IP Library Granted Patent US 10,260,000
Granted Patent B2
US 10,260,000 · App. 13/356,004 · Granted Apr 16, 2019

Etching of plastic using acidic solutions containing trivalent manganese

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Quick Facts
Patent No.
US 10,260,000
App. No.
13/356,004
Granted
Apr 16, 2019
Kind
B2
Abstract

A method of preparing a solution capable of etching a platable plastic. The method comprises the steps of: (a) providing an electrolyte comprising a solution of manganese(II) in a solution of 9 to 15 molar sulfuric acid or phosphoric acid to an electrolytic cell; (b) applying a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode; and (c) oxidizing the electrolyte to form manganese(III) ions, wherein the manganese(III) ions form a metastable sulfate complex. Thereafter, a platable plastic may be immersed in the metastable sulfate complex for a period of time to etch the platable substrate prior to subsequent plating steps.

Claims (29)

1. A method of preparing a solution capable of etching a platable plastic, the method comprising the steps of:

providing an electrolyte comprising manganese(II) ions in a solution of about 9 to 15 molar sulfuric acid or phosphoric acid to an electrolytic cell;

applying a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode; and

oxidizing the electrolyte to form manganese(III) ions, wherein the manganese(III) ions form a metastable sulfate or phosphate complex,

wherein the solution additionally comprises colloidal manganese dioxide.

2. The method according to claim 1 , wherein the acid is sulfuric acid.

3. The method according to claim 2 , wherein the sulfuric acid has a concentration of 12 to 13 molar.

4. The method according to claim 1 , wherein the manganese(II) ions are selected from the group consisting of manganese sulfate, manganese carbonate and manganese hydroxide.

5. The method according to claim 1 , wherein the concentration of the manganese(II) ions in the electrolyte is between about 0.005 molar and saturation.

6. The method according to claim 1 , wherein the cathode comprises a material selected from the group consisting of platinum, platinized titanium, iridium/tantalum oxide, and niobium.

7. The method according to claim 6 , wherein the cathode is platinized titanium or platinum.

8. The method according to claim 1 , wherein the area of the anode is larger than the area of the cathode.

9. The method according to claim 8 , wherein the area ratio of the anode to the cathode is at least about 10:1.

10. The method according to claim 1 , wherein the anode current density is between about 0.1 to about 0.4 A/dm 2 .

11. The method according to claim 1 , wherein the temperature of the electrolyte is maintained between about 30° C. and about 80° C.

12. The method according to claim 1 ,

wherein the electrolyte does not contain any permanganate.

13. A method of preparing a solution capable of etching a platable plastic, the method comprising the steps of:

providing an electrolyte comprising manganese(II) ions in a solution of about 9 to 15 molar sulfuric acid or phosphoric acid to an electrolytic cell;

applying a current to the electrolytic cell, wherein the electrolytic cell comprises an anode and a cathode;

oxidizing the electrolyte to form manganese(III) ions, wherein the manganese(III) ions form a metastable sulfate or phosphate complex, and immersing the platable plastic in the metastable sulfate complex for a period of time to etch the platable substrate;

wherein the platable plastic is immersed in the metastable sulfate complex for about 20 to about 30 minutes.

14. The method according to claim 13 , wherein the platable plastic comprises acrylonitrile-butadiene-styrene or acrylonitrile-butadiene-styrene/polycarbonate.

15. An electrolyte capable of etching a platable plastic, the electrolyte comprising manganese(III) ions in a solution of 9 to 15 molar sulfuric acid or phosphoric acid,

wherein the electrolyte additionally comprises colloidal manganese dioxide.

16. The electrolyte according to claim 15 , wherein the acid is sulfuric acid.

17. The electrolyte according to claim 16 , wherein the sulfuric acid has a concentration of 12 to 13 molar.

18. The electrolyte according to claim 15 , wherein the concentration of the manganese(III) ions in the electrolyte is between about 0.005 molar and saturation.

19. The electrolyte according to claim 15 , wherein the electrolyte does not contain any permanganate.

Assignments (7)
ASSIGNMENT OF SECURITY INTEREST IN PATENT COLLATERAL Recorded Nov 17, 2022
From: BARCLAYS BANK PLC
To: CITIBANK, N.A.
Reel/Frame 061956/0643 →
SECURITY INTEREST Recorded Feb 5, 2019
From: MACDERMID ACUMEN, INC.
To: BARCLAYS BANK PLC, AS COLLATERAL AGENT
Reel/Frame 048260/0828 →
RELEASE OF SECURITY INTEREST Recorded Feb 4, 2019
From: BARCLAYS BANK PLC, AS COLLATERAL AGENT
To: MACDERMID ACUMEN, INC.
Reel/Frame 048232/0405 →
ASSIGNMENT AND ASSUMPTION OF SECURITY INTERESTS AT REEL/FRAME NOS. 30831/0549, 30833/0660, 30831/0606, 30833/0700, AND 30833/0727 Recorded Nov 1, 2013
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS FIRST LIEN COLLATERAL AGENT
To: BARCLAYS BANK PLC, AS SUCCESSOR COLLATERAL AGENT
Reel/Frame 031536/0778 →
RELEASE OF SECURITY INTEREST IN PATENT COLLATERAL AT REEL/FRAME NO. 30831/0675 Recorded Nov 1, 2013
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS SECOND LIEN COLLATERAL AGENT
To: MACDERMID ACUMEN, INC.
Reel/Frame 031537/0094 →
FIRST LIEN PATENT SECURITY AGREEMENT Recorded Jul 19, 2013
From: MACDERMID ACUMEN, INC.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS FIRST LIEN COLLATERAL AGENT
Reel/Frame 030831/0549 →
SECOND LIEN PATENT SECURITY AGREEMENT Recorded Jul 19, 2013
From: MACDERMID ACUMEN, INC.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS SECOND LIEN COLLATERAL AGENT
Reel/Frame 030831/0675 →