WO2017184348A1 - Articles à revêtement de polyaniline et procédés préparatoires - Google Patents

Articles à revêtement de polyaniline et procédés préparatoires Download PDF

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Publication number
WO2017184348A1
WO2017184348A1 PCT/US2017/026268 US2017026268W WO2017184348A1 WO 2017184348 A1 WO2017184348 A1 WO 2017184348A1 US 2017026268 W US2017026268 W US 2017026268W WO 2017184348 A1 WO2017184348 A1 WO 2017184348A1
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WIPO (PCT)
Prior art keywords
aniline
substrate
crosslinked polymer
supporting side
polymer
Prior art date
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PCT/US2017/026268
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English (en)
Inventor
Thomas B. Brust
Anne Troxell Wyand
Grace Ann Bennett
Catherine A. Falkner
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Eastman Kodak Company
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Filing date
Publication date
Priority claimed from US15/133,336 external-priority patent/US9718935B1/en
Priority claimed from US15/133,583 external-priority patent/US9644112B1/en
Priority claimed from US15/133,295 external-priority patent/US10059821B2/en
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Publication of WO2017184348A1 publication Critical patent/WO2017184348A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G03F7/0957—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer with sensitive layers on both sides of the substrate
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • This invention relates to a method for providing uniform layers or patterns of electrically-conductive polyaniline disposed within, on top of, or both within and on top of, crosslinked polymers that are derived from water-soluble reactive polymers comprising pendant sulfonic acid or sulfonate groups and pendant groups that are crosslinkable through [2+2] photocycloaddition.
  • the articles provided by such methods can have layers or patterns of the electrically - conductive polyaniline on one or both supporting sides of a substrate.
  • Polyaniline is the polymer formed by chemical or electrochemical oxidative polymerization of aniline.
  • Polyaniline can vary in its degree of oxidation and protonation depending upon the conditions of the polymerization and the presence of a source of acidic protons.
  • emeraldine salt In its partially oxidized and protonated form called emeraldine salt, it is electrically-conductive and thus has attracted great attention for several decades to determine the basic physics of its electrical conductivity and to realize its potential in numerous applications ranging from chemical and bio-sensors, electrochromic windows, light emitting diodes, batteries, supercapacitors, photovoltaics, anti-corrosion coatings, and even artificial muscles.
  • Recent literature highlight the unique physical character of coatings employing polyaniline and its various composites with graphene, carbon nanotubes, and a wide variety of nano-particles and nano- structures.
  • a film of polyaniline can be readily formed by oxidation at an anode surface during electropolymerization.
  • This polymerization process has the limitation of requiring a conductive substrate and would likely be difficult for flexible roll-to-roll coating and manufacturing operations.
  • Typical chemical oxidative polymerization of polyaniline produces a powder that is insoluble in water and sparingly soluble in solvents such as N-methyl pyrrolidone if crosslinking through the aniline monomer ortho-position is limited in the polymerization process.
  • this PANI powder should be not over-oxidized and should be partially protonated or doped with a strong acid such as hydrochloric acid or a sulfonic acid such as >-toluene sulfonic acid or camphor sulfonic acid that will not volatilize from within a thin coating.
  • a strong acid such as hydrochloric acid or a sulfonic acid such as >-toluene sulfonic acid or camphor sulfonic acid that will not volatilize from within a thin coating.
  • Such polymerization can also be carried out in the presence of an acidic polymer such as poly(styrene sulfonic acid) that forms a polymer complex providing aqueous solubility and a permanent acidic dopant for conductivity similar to the conductive polymer composite of poly(3,4-ethylenedioxythiophene)(PEDOT) and poly(styrene sulfonic acid)(PSS) typically referred to in the art as PEDOT:PSS.
  • PDOT poly(3,4-ethylenedioxythiophene)
  • PSS poly(styrene sulfonic acid)
  • PANI PANI
  • Printing methods such as screen, flexographic, gravure, and inkjet are possible and have been discussed in the literature.
  • Such PANI printed images will still be soluble in some solvents used during printing and may exhibit problems with durability or compatibility with other materials required for a making such devices.
  • Patterning of polyaniline films has been carried out using traditional lithographic methods where a soluble polyaniline coating is masked by an imaging polymer and the unmasked PANI is dissolved. The masking polymer may then be removed if necessary if the underlying PANI is not soluble in the solvent for the mask polymer.
  • Vacuum deposition and etching methods well known in the semiconductor industry could also be used to form coatings and patterns, but the process is expensive and does not lend itself to simple roll-to-roll coatings operations.
  • U. S. Patent 6,045,977 (Chandross et al.) describes a method for making a device in which a conductive PANI salt layer is formed on a substrate and patterned into a desired configuration.
  • U.S. Patent 8,932,494 (Liao et al.) describes a method for forming electrically-conductive PANI-based composites by photo-irradiation a base form of PANI and a photo acid generator that is sensitive to the irradiation, converting the non-conducting base form of PANI to conductive PANI salt in a polymer composite.
  • the present invention provides a method for providing an electrically-conductive polyaniline partem, the method comprising:
  • 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;
  • 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.
  • Such method can further comprise:
  • the method can further comprising:
  • 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.
  • the method can also comprise: 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,
  • This invention also provides a method for providing an electrically- conductive polyaniline pattern, the method comprising:
  • 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;
  • 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 pattem of electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the crosslinked polymer only.
  • the method further comprises: 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.
  • the method of this invention can further comprise:
  • 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 pattem of electrically-conductive polyaniline disposed either within, on top of, or both within or on top of, the pattern of crosslinked polymer only on the opposing supporting side of the substrate.
  • This invention further provides an article comprising a substrate having a supporting side and an opposing supporting side, the article having disposed on the 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 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.
  • the article of this invention further has 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.
  • the article further has 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.
  • an article of the present invention comprises 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 partem 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.
  • the article of this invention further has 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.
  • the present invention provides a method for providing electrically - conductive polyaniline patterns or layers formed by oxidative polymerization of aniline, which polyaniline is disposed either within, on top of, or both within or on top of, within a pattern or layer of crosslinked polymer that serves as a durable and water-insoluble high resolution "template” as well as a polymerization catalyst and a stable dopant (provided by the pendant sulfonic acid or sulfonate groups) for enteral dine salt formation.
  • the crosslinked polymer template can be formed by crosslinking an aqueous-soluble reactive polymer comprising two essential recurring units: (a) recurring units comprising sulfonic acid or sulfonate groups, and (b) recurring units that can be crosslinked via [2+2]
  • the water-soluble reactive polymer can be printed or otherwise disposed on one or both supportive sides of a suitable substrate such as a continuous flexible polymeric web and photo-crosslinked to form an insoluble hydrogel pattern, or it can be uniformly disposed onto the substrate and photo-patterned like a water-developable negative photo-resist.
  • the resulting insoluble hydrogel (crosslinked) partem can be then immersed in an acidic aniline oxidizing (polymerization) bath where electrically- conductive emeraldine salt polyaniline grows within and on the crosslinked polymer at room temperature in for example 20 to 30 minutes.
  • the catalytic properties of the crosslinked polymer can be improved by its immersion in a metal catalyst solution for example to form a ferric ion-polymer complex that reduces the aniline polymerization time to about 3 to 10 minutes with better selectivity for forming polyaniline only within or on the crosslinked template polymer.
  • the present invention provides a simple route to electrically-conductive, water- insoluble, highly durable, and high resolution polyaniline layers or patterns that require no post-processing of the polyaniline.
  • the formation of patterns of the template polymer that can be photo-crosslinked on a substrate can be readily achieved using a variety of printing methods such as inkjet, gravure, screen printing, or photolithography when high resolution is required.
  • the polyaniline formed within, on top of, or both within and on top of, the resulting crosslinked polymer requires no further processing to become electrically-conductive due to the inherent doping properties of the crosslinked template polymer.
  • weight % refers to the amount of a component or material based on the total solids of a composition, formulation, pattern, or layer. Unless otherwise indicated, the percentages can be the same for either a dry layer or partem, or for the total solids of the formulation or composition.
  • homopolymer is meant to refer to polymeric materials that have the same repeating or recurring unit along a polymer backbone.
  • copolymer refers to polymeric materials composed of two or more different repeating or recurring units that are arranged in any order (randomly or otherwise) along the water-soluble reactive polymer backbone.
  • the recurring units can be arranged randomly along the reactive polymer backbone, or there can be blocks of recurring units that occur naturally during the polymerization process.
  • Such water-soluble reactive polymers are copolymers.
  • Recurring units in the water-soluble reactive polymers described herein can be generally derived from the corresponding ethylenically unsaturated polymerizable monomers used in a polymerization process, which ethylenically unsaturated polymerizable monomers have the desired functional and pendant groups.
  • desired pendant groups can be incorporated within recurring units after polymerization of ethylenically unsaturated polymerizable monomers by reaction with requisite precursor pendant groups.
  • polymerization is used herein to mean the combining, for example by covalent bonding, of a large number of smaller molecules, such as monomers, to form very large molecules, that is, macromolecules or polymers.
  • the monomers can be combined to form only linear macromolecules or they can be combined to form three-dimensional macromolecules that are commonly referred to as crosslinked polymers.
  • One type of polymerization that can be carried out in the practice of this invention is free radical polymerization when free radically ethylenically unsaturated polymerizable monomers and suitable free radical generating initiators are present.
  • water-soluble reactive polymer is used herein to refer to the copolymers described below that have the essential recurring units and described properties and that can be used in the photocurable compositions, articles, and methods described herein, and which copolymers are sensitive to ultraviolet radiation so that crosslinking occurs using the pendant groups in the (b) recurring units noted below.
  • water-soluble is used to mean that the minimum solubility in water of a given water-soluble reactive polymer is at least 0.1 weight % at 25°C and a homogeneous solutions are formed in water.
  • crosslinked polymer is used herein to refer to the crosslinked form of the corresponding water-soluble reactive polymer.
