brilliant.
- Especially preferred surfactants used in the present invention include the class of substituted glycine derivatives known commercially as the Hamposyls, and also the sulfonated naphthalene - formaldehyde condensates known commercially as Blancol N or Rhodacal N, and their aqueous solutions. Both of these classes of surfactants have been used previously for conventional (cyanide based) silver plating.
- the plating solutions of this invention produce mirror-bright to brilliant deposits over a range of pH from about 9 to about 13. Certain practical considerations act to limit this range somewhat.
- the corrosivity of the solutions toward silver anodes increases generally with increasing pH from about pH 9.5 to about pH 13. It also happens that 2,2'-dipyridyl is subject to hydrolysis at pH values above about 10.5, the rate of hydrolysis increasing with increasing pH.
- an optimum pH range of about 10-11 is arrived at.
- plating solutions of this invention are given as follows.
- silver is added as a preformed complex formed by the reaction of silver oxide with hydantoin, or with a substituted hydantoin, such as 5,5-dimethyl- hydantoin, as appropriate. No foreign ions are thus introduced.
- substituted hydantoin compounds can likewise be employed.
- Methyl-hydantoin, other alkyl- hydantoins, other dialkyl-hydantoins, and the like are useful herein. See the hydantoin compounds of U.S. Patent No. 5,750,018 for additional examples.
- the solution pH was approximately 11.0.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation.
- the deposit obtained was white and mirror-bright at indicated current densities from about 5-20 niA/cm 2 .
- the solution pH was approximately 11.0.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature v/ith moving- vane agitation.
- the deposit obtained was white and mirror-bright at indicated current densities from near zero to about 12.5 n A/cm 2 .
- a plating solution was made up as in Example 2, but additionally containing approximately 0.6 grams of Rhodacal N in the form of an aqueous solution.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving-vane agitation. The deposit obtained was brilliant mirror- bright white at current densities from near zero to greater that 20 mA/cm 2 .
- a plating solution was made up as in Example 3 except containing approximately 0.4 grams of Hamposyl L as an aqueous solution solubilized by potassium hydroxide in place of the Rhodacal N.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to greater than 20 mA/cm 2 .
- a plating solution was made up as in Example 3 except containing 1.3 grams of 2-aminopyridine in place of nicotinamide.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to greater than 20 mA/cm 2 .
- a plating solution was made up as in Example 5 except containing 0.8 grams of 3-aminopyridine in place of 2-aminopyridine.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to greater than 20 mA/cm 2 .
- the solution pH was approximately 11.0.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature s .. ⁇ th moving- vane agitation.
- the deposit obtained was white and hazy-bright from near zero to about 5 niA/'cm 2 .
- a plating solution was made up as in Example 7 except additionally containing 26.4 grams of nicotinamide.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving-vane agitation.
- the deposit obtained was white and mirror-bright at current densities from near zero to greater than 20 mA/cm .
- a plating solution was made up as in Example 8 except additionally containing 0.16 grams of Hamposyl L in the form of an aqueous solution solubilized with potassium hydroxide.
- a test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- ane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to 20 mA/cm 2 .
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Disclosed is an electroplating solution for the deposition of silver; said solution containing silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also containing an excess of the hydantoin or substituted hydantoin compound employed, together with an effective quantity of a nonprecipitating electrolyte salt, and also an effective quantity of 2,2' dipyridyl for the purpose of obtaining a mirror-bright to brilliant deposit.
Description
NON-CYANIDE SILVER PLATING BATH COMPOSITION
PRIORITY CLAIM
This application claims priority from copending United States Patent Application Serial No. 10/785,297, filed 24 February 2004.
BACKGROUND OF THE INVENTION
Numerous non-cyanide silver plating processes have been attempted (1). Of these, the only ones to have achieved commercial success have been those employing succinimide, either as a premanufactured silver complex (2, 3), or as a reagent. Succinimide undergoes hydrolysis at pH values above neutrality, which in turn causes the pH of the plating solution, normally in the range of 8 to 9 or so, to become unstable; and also to require frequent replenishment of the succinimide.
Hydantoin (CAS Number 461-72-3) is a cyclic diimide possessing structural features similar to succinimide, and similarly effective as a complexing agent for silver. A series of substituted hydantoins exist, of which the most commonly available commercially is 5,5-dimethylhydantoin (CAS No. 77-71-4). As a class, the hydantoins are soluble in moderate-to-strongly alkaline (pH > 8) solutions, are capable of forming complexes with silver and other metals, and are more resistant to hydrolysis than succinimide. Asakawa (4) patented non-cyanide plating solutions for
silver in which silver salts are added together with a hydantoin compound and an inorganic or organic acid salt for the purpose of providing electrical conductivity.
