Method of preparing article with polyaniline coating

1. A method for providing an electrically-conductive polyaniline pattern, the method comprising:

providing a uniform layer of a photocurable composition on a supporting side of a substrate, the photocurable composition comprising a water-soluble reactive polymer comprising (a) greater than 40 mol % of recurring units comprising sulfonic acid or sulfonate groups, (b) at least 5 mol % of recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition, all amounts based on the total recurring units in the water-soluble reactive polymer;

exposing the photocurable composition to radiation sufficient to cause crosslinking via [2+2] photocycloaddition of the (b) recurring units, thereby forming a crosslinked polymer on the supporting side of the substrate; and

contacting the crosslinked polymer with an aniline reactive composition comprising an aniline monomer and up to 0.5 molar of an aniline oxidizing agent, in a molar ratio of from 1:0.5 to 1:1.5 of the aniline monomer to the aniline oxidizing agent, thereby forming an electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the crosslinked polymer.

2. The method of claim 1 , comprising:

exposing the uniform layer of the photocurable composition in an imagewise fashion, thereby forming a pattern of crosslinked regions comprising crosslinked polymer and non-crosslinked regions comprising non-crosslinked, water-soluble reactive polymer on the supporting side of the substrate,

removing the non-crosslinked, water-soluble reactive polymer from the supporting side of the substrate, and

contacting the crosslinked polymer with the aniline reactive composition, thereby forming a pattern of the electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the crosslinked polymer.

3. The method of claim 1 , wherein the aniline reactive composition comprises a persulfate as the aniline oxidizing agent.

4. The method of claim 1 , wherein the aniline reactive composition is acidic.

5. The method of claim 1 , further comprising:

between removing any non-crosslinked water-soluble reactive polymer from the supporting side of the substrate and contacting the crosslinked polymer with the aniline reactive composition, contacting the crosslinked polymer with a solution of at least 0.1 molar ferric ions as an aniline oxidation agent.

6. The method of claim 1 , wherein the exposing is carried out using electromagnetic radiation having a wavelength of at least 200 nm and up to and including 450 nm.

7. The method of claim 1 , wherein the water-soluble reactive polymer comprises at least 50 mol % and up to and including 80 mol % of the (a) recurring units comprising sulfonic acid or sulfonate groups, based on the total recurring units in the water-soluble reactive polymer.

8. The method of claim 1 , wherein the water-soluble reactive polymer comprises at least 5 mol % and up to and including 30 mol % of the (b) recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition based on the total recurring units in the reactive polymer.

9. The method of claim 1 , wherein the reactive polymer further comprises at least 1 mol % and up to and including 65 mol % of (c) recurring units comprising a pendant hydroxyl, amide, or carboxylic acid group, based on the total recurring units in the reactive polymer.

10. The method of claim 1 , wherein the (b) recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition comprise:

(i) a photosensitive —C(═O)—CR═CR 1 —Y group wherein R and R 1 are independently hydrogen or an alkyl group having 1 to 7 carbon atoms, a 5- to 6-membered cycloalkyl group, an alkoxy group having 1 to 7 carbon atoms, a phenyl group, or a phenoxy group, and Y is an aryl or heteroaryl group;

(ii) a photosensitive, non-aromatic unsaturated carbocyclic group;

(iii) a photosensitive, aromatic or non-aromatic heterocyclic group comprising a carbon-carbon double bond that is conjugated with an electron withdrawing group;

(iv) a photosensitive non-aromatic unsaturated heterocyclic group comprising one or more amide groups that are conjugated with a carbon-carbon double bond, which photosensitive non-aromatic unsaturated heterocyclic group is linked to the water-soluble backbone at an amide nitrogen atom; or

(v) a photosensitive substituted or unsubstituted 1,2-diarylethylene group.