  • aqueous-based refers to solutions, baths, or dispersions in which the predominant solvent, or at least 50 weight % of the solvents, is water.
  • mol % when used in reference to recurring units in water-soluble reactive polymers, refers to either the nominal (theoretical) amount of a recurring unit based on the molecular weight of ethylenically unsaturated polymerizable monomer used in the polymerization process, or to the actual amount of recurring units in the resulting water-soluble reactive polymer as determined using suitable analytical techniques and equipment.
  • group particularly when used to define a substituent of a defined moiety, can itself be substituted or unsubstituted (for example and alkyl group” refers to a substituted or
  • substituents on any of the mentioned groups can include known substituents such as: halogen (for example, chloro, fluoro, bromo, and iodo); cyano; nitro; amino; alkoxy particularly those with 1 to 12 carbon atoms (for example, methoxy and ethoxy); substituted or unsubstituted alkyl groups, particularly lower alkyl groups (for example, methyl and trifluoromethyl); alkenyl or thioalkyl (for example, methylthio and ethylthio), particularly either of those with 1 to 12 carbon atoms; substituted and
  • unsubstituted aryl particularly those having from 6 to 20 carbon atoms in the aromatic ring (for example, phenyl); and substituted or unsubstituted heteroaryl, particularly those having a 5- or 6-membered ring containing 1 to 3 heteroatoms selected from N, O, S or Se (for example, pyridyl, thienyl, furyl, pyrrolyl, and their corresponding benzo and naptho analogs); and other substituents that would be readily apparent in the art.
  • Alkyl substituents particularly contain 1 to 12 carbon atoms and specifically include "lower alkyl” that is having from 1 to 6 carbon atoms, for example, methyl, ethyl, and /-butyl. Further, with regard to any alkyl group, alkylene group or alkenyl group, it will be understood that these can be branched or unbranched and include ring (cyclic) structures.
  • UV radiation is used herein to refer to electromagnetic radiation having a wavelength ( max) of at least 150 nm and up to and including 450 nm.
  • Mw weight average molecular weights
  • SEC Size Exclusion Chromatography
  • each dimension "average” is determined from at least 2 measurements of the specific dimension using appropriate measurement techniques and equipment that would be known to one skilled in the art.
  • the average dry thickness of photocurable, crosslinked polymer, or polyaniline layers described herein can be determined from the average of at least 2 separate measurements taken of a dry layer, for example, using electron microscopy.
  • the average dry thickness or width of lines, grid lines, or other pattern features described herein can be the average of at least 2 separate measurements taken, for example, using electron microscopy.
  • the transparent substrate and all accompanying layers or patterns on one or both supporting sides are considered transparent meaning that its integrated transmittance over the noted visible region of the electromagnetic spectrum (for example from 410 nm to 700 nm) is 70% or more, or more likely at least 80% or even 90% or more, as measured for example using a spectrophotometer and known techniques.
  • the articles and methods described herein include the use of water- soluble reactive polymers that can be used to form crosslinked polymer layers or patterns useful as "templates" within or on which layers or patterns of electrically- conductive polyaniline can be formed.
  • Touch screen technology can comprise different touch sensor configurations including capacitive and resistive touch sensors.
  • Capacitive touch sensors can be used in electronic devices with touch-sensitive features. These electronic devices can include but are not limited to, televisions, monitors, and projectors that can be adapted to display images including text, graphics, video images, movies, still images, and presentations.
  • the image devices that can be used for these display devices can include cathode ray tubes (CRT), projectors, flat panel liquid crystal displays (LCD), light emitting diode (LED) systems, organic light emitting diode (OLED) systems, plasma systems, electroluminescent displays (ELD), and field emission displays (FED).
  • CTR cathode ray tubes
  • LCD flat panel liquid crystal displays
  • LED light emitting diode
  • OLED organic light emitting diode
  • plasma systems electroluminescent displays
  • ELD electroluminescent displays
  • FED field emission displays
  • the present invention can be used to prepare capacitive touch sensors that can be incorporated into electronic devices
  • the water-soluble reactive polymers can be used in such systems and methods with multiple printing members (such as flexographic printing members or inkjet printing) to form multiple high resolution electrically-conductive polyaniline images.
  • multiple electrically-conductive polyaniline patterns can be formed on one or both supporting sides of a substrate.
  • one electrically-conductive polyaniline pattern can be provided on one supporting side of the substrate and a different electrically-conductive polyaniline pattern can be provided on the opposing supporting side of the substrate that can be a continuous web.
  • the water-soluble reactive polymers useful in the practice of this invention have two essential features. They comprise pendant groups that are capable of crosslinking via [2+2] photocycloaddition (defined below) upon exposure to suitable radiation.
  • the water-soluble reactive polymers also comprise sulfonate or sulfonic acid groups that provide sufficient water-solubility or water-dispersibility as well as internal dopants for polyaniline formation after the water-soluble reactive polymer has been crosslinked.
  • the water-soluble reactive polymers can be supplied as compositions in appropriate media.
  • the water-soluble reactive polymers can be either condensation or vinyl polymers as long as the requisite pendant crosslinkable and water- solubilizing sulfonate or sulfonic acid groups are connected to and arranged along the water-soluble reactive polymer backbone.
  • the water- soluble reactive polymers are vinyl polymers derived from appropriately selected ethylenically unsaturated polymerizable monomers using known free radical solution polymerization techniques and conditions, initiators, surfactants, catalysts, and solvents, all of which would be readily apparent to one skilled in the art from the teaching provided herein.
  • the water-soluble reactive polymers used in the present invention comprise (a) recurring units comprising sulfonic acid or sulfonate groups, or mixtures of both sulfonic acid and sulfonate groups.
  • Such recurring units can be provided by polymerization of suitable ethylenically unsaturated polymerizable monomers containing such water-solubilizing groups such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methy 1-1 -propane sulfonic acid, 2- sulfoethyl methacrylate, 3 -sulfopropyl methacrylate, styrene sulfonates, and 3- sulfopropyl acrylate.
  • suitable ethylenically unsaturated polymerizable monomers containing such water-solubilizing groups such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methy 1-1 -propane sulfonic acid, 2- sulfoethyl methacrylate, 3 -sulfopropyl methacrylate, styren
  • such recurring units can be provided by polymerizing certain precursor ethylenically unsaturated polymerizable monomers that comprise pendant precursor groups that can in turn be reacted to provide the desired pendant sulfonic acid or sulfonate groups.
  • such monomers include but are not limited to, hydroxy or amino-containing compounds such as 2- hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-aminoethyl methacrylate, and 2-aminoethyl acrylate that can be reacted using a variety of sulfonating agents to provide the desired pendant sulfonic acid or sulfonate groups.
  • the recurring units described above having the sulfonic acid or sulfonate groups are present in the reactive polymers in an amount of at least 40 mol %, or more likely at least 50 mol % and up to and including 80 mol % or up to and including 95 mol %, all amounts based on the total recurring units in the water-soluble reactive polymer.
  • Crosslinkable (b) Recurring Units :
  • the water-soluble reactive polymers used in the present invention also comprise (b) recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition when appropriately exposed to suitable radiation.
  • photosensitive crosslinkable groups can be chosen from one or more of the following classes of photosensitive crosslinkable groups, all of which can be connected to a (b) recurring unit backbone that is derived from suitable ethylenically unsaturated polymerizable monomers:
  • 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
  • Multiple photosensitive crosslinkable groups can be present from the same or multiple different classes of the crosslinkable groups (i) through (v).
  • the noted photosensitive crosslinkable groups Upon exposure to suitable radiation having a max of at least 150 nm and up to and including 700 nm, or more likely exposure to radiation having a max of at least 150 nm and up to and including 450 nm, the noted photosensitive crosslinkable groups are electronically excited such that they can react with other pendant groups in the water-soluble reactive polymer to form crosslinks for example as the product of photocycloaddition reactions.
  • the water-soluble reactive polymers particularly become crosslinked among adjacent or proximate (molecularly near enough for [2+2] photocycloaddition crosslinking) crosslinkable groups during or after the noted irradiation.
  • essential crosslinking can be accomplished using the water- soluble reactive polymer without additional crosslinking agents.
  • crosslinking can be further provided using distinct compounds that are dispersed as crosslinking agents within the compositions or layers comprising one or more water-soluble reactive polymers.
  • Such crosslinking agents react at either the crosslinkable groups or at other pendant groups such as carboxylic acid groups depending upon the chemical structure of crosslinking agent.
  • crosslinking is achieved by having at least two of such crosslinkable groups in proximity that can react with one another.
  • the crosslinkable [2+2] photocycloaddition groups incorporated into the water-soluble reactive polymers can absorb photoexposing radiation as described above to form an electronically excited state that can undergo pericyclic ring formation to form stable covalent crosslinks. These crosslinks between the polymer chains cause the water-soluble reactive polymer to become water- insoluble (or crosslinked), although the water-insoluble (crosslinked) reacted polymer can still absorb and transport water, ions, or other small molecules.
  • the photoexposing radiation can be followed by additional curing or heating procedures (described below) to allow the excited [2+2] photocycloaddition groups to properly align with non-excited [2+2] photocycloaddition groups to form additional crosslinks. Curing can be shortened using heat with the curing irradiation.
  • the crosslinked, water-insoluble complex containing the crosslinked polymer is crosslinked at a level that imparts water-insolubility and adhesion to a substrate, but still allows rapid diffusion of water, metal ions, and other small molecules.
  • This type of water-compatible crosslinked material is sometimes referred to as a hydrogel.
  • the (b) recurring units comprising the noted photosensitive crosslinkable [2+2] photocycloaddition groups can be present in the water-soluble reactive polymers in an amount of at least 5 mol % or typically at least 5 mol % and up to and including 30 mol %, or even at least 10 mol % and up to and including 20 mol %, all amounts based on the total recurring units in the water- soluble reactive polymer.
