US4246077A
Expired / Lapsed
US
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Non-cyanide bright silver electroplating bath therefor, silver compounds and method of making silver compounds
Assignee: Technic Inc
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Filing: 1978-09-26
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Granted: 1981-01-20
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Expires: 1998-09-26
Abstract
Abstract A silver and silver alloy electroplating bath; electrolytic solution; water-soluble silver complex for incorporation therein; and the process for electrodeposition of silver and silver alloys; wherein the electrolytic solution and bath have a pH of at least 6, is free of cyanide, and comprises a water-soluble complex formed from the reaction of a silver salt or compound and an organic complexing agent selected from a pyrrolidine-2,5-dione or a 3-pyrroline-2.5-dione.
Inventors
- 👤 Edward Hradil
- 👤 Hana Hradil
- 👤 Alfred M. Weisberg
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 22:40
CPC Classifications
C; C07; C07D; C07D207/00; C07D207/02; C07D207/30; C07D207/34; C07D207/36; C07D207/40; C07D207/404; C07D207/416; C07D207/44; C07D207/444; C07D207/456; C25; C25D; C25D3/00; C25D3/02; C25D3/46
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
70 words
A water-soluble silver complex of the formulae: ##STR7## wherein M is an alkali metal cation or ammonium, R is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl or alkoxy moiety; ##STR8## wherein R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety; or ##STR9## wherein each of M, R and R' is as characterized hereinabove.
Claim 2
Dependent Claim
70 words
A water-soluble silver complex of the formulae: ##STR7## wherein M is an alkali metal cation or ammonium, R is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl or alkoxy moiety; ##STR8## wherein R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety; or ##STR9## wherein each of M, R and R' is as characterized hereinabove.
Claim 3
Dependent Claim
31 words
A water-soluble silver complex as claimed in claim 1, wherein said complex is a pyrrolidine-2,5-dione-containing complex; and any alkyl or alkoxy moieties present therein contain from 1 to 4 carbon atoms.
Claim 4
Dependent Claim
30 words
A water-souble silver complex as claimed in claim 1, wherein said complex is a 3-pyrroline-2,5-dione containing complex, and any alkyl moieties present therein contain from 1 to 4 carbon atoms.
Claim 5
Dependent Claim
20 words
A water-soluble silver complex as claimed in claim 3, wherein said complex is an alkali metal, or ammonium, silver dimaleimide.
Claim 6
Dependent Claim
16 words
A water-soluble silver complex as claimed in claim 4, wherein said complex is potassium silver dimaleimide.
Claim 7
Dependent Claim
17 words
A water-soluble silver complex as claimed in claim 4, wherein said complex is an ammonium silver dimaleimide.
Claim 8
Dependent Claim
20 words
A water-soluble silver complex as claimed in claim 2, wherein said complex is an alkali metal or ammonium silver disuccinimide.
Claim 9
Dependent Claim
16 words
A water-soluble silver complex as claimed in claim 7, wherein said complex is potassium silver disuccinimide.
Claim 10
Dependent Claim
16 words
A water-soluble silver complex as claimed in claim 7, wherein said complex is ammonium silver disuccinimide.
Claim 11
Dependent Claim
125 words
The process that comprises reacting 2 moles of a water-insoluble silver pyrrolidine-2,5-dione complex of the general formula: ##STR10## or a water-insoluble silver 3-pyrroline-2,5-dione complex of the general formula: ##STR11## wherein R is, in its instances of occurrence, the same or different, and is hydrogen, or an alkyl or alkoxy moiety; and R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety with one mole equivalent of a reactant cation comprising an alkali metal cation or ammonium, to form respectively a water-soluble silver complex of the general formula: ##STR12## wherein M is an alkali metal cation or ammonium corresponding to the reactant cation incorporated in the reaction and each of R and R' have the value assigned hereinabove.
