Conductive polymer colloidal compositions with selectivity for non-conductive surfaces

• US 6,899,829 B2
• Filed: 11/30/2001
• Issued: 05/31/2005
• Est. Priority Date: 11/30/2000
• Status: Active Grant

• Current Assignee: Shipley Company, LLC (Dow, Inc.)
• Original Assignee: Shipley Company, LLC (Dow, Inc.)
• Inventors: Houle, Patrick J., Shelnut, James G., Sonnenberg, Wade
• Primary Examiner(s): Kopec, Mark
• Application Number:
  US09/998,117
• Publication Number:
  US 20020110645A1
• Time in Patent Office: 1,278 Days
• Field of Search: 252/511, 252/510, 252/502, 252/519.3, 106/413, 106/445, 427/402, 427/96, 427/304, 427/407, 205/159, 205/125, 205/163, 205/118
• US Class Current: 427/97.1
• CPC Class Codes: H05K 3/188 by direct electroplating

Abstract

A conductive polymer colloidal composition that selectively forms a coating on a non-conductive surface. The conductive polymer colloidal composition is composed of a polymer and a sulfonate dopant. The conductive polymer colloidal composition may also contain conductive colloidal particles such as conductive carbon or metal salt particles, oxidants, stabilizers, and preservatives. The conductive polymer colloidal composition may be employed to selectively coat the non-conductive parts of printed wiring boards such that a uniform metal layer can be deposited on the conductive polymer coat. In addition to a uniform metal layer being formed over the conductive polymer, adhesion between the metal layer and the printed wiring board is improved.

Claims

1. A conductive polymer colloidal composition comprising:

a polymer, and a dopant having the following general formula;

R″

—

O—

(CH₂)_X—

(EO)_Y—

(CH₂)_Z—

SO₃—

R′

where R″

is H, methyl, ethyl, propyl or butyl group;

x is an integer of from 12 to 14;

y is an integer of from 1 to 14; and

z is an integer of from 1 to 5; and

R′

is H, methyl ethyl or M, where M is a cation.

2. The conductive polymer colloidal composition of claim 1, wherein the polymer comprises polypyrrole, polyaniline, polythiophene, polyfuran or mixtures thereof.

3. The conductive polymer colloidal composition of claim 1, further comprising conductive colloidal particles of carbon, metals and their salts, or mixtures thereof.

4. The conductive polymer colloidal composition of claim 1, further comprising a stabilizer.

5. The conductive polymer colloidal composition of claim 4, wherein the stabilizer comprises a non-ionic polyether having the general formula:

R′

″

O((CH_mCH_2mO)_a(CH_m′

CH_2m′

O))_b)H

where R′

″

is a hydrocarbon group having from 1 to 40 carbon atoms, m and m′

differ from each other and each is one or more integers of from 1 to 4, and a and b are integers varying between 0 and 1,000 provided that a+b is at least 3.

6. The conductive polymer colloidal composition of claim 4, wherein the stabilizer comprises a compound having the formula:

R′

″

O((CH_mCH_2mO)_a(CH_m′

CH_2m′

O))_bABD

where R′

″

is a hydrocarbon group having from 1 to 40 carbon atoms, m and m′

differ from each other and each is one or more integers of from 1 to 4, a and b are integers such that there are at least 20 ethoxylate groups in the formula, A is an anion, B is a counteracting cation, and D is an alkyl group of from 1 to 8 carbon atoms.

7. The conductive polymer colloidal composition of claim 4, wherein the stabilizer comprises a compound having the formula:

C_m″

H<sub>2m″

+1</sub>(OC₂H₄)_nOSO₃G

where m″

is an integer ranging from 3 to 20, G is an alkali metal and n is an integer between 3 and 1000.

8. A method for preparing a conductive polymer colloidal composition comprising:

a) adding monomers to a dispersant;

b) adding a dopant to the dispersant comprising the monomers, the dopant having a formula;

R″

—

O—

(CH₂)_X—

(EO)_Y—

(CH₂)_Z—

SO₃—

R′

where R″

is H, methyl, ethyl, propyl or butyl, x is an integer of from 12 to 14, y is an integer of from 1 to 14, z is an integer of from 1 to 5;

R′

is H, methyl, ethyl of M, where M is a cation; and

c) mixing the monomers and dopant to form the conductive polymer colloidal composition.

9. The method of claim 8, further comprising a conductive colloidal particles of carbon, metals and their salts or mixtures thereof.

10. The method of claim 8, further comprising an oxidant, a preservative, a stabilizer, or mixtures thereof.

11. The method of claim 10 , wherein the stabilizer comprises a non-ionic polyether having the formula:

R′

″

O((CH_mCH_2mO)_a(CH_m′

CH_2m′

O))_b)H

where R′

″

is a hydrocarbon group having from 1 to 40 carbon atoms, m and m′

differ from each other and each is one or more integers of from 1 to 4, and a and b are integers varying between 0 and 1,000 provided that a+b is at least 3.

12. The method of claim 10, wherein the stabilizer comprises a compound having the formula:

R′

″

O((CH_mCH_2mO)_a(CH_m′

CH_2m′

O))_bABD

where R″

′

is a hydrocarbon group having from 1 to 40 carbon atoms, m and m′

differ from each other and each is one or more integers of from 1 to 4, and a and b are integers such that are at least 20 ethoxylate groups in the formula, A is an anion, B is a counteracting cation, and D is an alkyl group having from 1 to 8 carbon atoms.

13. The method of claim 10, wherein the stabilizer comprises a compound having the formula:

C_m″

H2<sub>m″

+1</sub>(OC₂H₄)_nOSO₃G

where m″

is an integer ranging from 3 to 20, G is an alkali metal and n is an integer from 3 to 1000.

14. A method for plating a surface of a substrate comprising:

a) contacting the surface of the substrate with a conductive polymer colloidal composition to deposit a conductive polymer layer on the substrate, the conductive polymer colloidal composition comprises a polymer and a dopant, the dopant is a compound having the formula;

R″

—

O—

(CH₂)_X—

(EO)_Y—

(CH₂)_Z—

SO₃—

R′

where R″

is H, methyl, ethyl, propyl or butyl, x is an integer of from 12 to 14, y is an integer of from 1 to 14, z is an integer of from 1 to 5;

R′

is H, methyl, ethyl of M, where M is a cation; and

b) depositing a metal on the conductive polymer layer of the substrate.

15. The method of claim 14, wherein the conductive polymer colloidal composition further comprises conductive colloidal particles of carbon.

16. The method of claim 14, wherein the substrate is a printed wiring board.

17. The method of claim 16, wherein printed wiring is multi-layered.