US2015047984A1PendingUtilityA1
Coating technology
Est. expiryJan 12, 2032(~5.5 yrs left)· nominal 20-yr term from priority
C25D 3/50C25D 3/52
29
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Claims
Abstract
An aqueous platinum electroplating bath includes: a) a source of platinum ions; and b) a source of borate ions. The aqueous platinum electroplating bath may optionally include one or more levellers. A method of using the platinum electroplating bath for electroplating platinum or a platinum alloy onto a substrate is also described.
Claims
exact text as granted — not AI-modified1 - 30 . (canceled)
31 . An aqueous platinum electroplating bath comprising:
a) at least one platinum plating salt or complex; and b) a source of borate ions
wherein the platinum plating salt or complex is a platinum borate salt or complex or is selected from the group consisting of diammine dinitroplatinum(II), tetraammineplatinum(II) hydrogen orthophosphate, tetraammineplatinum(II) hydrogen carbonate, tetraammineplatinum(II) hydroxide, tetraammineplatinum(II) sulphate and tetraammineplatinum(II) nitrate,
and wherein the bath has a pH in the range from 6 to 9 when it is in use or ready for use.
32 . The bath according to claim 31 , wherein the source of borate ions
(a) is boron-containing acid optionally in combination with at least one borate salt, wherein the boron-containing acid is optionally selected from the group consisting of boric acid, tetraboric acid and pyroboric acid; or (b) is a metaborate salt optionally in combination with at least one other borate salt;
wherein the borate salt is optionally selected from the group consisting of alkali metal metaborates, alkali metal tetraborates, alkali metal biborates, alkali metal pentaborates, alkaline earth metal metaborates, alkaline earth metal tetraborates, alkaline earth metal biborates and alkaline earth metal pentaborates.
33 . The bath according to claim 31 , wherein the platinum ion concentration is about 0.1 to about 30 g/litre, and/or wherein the borate ion concentration is about 0.1 to about 90 g/litre.
34 . The bath according to claim 31 further comprising at least one leveller.
35 . The bath according to claim 34 , wherein the leveller comprises at least one unsaturated carbon-carbon or unsaturated carbon-heteroatom bond.
36 . The bath according to claim 34 , wherein the leveller is selected from the group consisting of at least one:
a) substituted or unsubstituted saccharine or salt thereof; b) substituted or unsubstituted benzopyranone; c) substituted or unsubstituted benzaldehyde or derivative thereof; d) substituted or unsubstituted alkene provided the alkene is not ethylene; e) substituted or unsubstituted alkyne provided the alkyne is not acetylene; f) substituted or unsubstituted alkylnitrile; g) substituted or unsubstituted pyridine or addition salt thereof; h) substituted or unsubstituted triazole; and i) substituted or unsubstituted pyridinium salt.
37 . The bath according to claim 34 wherein the leveller is:
(i) a compound of formula (1) or salts thereof:
wherein m is 0, 1, 2, 3 or 4;
each R 1 is independently an unsubstituted C 1 -C 10 alkyl group; R 2 is selected from the group consisting of H, unsubstituted C 1 -C 10 alkyl, an alkali metal ion and an alkaline earth metal ion;
(ii) a compound of formula (2a), (2b) or (2c):
wherein n is 0, 1, 2, 3 or 4;
p is 0, 1 or 2;
each R 10 and R 11 is independently selected from an unsubstituted C 1 -C 10 alkyl group;
(iii) a compound of formula (3a) or (3b):
wherein R 20 is selected from the group consisting of H and —OR 23 ; and
R 21 and R 22 are independently selected from the group consisting of H, —C(O)R 24 and unsubstituted C 1 -C 10 -alkyl; and
R 23 and R 24 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(iv) a compound of formula (4):
wherein each R 30 , R 31 , R 32 and R 33 is independently selected from the group consisting of H, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, —CO 2 R 34 , —NR 34 R 35 , —CONR 34 R 35 and —CN, provided that R 30 , R 31 , R 32 and R 33 are not all H,
