US4075066A
Expired / Lapsed
US
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Electroplating zinc, ammonia-free acid zinc plating bath therefor and additive composition therefor
Assignee: Hull R O and Co Inc
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Filing: 1977-01-27
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Granted: 1978-02-21
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Expires: 1997-01-27
Abstract
Abstract The present invention provides an ammonia-free acid zinc plating bath for electrodepositing bright zinc on a substrate in which the zinc deposit produced thereby is ductile and presents a glossy to bright coating on the substrate over a wide cathodic current density range. The ammonia-free acid zinc plating baths of the invention comprise zinc ions, chloride ions, at least one polyoxyalkylated naphthol, at least one aromatic carboxylic acid or bath-soluble salt thereof, and at least one anionic aromatic sulfonic acid or bath-soluble salt thereof. In addition to the above components, the ammonia-free acid zinc plating baths of the invention may contain at least one nonionic polyoxyethylene compound and at least one aromatic aldehyde, ketone, or mixtures thereof. The ammonia-free acid zinc plating baths of the invention are free from significant amounts of complexing agents that would impede the removal of zinc ions from the baths prior to disposal.
Inventors
- 👤 William Edward Eckles
- 👤 Valerie Canaris
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-04 08:23
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/22
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
39 words
An ammonia-free aqueous acid zinc electroplating bath comprising zinc ions, chloride ions, at least one polyoxyalkylated naphthol, at least one aromatic carboxylic acid or bath-soluble salt thereof, and at least one anionic aromatic sulfonic acid or bath-soluble salt thereof.
Claim 2
Dependent Claim
39 words
An ammonia-free aqueous acid zinc electroplating bath comprising zinc ions, chloride ions, at least one polyoxyalkylated naphthol, at least one aromatic carboxylic acid or bath-soluble salt thereof, and at least one anionic aromatic sulfonic acid or bath-soluble salt thereof.
Claim 3
Dependent Claim
97 words
The electroplating bath of claim 1 wherein the bath also contains at least one nonionic polyoxyethylene compound selected from the compounds of the formula: ##STR5## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from a reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 4
Dependent Claim
20 words
The electroplating bath of claim 2 wherein the bath also contains at least one aromatic aldehyde, ketone, or mixtures thereof.
Claim 5
Dependent Claim
13 words
The electroplating bath of claim 3 wherein the aromatic ketone is benzylidene acetone.
Claim 6
Dependent Claim
23 words
The electroplating bath of claim 1 wherein the polyoxyalkylated naphthol has the formula: ##STR6## wherein y is from about 6 to about 40.
Claim 7
Dependent Claim
16 words
The electroplating bath of claim 5 wherein the polyoxyalkylated naphthol is derived from a β- naphthol.
Claim 8
Dependent Claim
28 words
The electroplating bath of claim 1 wherein the aromatic carboxylic acid is benzoic acid, salicylic acid, a bath-soluble salt thereof, or mixtures of two or more of these.
Claim 9
Dependent Claim
25 words
The electroplating bath of claim 1 wherein the anionic aromatic sulfonic acid is a compound obtained by the polycondensation of formaldehyde and aromatic sulfonic acid.
Claim 10
Dependent Claim
16 words
The electroplating bath of claim 8 wherein the aromatic sulfonic acid is a naphthalene sulfonic acid.
Claim 11
Dependent Claim
61 words
The electroplating bath of claim 9 wherein the polycondensation product of formaldehyde and naphthalene sulfonic acid is a water-soluble condensation product of formaldehyde with at least two naphthalene sulfonic acids linked by methylene bridges and which contains from one to three sulfonic acid groups in an amount effective to impart ductility and malleability to the zinc deposit obtained from said bath.
Claim 12
Dependent Claim
20 words
The electroplating bath of claim 1 wherein the bath-soluble aromatic sulfonic acid salt is a salt of tetrahydronaphthalene sulfonic acid.
