CORROSION PROTECTION OF BRONZES

• US 20080314283A1
• Filed: 06/21/2007
• Published: 12/25/2008
• Est. Priority Date: 06/21/2007
• Status: Active Grant

• Current Assignee: MacDermid Enthone Inc. (Element Solutions Inc)
• Original Assignee: Enthone Incorporated (Element Solutions Inc)
• Inventors: Abys, Joseph A., Sun, Shenliang, Antonellis, Theodore, Zschintzsch, Katrin, Kudrak, Edward J.
• Granted Patent: US 10,017,863 B2
• Time in Patent Office: Days
• US Class Current: 106/14.42
• CPC Class Codes: C23C 22/03 containing phosphorus compounds
• CPC Class Codes: C23F 11/10 using organic inhibitors

Abstract

A method and composition for enhancing corrosion resistance, wear resistance, and contact resistance of a substrate comprising a copper or copper alloy surface. The composition comprises a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and mixtures thereof; a nitrogen-containing organic compound selected from the group consisting of primary amine, secondary amine, tertiary amine, and aromatic heterocycle comprising nitrogen; and an alcohol.

Claims

1. A composition for enhancing corrosion resistance, wear resistance, and contact resistance of a metal substrate comprising a copper or copper alloy layer on a surface thereof, the composition comprising:

a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and combinations thereof;

a nitrogen-containing organic compound selected from the group consisting of primary amine, secondary amine, tertiary amine, aromatic heterocycle comprising nitrogen, and combinations thereof; and

an alcohol having a boiling point of at least about 90°

C.

2. The composition of claim 1 wherein the phosphorus oxide compound has the structure (I):

wherein R₁ is a hydrocarbyl having between one carbon atom and 24 carbon atoms; and

R₂ and R₃ are each independently or together hydrogen, a charge balancing cation, or a hydrocarbyl having between one carbon atom and four carbon atoms.

3. The composition of claim 2 wherein the phosphorus oxide compound is selected from the group consisting of ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, tert-butylphosphonic acid, pentylphosphonic acids, hexylphosphonic acids, heptylphosphonic acids, n-octylphosphonic acid, n-decyl phosphonic acid, n-dodecyl phosphonic acid, n-tetradecyl phosphonic acid, n-hexadecyl phosphonic acid, n-octadecyl phosphonic acid, their salts, their esters, and combinations thereof.

4. The composition of claim 2 wherein the phosphorus oxide compound is selected from the group consisting of methylenediphosphonic acid, vinylphosphonic acid, allylphosphonic acid, phenyl phosphonic acid, benzyl phosphonic acid, (ortho-tolyl)phosphonic acid, (meta-tolyl)phosphonic acid, (para-tolyl)phosphonic acid, (4-ethylphenyl)phosphonic acid, (2,4-xylyl)phosphonic acid, (3,4-xylyl)phosphonic acid, (2,5-xylyl)phosphonic acid, (3,5-xylyl)phosphonic acid, their salts, their esters, and combinations thereof.

5. The composition of claim 2 wherein the phosphorus oxide compound is selected from the group consisting of phosphonoacetic acid, 3-phosphonopropionic acid, salts thereof, esters thereof, and combinations thereof.

6. The composition of claim 1 wherein the phosphorus oxide compound has the structure (II):

wherein R₁ is a hydrocarbyl having between one carbon atom and 24 carbon atoms; and

R₂ and R₃ are each independently or together hydrogen, a charge balancing cation, or a hydrocarbyl having between one carbon atom and four carbon atoms.

7. The composition of claim 6 wherein the phosphorus oxide compound is selected from the group consisting of ethylphosphoric acid, n-propylphosphoric acid, isopropylphosphoric acid, n-butylphosphoric acid, tert-butylphosphoric acid, pentylphosphoric acids, hexylphosphoric acids, heptylphosphoric acids, n-octylphosphoric acid, n-decyl phosphoric acid, n-undecyl phosphoric acid, n-dodecyl phosphoric acid, n-tridecyl phosphoric acid, n-tetradecyl phosphoric acid, n-hexadecyl phosphoric acid, n-octadecyl phosphoric acid, their salts, their esters, and combinations thereof.

