US3904792A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Catalyst solution for electroless metal deposition on a substrate
Assignee: Shipley Co Inc
•
Filing: 1973-06-27
•
Granted: 1975-09-09
•
Expires: 1993-06-27
Abstract
Abstract The invention disclosed herein is a catalyst for activating a substrate prior to electroless metal plating and to a process for making the same. The catalyst comprises the product resulting from the admixture of an acid soluble salt of a catalytic metal, a stannous salt, an acid and an extraneous source of halide ions. The extraneous source of halide ions provides an excess of halide ions in the catalyst formulation over that found in prior art formulations. The catalyst differs from prior art catalysts in the excess of halide ions and is an improvement as it may be used at a higher pH to catalyze substrates normally attacked by strong acids, is more stable and is adsorbed onto substrates to a greater extent than prior art catalysts.
Inventors
- 👤 Michael Gulla
- 👤 Jr William A Conlan
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 10:09
CPC Classifications
C; C23; C23C; C23C18/00; C23C18/16; C23C18/18; C23C18/20; C23C18/28
Claims Analysis
Total Claims: 64
Claim 1
Independent Claim
149 words
A CATALYST FORMULATION FOR CATALZING A SUBSTRATE PRIOR TO ELECTROLESS METAL DEPOSITION, SAID FORMULATION COMPRISING THE PRODUCT OF ADMIXTURE OF (1) CATALYTIC PRECIOUS METAL IONS, (2) STANNOUS IONS IN AN AMOUNT IN MOLAR EXCESS OF SAID CATALYTIC METAL IONS, THE RATIO OF SAID STANNOUS IONS TO SAID PRECIOUS METAL IONS VARYING BETWEEN 2:1 AND 100:1, (3) HYDROGEN IONS IN AN AMOUNT SUFFICIENT TO PROVIDE A FORMULATION HAVING A PH LESS THAN ABOUT 3.5 AND (4) EXTRANEOUS HALIDE IONS OTHER THAN IODINE IONS, THE CONCENTRATION OF SAID EXTRANEOUS HALIDE IONS AT A PH BELOW THE PRECIPITATION POINT OF THE CATALYST BEING SUFFICIENT TO MAKE THE TOTAL HALIDE ION CONCENTRATION AT LEAST 0.2 MOLES PER LITER IN EXCESS OF THE CONCENTRATION OF HALIDE IONS PROVIDED BY ALL OTHER CATALYST COMPONENTS AND AT A PH AT OR ABOVE THE PRECIPATION POINT BEING AT LEAST SUFFICIENT TO PREVENT THE FORMATION OF A PRECIPITATE.
Claim 2
Dependent Claim
149 words
A CATALYST FORMULATION FOR CATALZING A SUBSTRATE PRIOR TO ELECTROLESS METAL DEPOSITION, SAID FORMULATION COMPRISING THE PRODUCT OF ADMIXTURE OF (1) CATALYTIC PRECIOUS METAL IONS, (2) STANNOUS IONS IN AN AMOUNT IN MOLAR EXCESS OF SAID CATALYTIC METAL IONS, THE RATIO OF SAID STANNOUS IONS TO SAID PRECIOUS METAL IONS VARYING BETWEEN 2:1 AND 100:1, (3) HYDROGEN IONS IN AN AMOUNT SUFFICIENT TO PROVIDE A FORMULATION HAVING A PH LESS THAN ABOUT 3.5 AND (4) EXTRANEOUS HALIDE IONS OTHER THAN IODINE IONS, THE CONCENTRATION OF SAID EXTRANEOUS HALIDE IONS AT A PH BELOW THE PRECIPITATION POINT OF THE CATALYST BEING SUFFICIENT TO MAKE THE TOTAL HALIDE ION CONCENTRATION AT LEAST 0.2 MOLES PER LITER IN EXCESS OF THE CONCENTRATION OF HALIDE IONS PROVIDED BY ALL OTHER CATALYST COMPONENTS AND AT A PH AT OR ABOVE THE PRECIPATION POINT BEING AT LEAST SUFFICIENT TO PREVENT THE FORMATION OF A PRECIPITATE.
