US4134803A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Nitrogen and sulfur compositions and acid copper plating baths
Assignee: Hull R O and Co Inc
•
Filing: 1977-12-21
•
Granted: 1979-01-16
•
Expires: 1997-12-21
Abstract
Abstract Nitrogen and sulfur compositions are described which are useful in aqueous acidic plating baths and processes for electrodepositing bright and level copper coatings. The compositions are prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, and (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, in (c) an aqueous alkaline medium. Particularly bright and level deposits are obtained when the reaction mixture used to form the composition also contains an aliphatic aldehyde containing up to three carbon atoms. The presence of the above-described brightening and leveling agents in acid copper plating baths produces a lustrous, smooth and level deposit of copper over a wide range of current densities, particularly when wetting agents are included in the plating baths.
Inventors
- 👤 William E. Eckles
- 👤 Thomas W. Starinshak
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 00:29
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/38
Claims Analysis
Total Claims: 44
Claim 1
Independent Claim
83 words
A nitrogen and sulfur composition prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde having up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 2
Dependent Claim
83 words
A nitrogen and sulfur composition prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde having up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 3
Dependent Claim
21 words
The composition of claim 1 wherein R and R' are each independently alkyl radicals containing from one to five carbon atoms.
Claim 4
Dependent Claim
9 words
The composition of claim 1 wherein X is chlorine.
Claim 5
Dependent Claim
9 words
The composition of claim 1 wherein n is one.
Claim 6
Dependent Claim
13 words
The composition of claim 1 wherein the aliphatic aldehyde is formaldehyde or paraformaldehyde.
Claim 7
Dependent Claim
19 words
The composition of claim 1 wherein the mole ratio of disulfide to sulfonic acid to aldehyde is about 0.5:1:1.
Claim 8
Dependent Claim
23 words
The composition of claim 6 wherein the alkaline medium contains about 1 mole of an alkali metal hydroxide per mole of sulfonic acid.
Claim 9
Dependent Claim
81 words
A nitrogen and sulfur composition prepared by heating a mixture comprising (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently lower alkyl groups containing up to about 5 carbon atoms, (b) a halo hydroxy sulfonic acid having the formula XCH.sub.2 CHOHCH.sub.2 SO.sub.3 M wherein X is a halogen and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde having up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 10
Dependent Claim
81 words
A nitrogen and sulfur composition prepared by heating a mixture comprising (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently lower alkyl groups containing up to about 5 carbon atoms, (b) a halo hydroxy sulfonic acid having the formula XCH.sub.2 CHOHCH.sub.2 SO.sub.3 M wherein X is a halogen and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde having up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 11
Dependent Claim
13 words
The composition of claim 8 wherein the aliphatic aldehyde is formaldehyde or paraformaldehyde.
Claim 12
Dependent Claim
22 words
The composition of claim 8 wherein the aqueous alkaline medium comprises an alkali metal hydroxide dissolved in water or an alcohol:water mixture.
Claim 13
Dependent Claim
21 words
The composition of claim 10 wherein the mole ratio of disulfide to sulfonic acid to aldehyde to hydroxide is about 0.5:1:1:1.
Claim 14
Independent Claim
115 words
A method of electrodepositing copper coatings on a substrate which comprises electroplating said substrate in an aqueous acidic bath comprising one or more bath-soluble copper salts, free acid, and at least one bath soluble organic brightener composition prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde containing up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 15
Independent Claim
115 words
A method of electrodepositing copper coatings on a substrate which comprises electroplating said substrate in an aqueous acidic bath comprising one or more bath-soluble copper salts, free acid, and at least one bath soluble organic brightener composition prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde containing up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 16
Dependent Claim
13 words
The method of claim 12 wherein the aliphatic aldehyde is formaldehyde or paraformaldehyde.
Claim 17
Dependent Claim
22 words
The method of claim 13 wherein the aqueous alkaline medium comprises an alkali metal hydroxide dissolved in water or an alcohol:water mixture.
Claim 18
Dependent Claim
21 words
The method of claim 14 wherein the mole ratio of disulfide to sulfonic acid to aldehyde to hydroxide is about 0.5:1:1:1.
Claim 19
Dependent Claim
32 words
The method of claim 12 wherein the aqueous acidic bath contains the organic brightener composition in an amount which is sufficient to provide a level and bright copper electrodeposit on the substrate.
Claim 20
Dependent Claim
23 words
The method of claim 16 wherein the brightener is present in the bath in an amount at least about 0.001 gm. per liter.
Claim 21
Dependent Claim
13 words
The method of claim 12 wherein the bath also contains a wetting agent.
Claim 22
Dependent Claim
13 words
The method of claim 18 wherein the wetting agent is a polyoxyalkylated naphthol.
Claim 23
Dependent Claim
15 words
The method of claim 19 wherein the polyoxyalkylated naphthol is derived from a beta naphthol.
Claim 24
Dependent Claim
22 words
The method of claim 18 wherein the polyoxyalkylated naphthol has the formula ##STR2## wherein y is from about 6 to about 40.
Claim 25
Dependent Claim
18 words
The method of claim 18 wherein the wetting agent is a polyoxyalkylene glycol or a polyoxyalkylene glycol ether.