wherein the substituents are selected from the group consisting of at least one —OH, —CO 2 R 36 , —OC(O)R 36 , —NR 36 R 37 , —CONR 36 R 37 , —CN, —SO 3 − Na + and —SO 3 − K + ;
R 34 and R 35 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl; and
R 36 and R 37 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(v) a compound of formula (5):
R 40 R 41 (5)
wherein R 40 and R 41 are independently selected from the group consisting of H, unsubstituted C 1 -C 10 -alkyl and substituted C 1 -C 10 -alkyl, provided that R 40 and R 41 are not both H,
wherein the substituents are selected from the group consisting of at least one of —OH, —CO 2 R 42 , —OC(O)R 42 , —NR 42 R 43 , —CONR 42 R 43 , —CN, —SO 3 − Na + and —SO 3 − K + ;
R 42 and R 43 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(vi) a compound of formula (6):
R 50 —CN (6)
wherein R 50 is a substituted or unsubstituted C 1 -C 10 -alkyl, and the substituents are selected from the group consisting of at least one of —OR 51 , —CO 2 R 51 , —OC(O)R 51 , —NR 51 R 52 and —CN; and
wherein R 51 and R 52 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(vii) a compound of formula (7a), (7b) or (7c):
wherein R 60 and R 61 are independently selected from the group consisting of —OH, —CN, —CONR 62 R 63 , —CO 2 R 62 , —COR 63 , N-(unsubstituted C 1 -C 10 -alkyl)-pyrrolidinyl, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, unsubstituted C 2 -C 10 -alkenyl, substituted C 2 -C 10 -alkenyl, —SO 2 —R 63 , —N═N-(unsubstituted C 6 -C 10 -aryl), —N═N-(substituted C 6 -C 20 aryl), unsubstituted pyridyl, substituted pyridyl,
wherein the substituents are independently selected from the group consisting of at least one of —CN, —CONR 64 R 65 , —COR 65 , —CO 2 R 64 , —OH, —NR 64 R 65 and ═NR 64 ;
R 62 is selected from the group consisting of H, —OH and unsubstituted C 1 -C 10 -alkyl;
R 63 is selected from the group consisting of H, —OH, unsubstituted C 1 -C 10 -alkyl, unsubstituted C 1 -C 10 -alkyl-CO 2 H, —NH 2 , —NH (unsubstituted C 1 -C 10 -alkyl), —N (unsubstituted C 1 -C 10 -alkyl) 2 ;
R 64 is selected from the groups defined for R 62 ;
R 65 is selected from the groups defined for R 63 ;
each x is 0, 1, 2 or 3; and
each y is 0, 1, 2, 3 or 4;
(viii) a compound of formula (8):
wherein R 70 is selected from a group consisting of H, —CO 2 R 72 and —NR 72 R 73 ;
R 71 is selected from a group consisting of H and unsubstituted C 1 -C 10 -alkyl;
R 72 and R 73 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
one of X 1 and X 2 is C—R 74 and the other of X 1 and X 2 is N; and
R 74 is selected from a group as defined for R 70 ; or
(ix) a compound of formula (9a), (9b) or (9c):
wherein R 60 and R 61 are independently selected from the group consisting of —OH, —CN, —CONR 62 R 63 , —CO 2 R 62 , —COR 63 , N-(unsubstituted C 1 -C 10 -alkyl)-pyrrolidinyl, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, unsubstituted C 2 -C 10 -alkenyl, substituted C 2 -C 10 -alkenyl, —SO 2 —R 63 , —N═N-(unsubstituted C 6 -C 10 -aryl), —N═N-(substituted C 6 -C 20 -aryl), unsubstituted pyridyl, substituted pyridyl,
wherein the substituents are independently selected from the group consisting of at least one —CN, —CONR 64 R 65 , —COR 65 , —CO 2 R 64 , —OH, —NR 64 R 65 and ═NR 64 ;
R 62 is selected from the group consisting of H, —OH and unsubstituted C 1 -C 10 -alkyl;
R 63 is selected from the group consisting of H, —OH, unsubstituted C 1 -C 10 -alkyl, unsubstituted C 1 -C 10 -alkyl-CO 2 H, —NH 2 , —NH (unsubstituted C 1 -C 10 -alkyl), —N (unsubstituted C 1 -C 10 -alkyl) 2 ;
R 64 is selected from the groups defined for R 62 ;
R 65 is selected from the groups defined for R 63 ;
R 82 is selected from the group consisting of —O − and unsubstituted C 1 -C 10 -alkyl;
Z is a counterion when R 82 is an unsubstituted C 1 -C 10 -alkyl;
each x is 0, 1, 2 or 3; and
each y is 0, 1, 2, 3 or 4.
38 . The bath according to claim 34 wherein the leveller is at least one substituted or unsubstituted polyalkyleneimines.