8. The composition of claim 6 wherein the phosphorus oxide compound is selected from the group consisting of allyl phosphate, diethyl phosphate, diisopropyl phosphate, dibutyl phosphate, triisobutylphosphate, phenyl phosphate, diphenyl phosphate, 1-naphthyl phosphate, 2-naphthyl phosphate, their salts, their esters, and combinations thereof.

9. The composition of claim 1 wherein the nitrogen-containing organic compound is selected from among the primary amine, the secondary amine, the tertiary amine, and combinations thereof, and the nitrogen-containing organic compound has the following structure (III):

wherein R₁, R₂, and R₃ are each independently hydrogen or a hydrocarbyl having between one carbon atom and about 24 carbon atoms; and

at least one of R₁, R₂, and R₃ is a hydrocarbyl having between one carbon atom and about 24 carbon atoms.

10. The composition of claim 9 wherein the nitrogen-containing organic compound is the primary amine selected from the group consisting of aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 1-aminopentane, 2-aminopentane, 3-aminopentane, neo-pentylamine, 1-aminohexane, 2-aminohexane, 1-aminoheptane, 2-aminoheptane, 1-aminooctane, 2-aminooctane, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminotetradecane, 1-aminopentadecane, 1-aminohexadecane, 1-aminoheptadecane, 1-aminooctadecane, 1-aminoeicosane, and combinations thereof.

11. The composition of claim 1 wherein the nitrogen-containing organic compound is the aromatic heterocycle comprising nitrogen, and the aromatic heterocycle comprising nitrogen has the following structure (IV):

wherein R₁, R₂, R₃, R₄, and R₅ is an atom selected from the group consisting of carbon and nitrogen wherein between one and four of the R₁, R₂, R₃, R₄, and R₅ groups are nitrogen and between one and four of the R₁, R₂, R₃, R₄, and R₅ groups are carbon; and

R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ are each independently selected from the group consisting of hydrogen, carbon, sulfur, oxygen, and nitrogen.

12. The composition of claim 11 wherein any one or more of R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ is carbon, and the carbon is part of an aliphatic group having between one carbon atom and 24 carbon atoms or part of an aryl group having between five carbon atoms and fourteen carbon atoms.

13. The composition of claim 11 wherein any two consecutive R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ form together with the carbon or nitrogen atoms to which they are bonded a six-membered aromatic ring.

14. The composition of claim 11 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of pyrrole (1H-azole);

imidazole (1,3-diazole);

pyrazole (1,2-diazole);

1,2,3-triazole;

1,2,4-triazole;

tetrazole;

isoindole;

benzimidazole (1,3-benzodiazole);

indazole (1,2-benzodiazole);

1H-benzotriazole;

2H-benzotriazole;

imidazo[4,5-b]pyridine;

indole (1H-Benzo[b]pyrrole);

purine (7H-Imidazo[4,5-d]pyrimidine);

pyrazolo[3,4-d]pyrimidine;

Triazolo[4,5-d]pyrimidine; and

combinations thereof.

15. The composition of claim 11 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of imidazole (1,3-diazole), benzimidazole (1,3-benzodiazole), 1H-benzotriazole, and 2H-benzotriazole.

16. The composition of claim 1 wherein a concentration of the phosphorus oxide compound is between about 0.1% by weight and about 5% by weight and a concentration of the nitrogen-containing organic compound is between about 0.1% by weight and about 1.0% by weight.

17. The composition of claim 1 wherein the alcohol has a boiling point of at least about 110°

C.

18. The composition of claim 1 wherein the alcohol has a boiling point of at least about 150°

C.