Asakawa teaches the use of various sulfur-containing compounds as gloss- controlling agents for the deposits from the plating solutions of his invention, and states that with the use of such additives deposit appearance suitable for decorative applications can be obtained. There is no mention of mirror-bright appearance, however, and the Examples provided do not appear to indicate that mirror-bright deposits would be obtained, hi particular, all of the Examples cited include significant quantities of chloride ion, which is a known precipitant for silver and highly likely to form insulating films at the anodes.
Since much commercial silver plating is for the purpose of obtaining mirror- bright to brilliant deposits, it would clearly be desirable to electroplate such deposits from a non-cyanide plating solution, thus saving the costs of cyanide waste treatment, and also of subsequent polishing and buffing.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide a non-cyanide plating solution for the deposition of silver, said solution being capable of yielding mirror- bright to brilliant deposits. It is a further object that the plating solution thus provided be as chemically stable as possible, and free of chemical precipitants.
One preferred embodiment of the present invention is an electroplating solution for the deposition of silver; said solution comprising silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also comprising an excess (i.e., more than a stoichiometric amount based on the silver) of the hydantoin or substituted hydantoin compound, together with an effective quantity of a nonprecipitating electrolyte salt, and also an effective quantity of 2,2' dipyridyl for the purpose of obtaining a mirror-bright to brilliant deposit. An excess amount of the hydantoin or substituted hydantoin compound ensures the complete (or
nearly complete) complexation of the silver.
Preferably, the electroplating solution further comprises an effective quantity of a pyridine or substituted pyridine compound for the purpose of improving the overall brightness of the deposit obtained. Advantageously, the electroplating solution further comprises an effective quantity of surface-active material for the purpose of further improving the overall brightness and brilliance of the deposit obtained.
In certain preferred embodiments the surface-active material is selected from the group consisting of Hamposyl C, Hamposyl L, Hamposyl O, Blancol, Blancol N, Rhodacal, and Rhodacal N. These commercially available materials are genetically described as follows; cocoyl sarcosine, lauroyl sarcosine, oleoyl sarcosine, sulfonated naphthalene formaldehyde condensate, sodium salt of ethoxylated sulfonated naphthalene condensate, napthalene formaldehyde sulfonate, and sodium naphthalene formaldehyde sulfonate.
In certain preferred embodiments, the pyridine or substituted pyridine compound is selected from the group consisting of nicotinamide, isonicotinarnide, 2- amino-pyridine, 3-aminopyridine, nicotinic acid and its salts, and isonicotinic acid and its salts. In certain preferred embodiments, the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
Another preferred embodiment of the present invention is a process for the formation of a mirror-bright to brilliant electrodeposit of silver on a substrate comprising the step of: electroplating said substrate in an electroplating solution, said solution comprising silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also comprising an excess of the hydantoin or substituted hydantoin compound, together with an effective quantity of a nonprecipitating
electrolyte salt, and an effective quantity of 2,2' dipyridyl for the formation of a mirror-bright to brilliant deposit.
Preferably, the electroplating solution used in the process of the invention further comprises an effective quantity of a pyridine or substituted pyridine compound for the purpose of improving the overall brightness of the deposit obtained. Advantageously, the electroplating solution used in the process of the invention further comprises an effective quantity of surface-active material for the purpose of further improving the overall brightness and brilliance of the deposit obtained.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
It has been found that in moderately alkaline plating solutions (i.e., a pH > 9) containing silver in the form of a complex formed with hydantoin or a substituted hydantoin, together with a nonprecipitating electrolyte salt, addition of 2,2'-dipyridyl (CAS No. 366-18-7), either alone or in conjunction with other substituted pyridines and/or surfactants, produces mirror-bright to brilliant deposits.
As used herein, the terms "nonprecipitating electrolyte salts" refer to salts of acids the silver salts of which are soluble. Examples of such nonprecipitating electrolyte salts would include the sodium, potassium, or ammonium salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic and lactic acids. Such materials do not cause film formation at the anodes, and in some cases promote anode corrosion. Additionally, the silver-hydantoin complexes of this invention arc premanufactured in that form to the plating solution, together with an excess of the hydantoin and the nonprecipitating electrolyte salt.
Addition of 2,2'- dipyridyl to the plating solutions of this invention, usually in amounts in the range of about 0.1 to 10 grams per liter, produces bright deposits over a current density range from about 5-20 mA/cm2 for solutions operated at room temperature. Addition of further quantities of various substituted pyridine compounds, usually in amounts greater than that of the 2,2'-dipyridyl itself, expands
the range of usable current density from about 1 to 30 mA/cm2, and improves the uniformity and whiteness of the entire deposit. Preferred substituted pyridine compounds for the purposes of this invention include nicotinamide, isonicotinamide, 2-aminopyridine, 3-aminopyridine, nicotinic acid and its salts, and isonicotinic acid and its salts. These are added in amounts from about 2.5 to 100 grams per liter, depending on other parameters of the plating solution. It should be pointed out that in the absence of 2,2 '-dipyridyl, addition of substituted pyridine compounds is generally ineffective for the purposes of this invention. It should also be pointed out that additions of 4,4'-dipyridyl and 1,10-phenanthroline arc likewise ineffective for the purposes of this invention.