11. The method of claim 1 , wherein the (b) recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition are selected from one or more of the following monomers:

2-cinnamoyl-ethyl methacrylate;

2-cinnamoyl-ethyl acrylate;

2-[3-(3-pyridyl)acryloyl]ethyl methacrylate;

2-cyclopropene-1-carboxylic acid, 2,3-diphenyl-, 2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl ester;

2-cyclopropene-1-carboxylic acid, 2,3-diphenyl-, 2-[(2-methyl-l-oxo-2-propen-1-yl)amino]ethyl ester;

4-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy)styrene;

4-(2,3-diphenyl-2-cyclopropene-1-carbonylamino)styrene;

4-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy)ethane;

7-(2-methacryloyloxyethoxy)-4-methylcoumarin;

7-(2-methacryloyloxyethoxy)-coumarin;

7-(3-methacryloyloxysulfopropyl)-4-methylcoumarin;

7-(methacryloyloxy)-4-methylcoumarin;

6-(methacryloyloxy)-4-methylcoumarin;

6-(2-methacryloyloxyethoxy)-4-methylcoumarin;

7-(2-methacryloyloxyethoxy)-quinoline-2-one;

7-(2-methacryloyloxyethoxy)-4-methylquinoline-2-one;

5-(2-methacryloyloxyethoxy)-naphthoquinone;

N-(2-methacryloyloxyethyl)-2,3 -dimethylmaleimide;

3-(2-(methacryloyloxyethyl)-thymine;

1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridinium trifluormethylsulfonate;

1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]quinolinium trifluoromethylsulfonate;

1-methyl-2-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]thiazoliurn trifluoromethylsulfonate;

4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridine; and

1-phenyl-2-[(4-(2-methacryloxyethyl)-carbonyloxyphenyl)]ethylene.

12. The method claim 1 , wherein the substrate is a continuous polymeric web having an integrated transmittance of at least 90%.

13. The method of claim 1 , wherein the photocurable composition further comprises at least 0.1 weight % of a photosensitizer.

14. The method of claim 1 , further comprising:

providing a uniform layer of the same or different photocurable composition on an opposing supporting side of the substrate

exposing the same or different photocurable composition on the opposing supporting side of the substrate to radiation sufficient to cause crosslinking via [2+2] photocycloaddition of the (b) recurring units, thereby forming a crosslinked polymer on the opposing supporting side of the substrate; and

contacting the crosslinked polymer on the opposing supporting side of the substrate with an aniline reactive composition comprising an aniline monomer and up to 0.5 molar of an aniline oxidizing agent, in a molar ratio of from 1:0.5 to 1:1.5 of the aniline monomer to the aniline oxidizing agent, thereby forming an electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the crosslinked polymer on the opposing supporting side of the substrate.

15. The method of claim 14 , wherein the substrate is a continuous polymeric web having an integrated transmittance of at least 90%.

16. The method of claim 14 , comprising:

exposing the uniform layer of the photocurable composition on the opposing supporting side of the substrate in an imagewise fashion, thereby forming a pattern of crosslinked regions comprising crosslinked polymer and non-crosslinked regions comprising non-crosslinked, water-soluble reactive polymer on the opposing supporting side of the substrate,

removing the non-crosslinked, water-soluble reactive polymer from the opposing supporting side of the substrate to form a pattern of crosslinked polymer on the opposing supporting side of the substrate, and

contacting the pattern of crosslinked polymer on the opposing supporting side of the substrate with the aniline reactive composition, thereby forming a pattern of the electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the pattern of crosslinked polymer on the opposing supporting side of the substrate.

17. The method of claim 1 , wherein the photocurable composition further comprises graphene, carbon nanotubes, graphite, carbon black, or other conductive carbon-containing material in an amount of at least 0.1 weight %, based on the total dry weight of the photocurable composition.

18. The method of claim 1 , wherein the photocurable composition further comprises carbon-coated metal particles.

19. The method of claim 1 , wherein the photocurable composition further comprises carbon-coated silver particles or carbon-coated copper particles.

20. The method of claim 1 , further comprising, between removing any non-crosslinked water-soluble reactive polymer from the supporting side of the substrate and contacting the crosslinked polymer with the aniline reactive composition, contacting the crosslinked polymer with a metal ion catalyst for aniline oxidation, followed by rinsing the crosslinked polymer.