39 . The bath according to claim 31 , further comprising one or more other platinum group metal or base metal plating salts or complexes.
40 . The bath according to claim 31 , wherein the rate of plating is about ≧0.5 microns thickness of platinum or platinum alloy per hour.
41 . The bath according to claim 31 , wherein the bath is used at temperatures from about room temperature to about 100° C.
42 . The bath according to claim 31 further comprising one or more brighteners, surfactants or wetting agents.
43 . The bath according to claim 35 , wherein the leveller is selected from the group consisting of at least one:
a) substituted or unsubstituted saccharine or salt thereof; b) substituted or unsubstituted benzopyranone; c) substituted or unsubstituted benzaldehyde or derivative thereof; d) substituted or unsubstituted alkene provided the alkene is not ethylene; e) substituted or unsubstituted alkyne provided the alkyne is not acetylene; f) substituted or unsubstituted alkylnitrile; g) substituted or unsubstituted pyridine or addition salt thereof; h) substituted or unsubstituted triazole; and i) substituted or unsubstituted pyridinium salt.
44 . The bath according to claim 35 wherein the leveller is:
(i) a compound of formula (1) or salts thereof:
wherein m is 0, 1, 2, 3 or 4;
each R 1 is independently an unsubstituted C 1 -C 10 alkyl group;
R 2 is selected from the group consisting of H, unsubstituted C 1 -C 10 alkyl, an alkali metal ion and an alkaline earth metal ion;
(ii) a compound of formula (2a), (2b) or (2c):
wherein n is 0, 1, 2, 3 or 4;
p is 0, 1 or 2;
each R 10 and R 11 is independently selected from an unsubstituted C 1 -C 10 alkyl group;
(iii) a compound of formula (3a) or (3b):
wherein R 20 is selected from the group consisting of H and —OR 23 ; and
R 21 and R 22 are independently selected from the group consisting of H, —C(O)R 24 and unsubstituted C 1 -C 10 -alkyl; and
R 23 and R 24 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(iv) a compound of formula (4):
wherein each R 30 , R 31 , R 32 and R 33 is independently selected from the group consisting of H, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, —CO 2 R 34 , —NR 34 R 35 , —CONR 34 R 35 and —CN, provided that R 30 , R 31 , R 32 and R 33 are not all H,
wherein the substituents are selected from the group consisting of at least one —OH, —CO 2 R 36 , —OC(O)R 36 , —NR 36 R 37 , —CONR 36 R 37 , —CN, —SO 3 − Na + and —SO 3 − K + ;
R 34 and R 35 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl; and
R 36 and R 37 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(v) a compound of formula (5):
R 40 R 41 (5)
wherein R 40 and R 41 are independently selected from the group consisting of H, unsubstituted C 1 -C 10 -alkyl and substituted C 1 -C 10 -alkyl, provided that R 40 and R 41 are not both H,
wherein the substituents are selected from the group consisting of at least one of —OH, —CO 2 R 42 , —OC(O)R 42 , —NR 42 R 43 , —CONR 42 R 43 , —CN, —SO 3 − Na + and —SO 3 − K + ;
R 42 and R 43 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(vi) a compound of formula (6):
R 50 —CN (6)
wherein R 50 is a substituted or unsubstituted C 1 -C 10 -alkyl, and the substituents are selected from the group consisting of at least one of —OR 51 , —CO 2 R 51 , —OC(O)R 51 , —NR 51 R 52 and —CN; and
wherein R 51 and R 52 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(vii) a compound of formula (7a), (7b) or (7c):
wherein R 60 and R 61 are independently selected from the group consisting of —OH, —CN, —CONR 62 R 63 , —CO 2 R 62 , —COR 63 , N-(unsubstituted C 1 -C 10 -alkyl)-pyrrolidinyl, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, unsubstituted C 2 -C 10 -alkenyl, substituted C 2 -C 10 -alkenyl, —SO 2 —R 63 , —N═N-(unsubstituted C 6 -C 10 -aryl), —N═N-(substituted C 6 -C 20 -aryl), unsubstituted pyridyl, substituted pyridyl,