Finally, it has been discovered that the addition of a suitable surfactant to the plating solutions of this invention containing both 2,2,-dipyridyl and a substituted pyridine compound, produces an overall improvement of deposit brightness from mirror-bright to brilliant. Especially preferred surfactants used in the present invention include the class of substituted glycine derivatives known commercially as the Hamposyls, and also the sulfonated naphthalene - formaldehyde condensates known commercially as Blancol N or Rhodacal N, and their aqueous solutions. Both of these classes of surfactants have been used previously for conventional (cyanide based) silver plating.
The plating solutions of this invention produce mirror-bright to brilliant deposits over a range of pH from about 9 to about 13. Certain practical considerations act to limit this range somewhat. The corrosivity of the solutions toward silver anodes increases generally with increasing pH from about pH 9.5 to about pH 13. It also happens that 2,2'-dipyridyl is subject to hydrolysis at pH values above about 10.5, the rate of hydrolysis increasing with increasing pH. In order to obtain adequate replenishment of silver from the anodes and to preserve the useful life of the brightener chemicals, an optimum pH range of about 10-11 is arrived at.
Some Examples of plating solutions of this invention are given as follows. In each of the Examples, silver is added as a preformed complex formed by the reaction
of silver oxide with hydantoin, or with a substituted hydantoin, such as 5,5-dimethyl- hydantoin, as appropriate. No foreign ions are thus introduced. Other substituted hydantoin compounds can likewise be employed. Methyl-hydantoin, other alkyl- hydantoins, other dialkyl-hydantoins, and the like are useful herein. See the hydantoin compounds of U.S. Patent No. 5,750,018 for additional examples.
Example 1
Sufficient water was used to form one liter of a solution containing the following:
Potassium hydroxide 60 grams Sulfamic Acid 52.5 grams 5,5-dimethylhydantoin 60 grams Silver as complex with 5,5-dimethylhydantoin 25 grams Ag 2,2 '-dipyridyl 0.8 grams
The solution pH was approximately 11.0. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was white and mirror-bright at indicated current densities from about 5-20 niA/cm2.
Example 2
Sufficient water was used to form one liter of a solution containing the following:
Potassium hydroxide 60 grams Sulfamic Acid 52.5 grams 5,5-dimethylhydantoin 60 grams Silver as complex with
5 , 5 -dimethylhydantoin 25 grams Ag 2,2 '-dipyridyl 0.40 grams Nicotinamide 4.0 grams
The solution pH was approximately 11.0. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature v/ith moving- vane agitation. The deposit obtained was white and mirror-bright at indicated current densities from near zero to about 12.5 n A/cm2.
Example 3
A plating solution was made up as in Example 2, but additionally containing approximately 0.6 grams of Rhodacal N in the form of an aqueous solution. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving-vane agitation. The deposit obtained was brilliant mirror- bright white at current densities from near zero to greater that 20 mA/cm2.
Example 4
A plating solution was made up as in Example 3 except containing approximately 0.4 grams of Hamposyl L as an aqueous solution solubilized by potassium hydroxide in place of the Rhodacal N. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to greater than 20 mA/cm2.
Example 5
A plating solution was made up as in Example 3 except containing 1.3 grams of 2-aminopyridine in place of nicotinamide. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was brilliant mirror-bright white at current
densities from near zero to greater than 20 mA/cm2.
Example 6
A plating solution was made up as in Example 5 except containing 0.8 grams of 3-aminopyridine in place of 2-aminopyridine. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- vane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to greater than 20 mA/cm2.
Example 7
Sufficient water was used to form one liter of a solution containing the following:
Potassium hydroxide 45 grams Sulfamic Acid 45 grains Hydantoin 45 grams Silver as complex with hydantoin 25 grams Ag 2,2' dipyridyl 2.64 grams
The solution pH was approximately 11.0. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperatures ..ϊth moving- vane agitation. The deposit obtained was white and hazy-bright from near zero to about 5 niA/'cm2.
Example 8
A plating solution was made up as in Example 7 except additionally containing 26.4 grams of nicotinamide. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving-vane
agitation. The deposit obtained was white and mirror-bright at current densities from near zero to greater than 20 mA/cm .
Example 9
A plating solution was made up as in Example 8 except additionally containing 0.16 grams of Hamposyl L in the form of an aqueous solution solubilized with potassium hydroxide. A test panel was plated from this solution in a Hull cell at 0.5 ampere for 5 minutes at room temperature with moving- ane agitation. The deposit obtained was brilliant mirror-bright white at current densities from near zero to 20 mA/cm2.