  • R and R 1 can be independently hydrogen or substituted or unsubstituted alkyl groups having at least 1 to 7 carbon atoms (including substituted or unsubstituted methyl, ethyl, isopropyl, /-butyl, hexyl, and benzyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted cycloalkyl group having 5 or 6 carbon atoms in the ring (such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms (such as methoxy, ethoxy, benzoxy, and others readily apparent to one
  • R and R 1 can be independently hydrogen or substituted or unsubstituted methyl, ethyl or phenyl groups, especially when Y is a substituted or unsubstituted phenyl group as described below.
  • Y can be a substituted or unsubstituted carbocyclic aryl group, or a substituted or unsubstituted heteroaryl group having one or more heteroatoms (oxygen, sulfur, or nitrogen) and sufficient carbon atoms to complete an aromatic heterocyclic ring.
  • Such aromatic rings can have one or more substituents that do not adversely affect the desired behavior in the crosslinking reactions induced by the irradiation described herein.
  • Useful Y groups can be either heterocyclic or carbocyclic rings having desired aromaticity and any of these rings can be substituted with one or more substituents that do not adversely affect the function of the reactive polymer.
  • Representative aromatic Y groups include but are not limited to, substituted or unsubstituted phenyl, naphthyl, anthracyl, 4-nitrophenyl, 2,4-dichlorophenyl, 4- ethylphenyl, tolyl, 4-dodecylphenyl, 2-nitro-3-chlorophenyl, 4-methoxy phenyl, 2- furyl, 2-thienyl, 3-indolyl, and 3-pyridyl rings.
  • substituted or unsubstituted phenyl rings are particularly useful including but not limited to phenyl, tolyl, xylyl, 4-methoxyphenyl, hydroxyphenyl, and chlorophenyl groups.
  • Substituted or unsubstituted phenyl or 3-pyridyl groups are particularly useful Y groups.
  • R, R 1 , and Y are as defined above.
  • R 2 can be a divalent linking group including but are not limited to, substituted or unsubstituted alkylene (including haloalkylenes and cyanoalkylenes), alkyleneoxy,
  • a skilled worker in polymer chemistry would be able to design other useful linking groups using suitable number of carbon and hetero (oxygen, nitrogen, or sulfur) atoms in an order and arrangement that are chemically possible.
  • Particularly useful R 2 divalent groups are substituted or unsubstituted alkylene groups such as substituted or unsubstituted ethylene or propylenes.
  • R 3 , R 4 , and R 5 can be independently hydrogen, a halogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cyclohexyl group, or a substituted or unsubstituted phenyl group.
  • R 3 , R 4 , and R 5 can be independently hydrogen, chloro, methyl, or ethyl groups.
  • Some particularly useful ethylenically unsaturated polymerizable monomers from which -Ai- recurring units can be derived include:
  • the -Ai- recurring units can also be formed after formation of a water-soluble precursor reactive polymer having precursor -Ai- recurring units.
  • a water-soluble precursor reactive polymer can be prepared with recurring units derived from vinyl alcohols or acrylate monomers having pendant hydroxyl groups, and the pendant hydroxyl groups can be reacted with cinnamoyl chloride (or similar substituted cinnamoyl-like chloride reactants) to form the desired -Ai- (or similar) recurring units with pendant precursor groups such as alcohols or amines that are already present before the reaction to form the -Ai- recurring units.
  • Another class of useful photosensitive crosslinkable groups arranged along the water-soluble reactive polymer backbone can comprise pendant photosensitive (crosslinkable), non-aromatic unsaturated carbocyclic groups including but not limited to, cyclopropene groups, cyclobutene groups, cyclopentadiene groups, cyclohexene groups, cyclohexadiene groups, cycloheptene groups, cycloheptadiene groups, cycloheptatriene groups, cyclooctene groups, indene groups, dihydronaphthalene groups, and norbornene groups. Any of these photosensitive groups can be substituted with one or more substituents that will not interfere with the desired properties of the water-soluble reactive polymer. Where appropriate, such non-aromatic unsaturated carbocyclic groups can also contain one or more carbon-containing fused rings.
  • the cyclopropene groups including the unsaturated cyclopropene groups can be particularly useful.
  • R, R 1 , and R 2 in Structure (- ⁇ -) can be independently hydrogen or substituted or unsubstituted alkyl groups having at least 1 to 7 carbon atoms (including substituted or unsubstituted methyl, ethyl, isopropyl, /-butyl, hexyl, and benzyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted cycloalkyl group having 5 or 6 carbon atoms in the ring (such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups, and others that would be readily apparent to one skilled in the art), substituted or
  • R and R 1 can also be nitro, cyano, or halogen groups.
  • R, R 1 , and R 2 in Structure (-An-) can be independently hydrogen or substituted or unsubstituted methyl, ethyl or phi groups, and more particularly, each of these groups is hydrogen or methyl.
  • E can be a divalent linking group including but not limited to, substituted or unsubstituted alkylene (including haloalkylenes and
  • divalent hydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear, branched, or cyclic form), carbonyloxy, oxycarbonyl, amido, keto, carbonate, carbamate, and urea.
  • a skilled worker in polymer chemistry would be able to design other useful linking groups using suitable number of carbon and hetero (oxygen, nitrogen, or sulfur) atoms in an order and arrangement that are chemically possible.
  • Particularly useful E divalent groups are substituted or unsubstituted alkylene groups such as substituted or unsubstituted ethylene or propylenes, or oxycarbonyl.
  • Di can represent the carbon atoms necessary to complete a three-membered to seven-membered non-aromatic unsaturated carbocyclic group (or ring), or particularly the carbon atoms necessary to complete a non-aromatic, unsaturated 3-membered to 7-membered carbocyclic group (or ring) such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, or a cycloheptene ring.
  • Di can also represent the saturated or unsaturated carbon atoms to provide an indene or dihydronaphthalene group, or poly cyclic rings such as a norbornene group.
  • R 3 can be hydrogen, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (such as methyl, ethyl, isopropyl, amyl, hexyl, nonyl, decyl, and dodecyl), or a substituted or
  • unsubstituted aryl group having 6 or 10 carbon atoms in the ring can be substituted with one or more hydroxy, halogen, carbonyl, cyano, alkyl, or alkoxy groups.
  • m can represent the molar amounts of the recurring units that would satisfy the amounts described above for the water- soluble polymer.
  • R, R 1 , R 2 , R 3 , and E are as defined above for Structure (-Ai-).
  • These recurring units can be derived from suitable ethylenically unsaturated polymerizable monomers that can then be polymerized under suitable conditions to provide useful water-soluble reactive polymers.
  • the carbon-carbon double bond is conjugated with one or two of the same or different electron withdrawing groups, and in most embodiments, the carbon-carbon double bond is conjugated with only one electron withdrawing group.
  • the pendant photosensitive, aromatic or non-aromatic heterocyclic groups can be single ring groups formed of carbon and hetero atoms (such as nitrogen, sulfur, and oxygen), or they can be fused ring groups with two or more fused rings formed from carbon and suitable heteroatoms.
  • electron withdrawing groups that can be conjugated with the carbon-carbon double bond would be readily apparent to one skilled in the art as the term "electron withdrawing" in reference to a chemical group is well known in the art. However, it is particularly useful when such electron withdrawing groups include but are not limited to, carbonyl, ester, thioester, amide, imine, amidine, ether, thioether, and amine groups (or moieties).
  • the photosensitive (crosslinkable) aromatic or non-aromatic heterocyclic group can be a cyclic group that comprises an ⁇ , ⁇ -unsaturated ketone, ⁇ , ⁇ -unsaturated lactone, ⁇ , ⁇ -unsaturated lactam, ⁇ , ⁇ -unsaturated ether, ⁇ , ⁇ -unsaturated thioether, or ⁇ , ⁇ - unsaturated amine group.
  • photosensitive (crosslinkable) aromatic or non-aromatic heterocyclic groups those containing a carbonyl group are particularly useful.
  • the water-soluble reactive polymers can comprise pendant photosensitive, aromatic or non-aromatic heterocyclic groups selected from the group consisting of coumarin, thiocoumarin, quinone, benzoquinone, naphthoquinone, pyran, thiopyran, benzopyran, benzothiopyran, pyranone, thiopyranone, pyridinone, quinoline, and quinolinone groups.
  • pendant photosensitive coumarin or quinolinone groups are useful and the pendant photosensitive coumarin groups are most useful because they can be readily prepared. Any of the photosensitive aromatic or non-aromatic heterocyclic groups can be substituted with one or more substituents that will not interfere with the desired properties of the water-soluble reactive polymer.
  • R, R 1 , and R 2 can be independently hydrogen or substituted or unsubstituted alkyl groups having at least 1 to 7 carbon atoms (including substituted or unsubstituted methyl, ethyl, isopropyl, /-butyl, hexyl, and benzyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted cycloalkyl group having 5 or 6 carbon atoms in the ring (such as cyclopentyl, cyclohexyl, 4- methylcyclohexyl, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms (such as methoxy
  • R, R 1 , and R 2 can be independently hydrogen or substituted or unsubstituted methyl, ethyl or phenyl groups, and more particularly, each of these groups can be hydrogen or methyl.
  • E in Structure (-Aiii-) can be a single bond or divalent linking group that can be connected to a carbon atom within Di. Thus, while E appears to be connected directly to Di, E can be connected to any carbon represented by Di.
  • E can be a divalent linking group including but not limited to, substituted or unsubstituted alkylene (including haloalkylenes and
  • cyanoalkylenes alkyleneoxy, alkoxyalkylene, iminoalkylene, cycloalkylene, aralkylene, cycloalkylene-alkylene, aryloxyalkylene groups wherein the divalent hydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear, branched, or cyclic form), carbonyloxy, oxycarbonyl, amido, keto, carbonate, carbamate, and urea.
  • a skilled worker in polymer chemistry would be able to design other useful linking groups using suitable number of carbon and hetero (oxygen, nitrogen, or sulfur) atoms in an order and arrangement that are chemically possible.