Claim 3
Dependent Claim
13 words
The formulation of claim 1 where the pH is below the precipitation point.
Claim 4
Dependent Claim
31 words
The formulation of claim 2 where the total halide ion concentration is from 0.2 moles in excess of the concentration of halide ions provided by all other catalyst components to saturation.
Claim 5
Dependent Claim
31 words
The formulation of claim 2 where the total halide ion concentration is from 0.5 moles in excess of the concentration of halide ions provided from all other catalyst components to saturation.
Claim 6
Dependent Claim
15 words
The formulation of claim 1 where the pH is at or above the precipitation point.
Claim 7
Dependent Claim
30 words
The formulation of claim 5 where the total halide ion concentration varies from at least 0.2 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 8
Dependent Claim
30 words
The formulation of claim 5 where the total halide ion concentration varies from at least 0.5 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 9
Dependent Claim
16 words
The formulation of claim 1 where all halide ions in the catalyst formulation are chloride ions.
Claim 10
Dependent Claim
15 words
The formulation of claim 8 where the pH varies between about 0.9 and about 3.5.
Claim 11
Dependent Claim
14 words
The formulation of claim 8 where the pH varies between about 0.9 and 2.5.
Claim 12
Dependent Claim
181 words
A catalyst formulation for catalyzing a substrate prior to electroless metal deposition, said formulation comprising the product of admixture of (1) a catalytic metal salt selected from the group of gold, silver, and platinum family salts, the concentration of said catalytic metal salt not exceeding 5 grams per liter of solution, (2) a stannous salt in an amount such that the stannous ion concentration is in molar excess of the catalytic metal ion concentration, the molar ratio of said stannous ions to catalytic metal ions varying between about 2:1 and 100:1, (3) hydrogen ions in an amount sufficient to provide a formulation having a pH less than about 3.5, and (4) a halide salt other than an Iodine salt in an amount such that the total halide ion concentration at a pH below the precipitation point of the catalyst is at least 0.2 moles per liter in excess of the concentration of halide ions provided by all other catalyst components and at a pH at or above the precipitation point is at least sufficient to prevent the formation of a precipitate.
Claim 13
Dependent Claim
181 words
A catalyst formulation for catalyzing a substrate prior to electroless metal deposition, said formulation comprising the product of admixture of (1) a catalytic metal salt selected from the group of gold, silver, and platinum family salts, the concentration of said catalytic metal salt not exceeding 5 grams per liter of solution, (2) a stannous salt in an amount such that the stannous ion concentration is in molar excess of the catalytic metal ion concentration, the molar ratio of said stannous ions to catalytic metal ions varying between about 2:1 and 100:1, (3) hydrogen ions in an amount sufficient to provide a formulation having a pH less than about 3.5, and (4) a halide salt other than an Iodine salt in an amount such that the total halide ion concentration at a pH below the precipitation point of the catalyst is at least 0.2 moles per liter in excess of the concentration of halide ions provided by all other catalyst components and at a pH at or above the precipitation point is at least sufficient to prevent the formation of a precipitate.
Claim 14
Dependent Claim
39 words
The formulation of claim 11 where the pH is below the precipitation point and the total halide ion concentration is from 0.2 moles in excess of the concentration of halide ions provided by all other catalyst components to saturation.
Claim 15
Dependent Claim
30 words
The formulation of claim 12 where the total halide ion concentration is from 0.5 moles in excess of the concentration of halide ions from all other catalyst components to saturation.
Claim 16
Dependent Claim
40 words
The formulation of claim 11 where the pH is at or above the precipitation point and the total halide ion concentration varies from at least 0.2 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 17
Dependent Claim
30 words
The formulation of claim 14 where the total halide ion concentration varies from at least 0.5 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 18
Dependent Claim
12 words
The formulation of claim 11 where all halide ions are chloride ions.