19. The composition of claim 1 wherein the alcohol is selected from the group consisting of n-propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, iso-butanol, 1-pentanol, 2-pentanol, other pentanols, 1-hexanol, other hexanols, heptanols, 1-octanol, 2-octanol, and other octanols, 1-decanol and other decanols, phenol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methoxyethanol, ethylene glycol, glycerol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, 2-(cyclohexyloxy)ethanol, 1-(2-furyl)ethanol, 2-ethoxyethanol, and combinations thereof.

20. The composition of claim 1 wherein the alcohol is 2-ethoxyethanol.

21. A method for enhancing corrosion resistance, wear resistance, and contact resistance of a metal substrate comprising a copper or copper alloy layer on a surface thereof, the method comprising:

exposing the substrate to a composition comprising a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and combinations thereof;

a nitrogen-containing organic compound selected from the group consisting of primary amine, secondary amine, tertiary amine, aromatic heterocycle comprising nitrogen, and combinations thereof; and

an alcohol having a boiling point of at least about 90°

C.

22. The method of claim 21 wherein the phosphorus oxide compound has the structure (I):

wherein R₁ is a hydrocarbyl having between one carbon atom and 24 carbon atoms; and

R₂ and R₃ are each independently or together hydrogen, a charge balancing cation, or a hydrocarbyl having between one carbon atom and four carbon atoms.

23. The method of claim 22 wherein the phosphorus oxide compound is selected from the group consisting of ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, n-butylphosphonic acid, tert-butylphosphonic acid, pentylphosphonic acids, hexylphosphonic acids, heptylphosphonic acids, n-octylphosphonic acid, n-decyl phosphonic acid, n-dodecyl phosphonic acid, n-tetradecyl phosphonic acid, n-hexadecyl phosphonic acid, n-octadecyl phosphonic acid, their salts, their esters, and combinations thereof.

24. The method of claim 22 wherein the phosphorus oxide compound is selected from the group consisting of methylenediphosphonic acid, vinylphosphonic acid, allylphosphonic acid, phenyl phosphonic acid, benzyl phosphonic acid, (ortho-tolyl)phosphonic acid, (meta-tolyl)phosphonic acid, (para-tolyl)phosphonic acid, (4-ethylphenyl)phosphonic acid, (2,4-xylyl)phosphonic acid, (3,4-xylyl)phosphonic acid, (2,5-xylyl)phosphonic acid, (3,5-xylyl)phosphonic acid, their salts, their esters, and combinations thereof.

25. The method of claim 22 wherein the phosphorus oxide compound is selected from the group consisting of phosphonoacetic acid, 3-phosphonopropionic acid, salts thereof, esters thereof, and combinations thereof.

26. The method of claim 21 wherein the phosphorus oxide compound has the structure (II):

wherein R₁ is a hydrocarbyl having between one carbon atom and 24 carbon atoms; and

R₂ and R₃ are each independently or together hydrogen, a charge balancing cation, or a hydrocarbyl having between one carbon atom and four carbon atoms.

27. The method of claim 26 wherein the phosphorus oxide compound is selected from the group consisting of ethylphosphoric acid, n-propylphosphoric acid, isopropylphosphoric acid, n-butylphosphoric acid, tert-butylphosphoric acid, pentylphosphoric acids, hexylphosphoric acids, heptylphosphoric acids, n-octylphosphoric acid, n-decyl phosphoric acid, n-undecyl phosphoric acid, n-dodecyl phosphoric acid, n-tridecyl phosphoric acid, n-tetradecyl phosphoric acid, n-hexadecyl phosphoric acid, n-octadecyl phosphoric acid, their salts, their esters, and combinations thereof.

28. The method of claim 26 wherein the phosphorus oxide compound is selected from the group consisting of allyl phosphate, diethyl phosphate, diisopropyl phosphate, dibutyl phosphate, triisobutylphosphate, phenyl phosphate, diphenyl phosphate, 1-naphthyl phosphate, 2-naphthyl phosphate, their salts, their esters, and combinations thereof.

