Method of preparing article with polyaniline pattern

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

providing a pattern 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, and optionally (c) at least 1 mol % of recurring units comprising a pendant amide, hydroxyl, lactam, phosphonic acid, phosphonate, carboxylic acid, or carboxylate group, all amounts based on the total recurring units in the water-soluble reactive polymer;

exposing the pattern of the photocurable composition to radiation sufficient to cause crosslinking via [2+2] photocycloaddition of the (b) recurring units to form a pattern of crosslinked polymer;

optionally rinsing the pattern of crosslinked polymer;

optionally, contacting the crosslinked polymer with metal ion catalyst for aniline oxidation, followed by rinsing the crosslinked polymer, 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 a pattern of electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the crosslinked polymer only.

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

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

4. The method of claim 1 , further comprising:

after the exposing and before 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 the metal ion catalyst for aniline oxidation.

5. 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.

6. 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.

7. 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.

8. The method of claim 1 , wherein the reactive polymer 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.

9. 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.

10. 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-oxyethyl methacrylate;

2-cinnamoyl-oxyethyl 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-1-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]thiazolium trifluoromethylsulfonate;

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

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

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

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

13. The method of claim 1 , further comprising:

providing a pattern of the same or different photocurable composition on an opposing supporting side of the substrate;

exposing the pattern of 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;

optionally rinsing the pattern of crosslinked polymer on the opposing supporting side of the substrate;

optionally, contacting the pattern of crosslinked polymer on the opposing supporting side of the substrate with metal ion catalyst for aniline oxidation, followed by rinsing the 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 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 a pattern of 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.

14. The method claim 13 , wherein the substrate is a continuous polymeric web having an integrated transmittance of at least 90%.

15. The method of claim 1 , wherein the photocurable composition further comprises graphene, carbon nanotubes, graphite, 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.

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

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

18. The method of claim 1 , wherein the pattern of the photocurable composition is provided using inkjet printing, flexographic printing, gravure printing, or screen printing.