Claim 12
Dependent Claim
125 words
The process that comprises reacting 2 moles of a water-insoluble silver pyrrolidine-2,5-dione complex of the general formula: ##STR10## or a water-insoluble silver 3-pyrroline-2,5-dione complex of the general formula: ##STR11## wherein R is, in its instances of occurrence, the same or different, and is hydrogen, or an alkyl or alkoxy moiety; and R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety with one mole equivalent of a reactant cation comprising an alkali metal cation or ammonium, to form respectively a water-soluble silver complex of the general formula: ##STR12## wherein M is an alkali metal cation or ammonium corresponding to the reactant cation incorporated in the reaction and each of R and R' have the value assigned hereinabove.
Claim 13
Dependent Claim
30 words
A process as claimed in claim 10 wherein said water-insoluble silver complex is silver succinimide; said alkali metal cation is potassium; and said water-soluble silver complex is potassium silver disuccinimide.
Claim 14
Dependent Claim
122 words
The process that comprises contacting one mole of a water-insoluble silver pyrrolidine-2,5-dione complex of the general formula (I): ##STR13## or a water-insoluble silver 3-pyrroline-2,5-dione complex of the general formula (II): ##STR14## wherein R is, in its instance of occurrence, the same or different, and is hydrogen, or an alkyl or alkoxy moiety; and R' is, in its instances of occurrence, the same or different, and is hydrogen, or an alkyl moiety with at least one mole equivalent of a pyrrolidine-2,5-dione of the general formula (III): ##STR15## wherein R is as defined above; or a 3-pyrroline-2,5-dione of the formula: ##STR16## wherein R' is as defined above; with a base containing an alkali metal or ammonium cation to form a corresponding water-soluble silver complex.
Claim 15
Dependent Claim
122 words
The process that comprises contacting one mole of a water-insoluble silver pyrrolidine-2,5-dione complex of the general formula (I): ##STR13## or a water-insoluble silver 3-pyrroline-2,5-dione complex of the general formula (II): ##STR14## wherein R is, in its instance of occurrence, the same or different, and is hydrogen, or an alkyl or alkoxy moiety; and R' is, in its instances of occurrence, the same or different, and is hydrogen, or an alkyl moiety with at least one mole equivalent of a pyrrolidine-2,5-dione of the general formula (III): ##STR15## wherein R is as defined above; or a 3-pyrroline-2,5-dione of the formula: ##STR16## wherein R' is as defined above; with a base containing an alkali metal or ammonium cation to form a corresponding water-soluble silver complex.
Claim 16
Dependent Claim
37 words
A process as claimed in claim 12, wherein one mole of said water-insoluble silver pyrrolidine-2,5-dione complex is contacted with at least one mole of said pyrrolidine-2,5-dione and wherein said base contains a sodium, potassium or ammonium cation.
Claim 17
Dependent Claim
26 words
A process as claimed in claim 12 wherein said water-insoluble silver pyrrolidine-2,5-dione complex is silver succinimide and said pyrrolidine-2,5-dione is succinimide and said cation is potassium.
Claim 18
Dependent Claim
36 words
A process as claimed in claim 12 wherein one mole of said water-insoluble silver 3-pyrroline-2,5-dione is contacted with at least one mole of said 3-pyrroline-2,5-dione and wherein said base contains a sodium, potassium or ammonium cation.
Claim 19
Dependent Claim
19 words
A process as claimed in claim 12 wherein said water-insoluble silver 3-pyrroline-2,5-dione is maleimide and said cation is potassium.
Claim 20
Dependent Claim
95 words
An aqueous, cyanide-free, electroplating bath for the electrodeposition of silver and silver alloys comprising an aqueous solution having a pH of 6 to 14 and incorporating a water-soluble silver complex of the general formula: ##STR17## or the general formula: ##STR18## or mixtures thereof; and where, in the foregoing formulae, M is an alkali-metal cation or ammonium, R is, in its instances of occurence, the same or different, and is hydrogen or an alkyl or alkoxy moiety, and R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety.
Claim 21
Dependent Claim
95 words
An aqueous, cyanide-free, electroplating bath for the electrodeposition of silver and silver alloys comprising an aqueous solution having a pH of 6 to 14 and incorporating a water-soluble silver complex of the general formula: ##STR17## or the general formula: ##STR18## or mixtures thereof; and where, in the foregoing formulae, M is an alkali-metal cation or ammonium, R is, in its instances of occurence, the same or different, and is hydrogen or an alkyl or alkoxy moiety, and R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety.