It will be apparent to those skilled in the art that the Examples provided herein are illustrative of the present invention, but do not represent the totality of the useful embodiments thereof.
REFERENCES
The following documents are related to the present invention as prior art:
1. Modern Electroplating, 4th Edition, M. Schelesinger and M. Paunovic, Eds., John Wiley, New York 2000, pp. 227 ff.
2. E. Hradil, H. Hradil, and A. M. Weisberg, U.S. Patent 4,126,524 (1978).
3. E. Hradil, H. Hradil and A. M. Weisberg U. S. Patent 4,246,077 (1981).
4. T. Asakawa, U S. Patent 5,601,696 (1997)
5. W. Brasch, U. S. Patent 5,750,018 (1998)
Claims
1. An electroplating solution for the deposition of silver; said solution comprising silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also comprising an excess of the hydantoin or substituted hydantoin compound, together with an effective quantity of a nonprecipitating electrolyte salt, and also an effective quantity of 2,2' dipyridyl for the purpose of obtaining a mirror-bright to brilliant deposit.
2. The electroplating solution of Claim 1, further comprising an effective quantity of a pyridine or substituted pyridine compound for the purpose of improving the overall brightness of the deposit obtained.
3. The electroplating solution of Claim 1 or 2, further comprising an effective quantity of surface-active material for the purpose of further improving the overall brightness and brilliance of the deposit obtained.
4. The electroplating solution of Claim 3, wherein the surface-active material is selected from the group consisting of substituted glycine derivatives and sulfonated naphthalene - formaldehyde condensates.
5. The electroplating solution of Claims 1 or 2, wherein the pyridine or substituted pyridine compound is selected from the group consisting of nicotinamide, isonicotinamide, 2-aminopyridine, 3-aminopyridine, nicotinic acid and its salts, and isonicotinic acid and its salts.
6. The electroplating solution of Claim 4, wherein the surface-active material is selected from the group consisting of substituted, glycine derivatives and sulfonated naphthalene - formaldehyde condensates.
7. The electroplating solution of Claim 1 or 2, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
8. The electroplating solution of Claim 3, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
9. The electroplating solution of Claim 4, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
10. The electroplating solution of Claim 5, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
11. The electroplating solution of Claim 6, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
12. A process for the formation of a mirror-bright to brilliant electrodeposit of silver on a substrate comprising the step of: electroplating said substrate in an electroplating solution, said solution comprising silver in the form of a complex of silver with hydantoin or a substituted hydantoin compound; said solution also comprising an excess of the hydantoin or substituted hydantoin compound, together with an effective quantity of a nonprecipitating electrolyte salt, and an effective quantity of 2,2' dipyridyl for the formation of a mirror-bright to brilliant deposit.
13. The process of Claim 12, wherein the electroplating solution further comprises an effective quantity of a pyridine or substituted pyridine compound for the purpose of improving the overall brightness of the deposit obtained.
14. The process of Claim 12 or 13, wherein the electroplating solution further comprises an effective quantity of surface-active material for the purpose of further improving the overall brightness and brilliance of the deposit obtained.
15. The process of Claim 14, wherein the surface-active material is selected from the group consisting of substituted glycine derivatives and sulfonated naphthalene - formaldehyde condensates.
16. The process of Claim 13, wherein the pyridine or substituted pyridine compound is selected from the group consisting of nicotinamide, isonicotinamide, 2- aminopyridine, 3-aminopyridine, nicotinic acid and its salts, and isonicotinic acid and its salts.
17. The process of Claim 16, wherein the surface- active material is selected from the group consisting of substituted glycine derivatives and sulfonated naphthalene - formaldehyde condensates.
18. The process of Claim 12 or 13 , wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
19. The process of Claim 14, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
20. The electroplating solution of Claim 15, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
21. The electroplating solution of Claim 16, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
22. The electroplating solution of Claim 17, wherein the nonprecipitating electrolyte salt is selected from the group consisting of the salts of sulfamic, hydrofluoric, nitric, fluoboric, glycolic, and lactic acids.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/785,297 | 2004-02-24 | ||
| US10/785,297 US20050183961A1 (en) | 2004-02-24 | 2004-02-24 | Non-cyanide silver plating bath composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005083156A1 true WO2005083156A1 (en) | 2005-09-09 |
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ID=34861596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2005/000672 WO2005083156A1 (en) | 2004-02-24 | 2005-01-10 | Non-cyanide silver plating bath composition |
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| WO (1) | WO2005083156A1 (en) |
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| US20070151863A1 (en) | 2007-07-05 |
| US20050183961A1 (en) | 2005-08-25 |
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