IP Library Granted Patent US 9,644,112
Granted Patent B1
US 9,644,112 · App. 15/133,583 · Granted May 9, 2017

Articles having electrically-conductive layer or pattern

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Quick Facts
Patent No.
US 9,644,112
App. No.
15/133,583
Granted
May 9, 2017
Kind
B1
Abstract

Articles are designed with a substrate and have either a uniform layer or pattern of electrically-conductive polyaniline on one or both supporting sides of the substrate. The electrically-conductive polyaniline is disposed either within, on top of, or both within and on top of, a uniform or pattern of a crosslinked polymer that is derived from a photocurable composition comprising 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.

Claims (54)

1. An article comprising a substrate having a supporting side and an opposing supporting side, the article having disposed on the supporting side, electically-conductive polyaniline that is disposed either within, on top of, or both within and on top of, a uniform layer of a crosslinked polymer derived from a photocurable composition comprising 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.

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

3. The article 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.

4. The article 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.

5. The article 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.

6. The article 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.

7. The article 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-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.

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

9. The article of claim 1 , wherein the uniform layer of the crosslinked polymer 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.

10. The article of claim 1 , further having disposed on the opposing supporting side, electrically-conductive polyaniline that is disposed either within, on top of, or both within and on top of, a uniform layer of a crosslinked polymer that is the same as or different from the crosslinked polymer disposed on the supporting side of the substrate.

11. The article of claim 1 , further having disposed on the opposing supporting side, electrically-conductive polyaniline that is disposed either within, on top of, or both within and on top of, a pattern of a crosslinked polymer that is the same as or different from the crosslinked polymer disposed on the supporting side of the substrate.

12. The article of claim 1 , further having disposed on the opposing supporting side, a pattern of electrically-conductive polyaniline that is disposed either within, on top of, or both within and on top of, a pattern of a crosslinked polymer that is the same as or different from the crosslinked polymer disposed on the supporting side of the substrate.

13. An article comprising a substrate having a supporting side and an opposing supporting side, the article having disposed on the supporting side, a pattern of electrically-conductive polyaniline that is disposed either within, on top of, or both within and on top of, a pattern of a crosslinked polymer derived from a photocurable composition comprising 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 aid, phosphonate, carboxylic acid, or carboxylate group, all amounts based on the total recurring units in the water-soluble reactive polymer.

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

15. The article of claim 13 , 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.

16. The article of claim 13 , 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.

17. The article of claim 13 , 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.

18. The article of claim 13 , 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.

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

20. The article of claim 13 , wherein the pattern of the crosslinked polymer 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.

Assignments (13)
RELEASE OF SECURITY INTEREST IN INTELLECTUAL PROPERTY Recorded Jul 24, 2023
From: EASTMAN KODAK COMPANY
To: BANK OF AMERICA, N.A.
Reel/Frame 064364/0847 →
NOTICE OF SECURITY INTERESTS Recorded Mar 4, 2021
From: EASTMAN KODAK COMPANY
To: BANK OF AMERICA, N.A., AS AGENT
Reel/Frame 056984/0001 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Mar 4, 2021
From: EASTMAN KODAK COMPANY
To: ALTER DOMUS (US) LLC
Reel/Frame 056733/0681 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Mar 4, 2021
From: EASTMAN KODAK COMPANY
To: ALTER DOMUS (US) LLC
Reel/Frame 056734/0001 →
INTELLECTUAL PROPERTY SECURITY AGREEMENT Recorded Mar 4, 2021
From: EASTMAN KODAK COMPANY
To: ALTER DOMUS (US) LLC
Reel/Frame 056734/0233 →
RELEASE OF SECURITY INTEREST Recorded Jan 24, 2020
From: BARCLAYS BANK PLC
To: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST) INC.; KODAK AMERICAS LTD.; KODAK REALTY INC.; LASER PACIFIC MEDIA CORPORATION; QUALEX INC.; KODAK PHILIPPINES LTD.; NPEC INC.
Reel/Frame 052773/0001 →
RELEASE OF SECURITY INTEREST Recorded Jul 30, 2019
From: JP MORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
To: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; PFC, INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK IMAGING NETWORK, INC.; KODAK PORTUGUESA LIMITED; KODAK REALTY, INC.; LASER PACIFIC MEDIA CORPORATION; PAKON, INC.; QUALEX, INC.; KODAK PHILIPPINES, LTD.; NPEC, INC.; CREO MANUFACTURING AMERICA LLC; KODAK AVIATION LEASING LLC
Reel/Frame 049901/0001 →
RELEASE OF SECURITY INTEREST Recorded Jul 22, 2019
From: JP MORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
To: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC, INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK IMAGING NETWORK, INC.; KODAK PORTUGUESA LIMITED; KODAK REALTY, INC.; LASER PACIFIC MEDIA CORPORATION; PAKON, INC.; QUALEX, INC.; KODAK PHILIPPINES, LTD.; NPEC, INC.; CREO MANUFACTURING AMERICA LLC; KODAK AVIATION LEASING LLC
Reel/Frame 050239/0001 →
SECURITY INTEREST Recorded Jan 13, 2017
From: EASTMAN KODAK COMPANY
To: BANK OF AMERICA, N.A., AS AGENT
Reel/Frame 041042/0877 →
SECURITY INTEREST Recorded May 17, 2016
From: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK REALTY, INC.; LASER-PACIFIC MEDIA CORPORATION; QUALEX; KODAK PHILIPPINES, LTD.; NPEC INC.
To: BARCLAYS BANK PLC, AS ADMINISTRATIVE AGENT
Reel/Frame 038616/0868 →
SECURITY INTEREST Recorded May 17, 2016
From: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK REALTY, INC.; LASER-PACIFIC MEDIA CORPORATION; QUALEX INC.; KODAK PHILIPPINES, LTD.; NPEC INC.
To: BANK OF AMERICA N.A.
Reel/Frame 038617/0198 →
SECURITY INTEREST Recorded May 17, 2016
From: EASTMAN KODAK COMPANY; FAR EAST DEVELOPMENT LTD.; FPC INC.; KODAK (NEAR EAST), INC.; KODAK AMERICAS, LTD.; KODAK REALTY, INC.; LASER-PACIFIC MEDIA CORPORATION; QUALEX INC.; KODAK PHILIPPINES, LTD.; NPEC, INC.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 038615/0973 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 20, 2016
From: BRUST, THOMAS B.; WYAND, ANNE TROXELL; BENNETT, GRACE ANN; FALKNER, CATHERINE A.
To: EASTMAN KODAK COMPANY
Reel/Frame 038331/0854 →