  • Particularly useful E divalent groups are substituted or unsubstituted alkylene groups such as substituted or unsubstituted ethylene or propylenes or oxycarbonyl.
  • Di represents the carbon and hetero (sulfur, oxygen, or nitrogen particularly) atoms necessary to complete a three-membered to fourteen-membered aromatic or non-aromatic heterocyclic group (or ring) that includes the carbon-carbon double bond shown in Structure (-Aiii-).
  • R 3 groups defined below
  • Di or at least one of the R 3 groups comprises at least one (and optionally more) electron withdrawing groups that are conjugated with the carbon-carbon double bond shown in Structure (-Aiii-).
  • Di can also represent the saturated or unsaturated carbon or hetero atoms to provide one or more fused rings such as naphthoquinone, benzopyran, benzothiopyran, benzopyran-2-one (coumarin), quinoline, and quinolinone polyrings.
  • Other useful Di ring systems optionally comprising at least one electron withdrawing group that is conjugated with the carbon-carbon double bond would be readily apparent to one skilled in the art.
  • R 3 is hydrogen, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (such as methyl, ethyl, isopropyl, amyl, hexyl, nonyl, decyl, and dodecyl), a substituted or unsubstituted aryl group having 6 or 10 carbon atoms in the ring, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms (such as methoxy, 2-ethoxy, /-butoxy, and ft-hexoxy), substituted or unsubstituted aryloxy group having 6 or 10 carbon atoms in the ring (such as phenoxy and naphthoxy), cyano, halo, or carbonyl- containing group.
  • Such carbonyl-containing groups include but are not limited to, aldehyde, ketone, carboxylic acid, ester, and amide groups.
  • m can represent the molar amounts of the noted recurring units as described above for the water-soluble reactive polymers.
  • the useful (b) recurring units can be derived from suitable ethylenically unsaturated polymerizable monomers that can then be polymerized under suitable conditions to provide useful water-soluble reactive polymers.
  • such heterocyclic groups have only one or two amide groups and the carbon-carbon double bond is conjugated with the one or two amide groups arranged within the non-aromatic unsaturated heterocyclic group (ring).
  • the carbon-carbon double bond is conjugated with the only one amide group in the non-aromatic unsaturated heterocyclic group (ring).
  • the pendant photosensitive, non-aromatic unsaturated heterocyclic groups can be single ring groups formed of carbon and hetero atoms (such as nitrogen, sulfur, and oxygen), or they can be fused ring groups with two or more fused rings formed from carbon and suitable heteroatoms.
  • Particularly useful water-soluble reactive polymers can comprise pendant photosensitive, non-aromatic unsaturated heterocyclic groups selected from the group consisting of substituted or unsubstituted maleimide and thymine groups.
  • the substituted maleimide groups are most useful because they can be readily prepared.
  • any of the photosensitive non-aromatic unsaturated heterocyclic groups can be substituted with one or more substituents that will not interfere with the desired properties of the water-soluble reactive polymer and the reactions necessary for crosslinking.
  • useful (b) recurring units also can be represented by the following Structure (-Ai v -):
  • R, R, and R can be independently hydrogen or substituted or unsubstituted alkyl groups having at least 1 to 7 carbon atoms (including substituted or unsubstituted methyl, ethyl, isopropyl, /-butyl, hexyl, and benzyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted cycloalkyl group having 5 or 6 carbon atoms in the ring (such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms (such as methoxy, ethoxy,
  • R, R , and R can be independently hydrogen or substituted or unsubstituted methyl, ethyl or phenyl groups, and more particularly, each of these groups can be hydrogen or methyl.
  • L can be a single bond or divalent linking group that can be connected to a nitrogen atom (as shown) within the
  • L can be a divalent hydrocarbon or aliphatic linking group that generally include 1 to 10 carbon, nitrogen, or oxygen atoms in the chain and can include but not limited to, substituted or unsubstituted alkylene (including haloalkylenes and
  • divalent hydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear, branched, or cyclic form) and can be connected or interrupted with heteroatom- containing groups such as oxy, carbonyl, carbonyloxy, oxycarbonyl, amino, amido, carbonate, carbamate, and urea, or any combination thereof.
  • L divalent groups are substituted or unsubstituted alkylene groups such as substituted or unsubstituted methylene, ethylene, or a propylene (any isomer), or such groups can be used in combination with an oxy carbonyl (such as from an acrylic acid ester group).
  • X represents the 1 to 3 carbon and heteroatoms (usually nitrogen atoms), which in combination with the remaining shown nitrogen and carbon atoms, complete a five- to seven-membered photosensitive non-aromatic unsaturated heterocyclic ring.
  • X represents at least one carbon atom (for example, a carbonyl carbon atom), or at least one carbon atom (for example, a carbonyl carbon atom) and at least one nitrogen atom such that the resulting amide group is conjugated with the shown carbon-carbon double bond.
  • R 1 and R 2 are independently hydrogen or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (such as substituted or unsubstituted methyl, ethyl, isopropyl, amyl, hexyl, nonyl, and decyl groups), or a substituted or unsubstituted cycloalkyl group having 5 or 6 carbon atoms in the unsaturated carbocyclic ring (such as substituted cyclohexyl groups).
  • R 1 and R 2 are likely to be the same group such as hydrogen, or unsubstituted methyl or unsubstituted ethyl groups.
  • R, R', R", L, R 1 , and R 2 are as defined above in Structure (-Aiv-) and m is defined below.
  • R 3 and R 4 are independently hydrogen, or substituted or unsubstituted alkyl groups or substituted or substituted cycloalkyl groups for example as used to define R 1 and R 2 shown above.
  • a water-soluble reactive polymer used in this invention can comprise a variety of different photosensitive non-aromatic unsaturated heterocyclic groups in recurring units.
  • the water-soluble reactive polymer can have (b) recurring units represented by both Structures (- Aivi-) and either (-Ai v2 -) or (-Ai V 3-).
  • the water-soluble reactive polymer can have (b) recurring units represented by both Structures (-Ai v2 -) and (- Aiv3-).
  • the water-soluble reactive polymer can have (b) recurring units represented by all of Structure (-Aivi-), (-Ai v2 -), and (-Ai V 3-).
  • the useful recurring units can be derived from suitable ethylenically unsaturated polymerizable monomers that can then be polymerized under suitable conditions to provide useful water-soluble reactive polymers.
  • Still another class (v) of useful photosensitive and crosslinkable pendant groups comprises photosensitive substituted or unsubstituted 1,2- diarylethylene groups.
  • Such groups can be generally represented as -An- ethylene-Ar2 wherein An is a divalent, substituted or unsubstituted heterocyclic or carbocyclic aromatic group and An is a monovalent, substituted or unsubstituted heterocyclic or carbocyclic aromatic group.
  • some useful water-soluble reactive polymers comprise pendant groups comprising photosensitive substituted or unsubstituted 1 ,2-diaryl ethylene groups selected from stilbene, styrylnaphthalene,
  • styrylthiazole styrylthiazolium
  • naphthrylphenyl naphthylene-ethylene-phenyl
  • naphthrylpyridinium naphthylthiazolium
  • 1 -pyridyl-2-thiazolylethylene 1 ,2- pyridiylethylene groups.
  • the pendant groups comprising photosensitive stilbene, styrylpyridinium, styrylquinoline, or styrylthiazolium groups are particularly useful.
  • any of the photosensitive 1,2-diarylethylene groups can be substituted with one or more substituents that will not interfere with the desired properties of the water-soluble reactive polymer and the reactions necessary for cros slinking.
  • Such useful (b) recurring units can be represented by the following Structure (-A v -) showing both water-soluble reactive polymer backbone and pendant groups attached thereto:
  • R, R , and R can be independently hydrogen or substituted or unsubstituted alkyl groups having at least 1 to 7 carbon atoms (including substituted or unsubstituted methyl, ethyl, isopropyl, /-butyl, hexyl, and benzyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted cycloalkyl group having 5 or 6 carbon atoms in the ring (such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups, and others that would be readily apparent to one skilled in the art), substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms (such as methoxy, ethoxy,
  • R, R , and R can be independently hydrogen or substituted or unsubstituted methyl, ethyl or phenyl groups, and more particularly, each of these groups can be hydrogen or substituted or unsubstituted methyl groups.
  • L can be a single bond or divalent linking group that can be connected to a nitrogen atom (as shown) within the
  • L can be a divalent hydrocarbon or aliphatic linking group that generally include 1 to 10 carbon, nitrogen, or oxygen atoms in the chain and can include but not limited to, substituted or unsubstituted alkylene (including haloalkylenes and
  • divalent hydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear, branched, or cyclic form) and can be connected or interrupted with heteroatom- containing groups such as oxy, carbonyl, carbonyloxy, oxycarbonyl, amino, amido, carbonate, carbamate, and urea, or any combination thereof.
  • L divalent groups can be substituted or unsubstituted alkylene groups such as substituted or unsubstituted methylene, ethylene, or a propylene (any isomer), or such groups can be used in combination with an oxycarbonyl (such as from an acrylic acid ester group), and aliphatic groups comprising a carbonyloxy group directly attached to the water-soluble reactive polymer backbone.
  • An is a divalent carbocyclic or heterocyclic aromatic group that can be substituted or unsubstituted.
  • An can be substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridinylene, substituted or
  • the one or more substituents can be any moiety that will not adversely affect the photosensitivity of the pendant group or any other properties intended for the water-soluble reactive polymer.
  • useful substituents can include but are not limited to methyl groups and ethyl groups.
  • Particularly useful An groups are substituted or unsubstituted phenylene and pyridinium groups.
  • An can be a substituted or unsubstituted carbocyclic or heterocyclic aromatic group as defined for An except that An is monovalent as shown in Structure (-A v -).
  • An groups are substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted pyridine, substituted or unsubstituted pyridinium, substituted or unsubstituted quinoline, substituted or unsubstituted quinolinium, substituted or unsubstituted thiazole, and substituted or unsubstituted thiazolium groups, with substituted or unsubstituted phenyl, substituted or unsubstituted pyridinium, substituted or unsubstituted quinolinium groups, and substituted or unsubstituted thiazolium groups being particularly useful.