Claim 13
Dependent Claim
40 words
The electroplating bath of claim 1 wherein the bath-soluble salt of the aromatic sulfonic acid is a mixture of a sodium salt of a polycondensation product of formaldehyde and naphthalene sulfonic acid and the sodium salt of tetrahydronaphthalene sulfonic acid.
Claim 14
Dependent Claim
230 words
An ammonia-free aqueous acid zinc electroplating bath comprising from about 22 to 55 grams per liter of zinc ion, from about 75 to about 150 grams per liter of chloride ion, from about 0 to about 40 grams per liter of boric acid, at least one polyoxyalkylated naphthol in an amount sufficient to provide a bright and level zinc deposit, from about 5 to about 15 grams per liter of bath-soluble tetrahydronaphthalene sulfonate, from zero to about 1.5 grams per liter of at least one bath-soluble salt of the polycondensation product of formaldehyde and naphthalene sulfonic acid, from about one to about ten grams per liter of at least one aromatic carboxylic acid or water-soluble salt thereof, from about 0 to about 1.0 grams per liter of at least one aromatic aldehyde, ketone or mixtures thereof, and from 0 to 2.5 grams per liter of at least one polyoxyethylene compound selected from the compounds of the formula: ##STR7## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from the reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 15
Dependent Claim
230 words
An ammonia-free aqueous acid zinc electroplating bath comprising from about 22 to 55 grams per liter of zinc ion, from about 75 to about 150 grams per liter of chloride ion, from about 0 to about 40 grams per liter of boric acid, at least one polyoxyalkylated naphthol in an amount sufficient to provide a bright and level zinc deposit, from about 5 to about 15 grams per liter of bath-soluble tetrahydronaphthalene sulfonate, from zero to about 1.5 grams per liter of at least one bath-soluble salt of the polycondensation product of formaldehyde and naphthalene sulfonic acid, from about one to about ten grams per liter of at least one aromatic carboxylic acid or water-soluble salt thereof, from about 0 to about 1.0 grams per liter of at least one aromatic aldehyde, ketone or mixtures thereof, and from 0 to 2.5 grams per liter of at least one polyoxyethylene compound selected from the compounds of the formula: ##STR7## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from the reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 16
Dependent Claim
22 words
The electroplating bath of claim 13 wherein the polyoxyalkylated naphthol has the formula: ##STR8## wherein y is from about 6 to 40.
Claim 17
Dependent Claim
61 words
The electroplating bath of claim 13 wherein the polycondensation product of formaldehyde and naphthalene sulfonic acid is a water-soluble condensation product of formaldehyde with at least two naphthalene sulfonic acids linked by methylene bridges and which contains from one to three sulfonic acid groups in an amount effective to impart ductility and malleability to the zinc deposit obained from said bath.
Claim 18
Dependent Claim
28 words
The electroplating bath of claim 13 wherein the aromatic carboxylic acid is benzoic acid, salicylic acid, a bath-soluble salt thereof or mixtures of two or more of these.
Claim 19
Dependent Claim
13 words
The electroplating bath of claim 13 wherein the aromatic ketone is benzylidene acetone.
Claim 20
Dependent Claim
26 words
The electroplating bath of claim 13 wherein the polyoxyethylene compound is derived by reacting about 10 moles of ethylene oxide with about 1 mole of 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
Claim 21
Independent Claim
54 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating said substrate in an ammonia-free aqueous acidic zinc bath comprising zinc ions, chloride ions, at least one polyoxyalkylated naphthol, at least one aromatic carboxylic acid or bath-soluble salt thereof, and at least one anionic aromatic sulfonic acid or bath-soluble salt thereof.
Claim 22
Independent Claim
54 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating said substrate in an ammonia-free aqueous acidic zinc bath comprising zinc ions, chloride ions, at least one polyoxyalkylated naphthol, at least one aromatic carboxylic acid or bath-soluble salt thereof, and at least one anionic aromatic sulfonic acid or bath-soluble salt thereof.