Claim 19
Dependent Claim
14 words
The formulation of claim 16 where the pH varies between about 0.9 and 3.5.
Claim 20
Dependent Claim
14 words
The formulation of claim 16 where the pH varies between about 0.9 and 2.5.
Claim 21
Dependent Claim
34 words
The formulation of claim 11 where the ratio of the stannous ion from the stannous salt to the catalytic metal ion from the salt of the catalytic metal varies between about 10:1 and 40:1.
Claim 22
Dependent Claim
13 words
The formulation of claim 19 where the catalytic metal salt is palladium chloride.
Claim 23
Dependent Claim
190 words
A catalyst formulation for catalyzing a substrate prior to electroless metal deposition, said formulation comprising the product of admixture of (1) a catalytic metal halide selected from the group of gold halide, silver halide and platinum family halides, the concentration of said catalytic metal halide not exceeding about 5 grams per liter of solution, (2) a stannous halide in an amount such that the stannous ion concentration is in molar excess of the catalytic metal ion concentration, the molar ratio of said stannous ion to catalytic metal ion varying between 2:1 and 100:1, (3) a hydrohalide acid in an amount sufficient to provide a formulation having a pH less than about 3.5 and (4) a halide salt in an amount such that the total halide ion concentration at a pH below the precipitation point of the catalyst is at least 0.2 moles per liter in excess of the concentration of halide ions provided by all other catalyst components and at a ph at or above the precipitation point of the catalyst, is at least sufficient to prevent the formation of a precipitate, said formulation being substantially free of iodide ions.
Claim 24
Dependent Claim
190 words
A catalyst formulation for catalyzing a substrate prior to electroless metal deposition, said formulation comprising the product of admixture of (1) a catalytic metal halide selected from the group of gold halide, silver halide and platinum family halides, the concentration of said catalytic metal halide not exceeding about 5 grams per liter of solution, (2) a stannous halide in an amount such that the stannous ion concentration is in molar excess of the catalytic metal ion concentration, the molar ratio of said stannous ion to catalytic metal ion varying between 2:1 and 100:1, (3) a hydrohalide acid in an amount sufficient to provide a formulation having a pH less than about 3.5 and (4) a halide salt in an amount such that the total halide ion concentration at a pH below the precipitation point of the catalyst is at least 0.2 moles per liter in excess of the concentration of halide ions provided by all other catalyst components and at a ph at or above the precipitation point of the catalyst, is at least sufficient to prevent the formation of a precipitate, said formulation being substantially free of iodide ions.
Claim 25
Dependent Claim
39 words
The formulation of claim 21 where the pH is below the precipitation point and the total halide ion concentration is from 0.2 moles in excess of the concentration of halide ions provided by all other catalyst components to saturation.
Claim 26
Dependent Claim
31 words
The formulation of claim 22 where the total halide ion concentration is from 0.5 moles in excess of the concentration of halide ions provided from all other catalyst components to saturation.
Claim 27
Dependent Claim
43 words
The formulation of claim 21 where the pH is at or above the precipitation point of the catalyst and the total halide ion concentration varies from at least 0.2 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 28
Dependent Claim
30 words
The formulation of claim 24 where the total halide ion concentration varies from at least 0.5 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 29
Dependent Claim
12 words
The formulation of claim 21 where all halide ions are chloride ions.
Claim 30
Dependent Claim
14 words
The formulation of claim 26 where the pH varies between about 0.9 and 3.5.
Claim 31
Dependent Claim
14 words
The formulation of claim 26 where the pH varies between about 0.9 and 2.5.
Claim 32
Dependent Claim
34 words
The formulation of claim 21 where the ratio of the stannous ions from the stannous halide to the catalytic metal ions from the halide of the catalytic metal varies between about 10:1 and 40:1.