  • An aromatic rings can be quaternary aromatic rings having a positive nitrogen atom, and a suitable counterion, such as trifluoromethylsulfonate, is then present.
  • a suitable counterion such as trifluoromethylsulfonate
  • R 1 and R 2 are independently hydrogen or substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms (such as substituted or unsubstituted methyl, ethyl, isopropyl, amyl, hexyl, nonyl, and decyl groups), or substituted or unsubstituted cycloalkyl groups having 5 or 6 carbon atoms in the unsaturated carbocyclic ring (such as substituted cyclohexyl groups).
  • R 1 and R 2 are likely to be the same group such as hydrogen, or unsubstituted methyl or unsubstituted ethyl groups.
  • the water-soluble reactive polymer comprises (b) recurring units represented by the following Structure (-A v i-) also showing water-soluble reactive polymer backbone to which pendant groups are attached:
  • R, R', R" are as defined above and are particularly hydrogen or methyl
  • L is as described above and particularly comprises a carbonyloxy group directly attached to the backbone
  • R 1 and R 2 can be independently hydrogen, methyl, or ethyl
  • R 3 can be a suitable substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aryl group
  • X " can be a suitable counterion as described above
  • m is as defined below.
  • m can represent the molar amounts of the (b) recurring units as described above for the water-soluble reactive polymers.
  • Some useful (b) recurring units of this class can be derived from: l-methyl-4-[2-(4-(2-methacryloxyethyl)- carbonyloxyphenyl)ethenyl]pyridinium trifluormethylsulfonate;
  • Such useful (b) recurring units can be derived from suitable ethylenically unsaturated polymerizable monomers that can then be polymerized under suitable conditions to provide useful water-soluble reactive polymers. More likely, such monomers are prepared by attaching a 1,2-diarylethylene group to a polymerizable acrylic group through a linking group by formation of an ester, amide or ether bond.
  • 4-formylbenzoic acid can be easily condensed with 4-methylpyridine to form a styrylpyridine group with a carboxylic acid functionality suitable for attachment to a linking group on an acrylic monomer such as 2-hydroxyethylmethacrylate.
  • the carboxylic acid and the hydroxyethyl groups can then be attached by a variety of ester forming reactions well known in the art including the known Mitsunobu reaction.
  • Optional (c) and (d) Recurring Units
  • the water-soluble reactive polymers used according to the present invention can optionally comprise at least 1 mol % and up to and including 65 mol %, or typically at least 1 mol % and up to and including 30 mol %, or even at least 1 mol % and up to and including 15 mol %, of (c) recurring units comprising pendant amide, hydroxyl, lactam, phosphonic acid (or phosphonate), or carboxylic acid (or carboxylate) groups, all based on the total amount of recurring units in the water-soluble reactive polymer.
  • Recurring units comprising pendant hydroxyl, amide, or carboxylic acid groups are particularly useful. It is also useful to have (c) recurring units that comprise multiple different pendant groups from the noted list of pendant groups.
  • Useful pendant precursor groups include but are not limited to, anhydrides, alcohols, amines, lactam, lactone, amide, and ester groups that can be used to provide the various groups noted above for the (c) recurring units.
  • useful (c) recurring units can be represented by the following Structure (-C-):
  • B' represents a pendant amide, hydroxy, lactam, phosphonic acid, or carboxylic acid group or precursor groups that can be appropriately converted, which group can be directly attached to the water-soluble reactive polymer backbone or it can be attached through a suitable divalent linking group.
  • some useful ethylenically unsaturated polymerizable monomers from which the (c) recurring units can be derived include but are not limited to, (meth)acrylic acid, itaconic acid, maleic anhydride, fumaric acid, citraconic acid, vinyl benzoic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, (meth)acrylamide, N-vinyl pyrrolidone,2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, vinyl phosphonic acid, N-isopropyl acrylamide, and dimethyl acrylamide.
  • the water-soluble reactive polymers can optionally comprise one or more additional recurring units that are different from all (a), (b), and (c) recurring units, and herein identified as optional (d) recurring units, in an amount of less than 40 mol %, or up to and including 30 mol %, all based on the total recurring units in the water-soluble reactive polymer.
  • (d) recurring units can be present with (a) and (b) recurring units but (c) recurring units can be absent.
  • Such additional (d) recurring units can be derived from one or more ethylenically unsaturated polymerizable monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, styrene and styrene derivatives, vinyl ethers, vinyl benzoates, vinylidene halides, vinyl halides, vinyl imides, and other materials that a skilled worker in the art would understand could provide desirable properties to the water-soluble reactive polymer.
  • Such (d) recurring units can be represented by Structure (-D-) as follows:
  • pendant D groups in Structure (-D-) can be for example, hydrogen, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, alkyl ester groups, aryl ester groups, halogens, or ether groups.
  • some (d) recurring units can comprise an epoxy (such as a glycidyl group) or epithiopropyl group derived for example from glycidyl methacrylate or glycidyl acrylate.
  • an epoxy such as a glycidyl group
  • epithiopropyl group derived for example from glycidyl methacrylate or glycidyl acrylate.
  • R, R', and R" can be the same or different hydrogen, methyl, ethyl, or chloro groups and each type of recurring unit can have the same or different R, R', and R" groups along the reactive polymer backbone.
  • R, R', and R" are hydrogen or methyl, and R, R', and R" can be the same or different for the various (a), (b), (c), and (d) recurring units in a given water-soluble reactive polymer.
  • mol % amounts of the various recurring units defined herein for the water-soluble reactive polymers defined herein are meant to refer to the actual molar amounts present in the water-soluble reactive polymers. It is understood by one skilled in the art that the actual mol % values may differ from those theoretically possible from the amount of ethylenically unsaturated polymerizable monomers that are used in the polymerization reaction solution. However, under most polymerization conditions that allow high polymer yield and optimal reaction of all monomers, the actual mol % of each monomer is generally within + 15 mol% of the theoretical amounts.
  • Some representative water-soluble reactive polymer embodiments include but are not limited to, the following copolymers and terpolymers wherein the molar ratios are theoretical (nominal) amounts based on the actual molar ratio of ethylenically unsaturated polymerizable monomers used in the polymerization process.
  • the actual molar amounts of recurring units can differ from the theoretical (nominal) amounts of monomers if the polymerization reactions are not carried out to completion.
  • poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate-co-styrene-co-2-cinnamoyl-ethyl methacrylate) 70: 10:20 mol %)
  • poly(3-sulfopropyl methacrylate-co-methacrylic acid-co-butyl methacrylate-co-2-cinnamoyl-ethyl methacrylate) 70:5:5:20 mol %)
  • poly(3-sulfopropyl methacrylate potassium salt-co-acrylamide-co- 2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate potassium salt-co-acrylamide-co- 2-cinnamoyl-ethyl methacrylate) 70: 10:20 mol %)
  • poly(3-sulfopropyl methacrylate potassium salt-co-2 -hydroxy ethyl metacrylate-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate potassium salt-co-maleic anhydryde-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate potassium salt-co-maleic anhydryde-co-2-cinnamoyl-ethyl methacrylate) 70: 10:20 mol %)
  • poly(3-sulfopropyl methacrylate potassium salt-co-N-vinyl-2- pyrrolidone-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate potassium salt-co-vinyl phosphonic acid-co-2-cinnamoyl-ethyl methacrylate) 70: 10:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-2-cinnamoylethyl methacrylate) 80:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-2- cinnamoylethyl methacrylate) 50:30:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-2- cinnamoylethyl methacrylate) 70: 10:20 mol %)
  • poly(2-sulfoethyl methacrylate sodium salt-co-methacrylic acid-co- 2-cinnamoylethyl methacrylate) 70: 10:20 mol %)
  • poly(4-sulfobutyl methacrylate sodium salt-co-methacrylic acid-co- 2-cinnamoylethyl methacrylate) 70: 10:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-acrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-acrylamide-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-maleic anhydryde-co-7- (2-methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-N-vinyl-2-pyrrolidone- co-7-(2-methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-N-vinyl-2-pyrrolidone- co-7-(2-methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %)
  • poly(styrene sulfonic acid sodium salt-co-vinyl phosphonic acid- co-7-(2-methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-N-vinyl-2-pyrrolidone- co-methacrylic acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) 70:5:5:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) 50:30:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) 60:20:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) 70: 10:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) (75:5:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) (78:2:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-7-(2- methacryloxyethoxy)-4-methylcoumarin) 85:5: 10 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-N- (2-(methacryloxy)ethyl) dimethylmaleimide-) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate sodium salt-co-methacrylic acid- co-2-(2,3-diphenyl-2-cyclopropene-l-carbonyloxy)ethyl methacrylate) (50:30:20 mol %);
  • poly(3-sulfopropyl methacrylate sodium salt-co-methacrylic acid- co-2-(2,3-diphenyl-2-cyclopropene-l-carbonyloxy)ethyl methacrylate) 70: 10:20 mol %);
  • poly(styrene sulfonic acid sodium salt-co-methacrylic acid-co-2- (2,3-diphenyl-2-cyclopropene-l-carbonyloxy)ethyl methacrylate) 70: 10:20 mol
  • the water-soluble reactive polymers useful in the invention generally have a molecular weight (M w ) of at least 10,000 and up to and including 1 ,000,000, or less than 100,000 for some uses, and at least 100,000 and up to and including 500,000 for other uses, all values being measured by gel permeation chromatography (GPC) or by size exclusion chromatography (SEC).
  • M w molecular weight
  • Preparation of the water-soluble reactive polymers useful in the present invention can be accomplished by free radical initiated polymerization in the appropriate reaction solvent combination.