wherein the substituents are independently selected from the group consisting of at least one of —CN, —CONR 64 R 65 , —COR 65 , —CO 2 R 64 , —OH, —NR 64 R 65 and ═NR 64 ;
R 62 is selected from the group consisting of H, —OH and unsubstituted C 1 -C 10 -alkyl;
R 63 is selected from the group consisting of H, —OH, unsubstituted C 1 -C 10 -alkyl, unsubstituted C 1 -C 10 -alkyl-CO 2 H, —NH 2 , —NH (unsubstituted C 1 -C 10 -alkyl), —N (unsubstituted C 1 -C 10 -alkyl) 2 ;
R 64 is selected from the groups defined for R 62 ;
R 65 is selected from the groups defined for R 63 ;
each x is 0, 1, 2 or 3; and
each y is 0, 1, 2, 3 or 4;
(viii) a compound of formula (8):
wherein R 70 is selected from a group consisting of H, —CO 2 R 72 and —NR 72 R 73 ;
R 71 is selected from a group consisting of H and unsubstituted C 1 -C 10 -alkyl;
R 72 and R 73 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
one of X 1 and X 2 is C—R 74 and the other of X 1 and X 2 is N; and
R 74 is selected from a group as defined for R 70 ; or
(ix) a compound of formula (9a), (9b) or (9c):
wherein R 60 and R 61 are independently selected from the group consisting of —OH, —CN, —CONR 62 R 63 , —CO 2 R 62 , —COR 63 , N-(unsubstituted C 1 -C 10 -alkyl)-pyrrolidinyl, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, unsubstituted C 2 -C 10 -alkenyl, substituted C 2 -C 10 -alkenyl, —SO 2 —R 63 , —N═N-(unsubstituted C 6 -C 10 -aryl), —N═N-(substituted C 6 -C 20 -aryl), unsubstituted pyridyl, substituted pyridyl,
wherein the substituents are independently selected from the group consisting of at least one —CN, —CONR 64 R 65 , —COR 65 , —CO 2 R 64 , —OH, —NR 64 R 65 and ═NR 64 ;
R 62 is selected from the group consisting of H, —OH and unsubstituted C 1 -C 10 -alkyl;
R 63 is selected from the group consisting of H, —OH, unsubstituted C 1 -C 10 -alkyl, unsubstituted C 1 -C 10 -alkyl-CO 2 H, —NH 2 , —NH (unsubstituted C 1 -C 10 -alkyl), —N (unsubstituted C 1 -C 10 -alkyl) 2 ;
R 64 is selected from the groups defined for R 62 ;
R 65 is selected from the groups defined for R 63 ;
R 82 is selected from the group consisting of —O − and unsubstituted C 1 -C 10 -alkyl;
Z is a counterion when R 82 is an unsubstituted C 1 -C 10 -alkyl;
each x is 0, 1, 2 or 3; and
each y is 0, 1, 2, 3 or 4.
45 . The bath according to claim 36 wherein the leveller is:
(i) a compound of formula (1) or salts thereof:
wherein m is 0, 1, 2, 3 or 4;
each R 1 is independently an unsubstituted C 1 -C 10 alkyl group;
R 2 is selected from the group consisting of H, unsubstituted C 1 -C 10 alkyl, an alkali metal ion and an alkaline earth metal ion;
(ii) a compound of formula (2a), (2b) or (2c):
wherein n is 0, 1, 2, 3 or 4;
p is 0, 1 or 2;
each R 10 and R 11 is independently selected from an unsubstituted C 1 -C 10 alkyl group;
(iii) a compound of formula (3a) or (3b):
wherein R 20 is selected from the group consisting of H and —OR 23 ; and
R 21 and R 22 are independently selected from the group consisting of H, —C(O)R 24 and unsubstituted C 1 -C 10 -alkyl; and
R 23 and R 24 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(iv) a compound of formula (4):
wherein each R 30 , R 31 , R 32 and R 33 is independently selected from the group consisting of H, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10-alkyl, —CO 2 R 34 , —NR 34 R 35 , —CONR 34 R 35 and —CN, provided that R 30 , R 31 , R 32 and R 33 are not all H,
wherein the substituents are selected from the group consisting of at least one —OH, —CO 2 R 36 , —OC(O)R 36 , —NR 36 R 37 , —CONR 36 R 37 , —CN, —SO 3 − Na + and —SO 3 − K + ;
R 34 and R 35 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl; and
R 36 and R 37 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(v) a compound of formula (5):
R 40 R 41 (5)