29. The method of claim 21 wherein the nitrogen-containing organic compound is selected from among the primary amine, the secondary amine, the tertiary amine, and combinations thereof, and the nitrogen-containing organic compound has the following structure (III):

wherein R₁, R₂, and R₃ are each independently hydrogen or a hydrocarbyl having between one carbon atom and about 24 carbon atoms; and

at least one of R₁, R₂, and R₃ is a hydrocarbyl having between one carbon atom and about 24 carbon atoms.

30. The method of claim 29 wherein the nitrogen-containing organic compound is the primary amine selected from the group consisting of aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 1-aminopentane, 2-aminopentane, 3-aminopentane, neo-pentylamine, 1-aminohexane, 2-aminohexane, 1-aminoheptane, 2-aminoheptane, 1-aminooctane, 2-aminooctane, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminotetradecane, 1-aminopentadecane, 1-aminohexadecane, 1-aminoheptadecane, 1-aminooctadecane, 1-aminoeicosane, and combinations thereof.

31. The method of claim 21 wherein the nitrogen-containing organic compound is the aromatic heterocycle comprising nitrogen, and the aromatic heterocycle comprising nitrogen has the following structure (IV):

wherein R₁, R₂, R₃, R₄, and R₅ is an atom selected from the group consisting of carbon and nitrogen wherein between one and four of the R₁, R₂, R₃, R₄, and R₅ groups are nitrogen and between one and four of the R₁, R₂, R₃, R₄, and R₅ groups are carbon; and

R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ are each independently selected from the group consisting of hydrogen, carbon, sulfur, oxygen, and nitrogen.

32. The method of claim 31 wherein any one or more of R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ is carbon, and the carbon is part of an aliphatic group having between one carbon atom and 24 carbon atoms or part of an aryl group having between five carbon atoms and fourteen carbon atoms.

33. The method of claim 31 wherein any two consecutive R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ form together with the carbon or nitrogen atoms to which they are bonded a six-membered aromatic ring.

34. The method of claim 31 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of pyrrole (1H-azole);

imidazole (1,3-diazole);

pyrazole (1,2-diazole);

1,2,3-triazole;

1,2,4-triazole;

tetrazole;

isoindole;

benzimidazole (1,3-benzodiazole);

indazole (1,2-benzodiazole);

1H-benzotriazole;

2H-benzotriazole;

imidazo[4,5-b]pyridine;

indole (1H-Benzo[b]pyrrole);

purine (7H-Imidazo[4,5-d]pyrimidine);

pyrazolo[3,4-d]pyrimidine;

Triazolo[4,5-d]pyrimidine; and

combinations thereof.

35. The method of claim 31 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of imidazole (1,3-diazole), benzimidazole (1,3-benzodiazole), 1H-benzotriazole, and 2H-benzotriazole.

36. The method of claim 21 wherein a concentration of the phosphorus oxide compound is between about 0.1% by weight and about 5% by weight and a concentration of the nitrogen-containing organic compound is between about 0.1% by weight and about 1.0% by weight.

37. The method of claim 21 wherein the alcohol has a boiling point of at least about 110°

C.

38. The method of claim 21 wherein the alcohol has a boiling point of at least about 150°

C.

39. The method of claim 21 wherein the alcohol is selected from the group consisting of n-propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, iso-butanol, 1-pentanol, 2-pentanol, other pentanols, 1-hexanol, other hexanols, heptanols, 1-octanol, 2-octanol, and other octanols, 1-decanol and other decanols, phenol, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, 2-methoxyethanol, ethylene glycol, glycerol, diethylene glycol, triethylene glycol, diethylene glycol monomethyl ether, 2-(cyclohexyloxy)ethanol, 1-(2-furyl)ethanol, 2-ethoxyethanol, and combinations thereof.

40. The method of claim 21 wherein the alcohol is 2-ethoxyethanol.