  • the proper choice of reaction solvents is desirable for successful polymerization because of the wide disparity in polarity between the various ethylenically unsaturated polymerizable monomers with the ethylenically unsaturated polymerizable monomers providing the (a) recurring units being very polar or negatively charged and water soluble and the ethylenically unsaturated polymerizable monomers that provide (b) recurring units being relatively non-polar and hydrophobic. It is typical to require up to three reaction solvents in combination to facilitate a well-controlled polymerization.
  • Useful reaction solvents include but are not limited to, water, ketones such as methyl ethyl ketone (2-butanone), aprotic polar solvents such as N,N- dimethylacetamide, and alcohols such as isopropyl alcohol.
  • free radical initiators such as 2,2'-azodi(2-methylbutyronitrile) (AMBN) or azobis(isobutyronitrile) (AIBN) generally work well in these preparations of the reaction polymers.
  • the polymerization reaction is typically carried out at 60°C to 75°C for about 18 hours. Controlled or living radical polymerization methods (see for example, Qui et al, Progress in Polymer Science 26 (2001) 2083-2134) that can produce very narrow molecular weight distributions and highly controlled block copolymers could also be used.
  • Purification of useful water-soluble reactive polymers is best accomplished by dialysis because of their high water solubility. Additional water can be added to the completed reaction mixture that is then placed in a dialysis bag with a typical retention of polymer chains with an M w of 3500 Daltons or more. The dialysis bag containing the crude water-soluble reactive polymer is placed in a water washing bath for 1 to 2 days or longer if needed. After dialysis, the dilute water-soluble reactive polymer solution can be concentrated by evaporation to about 10 weight to 30 weight % solids which is suitable for storage and dilution to desired coating concentrations containing surfactants or humectants.
  • the water-soluble reactive polymers described herein can be incorporated into various photocurable compositions described below.
  • Such photocurable compositions can be incorporated into the various articles described below or used in various methods as described below.
  • Each photocurable composition described herein has only one essential component, that is, one or more water-soluble reactive polymers as described above.
  • the water-soluble reactive polymers can be used to form crosslinked reacted polymers (rendered water-insoluble) upon exposure to radiation having max of at least 150 nm and up to and including 700 nm, at least 150 nm and up to and including 450 nm, or of at least 250 nm and up to and including 450 nm, as described below. While various other optional components can be included as described below, only the water-soluble reactive polymer is essential for providing the desired articles and use in the methods.
  • One or more water-soluble reactive polymers can be present in the photocurable composition in an amount of at least 50 weight % and up to and including 100 weight %, or at least 70 weight % and up to and including 95 weight %, based on the total solids in the photocurable composition.
  • the photocurable compositions generally do not include separate crosslinking agents or crosslinking agent precursors because the water-soluble reactive polymer itself includes sufficient crosslinkable groups (described above). However, as noted above, if present, some (d) recurring units can also include additional crosslinking groups.
  • photosensitizers While not essential, it is sometimes desirable to enhance the sensitivity of some water-soluble reactive polymers to longer wavelengths by including one or more photosensitizers including triplet state photosensitizers.
  • photosensitizers are known in the art such as benzothiazole and naphthothiazole compounds as described in U. S. Patent 2,732,301 (Robertson et al), aromatic ketones as described in U. S. Patent 4,507,497 (Reilly, Jr.), and ketocoumarins, as described for example in U. S. Patents 4, 147,552 (Specht et al.) and 5,455,143 (Ali).
  • Particularly useful photosensitizers for long UV and visible light sensitivity include but are not limited to, 2-[bis(2-furoyl)methylene]-l- methyl-naphtho[l,2-d]thiazoline, 2-benzoylmethylene-l -methyl- - naphthothiazoline, 3,3'-carbonylbis(5,7-diethoxycoumarin), 3-(7-methoxy-3- coumarinoyl)- 1 -methylpyridinium fluorosulfate, 3-(7-methoxy-3-coumarinoyl)- 1 - methylpyridinium 4-toluenesulfonic acid, and 3-(7-methoxy-3-coumarinoyl)-l- methylpyridinium tetrafluoroborate.
  • Thioxanthones are also particularly useful for sensitizing the type (iv) [2+2] photocycloaddition groups such as dimethylmaleimide.
  • One or more photosensitizers can be present in a photocurable composition (and resulting dry layer) in an amount of at least 0.1 weight % and up to and including 10 weight %, or more likely at least 0.5 weight % and up to and including 5 weight %, based on the total solids in the photocurable composition (or total dry weight of the photocurable composition).
  • the photocurable compositions described herein can individually and optionally include one or more addenda such as film-forming compounds, surfactants (such as nonionic surfactants in an amount of up to 1 weight % based on total solids), humectants, plasticizers, filter dyes, viscosity modifiers, and any other optional components that would be readily apparent to one skilled in the art, and such addenda can be present in amounts that would also be readily apparent to one skilled in the art, depending upon the means that is used to dispose the photocurable composition onto a substrate.
  • addenda such as film-forming compounds, surfactants (such as nonionic surfactants in an amount of up to 1 weight % based on total solids), humectants, plasticizers, filter dyes, viscosity modifiers, and any other optional components that would be readily apparent to one skilled in the art, and such addenda can be present in amounts that would also be readily apparent to one skilled in the art, depending upon the means that is used to dispose the photocurable
  • the photocurable compositions comprise one or more carbon-containing materials such as carbon nanotubes, graphene, graphite, carbon black, or other conductive carbon-containing materials, in an amount of at least 0.1 weight %, or at least 0.5 weight % and up to and including 20 weight %, based on the total solids in the photocurable composition.
  • carbon-containing materials such as carbon nanotubes, graphene, graphite, carbon black, or other conductive carbon-containing materials, in an amount of at least 0.1 weight %, or at least 0.5 weight % and up to and including 20 weight %, based on the total solids in the photocurable composition.
  • Such materials can be obtained from various commercial sources.
  • the photocurable composition can also include conductive forms of carbon such as graphene, carbon nanotubes, and carbon- coated metal particles such as carbon-coated silver particles or carbon-coated copper particles, examples of which can be obtained from various commercial sources.
  • conductive forms of carbon such as graphene, carbon nanotubes, and carbon- coated metal particles such as carbon-coated silver particles or carbon-coated copper particles, examples of which can be obtained from various commercial sources.
  • Such materials can be present in an amount of at least 0.1 weight % and up to and including 50 weight %, based on the total solids of the photocurable composition.
  • the essential water-soluble reactive polymer and any optional materials described above are generally dissolved or dispersed in water or a mixture of water and water-miscible organic solvents to form a photocurable composition that can be applied to a suitable substrate (described below) in a suitable manner.
  • Useful water-miscible organic solvents include but are not limited to, alcohols such as methanol, ethanol, and isopropanol and polyols such as ethylene glycol, propylene glycol, and glycerol.
  • the amounts of the water- soluble reactive polymer and any optional compounds in the photocurable compositions can be readily determined by a skilled artisan for desired use in coating.
  • the water-soluble reactive polymer and any optional materials comprise at least 5 weight % and up to and including 50 weight % of the total photocurable composition, the remainder being the solvent(s) medium used for application.
  • the water-soluble reactive polymers in photocurable compositions described above can be used to prepare a variety of precursor articles that can be used for various purposes as described above, for example for preparing electrically-conductive elements (or articles).
  • a photocurable composition can be disposed in a suitable manner onto one or multiple surfaces (supporting surfaces or supporting sides) of a suitable substrate.
  • any of the photocurable compositions described above can be applied to a suitable substrate using any suitable method including but not limited to, spin coating, screen printing, bead coating, blade coating, curtain coating, or spray coating, inkjet printing, gravure printing, flexographic printing, or lithographic printing, from a suitable reservoir to form either a uniform layer or desired pattern of the photocurable composition containing one or more water-soluble reactive polymers.
  • Useful substrates can be chosen for a particular use or method as long as the substrate material will not be degraded by the photocurable composition or any treatments to which the resulting articles are subjected during the method of this invention.
  • the photocurable composition can be applied multiple times if desired to obtain a thicker coating of a layer or pattern, and dried between each coating or dried only after the last application. Water and any water-miscible organic solvents can be removed from the photocurable composition using any suitable drying technique.
  • the final dry layer or pattern of any photocurable composition can have an average dry thickness of at least 10 nm and up to and including 1 mm, with a dry thickness of at least 0.1 ⁇ and up to and including
  • Useful substrates can be composed of glass, quartz, and ceramics as well as a wide variety of flexible materials such as cellulosic papers and polymeric films composed of polyesters including poly(ethylene terephthalate) and poly(ethylene naphthalate), polycarbonates, polyamides, poly(meth)acrylates, or polyolefins.
  • Useful polymeric substrates can be formed by casting or extrusion methods. Laminates of various substrate materials can also be put together to form a composite substrate.
  • any of the substrates can be treated to improve adhesion using for example corona discharge, oxygen plasma, ozone or chemical treatments using silane compounds such as aminopropyltriethoxysilane.
  • the substrates can be of any suitable dry thickness including but not limited to at least 10 ⁇ and up to and including 10 mm, depending upon the intended use of the resulting articles.
  • Particularly useful substrates are flexible transparent polymeric substrates that are composed of poly(ethylene terephthalate) such as biaxially oriented poly (ethylene terephthalate) (PET) films.
  • PET films ranging in dry thickness of at least 50 ⁇ and up to and including 200 ⁇ , can also comprise, on at least one supporting side, a polymeric primer layer (also known as a subbing layer, adhesive layer, or binder layer) that can be added prior to or after film stretching.
  • Such polymeric primer layers can comprise poly(acrylonitrile-co- vinylidene chloride-co-acrylic acid), poly(methyl acrylate-co-vinylidene chloride- co-itaconic acid), poly(glycidyl methacrylate-co-butyl acrylate), or various water- dispersible polyesters, water-dispersible polyurethanes, or water-dispersible polyacrylics, as well as sub-micrometer silica particles.
  • the dry thickness of the primer layer can be at least 0.1 ⁇ and up to and including 1 ⁇ .
