Patent US5524339A successfully refreshed from Google Patents.
Patent US4076600A successfully refreshed from Google Patents.
US4076600A
Expired / Lapsed
US
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Leveling agent for acid zinc electroplating baths and method
Assignee: Hull R O and Co Inc
•
Filing: 1976-12-20
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Granted: 1978-02-28
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Expires: 1996-12-20
Abstract
Abstract An aqueous plating bath for the electrodeposition of a zinc coating on a substrate is disclosed and comprises zinc ions, and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble leveling phosphorus cations having the formula: R.sub.4 P ⊕ wherein each R is independently a hydroxy alkyl group. Baths are also described which contain, in addition to the phosphorus cations identified above, at least one nitrogen-containing compound obtained by reacting (a) ammonia, an aliphatic amine containing at least one primary amine group, or mixtures of two or more of any of these with (b) one or more epihalohydrins, glycerol halohydrins, or mixtures thereof, and at least one thiourea having the general formula: [R'.sub.2 N].sub.2 CS wherein each R' is independently hydrogen or an alkyl or alkenyl group. Methods for electrodeposition of level zinc deposits from such baths and additive compositions for preparing and maintaining the baths are disclosed.
Inventors
- 👤 Karen Huebner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 18:26
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/22; C07; C07F; C07F9/00; C07F9/02; C07F9/28; C07F9/54; C07F9/5407
Claims Analysis
Total Claims: 72
Claim 1
Independent Claim
52 words
An aqueous acidic plating bath for the electrodeposition of a zinc coating on a substrate which comprises zinc ions, and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble leveling phosphorus cations having the formula: R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group.
Claim 2
Dependent Claim
52 words
An aqueous acidic plating bath for the electrodeposition of a zinc coating on a substrate which comprises zinc ions, and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble leveling phosphorus cations having the formula: R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group.
Claim 3
Dependent Claim
14 words
The plating bath of claim 1 wherein each R is the hydroxy methyl group.
Claim 4
Dependent Claim
52 words
The plating bath of claim 1 wherein the bath also contains at least one nitrogen-containing compound obtained by reacting (a) ammonia, an aliphatic amine containing at least one primary amine group, or mixtures of two or more of any of these with (b) one or more epihalohydrins, glycerol halohydrins, or mixtures thereof.
Claim 5
Dependent Claim
17 words
The plating bath of claim 3 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin.
Claim 6
Dependent Claim
19 words
The plating bath of claim 4 wherein the molar ratio of ammonia and epichlorohydrin is at least about 2:1.
Claim 7
Dependent Claim
25 words
The plating bath of claim 5 wherein the ammonia and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 8
Dependent Claim
18 words
The plating bath of claim 3 wherein the nitrogen-containing compound is obtained by reacting ethylene diamine with epichlorohydrin.
Claim 9
Dependent Claim
20 words
The plating bath of claim 7 wherein the molar ratio of ethylene diamine and epichlorohydrin is at least about 1:1.
Claim 10
Dependent Claim
26 words
The plating bath of claim 7 wherein the ethylene diamine and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 11
Dependent Claim
31 words
The plating bath of claim 3 also containing at least one thiourea having the general formula: [R'.sub.2 N].sub.2 CH wherein each R' is independently hydrogen or an alkyl or alkenyl group.
Claim 12
Dependent Claim
10 words
The plating bath of claim 10 wherein R' is hydrogen.
Claim 13
Dependent Claim
24 words
The plating bath of claim 3 wherein (a) and (b) are reacted in the presence of water at a temperature below about 60° C.
Claim 14
Dependent Claim
54 words
An aqueous acidic plating bath for the electrodeposition of a zinc coating on a substrate which comprises zinc ions and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble phosphorus cations having the general formula: [R"CH(OH).sub.4 ]P.sup. ⊕ wherein each R" is independently hydrogen or a lower alkyl group.
Claim 15
Dependent Claim
54 words
An aqueous acidic plating bath for the electrodeposition of a zinc coating on a substrate which comprises zinc ions and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble phosphorus cations having the general formula: [R"CH(OH).sub.4 ]P.sup. ⊕ wherein each R" is independently hydrogen or a lower alkyl group.
Claim 16
Dependent Claim
10 words
The plating bath of claim 13 wherein R" is hydrogen.
Claim 17
Dependent Claim
52 words
The plating bath of claim 13 wherein the bath also contains at least one nitrogen-containing compound obtained by reacting (a) ammonia, an aliphatic amine containing at least one primary amine group or mixtures of two or more of any of these, with (b) one or more epihalohydrins, glycerol halohydrins, or mixtures thereof.
Claim 18
Dependent Claim
17 words
The plating bath of claim 15 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin.
Claim 19
Dependent Claim
19 words
The plating bath of claim 16 wherein the molar ratio of ammonia and epichlorohydrin is about at least 2:1.