Claim 33
Dependent Claim
13 words
The formulation of claim 29 where the catalytic metal salt is palladium chloride.
Claim 34
Dependent Claim
152 words
A catalyst formulation for catalyzing a substrate prior to electroless metal deposition, said formulation comprising the product of admixture of palladium chloride in an amount not exceeding 5 grams per liter of solution, stannous chloride in an amount such that the stannous ion concentration is in molar excess of the palladium ion concentration, the molar ratio of said stannous ions to palladium ions varying between 2:1 and 100: 1, hydrochloric acid in an amount sufficient to provide a formulation having a pH less than about 3.5 and a chloride salt in an amount such that the total chloride ion concentration at a pH below the precipitation point of the catalyst is at least 0.2 moles per liter in excess of the concentration of the chloride ions provided by all other catalyst components and at a pH at or above the precipitation point, is at least sufficient to prevent formation of a precipitate.
Claim 35
Dependent Claim
152 words
A catalyst formulation for catalyzing a substrate prior to electroless metal deposition, said formulation comprising the product of admixture of palladium chloride in an amount not exceeding 5 grams per liter of solution, stannous chloride in an amount such that the stannous ion concentration is in molar excess of the palladium ion concentration, the molar ratio of said stannous ions to palladium ions varying between 2:1 and 100: 1, hydrochloric acid in an amount sufficient to provide a formulation having a pH less than about 3.5 and a chloride salt in an amount such that the total chloride ion concentration at a pH below the precipitation point of the catalyst is at least 0.2 moles per liter in excess of the concentration of the chloride ions provided by all other catalyst components and at a pH at or above the precipitation point, is at least sufficient to prevent formation of a precipitate.
Claim 36
Dependent Claim
39 words
The formulation of claim 31 where the pH is below the precipitation point and the total chloride ion concentration is from 0.2 moles in excess of the concentration of chloride ions provided by all other catalyst components to saturation.
Claim 37
Dependent Claim
31 words
The formulation of claim 32 where the total chloride ion concentration is from 0.5 moles in excess of the concentration of the chloride ions from all other catalyst components to saturation.
Claim 38
Dependent Claim
40 words
The formulation of claim 31 where the pH is at or above the precipitation point and the total chloride ion concentration varies from at least 0.2 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 39
Dependent Claim
30 words
The formulation of claim 34 where the total chloride ion concentration varies from at least 0.5 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 40
Dependent Claim
14 words
The formulation of claim 31 where the pH varies between about 0.9 and 3.5.
Claim 41
Dependent Claim
14 words
The formulation of claim 31 where the pH varies between about 0.9 and 2.5.
Claim 42
Dependent Claim
30 words
The formulation of claim 31 where the ratio of the stannous ion from the stannous chloride to the palladium ions from the palladium chloride varies between about 10:1 and 40:1.
Claim 43
Dependent Claim
29 words
The formulation of claim 31 where the chloride salt is selected from the group consisting of aluminum chloride, magnesium chloride, sodium chloride, potassium chloride, calcium chloride and lithium chloride.
Claim 44
Dependent Claim
12 words
The formulation of claim 39 where the chloride salt is sodium chloride.
Claim 45
Dependent Claim
28 words
A method of catalyzing a substrate for electroless metal deposition comprising contacting said substrate with the formulation of claim 1 for a time sufficient to catalyze said substrate.
Claim 46
Dependent Claim
14 words
The process of claim 41 including the steps of acceleration and electroless metal plating.
Claim 47
Dependent Claim
28 words
A method of catalyzing a substrate for electroless metal deposition comprising contacting said substrate with the formulation of claim 11 for a time sufficient to catalyze said substrate.
Claim 48
Dependent Claim
14 words
The process of claim 43 including the steps of acceleration and electroless metal plating.
Claim 49
Dependent Claim
28 words
A method of catalyzing a substrate for electroless metal deposition comprising contacting said substrate with the formulation of claim 1 for a time sufficient to catalyze said substrate.