  • each of the substrates has an integrated transmittance of at least 80%, or at least 90% or even higher to provide articles that exhibit excellent transparency.
  • Such highly transparent substrates can be composed of glass (such as flexible glass) or polymeric films (such as polyester films) as described above.
  • the useful substrates can be in any suitable shape or size. They can be in the form of sheets, films, tubes, particles, or various 3-dimensional shapes depending upon the intended use. Some particularly useful substrates are in the form of continuous flexible polymeric webs that can be unrolled from a stock roll, treated in a suitable manner for example to apply a photocurable composition followed by various treatments (described below) and then rolled up in roll form for shipment or later use in roll-to-roll manufacturing processes.
  • the substrate can be provided in the form of a roll of a continuous polymeric web such as a roll of a continuous polyester web.
  • a substrate is in the form of a sheet or roll, it typically has two opposing planar surfaces known herein as a "supporting side” (or supporting planar surface) and an “opposing supporting side” (or opposing supporting planar surface).
  • a photocurable composition can be disposed in a suitable manner uniformly or pattemwise on one or both supporting sides of the substrate using the same or different photocurable compositions.
  • a precursor article can be prepared with a substrate by providing a uniform layer of a photocurable composition on a supporting side of the substrate, for example, uniformly on one or both supporting sides of a continuous polyester web using any suitable coating means that is well known in the art.
  • a pattern of a photocurable composition can be provided on one or both supporting sides of the substrate using a suitable "imaging” means such as inkjet printing, flexographic printing, lithographic printing, gravure printing, or screen printing.
  • a suitable "imaging” means such as inkjet printing, flexographic printing, lithographic printing, gravure printing, or screen printing. The procedures and equipment needed for such application are well known in the art.
  • the photocurable composition is exposed to radiation sufficient to cause crosslinking via [2+2] photocycloaddition of the (b) recurring units, thereby forming a crosslinked polymer on one or more supporting sides of the substrate.
  • Either uniform or pattemwise (imagewise) exposure can be carried out in a similar manner.
  • exposure can be carried out using radiation having a max of at least 150 nm and up to and including 700 nm or to radiation having a max of at least 200 nm and up to and including 450 nm.
  • This exposure can be provided with any suitable exposing source or device that provides the desired radiation including but not limited to, various arc lamps and LED sources.
  • the particular exposing source can be chosen depending upon the absorption characteristics of the photocurable composition used.
  • the exposing radiation can be projected through lenses and mirrors or through a lens or mask element that can be in physical contact or in proximity with a water-soluble complex.
  • Exposure time can range from a fraction (0.1) of a second and up to and including 10 minutes depending upon the intensity of the radiation source and the water-soluble reactive polymer used in the photocurable composition.
  • Suitable masks can be obtained by known methods including but not limited to photolithographic methods, flexographic methods, or vacuum deposition of a chrome mask onto a suitable substrate such as quartz or high quality optical glass followed by photolithographic patterning.
  • any non-crosslinked, water-soluble reactive polymer (for example, within the photocurable composition) can be removed from the one or more supporting sides of the substrate so that there is essentially none (or less than 10%, and particularly less than 5%, by weight of the original amount) remaining on the substrate. This can be done by washing, spraying, or immersing the article in water, aqueous alkaline solution, or another aqueous solution for a suitable time and temperature to remove most or all water-soluble reactive polymer from the substrate.
  • Contact with the aqueous solution can be carried out for a suitable time and temperature so that water-soluble reactive polymer is desirably removed in the non-exposed regions but little removal occurs in the exposed regions containing the crosslinked polymer.
  • the contact time can be at least 10 seconds and up to and including 10 minutes
  • the contact temperature can be at room temperature (about 20°C) and up to and including 95°C.
  • the crosslinked polymer is contacted with an aniline reactive composition in order to form electrically-conductive polyaniline disposed within, on top of, or both within and on top of, the crosslinked polymer.
  • electrically-conductive polyaniline is formed elsewhere, for example on bare substrate or on any remaining water-soluble reactive polymer.
  • significantly no electrically - conductive polyaniline it is meant that at least 95 weight % or even at least 99 weight %, of the formed electrically-conductive polyaniline is disposed within, on top of, or both within and on top of, the crosslinked polymer on the substrate.
  • aniline reactive composition comprises two essential components: (1) an aniline monomer in an amount of at least 0.01 molar or even at least 0.025 molar and up to and including 1 molar; and (2) at least 0.01 molar of an aniline oxidizing agent, that refers to a compound that can remove one or more electrons from the aniline molecules or polymers to form reactive radicals that can react with additional aniline to form and grow the polyaniline.
  • aniline oxidizing agents include but are not limited to, persulfate (such as potassium persulfate and ammonium persulfate), ozone, a peroxide (such as hydrogen peroxide), oxygen present in air, and other compounds that would be readily apparent to one skilled in the art.
  • persulfate such as potassium persulfate and ammonium persulfate
  • ozone a peroxide (such as hydrogen peroxide)
  • oxygen present in air and other compounds that would be readily apparent to one skilled in the art.
  • the choice of aniline oxidizing agents can also depend upon the presence of catalysts such as ferric or cupric ions.
  • aniline oxidizing agents can be used if desired.
  • the one or more aniline oxidizing agents are present in the aniline reactive composition in an amount of at least 0.01 molar and up to and including 1 molar, or even at least 0.025 molar and up to and including 0.5 molar.
  • the aniline reactive composition is acidic in pH and this can be accomplished by adding hydrochloric acid or sulfuric acid in an amount to obtain the desired pH.
  • the aniline oxidizing agent When a persulfate is used as the aniline oxidizing agent, it can be added within about 5 minutes of using the aniline reactive composition. Higher concentrations can be used to achieve shorter polymerization times but this should be balanced with the stability of the aniline reactive composition. It can be important to balance the amount of aniline monomer and the aniline oxidizing agent in the aniline reactive composition to control the degree of polymerization and formation of polyaniline.
  • the molar ratio of aniline monomer to the aniline oxidizing agent is from 1 :0.5 to and including 1 : 1.5, or more likely from 1 :0.75 to and including 1 : 1.25. A molar ratio greater than 1 : 1 can cause over oxidation that will decrease or eliminate the electrical conductivity of the polyaniline. Molar ratios below 1 :0.5 will provide insufficient polyaniline for eventual use in various devices.
  • Formation of polyaniline within, on top of, or both within and on top of, the crosslinked polymer can be carried out at any suitable temperature from below room temperature (about 0°C) up to and including 90°C, for a suitable time of at least 0.5 minute and up to and including 100 minutes. Higher temperatures will quicken polymerization.
  • the article containing the uniform layer or pattern of polyaniline can be removed from the aniline reactive composition and washed in water for up to 5 minutes to remove any remaining aniline monomer and aniline oxidizing agent.
  • the polyaniline layer or pattern can be suitably dried and is found to be electrically-conductive due to the inherent acid doping provided by the sulfonic acid or sulfonate groups in the crosslinked polymer.
  • Ferric (Fe +3 ) ion is particularly effective metal ion catalyst for aniline oxidation and it can be contacted with the crosslinked polymer coatings or patterns by simply immersing them in a ferric sulfate bath of typically 1 molar or less for less than 10 minutes, typically from 1 or 2 minutes, and then rinsing the crosslinked polymer treated in this manner with water before immersing contacting it with the aniline reactive composition.
  • polyaniline within, on top of, or both within and on top of, the crosslinked polymer coatings or patterns containing ferric ion will occur in 50% or less of the polymerization time without the ferric ions for a given polymerization bath and reaction temperature with no detectable polyaniline formation outside of the crosslinked polymer.
  • Other useful metal ion catalysts for aniline oxidation besides ferric ion can be used, including but not limited to, copper, silver, nickel, and cobalt ions depending on the aniline oxidizing agent used in the aniline reactive composition.
  • copper (II) ion can be used as a metal ion catalyst for aniline oxidation when a peroxide or ozone is used for the aniline oxidation agent.
  • Ferric ions or another metal ion catalyst can be used in a solution containing at least 0.1 molar metal ions, or even at least 0.5 molar metal ions and up to and including 1 molar metal ions.
  • the method according to this invention can further comprise:
  • One useful method of this invention uses multiple flexographic printing plates (for example, prepared as described above) in a printing station wherein each stack of flexographic printing plates has its own printing plate cylinder so that each flexographic printing plate is used to print individual substrates, or the stack of printing plates can be used to print multiple portions of photocurable composition in a single continuous web (on one or both opposing supporting sides).
  • the same or different photocurable composition can be "printed" or applied to a substrate (on same or opposing supporting sides) using the multiple flexographic printing plates.
  • a central impression cylinder can be used with a single impression cylinder mounted on a printing press frame.
  • the substrate or receiver element
  • the appropriate photocurable composition pattern is printed or formed on one or both supporting sides of the substrate.
  • an "in-line" flexographic printing process can be utilized in which the printing stations are arranged in a horizontal line and are driven by a common line shaft.
  • the printing stations can be coupled to exposure stations, cutting stations, folders, aniline reaction polymerization baths, and any other useful continuous processing stations or equipment.
  • a skilled worker could readily determine other useful configurations of equipment and stations using information that is available in the art. For example, an in-the-round imaging process is described in WO 2013/063084 (Jin et al).
  • the method comprises:
  • first photocurable composition partem from a photocurable composition as described herein, on at least a first portion of the continuous web, for example using a flexographic printing member,
  • Embodiments of this method can be carried out on a single supporting side of the substrate, or on opposing supporting sides of the substrate to provide the same or different patterns of polyaniline.
  • a plurality of portions having the same or different patterns of polyaniline can be provided on a continuous (for example, polyester) web (on one or both opposing supporting sides) according to the present invention.
  • a method of this invention can be used to provide a plurality of precursor articles, the method comprising:
  • a continuous web of a transparent substrate such as a continuous web of a transparent polyester
  • a method of this invention can be used to provide a plurality of electrically-conductive polyaniline patterns, and comprises:
  • each crosslinked polymer pattern being provided by irradiation of a photocurable composition as described above,
  • This method can be taken further by:
  • Such method embodiments can be carried out on one or both opposing supporting sides of the substrate (continuous web) using the same or different photocurable compositions and reactive aniline compositions.