Claim 20
Dependent Claim
25 words
The plating bath of claim 17 wherein the ammonia and epichlorohydrin are reacted in the presence of water at a temperature, below about 60° C.
Claim 21
Dependent Claim
18 words
The pating bath of claim 15 wherein the nitrogen-containing compound is obtained by reacting ethylene diamine with epichlorohydrin.
Claim 22
Dependent Claim
20 words
The plating bath of claim 19 wherein the molar ratio of ethylene diamine and epichlorohydrin is at least about 1:1.
Claim 23
Dependent Claim
26 words
The plating bath of claim 20 wherein the ethylene diamine and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 24
Dependent Claim
31 words
The plating bath of claim 15 also containing at least one thiourea having the general formula: [R'.sub.2 N].sub.2 CS wherein each R' is independently hydrogen, an alkyl, or an alkenyl group.
Claim 25
Dependent Claim
10 words
The plating bath of claim 22 wherein R' is hydrogen.
Claim 26
Dependent Claim
24 words
The plating bath of claim 15 wherein (a) and (b) are reacted in the presence of water at a temperature below about 60° C.
Claim 27
Independent Claim
57 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating said substrate in an aqueous acidic bath which comprises zinc ions, and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble leveling phosphorus cations having the formula: R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group.
Claim 28
Independent Claim
57 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating said substrate in an aqueous acidic bath which comprises zinc ions, and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble leveling phosphorus cations having the formula: R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group.
Claim 29
Dependent Claim
13 words
The method of claim 25 wherein each R is the hydroxy methyl group.
Claim 30
Dependent Claim
51 words
The method of claim 25 wherein the bath also contains at least one nitrogen-containing compound obtained by reacting (a) ammonia, an aliphatic amine containing at least one primary amine group, or mixtures of two or more of any of these with (b) one or more epihalohydrins, glycerol halohydrins, or mixtures thereof.
Claim 31
Dependent Claim
16 words
The method of claim 27 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin.
Claim 32
Dependent Claim
18 words
The method of claim 28 wherein the molar ratio of ammonia and epichlorohydrin is at least about 2:1.
Claim 33
Dependent Claim
24 words
The method of claim 29 wherein the ammonia and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 34
Dependent Claim
17 words
The method of claim 27 wherein the nitrogen-containing compound is obtained by reacting ethylene diamine with epichlorohydrin.
Claim 35
Dependent Claim
19 words
The method of claim 31 wherein the molar ratio of ethylene diamine and epichlorohydrin is at least about 1:1.
Claim 36
Dependent Claim
25 words
The method of claim 32 wherein the ethylene diamine and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 37
Dependent Claim
30 words
The method of claim 27 also containing at least one thiourea having the general formula: [R'.sub.2 N].sub.2 CS wherein each R' is independently hydrogen or an alkyl or alkenyl group.
Claim 38
Dependent Claim
9 words
The method of claim 26 wherein R' is hydrogen.
Claim 39
Dependent Claim
23 words
The method of claim 27 wherein (a) and (b) are reacted in the presence of water at a temperature below about 60° C.
Claim 40
Independent Claim
58 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating the substrate in an aqueous acidic bath which comprises zine ions and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble phosphorus cations having the general formula: [R"(CH(OH)].sub.4 P.sup.⊕ wherein each R" is independently hydrogen or a lower alkyl group.
Claim 41
Independent Claim
58 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating the substrate in an aqueous acidic bath which comprises zine ions and an amount, sufficient to provide a level zinc electrodeposit, of one or more bath-soluble phosphorus cations having the general formula: [R"(CH(OH)].sub.4 P.sup.⊕ wherein each R" is independently hydrogen or a lower alkyl group.
Claim 42
Dependent Claim
9 words
The method of claim 37 wherein R" is hydrogen.
Claim 43
Dependent Claim
24 words
The method of claim 38 wherein the bath contains from about 0.1 to about four grams of the phosphorus cation per liter of bath.
Claim 44
Dependent Claim
51 words
The method of claim 37 wherein the bath also contains at least one nitrogen-containing compound obtained by reacting (a) ammonia, an aliphatic amine containing at least one primary amine group or mixtures of two or more of any of these, with (b) one or more epihalohydrins, glycerol halohydrins, or mixtures thereof.
Claim 45
Dependent Claim
16 words
The method of claim 40 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin.
Claim 46
Dependent Claim
18 words
The method of claim 41 wherein the molar ratio of ammonia and epichlorohydrin is about at least 2:1.
Claim 47
Dependent Claim
24 words
The method of claim 42 wherein the ammonia and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 48
Dependent Claim
17 words
The method of claim 40 wherein the nitrogen-containing compound is obtained by reacting ethylene diamine with epichlorohydrin.
Claim 49
Dependent Claim
19 words
The method of claim 44 wherein the molar ratio of ethylene diamine and epichlorohydrin is at least about 1:1.