Claim 22
Dependent Claim
40 words
An aqueous, cyanide-free, electroplating bath for the electrodeposition of silver and silver alloys as claimed in claim 17 wherein said bath includes as a conductivity agent, a substituted or unsubstituted carboxylate of a monocarboxylic acid, dicarboxylic acid or tricarboxylic acid.
Claim 23
Dependent Claim
21 words
An electroplating bath as claimed in claim 18 wherein said carboxylate is citrate, acetate, maleate, succinate, malate, hydroxyacetate or mixtures thereof.
Claim 24
Dependent Claim
60 words
An aqueous, cyanide-free electroplating bath as claimed in claim 17, wherein there is incorporated, in addition to said silver complex, an alloying metal salt, wherein said alloying metal is gold, palladium or antimony or combinations thereof present in solution in an amount by weight of up to 50 grams per liter of solution as a coloring or hardening agent therefor.
Claim 25
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 20, wherein said alloying metal is gold.
Claim 26
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 20, wherein said alloying metal is antimony.
Claim 27
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 20, wherein said alloying metal is palladium.
Claim 28
Dependent Claim
158 words
An aqueous cyanide-free electroplating bath as claimed in claim 17, wherein said aqueous solution contains a brightener component, said brightener component being an amine of the formula: ##STR19## or the cross-linked derivatives thereof; and wherein R 2 is hydrogen, amino or phenyl; each of R 3 and R 4 is hydrogen or an alkyl, aminoalkyl, or hydroxyalkyl, radical, or a radical of the formula: ##STR20## where, in the foregoing formulae, any alkyl moiety included in R 3 and R 4 contains from 2 to 6 carbon atoms; and where each of R 3 and R 4 is a terminal radical; each such radical is an alkyl, aminoalkyl or hydroxyalkyl radical as defined hereinabove; m has a value of from 1 to 6; and each of x and y has a value of from 1 to a number sufficient, as the sum of x and y, to provide a polyalkylene polyamine having a molecular weight of up to 60,000.
Claim 29
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 24, wherein said amine is ethylene diamine.
Claim 30
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 24, wherein said amine is diethylene triamine.
Claim 31
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 24, wherein said amine is triethylene tetramine.
Claim 32
Dependent Claim
16 words
An aqueous, cyanide-free electroplating bath as claimed in claim 24, wherein said amine is benzyl amine.
Claim 33
Dependent Claim
135 words
In a process for the electrodeposition of silver and silver alloys by passing an electric current to a cathode to be plated, the improvement that comprises passing said current through an electroplating bath including an aqueous solution having a pH of 6 to 14 and a water-soluble silver complex of the general formula: ##STR21## or the general formula: ##STR22## or mixtures thereof; and where, in the foregoing general formulae, M is an alkali metal cation or ammonium, R is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl or alkoxy moiety, and R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety, and wherein said process is carried out at a temperature within the range of 20° C. to 40° C.
Claim 34
Dependent Claim
135 words
In a process for the electrodeposition of silver and silver alloys by passing an electric current to a cathode to be plated, the improvement that comprises passing said current through an electroplating bath including an aqueous solution having a pH of 6 to 14 and a water-soluble silver complex of the general formula: ##STR21## or the general formula: ##STR22## or mixtures thereof; and where, in the foregoing general formulae, M is an alkali metal cation or ammonium, R is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl or alkoxy moiety, and R' is, in its instances of occurrence, the same or different, and is hydrogen or an alkyl moiety, and wherein said process is carried out at a temperature within the range of 20° C. to 40° C.
Claim 35
Dependent Claim
25 words
A process as claimed in claim 29, wherein the cathodic current density is from 0.1 A per square decimeter to 3.0 A per square decimeter.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-01-20 | 1984-07-21 | 1985-01-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-01-20 | 1988-07-21 | 1989-01-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-01-20 | 1992-07-21 | 1993-01-20 | $7700.00 | Window Closed / Lapsed |