Copper-containing articles and methods for providing same
View Patent ↗A water-soluble composition includes reducible copper ions or copper nanoparticles complexed with a reactive polymer. The reactive polymer can be crosslinked using suitable irradiation to provide copper-containing water-insoluble complexes. The water-soluble composition can be used to provide various articles and electrically-conductive materials that can be assembled in electronic devices. The reactive polymer has greater than 1 mol % of recurring units comprising sulfonic acid or sulfonate groups, at least 5 mol % of recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition, and optionally at least 1 mol % of recurring units comprising a pendant amide, amine, hydroxyl, lactam, phosphonic acid, or carboxylic acid group.
1. A method for providing a copper-containing article, the method comprising:
disposing a copper-containing composition onto a first supporting side of a substrate, the copper-containing composition comprising a water-soluble complex of a reactive polymer with reducible copper ions, the reactive polymer comprising: (a) greater than 1 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, amine, hydroxyl, lactam, phosphonic acid, or carboxylic acid group, all amounts based on the total recurring units in the reactive polymer.
2. The method of claim 1 , wherein the recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition comprise:
(i) a photosensitive —C(═O)—CR═CR 1 —Y group wherein R and R 1 are independently hydrogen or an alkyl group having 1 to 7 carbon atoms, a 5- to 6-membered cycloalkyl group, an alkoxy group having 1 to 7 carbon atoms, a phenyl group, or a phenoxy group, and Y is an aryl or heteroaryl group;
(ii) a photosensitive, non-aromatic unsaturated carbocyclic group;
(iii) a photosensitive, aromatic or non-aromatic heterocyclic group comprising a carbon-carbon double bond that is conjugated with an electron withdrawing group, the photosensitive aromatic or non-aromatic heterocyclic group selected from the group consisting of coumarin, thiocoumarin, quinone, benzoquinone, naphthoquinone, pyran, thiopyran, benzopyran, benzothiopyran, pyranone, thiopyranone, pyridinone, quinoline, and quinolinone groups;
(iv) a photosensitive non-aromatic unsaturated heterocyclic group comprising one or more amide groups that are conjugated with a carbon-carbon double bond, which photosensitive non-aromatic unsaturated heterocyclic group is linked to the water-soluble backbone at an amide nitrogen atom; or
(v) a photosensitive substituted or unsubstituted 1,2-diarylethylene group.
3. The method of claim 1 , comprising disposing the copper-containing composition onto a supporting side of the substrate in a patternwise fashion using a flexographic printing member.
4. The method of claim 1 , further comprising:
reducing the reducible copper ions in the water-soluble complex to form copper nanoparticles in a water-soluble complex with the reactive polymer.
5. The method of claim 4 , further comprising:
after reducing the reducible copper ions, photoexposing the water-soluble complex of the reactive polymer with the copper nanoparticles to form a crosslinked water-insoluble complex of a crosslinked reacted polymer with the copper nanoparticles.
6. The method of claim 5 , wherein the photoexposing the water-soluble complex of the reactive polymer with the copper nanoparticles is performed in a patternwise fashion on the substrate.
7. The method of claim 1 , comprising:
disposing the copper-containing composition onto the first supporting side of a substrate,
disposing the same or different copper-containing composition onto an opposing second supporting side of the substrate,
photoexposing the water-soluble complex of the reactive polymer with the reducible copper ions on either or both of the first supporting side and opposing second supporting side of the substrate, to form a crosslinked water-insoluble complex of a crosslinked reacted polymer with reducible copper ions on either or both of the first supporting side and opposing supporting side of the substrate, and
optionally, removing any remaining water-soluble complex of the reactive polymer with the reducible copper ions from both the first supporting side and the opposing second supporting side of the substrate.
8. The method of claim 7 , comprising:
reducing the reducible copper ions in the crosslinked water-insoluble complex of the crosslinked reacted polymer with the reducible copper ions on either or both the first supporting side and the opposing second supporting side to form copper nanoparticles having an average diameter of at least 2 nm and up to and including 500 nm.
9. The method of claim 8 , comprising:
oxidizing the copper nanoparticles in the water-insoluble complex of the crosslinked reacted polymer with the copper nanoparticles on either or both the first supporting side and the opposing second supporting side to form copper oxide nanoparticles having an average diameter of at least 2 nm and up to and including 500 nm.
10. The method of claim 1 , wherein the substrate is a continuous web of transparent polymeric film having an integrated transmittance of at least 80%.