wherein R 40 and R 41 are independently selected from the group consisting of H, unsubstituted C 1 -C 10 -alkyl and substituted C 1 -C 10 -alkyl, provided that R 40 and R 41 are not both H,
wherein the substituents are selected from the group consisting of at least one of —OH, —CO 2 R 42 , —OC(O)R 42 , —NR 42 R 43 , —CONR 42 R 43 , —CN, —SO 3 − Na + and —SO 3 − K + ;
R 42 and R 43 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(vi) a compound of formula (6):
R 50 —CN (6)
wherein R 50 is a substituted or unsubstituted C 1 -C 10 -alkyl, and the substituents are selected from the group consisting of at least one of —OR 51 , —CO 2 R 51 , —OC(O)R 51 , —NR 51 R 52 and —CN; and
wherein R 51 and R 52 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
(vii) a compound of formula (7a), (7b) or (7c):
wherein R 60 and R 61 are independently selected from the group consisting of —OH, —CN, —CONR 62 R 63 , —CO 2 R 62 , —COR 63 , N-(unsubstituted C 1 -C 10 -alkyl)-pyrrolidinyl, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, unsubstituted C 2 -C 10 -alkenyl, substituted C 2 -C 10 -alkenyl, —SO 2 —R 63 , —N═N-(unsubstituted C 6 -C 10 -aryl), —N═N-(substituted C 6 -C 20 -aryl), unsubstituted pyridyl, substituted pyridyl,
wherein the substituents are independently selected from the group consisting of at least one of —CN, —CONR 64 R 65 , —COR 65 , —CO 2 R 64 , —OH, —NR 64 R 65 and ═NR 64 ;
R 62 is selected from the group consisting of H, —OH and unsubstituted C 1 -C 10 -alkyl;
R 63 is selected from the group consisting of H, —OH, unsubstituted C 1 -C 10 -alkyl, unsubstituted C 1 -C 10 -alkyl-CO 2 H, —NH 2 , —NH (unsubstituted C 1 -C 10 -alkyl), —N (unsubstituted C 1 -C 10 -alkyl) 2 ;
R 64 is selected from the groups defined for R 62 ;
R 65 is selected from the groups defined for R 63 ;
each x is 0, 1, 2 or 3; and
each y is 0, 1, 2, 3 or 4;
(viii) a compound of formula (8):
wherein R 70 is selected from a group consisting of H, —CO 2 R 72 and —NR 72 R 73 ;
R 71 is selected from a group consisting of H and unsubstituted C 1 -C 10 -alkyl;
R 72 and R 73 are independently selected from the group consisting of H and unsubstituted C 1 -C 10 -alkyl;
one of X 1 and X 2 is C—R 74 and the other of X 1 and X 2 is N; and
R 74 is selected from a group as defined for R 70 ; or
(ix) a compound of formula (9a), (9b) or (9c):
wherein R 60 and R 61 are independently selected from the group consisting of —OH, —CN, —CONR 62 R 63 , —CO 2 R 62 , —COR 63 , N-(unsubstituted C 1 -C 10 -alkyl)-pyrrolidinyl, unsubstituted C 1 -C 10 -alkyl, substituted C 1 -C 10 -alkyl, unsubstituted C 2 -C 10 -alkenyl, substituted C 2 -C 10 -alkenyl, —SO 2 —R 63 , —N═N-(unsubstituted C 6 -C 10 -aryl), —N═N-(substituted C 6 -C 20 -aryl), unsubstituted pyridyl, substituted pyridyl,
wherein the substituents are independently selected from the group consisting of at least one —CN, —CONR 64 R 65 , —COR 65 , —CO 2 R 64 , —OH, —NR 64 R 65 and ═NR 64 ;
R 62 is selected from the group consisting of H, —OH and unsubstituted C 1 -C 10 -alkyl;
R 63 is selected from the group consisting of H, —OH, unsubstituted C 1 -C 10 -alkyl, unsubstituted C 1 -C 10 -alkyl-CO 2 H, —NH 2 , —NH (unsubstituted C 1 -C 10 -alkyl), —N(unsubstituted C 1 -C 10 -alkyl) 2 ;
R 64 is selected from the groups defined for R 62 ;
R 65 is selected from the groups defined for R 63 ;
R 82 is selected from the group consisting of —O − and unsubstituted C 1 -C 10 -alkyl;
Z is a counterion when R 82 is an unsubstituted C 1 -C 10 -alkyl;
each x is 0, 1, 2 or 3; and
each y is 0, 1, 2, 3 or 4.
46 . A method of plating platinum or a platinum alloy onto a substrate, which comprises using an aqueous platinum electroplating bath as defined in claim 31 for electroplating the platinum or platinum alloy onto the substrate.Join the waitlist — get patent alerts
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