Claim 23
Dependent Claim
96 words
The method of claim 19 wherein the bath also contains at least one nonionic polyoxyethylene compound selected from the compounds of the formula: ##STR9## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from a reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 24
Dependent Claim
19 words
The method of claim 20 wherein the bath also contains at least one aromatic aldehyde, ketone, or mixtures thereof.
Claim 25
Dependent Claim
12 words
The method of claim 21 wherein the aromatic ketone is benzylidene acetone.
Claim 26
Dependent Claim
22 words
The method of claim 19 wherein the polyoxyalkylated naphthol has the formula: ##STR10## wherein y is from about 6 to about 40.
Claim 27
Dependent Claim
15 words
The method of claim 23 wherein the polyoxyalkylated naphthol is derived from a β- naphthol.
Claim 28
Dependent Claim
27 words
The method of claim 19 wherein the aromatic carboxylic acid is benzoic acid, salicylic acid, a bath-soluble salt thereof, or mixtures of two or more of these.
Claim 29
Dependent Claim
24 words
The method of claim 19 wherein the anionic aromatic sulfonic acid is a compound obtained by the polycondensation of formaldehyde and aromatic sulfonic acid.
Claim 30
Dependent Claim
15 words
The method of claim 26 wherein the aromatic sulfonic acid is a naphthalene sulfonic acid.
Claim 31
Dependent Claim
60 words
The method of claim 27 wherein the polycondensation product of formaldehyde and naphthalene sulfonic acid is a water-soluble condensation product of formaldehyde with at least two naphthalene sulfonic acids linked by methylene bridges and which contains from one to three sulfonic acid groups in an amount effective to impart ductility and malleability to the zinc deposit obtained from said bath.
Claim 32
Dependent Claim
22 words
The method of claim 19 wherein the bath-soluble salt of the aromatic sulfonic acid is a bath-soluble salt of tetrahydronaphthalene sulfonic acid.
Claim 33
Dependent Claim
39 words
The method of claim 19 wherein the bath-soluble salt of the aromatic sulfonic acid is a mixture of a sodium salt of a polycondensation product of formaldehyde and naphthalene sulfonic acid and the sodium salt of tetrahydronaphthalene sulfonic acid.
Claim 34
Independent Claim
246 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating said substrate in an ammonia-free aqueous acid zinc plating bath comprising from about 22 to 55 grams per liter of zinc ion, from about 75 to about 150 grams per liter of chloride ion, from about zero to about 40 grams per liter of boric acid, at least one polyoxyalkylated naphthol in an amount sufficient to provide a bright and level zinc deposit, from about 5 to about 15 grams per liter of bath-soluble tetrahydronaphthalene sulfonate, from 0 to about 1.5 grams per liter of at least one bath-soluble salt of the polycondensation product of formaldehyde and naphthalene sulfonic acid, from about one to about ten grams per liter of at least one aromatic carboxylic acid or water-soluble salt thereof, from about 0 to about 1.0 grams per liter of at least one aromatic aldehyde, ketone or mixtures thereof, and from 0 to 2.5 grams per liter of at least one polyoxyethylene compound selected from the compounds of the formula: ##STR11## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from the reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 35
Independent Claim
246 words
The method of electrodepositing a zinc coating on a substrate which comprises electroplating said substrate in an ammonia-free aqueous acid zinc plating bath comprising from about 22 to 55 grams per liter of zinc ion, from about 75 to about 150 grams per liter of chloride ion, from about zero to about 40 grams per liter of boric acid, at least one polyoxyalkylated naphthol in an amount sufficient to provide a bright and level zinc deposit, from about 5 to about 15 grams per liter of bath-soluble tetrahydronaphthalene sulfonate, from 0 to about 1.5 grams per liter of at least one bath-soluble salt of the polycondensation product of formaldehyde and naphthalene sulfonic acid, from about one to about ten grams per liter of at least one aromatic carboxylic acid or water-soluble salt thereof, from about 0 to about 1.0 grams per liter of at least one aromatic aldehyde, ketone or mixtures thereof, and from 0 to 2.5 grams per liter of at least one polyoxyethylene compound selected from the compounds of the formula: ##STR11## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from the reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 36
Dependent Claim
21 words
The method of claim 31 wherein the polyoxyalkylated naphthol has the formula: ##STR12## wherein y is from about 6 to 40.