Claim 50
Dependent Claim
14 words
The process of claim 45 including the steps of acceleration and electroless metal plating.
Claim 51
Dependent Claim
28 words
A method of catalyzing a substrate for electroless metal deposition comprising contacting said substrate with the formulation of claim 31 for a time sufficient to catalyze said substrate.
Claim 52
Dependent Claim
14 words
The process of claim 47 inclUding the steps of acceleration and electroless metal plating.
Claim 53
Dependent Claim
164 words
A process for stabilizing and retarding the precipitation point of a catalyst for catalyzing a substrate prior to electroless metal deposition, said catalyst comprising the product of admixture of (1) catalytic precious metal ions, (2) stannous ions in an amount in molar excess of said catalytic metal ions, the ratio of stannous ions to precious metal ions varying between 2:1 and 100:1, and (3) hydrogen ions in an amount sufficient to provide a formulation having a pH less than about 3.5, said process comprising adding extraneous halide ions, other than iodide ions, to said formulation, the concentration of said extraneous halide ions at a pH below the normal precipitation point of the catalyst being sufficient to make the total halide ion concentration at least 0.2 moles per liter in excess of the concentration of halide ions provided by all other catalyst components and at a pH at or above the normal precipitation point, being at least sufficient to prevent the formation of a precipitate.
Claim 54
Dependent Claim
164 words
A process for stabilizing and retarding the precipitation point of a catalyst for catalyzing a substrate prior to electroless metal deposition, said catalyst comprising the product of admixture of (1) catalytic precious metal ions, (2) stannous ions in an amount in molar excess of said catalytic metal ions, the ratio of stannous ions to precious metal ions varying between 2:1 and 100:1, and (3) hydrogen ions in an amount sufficient to provide a formulation having a pH less than about 3.5, said process comprising adding extraneous halide ions, other than iodide ions, to said formulation, the concentration of said extraneous halide ions at a pH below the normal precipitation point of the catalyst being sufficient to make the total halide ion concentration at least 0.2 moles per liter in excess of the concentration of halide ions provided by all other catalyst components and at a pH at or above the normal precipitation point, being at least sufficient to prevent the formation of a precipitate.
Claim 55
Dependent Claim
22 words
The process of claim 49 where the catalytic metal ions are palladium ions in a concentration not exceeding 5 grams per liter.
Claim 56
Dependent Claim
14 words
The process of claim 50 where the stannous ions are derived from stannous chloride.
Claim 57
Dependent Claim
13 words
The process of claim 51 where the ratio varies between 10:1 and 40:1.
Claim 58
Dependent Claim
14 words
The process of claim 51 where the hydrogen ions are derived from hydrochloric acid.
Claim 59
Dependent Claim
13 words
The process of claim 53 whre the pH varies between 0.9 and 3.5.
Claim 60
Dependent Claim
13 words
The process of claim 53 where the pH varies between 0.9 and 2.5.
Claim 61
Dependent Claim
42 words
The process of claim 53 where the pH is below the precipitation point of the catalyst and the total chloride ion concentration is from 0.2 moles in excess of the concentration of chloride ions provided by all other catalyst components to saturation.
Claim 62
Dependent Claim
31 words
The process of claim 56 where the total chloride ion concentration is from 0.5 moles in excess of the concentration of chloride ions provided by all other catalyst components to saturation.
Claim 63
Dependent Claim
29 words
The process of claim 55 where the total chloride ion concentration is at least 0.2 moles in excess of that required to prevent formation of a precipitate to saturation.
Claim 64
Dependent Claim
29 words
The process of claim 55 where the total chloride ion concentration is at least 0.5 moles in excess of that required to prevent formation of a precipitate to saturation.
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) | 1978-09-08 | 1979-03-10 | 1979-09-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-09-08 | 1983-03-10 | 1983-09-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-09-08 | 1987-03-10 | 1987-09-09 | $7700.00 | Window Closed / Lapsed |