Claim 50
Dependent Claim
25 words
The method of claim 45 wherein the ethylene diamine and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 51
Dependent Claim
30 words
The method of claim 40 also containing at least one thiourea having the general formula: [R'.sub.2 N].sub.2 CS wherein each R' is independently hydrogen, an alkyl, or an alkenyl group.
Claim 52
Dependent Claim
9 words
The method of claim 47 wherein R' is hydrogen.
Claim 53
Dependent Claim
23 words
The method of claim 40 wherein (a) and (b) are reacted in the presence of water at a temperature below about 60° C.
Claim 54
Dependent Claim
60 words
An additive composition for an aqueous acidic zinc electroplating bath comprising a mixture of a. one or more bath-soluble phosphorus cations having the formula R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group, and b. at least one thiourea having the formula [R'.sub.2 N].sub.2 CS wherein each R' is independently hydrogen or an alkyl or alkenyl group.
Claim 55
Dependent Claim
60 words
An additive composition for an aqueous acidic zinc electroplating bath comprising a mixture of a. one or more bath-soluble phosphorus cations having the formula R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group, and b. at least one thiourea having the formula [R'.sub.2 N].sub.2 CS wherein each R' is independently hydrogen or an alkyl or alkenyl group.
Claim 56
Dependent Claim
19 words
The additive composition of claim 50 wherein R is [R"CHOH] wherein R" is hydrogen or a lower alkyl group.
Claim 57
Dependent Claim
10 words
The additive composition of claim 51 wherein R" is hydrogen.
Claim 58
Dependent Claim
10 words
The additive composition of claim 50 wherein R' is hydrogen.
Claim 59
Dependent Claim
31 words
The additive composition of claim 50 wherein the mixture also contains (c) at least one nitrogen-containing compound obtained by reacting ammonia with one or more epihalohydrins, glycerol halohydrins, or mixtures thereof.
Claim 60
Dependent Claim
25 words
The additive composition of claim 54 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin in a molar ratio of at least 2:1.
Claim 61
Dependent Claim
29 words
The additive composition of claim 55 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin in the presence of water at a temperature below about 60° C.
Claim 62
Dependent Claim
37 words
The additive composition of claim 54 wherein the nitrogen-containing compound is obtained by reacting ammonia with one or more epichlorohydrins, glycerol halohydrins, or mixtures thereof in the presence of water at a temperature below about 60° C.
Claim 63
Dependent Claim
79 words
An additive composition for an aqueous acidic zinc electroplating bath comprising a mixture of a. one or more bath-soluble phosphorus cations having the formula R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group, and b. at least one nitrogen-containing compound obtained by reacting i. ammonia, an aliphatic amine containing at least one primary amine group, or mixtures of two or more of any of these with ii. one or more epihalohydrins, glycerol halohydrins or mixtures thereof.
Claim 64
Dependent Claim
79 words
An additive composition for an aqueous acidic zinc electroplating bath comprising a mixture of a. one or more bath-soluble phosphorus cations having the formula R.sub.4 P.sup. ⊕ wherein each R is independently a hydroxy alkyl group, and b. at least one nitrogen-containing compound obtained by reacting i. ammonia, an aliphatic amine containing at least one primary amine group, or mixtures of two or more of any of these with ii. one or more epihalohydrins, glycerol halohydrins or mixtures thereof.
Claim 65
Dependent Claim
19 words
The additive composition of claim 58 wherein R is [R"CHOH] wherein R" is hydrogen or a lower alkyl group.
Claim 66
Dependent Claim
10 words
The additive composition of claim 59 wherein R" is hydrogen.
Claim 67
Dependent Claim
26 words
The additive composition of claim 58 wherein the nitrogen-containing compound is obtained by reacting ammonia with epichlorohydrin in a molar ratio of at least about 2:1.
Claim 68
Dependent Claim
29 words
The additive composition of claim 61 wherein the nigrogen-containing compound is obtained by reacting ammonia with epichlorohydrin in the presence of water at a temperature below about 60° C.
Claim 69
Dependent Claim
18 words
The additive composition of claim 58 wherein the nitrogen-containing compound is obtained by reacting ethylene diamine with epichlorohydrin.
Claim 70
Dependent Claim
20 words
The additive composition of claim 63 wherein the molar ratio of ethylene diamine and epichlorohydrin is at least about 1:1.
Claim 71
Dependent Claim
26 words
The additive composition of claim 64 wherein the ethylene diamine and epichlorohydrin are reacted in the presence of water at a temperature below about 60° C.
Claim 72
Dependent Claim
30 words
The additive composition of claim 58 wherein the nitrogen-containing compound (b) is obtained by reacting (i) and (ii) in the presence of water at a temperature below about 60° C.
References Cited (Backward Citations)
US3884774A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-02-27 | 1981-08-29 | 1982-02-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-02-27 | 1985-08-29 | 1986-02-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-02-27 | 1989-08-29 | 1990-02-28 | $7700.00 | Window Closed / Lapsed |