Claim 37
Dependent Claim
60 words
The method of claim 31 wherein the polycondensation product of formaldehyde and naphthalene sulfonic acid is a water-soluble condensation product of formaldehyde with at least two naphthalene sulfonic acids linked by methylene bridges and which contains from one to three sulfonic acid groups in an amount effective to impart ductility and malleability to the zinc deposit obained from said bath.
Claim 38
Dependent Claim
27 words
The method of claim 31 wherein the aromatic carboxylic acid is benzoic acid, salicylic acid, a bath-soluble salt thereof or mixtures of two or more of these.
Claim 39
Dependent Claim
12 words
The method of claim 31 wherein the aromatic ketone is benzylidene acetone.
Claim 40
Dependent Claim
25 words
The method of claim 31 wherein the polyoxyethylene compound is derived by reacting about 10 moles of ethylene oxide with about one mole of 2,4,7,9-tetra-methyl-5-decyne-4,7-diol.
Claim 41
Dependent Claim
44 words
An additive composition for an aqueous acidic zinc electroplating bath comprising a mixture of: (a) at least one polyoxyalkylated naphthol, (b) at least one aromatic carboxylic acid or bath-soluble salt thereof, and (c) at least one anionic aromatic sulfonic acid or bath-soluble salt thereof.
Claim 42
Dependent Claim
44 words
An additive composition for an aqueous acidic zinc electroplating bath comprising a mixture of: (a) at least one polyoxyalkylated naphthol, (b) at least one aromatic carboxylic acid or bath-soluble salt thereof, and (c) at least one anionic aromatic sulfonic acid or bath-soluble salt thereof.
Claim 43
Dependent Claim
98 words
The additive composition of claim 37 wherein the mixture also contains (d) at least one nonionic polyoxyalkylene compound selected from the compounds of the formula: ##STR13## wherein m may be zero, the sum of m+n is at least 10, x is 1 or 2, and the compound is derived from a reaction of ethylene oxide with a polyol selected from the group consisting of 2,4,7,9-tetramethyl-5-decyne-4,7-diol; polyoxypropylene glycol of a molecular weight of at least about 9,000; and N,N,N',N'-tetrakis(polyoxypropylene glycol)ethylene diamine of a molecular weight of at least about 500; and wherein R is defined by the selected polyol.
Claim 44
Dependent Claim
21 words
The additive composition of claim 38 wherein the mixture also contains (e) at least one aromatic aldehyde, ketone, or mixtures thereof.
Claim 45
Dependent Claim
13 words
The additive composition of claim 39 wherein the aromatic aldehyde is benzylidine acetone.
Claim 46
Dependent Claim
26 words
The additive composition of claim 38 wherein the nonionic polyoxyethylene compound is derived by reacting about ten moles of ethylene oxide with one mole of 2,4,7,9-tetramethyl-5-decyne-4,7-diol.
Claim 47
Dependent Claim
21 words
The additive composition of claim 37 wherein the polyoxyalkylated naphthol comprises the product obtained by reacting ethylene oxide with β- naphthol.
Claim 48
Dependent Claim
28 words
The additive composition of claim 37 wherein the aromatic carboxylic acid is benzoic acid, salicylic acid, a bath-soluble salt thereof, or mixtures of two or more of these.
Claim 49
Dependent Claim
37 words
The additive composition of claim 37 wherein the anionic aromatic sulfonic acid comprises a mixture of a sodium salt of a polycondensation product of formaldehyde and naphthalene sulfonic acid and the sodium salt of tetrahydronaphthalene sulfonic acid.
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1981-02-20 | 1981-08-22 | 1982-02-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-02-20 | 1985-08-22 | 1986-02-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-02-20 | 1989-08-22 | 1990-02-21 | $7700.00 | Window Closed / Lapsed |