  • Useful product articles prepared according to the present invention can be formulated into chemical sensors, conductive layers in a battery, capacitor or supercapacitor structures, photovoltaics, and capacitive touch screen sensors that comprise suitable electrically-conductive grid lines, electrodes, electrical leads (tails), and electrical connectors.
  • the electrodes and tail can be formed by multiple printings of a photocurable composition described herein and forming polyaniline patterns thereon.
  • the electrodes can form an x-y grid that enables the recognition of the point at which the user has interacted with the sensor.
  • the grid can have 16 x 9 conductive lines or more and a size range of for example, from 2.5 mm by 2.5 mm to 2.1 m by 2.1 m.
  • Top electrodes in the product article can correspond to the Y axis and can be provided on a first supporting side of the substrate and bottom electrodes are electrically-conductive lines corresponding to the X axis that can be provided on the opposing supporting side of the substrate.
  • Product articles provided by the methods according to this invention can have various forms and arrangements of electrically-conductive polyaniline patterns.
  • the individual treatment features or steps described above for these methods can be carried out two or more times before proceeding to the next procedure or step.
  • multiple treatments with a metal ion catalyst, and multiple contacting with the aniline reactive composition can be carried out in sequence, using the same or different conditions and solutions. Sequential washing or rinsing steps can also be carried out where appropriate.
  • a method for providing an electrically-conductive polyaniline pattern comprising:
  • 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 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;
  • 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.
  • 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.
  • a method for providing an electrically-conductive polyaniline partem comprising:
  • 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;
  • 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 partem of electrically-conductive polyaniline disposed either within, on top of, or both within and on top of, the crosslinked polymer only.
  • 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 partem of crosslinked polymer on the opposing supporting side of the substrate.
  • aniline reactive composition comprises a persulfate as the aniline oxidizing agent. 12. The method of any of embodiments 1 to 1 1, wherein the aniline reactive composition is acidic.
  • 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.
  • 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.
  • 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.
  • the photocurable composition further comprises at least 0.1 weight % of a photos ensitizer.
  • 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.
  • Water-soluble reactive polymers useful in the present invention were prepared using the synthetic processes described as follows, using ethylenically unsaturated polymerizable monomers described below. Synthesis of 7-(2-Methacryloyloxyethoxy)-4-methylcoumarin Monomer:
  • the resulting precipitate was filtered, rinsed with another 1 liter of water, rinsed with heptane, and dried on the filter.
  • the monomer product was confirmed by NMR.
  • a portion of the product was further purified by silica gel chromatography with ethyl acetate. The ethyl acetate was removed by evaporation and the product was crystallized from heptane to obtain a white powder.
  • the reaction solution was dialyzed for about 18 hours and then concentrated to a 13.06 weight % solids solution that was suitable for application to a substrate.
  • the weight average molecular weight (M w ) of the resulting water-soluble reactive polymer was 258,000 as determined by size exclusion chromatography (SEC).
  • the reaction mixture was diluted with water to form a clear solution that was dialyzed for about 18 hours and then concentrated to a 14.06 weight % solids solution that was suitable for application to a substrate.
  • the weight average molecular weight (M w ) of the resulting water-soluble reactive polymer was 225,000 as determined by size exclusion chromatography (SEC).
  • the reaction mixture was purged for 30 minutes with nitrogen, capped with a septum, and set into a preheated oil bath at 75°C overnight.
  • the reaction mixture was then cooled and placed in a dialysis bag with MWCO of 3500 and dialyzed until the bag was fully swollen. The contents were then evaporated to a concentration of 9.76 weight % solids.
  • the weight average molecular weight (M w ) of the resulting water-soluble reactive polymer was 250,000 as determined by size exclusion chromatography (SEC).
  • An oxidative acidic aniline reactive composition (bath) was prepared as two parts that were combined just before the crosslinked reactive polymer patterns were immersed.
  • Part A consisted of a 500 ml solution that was 0.05 molar aniline and 0.25 molar hydrochloric acid.
  • Part B was a 500 ml solution of 0.05 molar ammonium persulfate. When ready for use, Part B was added to Part A with stirring for 5 minutes before contact with the crosslinked reactive polymer patterns.
  • a photocurable composition containing either 10 weight % of water-soluble Polymer A or 9.3 weight % of water-soluble Polymer D and 0.05 weight % of Dow TergitolTM 15-S-9 surfactant (Dow Chemical) was filtered with a 1 ⁇ syringe filter and spin coated at 1500 RPM onto PET, poly (ethylene terephthalate) film with a polymeric adhesion layer of a copolymer derived from glycidyl methacrylate and butyl acrylate.
  • the resulting precursor articles were exposed to 350 nm to 450 nm ultraviolet light through a chrome-on-quartz contact mask for 15 seconds (water- soluble reactive Polymer A and 60 seconds (water-soluble reactive Polymer D) then each was heated to 60°C for 60 seconds.
  • Each of the imagewise exposed and heated articles was then immersed in well agitated distilled water for 2 minutes to remove the water-soluble reactive polymer from the non-crosslinked regions from the PET substrate. All but one of the resulting patterned intermediate articles was then immersed in a 1 molar ferric sulfate solution for 2 minutes, rinsed with water for about 30 seconds, and dried.
  • Each of the intermediate articles having ferric ions attached to the crosslinked reactive polymer in the crosslinked patterns was then immersed in the acidic aniline reactive composition (bath) that had been stirring for 5 minutes after the two parts were combined as described above.
  • the articles having crosslinked patterns obtained using water-soluble reactive Polymer A that had been immersed in the ferric sulfate solution began turning emerald green at about 3 minutes but were not electrically-conductive at this point. These articles were then removed from the bath, rinsed in distilled water for at least 1 minute, and then dried in air.
  • Photocurable compositions comprising either 4 weight % of water- soluble reactive Polymer A, B, or C, 10 weight % of ethylene glycol, and 0.5 weight % of Tergitol® 15-S-9 surfactant (Dow Chemical) were prepared and each was filtered with a 1 um disk filter. Each filtered photocurable composition was then loaded as an "ink" into an ink cartridge designed for a consumer inkjet printer with a thermal ink jet print head.
  • Each of these inks was printed onto a PET substrate that has been pre-coated as described for Invention Example 1 to form a pattern of the photocurable composition in a precursor article.
  • Each pattern in the precursor articles was composed of interleaved 0.5 mm lines connected to a probe pad.
  • Each precursor article was allowed to air dry and then exposed to 350 nm to 450 nm ultraviolet light for 120 seconds to thoroughly crosslink the patterns of water-soluble reactive polymers in the ink jet printed photocurable composition.
  • Each exposed intermediate article was then immersed in the 1 molar ferric sulfate solution (described above) for 2 minutes, rinsed in distilled water for about 1 minute, and then dried.
  • the intermediate articles having ferric ions in the crosslinked water-soluble reactive polymer patterns were then immersed in the acidic aniline reactive composition described above.
  • Each crosslinked pattern began turning green after about 3 minutes.

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Abstract

Procédé utilisé pour fournir un motif de polyaniline électroconducteur grâce à la mise en place d'une couche uniforme ou d'un motif d'une composition photodurcissable sur un substrat. La composition photodurcissable comprend un polymère réactif soluble dans l'eau comprenant (a) plus de 40 % en moles d'unités récurrentes comprenant des groupes acide sulfonique ou sulfonate, et (b) au moins 5 % en moles d'unités récurrentes comprenant un groupe pendant pouvant se réticuler par l'intermédiaire d'une photocycloaddition [2+2]. La composition photodurcissable est exposée pour provoquer la réticulation par l'intermédiaire de la photocycloaddition [2+2] des unités récurrentes (b), ce qui permet de former une couche ou un motif uniforme d'un polymère réticulé. Le polymère réticulé est mis en contact avec une composition réactive d'aniline ayant un monomère d'aniline et jusqu'à 0,5 mole d'un agent oxydant d'aniline, ce qui permet de former une polyaniline électroconductrice disposée dans, sur, ou bien dans et sur le polymère réticulé.
PCT/US2017/026268 2016-04-20 2017-04-06 Articles à revêtement de polyaniline et procédés préparatoires WO2017184348A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US15/133,336 US9718935B1 (en) 2016-04-20 2016-04-20 Method of preparing article with polyaniline pattern
US15/133,583 US9644112B1 (en) 2016-04-20 2016-04-20 Articles having electrically-conductive layer or pattern
US15/133,336 2016-04-20
US15/133,295 US10059821B2 (en) 2016-04-20 2016-04-20 Method of preparing article with polyaniline coating
US15/133,583 2016-04-20
US15/133,295 2016-04-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5370825A (en) * 1993-03-03 1994-12-06 International Business Machines Corporation Water-soluble electrically conducting polymers, their synthesis and use
US6045977A (en) * 1998-02-19 2000-04-04 Lucent Technologies Inc. Process for patterning conductive polyaniline films
US20080038672A1 (en) * 2006-08-03 2008-02-14 Seiko Epson Corporation Method for manufacturing electronic device, electronic device, and electronic apparatus
US20160077438A1 (en) * 2014-09-12 2016-03-17 Thomas B. Brust Forming conductive metal patterns using water-soluble polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5370825A (en) * 1993-03-03 1994-12-06 International Business Machines Corporation Water-soluble electrically conducting polymers, their synthesis and use
US6045977A (en) * 1998-02-19 2000-04-04 Lucent Technologies Inc. Process for patterning conductive polyaniline films
US20080038672A1 (en) * 2006-08-03 2008-02-14 Seiko Epson Corporation Method for manufacturing electronic device, electronic device, and electronic apparatus
US20160077438A1 (en) * 2014-09-12 2016-03-17 Thomas B. Brust Forming conductive metal patterns using water-soluble polymers

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