Claim 26
Dependent Claim
24 words
The method of claim 22 wherein the wetting agent is a polyethylene oxide having a molecular weight of from about 400 to about 6,000.
Claim 27
Dependent Claim
29 words
The method of claim 18 wherein the wetting agent is a composition prepared by the addition of propylene oxide to ethylene diamine followed by the addition of ethylene oxide.
Claim 28
Dependent Claim
107 words
An aqueous acidic copper electroplating bath containing one or more bath-soluble copper salts, free acid, chloride ions and an effective amount of one or more bath-soluble organic brightener compounds prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde containing up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 29
Dependent Claim
107 words
An aqueous acidic copper electroplating bath containing one or more bath-soluble copper salts, free acid, chloride ions and an effective amount of one or more bath-soluble organic brightener compounds prepared by reacting a mixture of (a) a disulfide having the formula [RR'NCS.sub.2 ].sub.2 (Formula I) wherein R and R' are each independently hydrogen, alkyl or aryl groups, (b) a halo hydroxy sulfonic acid having the formula X(CH.sub.2).sub.n CHOH--CH.sub.2 SO.sub.3 M (Formula II) wherein X is a halogen, n is one or two and M is hydrogen or an alkali metal, and (c) an aliphatic aldehyde containing up to three carbon atoms, in (d) an aqueous alkaline medium.
Claim 30
Dependent Claim
27 words
The copper plating bath of claim 25 wherein R and R' in the disulfide are each independently alkyl radicals containing from 1 to about 5 carbon atoms.
Claim 31
Dependent Claim
15 words
The copper plating bath of claim 25 wherein X is chlorine and n is 1.
Claim 32
Dependent Claim
15 words
The copper plating bath of claim 25 wherein the aliphatic aldehyde is formaldehyde or paraformaldehyde.
Claim 33
Dependent Claim
24 words
The copper plating bath of claim 25 wherein the aqueous alkaline solution comprises an alkali metal hydroxide dissolved in water or an alcohol:water mixture.
Claim 34
Dependent Claim
23 words
The copper plating bath of claim 29 wherein the mole ratio of disulfide to sulfonic acid to aldehyde to hydroxide is about 0.5:1:1:1.
Claim 35
Dependent Claim
17 words
The copper plating bath of claim 25 wherein the bath also contains at least one wetting agent.
Claim 36
Dependent Claim
15 words
The copper plating bath of claim 31 wherein the wetting agent is a polyoxyalkylated naphthol.
Claim 37
Dependent Claim
24 words
The copper plating bath of claim 32 wherein the polyoxyalkylated naphthol has the formula ##STR3## wherein y is from about 6 to about 40.
Claim 38
Dependent Claim
40 words
The copper plating bath of claim 31 wherein the wetting agent is a polyalkylene glycol, a polyalkylene glycol ether, a composition prepared by addition of propylene oxide to ethylene diamine followed by the addition of ethylene oxide or mixtures thereof.
Claim 39
Dependent Claim
26 words
The copper plating bath of claim 34 wherein the wetting agent is a polyethylene oxide having a molecular weight of from about 400 to about 6,000.
Claim 40
Dependent Claim
28 words
The copper plating bath of claim 25 wherein the brightener composition is present in the bath in an amount from about 0.001 to about 1.0 gm. per liter.
Claim 41
Dependent Claim
107 words
An aqueous acid copper electroplating bath for producing bright and level copper deposits comprising per liter of bath from about (a) 165 to 250 grams of copper sulfate, (b) 45 to about 75 grams of sulfuric acid, (c) 0.03 to about 0.1 gram of chloride ion, (d) 0.01 to about 1.0 gram of the composition of claim 3, (e) 0 to about 2.0 gram of a polyalkyline glycol ether wetting agent, (f) 0 to about 2 grams of an ethoxylated beta-naphthol, and (g) 0 to about 2 gram of a composition prepared by addition of propylene oxide to ethylene diamine followed by the addition of ethylene oxide.
Claim 42
Dependent Claim
35 words
An additive composition for aqueous acidic copper electroplating baths comprising an aqueous mixture of (a) one or more bath-soluble leveling compositions of claim 1, and (b) a polyalkylene glycol or polyalkylene glycol ether wetting agent.
Claim 43
Dependent Claim
14 words
The additive composition of claim 38 wherein the composition also contains an ethoxylated beta-naphthol.
Claim 44
Dependent Claim
44 words
An additive composition for aqueous acidic copper electroplating baths comprising an aqueous mixture of (a) one or more bath-soluble compositions of claim 1, and (b) a composition prepared by the addition of propylene oxide to ethylene diamine followed by the addition of ethylene oxide.
References Cited (Backward Citations)
US3023215A
Cited
US2849351A
Cited
US3101305A
Cited
US3122549A
Cited
US3359297A
Cited
US3414493A
Cited
US3784454A
Cited
US3798138A
Cited
US3725220A
Cited
US4038161A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1982-01-15 | 1982-07-17 | 1983-01-16 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-01-15 | 1986-07-17 | 1987-01-16 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-01-15 | 1990-07-17 | 1991-01-16 | $7700.00 | Window Closed / Lapsed |