# US 2018/0022023 A1 · Electrically conductive ink for solvent-cast 3d printing > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0022023 A1 - Document ID: US20180022023A1 - Status: Published application - Kind: A1 - Application number: 15/654,094 - Filed: 2017-07-19 - Published: 2018-01-25 - Earliest claimed: 2016-07-20 - Assignees: Polyvalor, Limited Partnership - Applicants: Polyvalor, Limited Partnership - Inventors: DANIEL THERRIAULT; KAMBIZ CHIZARI - Web page: https://patentgrep.com/patent/US20180022023A1 ## CPC - B29C 64/153: using layers of powder being selectively joined, e.g. by selective laser sintering or melting - B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material - B33Y 10/00: Processes of additive manufacturing - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - C07C 19/03: Chloromethanes - C07C 31/02: Monohydroxylic acyclic alcohols - C07C 307/08: having nitrogen atoms of the sulfamide groups bound to carbon atoms of rings other than six-membered aromatic rings - C08B 37/003: {Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof} - C08J 3/075: Macromolecular gels - C09D 5/24: Electrically-conducting paints {(conductive materials H01B1/00)} - C09D 7/61: inorganic - C09D 7/70: {characterised by shape, e.g. fibres, flakes or microspheres} - C09D 105/08: Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof - B29K 2995/0005: Conductive - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08B: POLYSACCHARIDES; DERIVATIVES THEREOF (polysaccharides containing less than six saccharide radicals attached to each other by glycosidic linkages C07H; fermentation or enzyme-using processes C12P19/00; sugar industry C13; production of cellulose D21) - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS ## Abstract An ink for solvent-cast 3D printing is provided. The ink comprises a solution or gel of a polymer in a volatile solvent, and carbon nanotubes dispersed in the solution or gel. In the ink, the carbon nanotubes are present in a carbon nanotubes:polymer weight ratio between about 20:80 and about 40:60, and the polymer and carbon nanotubes total concentration is between about 20 and about 35 wt %, based on the total weight of the ink. There is also provided a 3D printer ink cartridge comprising the ink; a method of manufacturing the ink; a method of manufacturing a solvent-cast 3D printed material using the ink, a solvent-cast 3D printed material as well as uses thereof. ## Claims ### Claim 1 An ink for solvent-cast 3D printing, the ink comprising: a solution or a gel of a polymer in a volatile solvent, and carbon nanotubes dispersed in the solution or gel, wherein the carbon nanotubes are present in a carbon nanotubes:polymer weight ratio between about 20:80 and about 40:60, and wherein the polymer and carbon nanotubes total concentration is between about 20 and about 35 wt %, based on the total weight of the ink. ### Claim 2 (depends on 1) The ink of claim 1, wherein the polymer and carbon nanotubes total concentration is between about 25 and about 30 wt %, based on the total weight of the ink. ### Claim 3 (depends on 1) The ink of claim 1, wherein the polymer is poly(lactic acid), polystyrene, poly(methyl acrylate), poly(methyl methacrylate), poly(n-butyl acrylate), poly(2-hydroxyethyl methacrylate), poly(glycidyl methacrylate), poly(acrylic acid), poly(N—N-dimethylacrylamide), poly(l-vinyl anthracene), poly(2-vinyl pyridine), poly(4-vinyl pyridine), poly(N-vinyl carbazole), poly(N-vinyl carbazole), poly(N-vinyl imidazole), poly(vinyl benzyl chloride), poly(4-vinyl benzoic acid), poly(vinyl acetate), polycaprolactone, poly(11-[4-(4-butylphenylazo)phenoxy]-undecyl methacrylate) (poly(AzoMA)), poly(ferrocenyldimethylsilane), polyisoprene, polybutadiene, polyisobutylene, poly propylene glycol, poly(ethylene glycol), a polysaccharide, or a mixture thereof. ### Claim 4 (depends on 3) The ink of claim 3, wherein the polysaccharide is chitosan. ### Claim 5 (depends on 1) The ink of claim 1, wherein the solvent is dichloromethane (DCM), chloroform (CHCl3), tetrahydrofuran (THF), acetone, methanol (MeOH), ethanol (EtOH), or water. ### Claim 6 (depends on 1) The ink of claim 1, wherein the ink further comprises one or more additive. ### Claim 7 (depends on 1) The ink of claim 1, wherein the carbon nanotubes are single-wall carbon nanotubes or multiwall carbon nanotubes. ### Claim 8 (depends on 1) The ink of claim 1, wherein the polymer is poly(lactic acid) and the solvent is dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, or ethanol. ### Claim 9 (depends on 8) The ink of claim 8, wherein the solvent is dichloromethane. ### Claim 10 (depends on 1) The ink of claim 1, wherein the polymer is chitosan, the solvent is water, and the solution or gel of the polymer in the volatile solvent is a chitosan hydrogel. ### Claim 11 (depends on 10) The ink of claim 10, wherein the ink further comprises one or more weak organic acid. ### Claim 12 (depends on 11) The ink of claim 11, wherein the ink comprises 70 vol % acetic acid alone or together with 10 vol % lactic acid and 3 wt % citric acid, the vol % being based on the total volume of the water and acids and the wt % being based on the total weight of the water and acids. ### Claim 13 (depends on 1) A method of manufacturing the solvent-cast 3D printing ink of claim 1, the method comprising the steps of: a) providing a solution or a gel of a polymer in a solvent, b) providing carbon nanotubes in a carbon nanotubes:polymer weight ratio of between about 20:80 and about 40:60, c) dispersing the carbon nanotubes in the solution or gel of the polymer by ball milling, thereby producing the ink, and d) avoid drying the ink, thus keeping the solvent in the ink, until the ink is used for solvent-cast 3D printing. ### Claim 14 (depends on 13) The method of claim 13, wherein the concentration of the polymer in the solution or gel of step a) is between about 2 wt % and about 15 wt, based on the total weight of the solution or gel. ### Claim 15 (depends on 13) The method of claim 13, wherein the ball milling in step c) is carried out for 10 to 30 minutes. ### Claim 16 (depends on 13) The method of claim 13, further comprising, before or after step d), the step of adding solvent, or removing part of the solvent so that the polymer and carbon nanotubes total concentration in the ink is between about 20 and about 35 wt %, based on the total weight of the ink. ### Claim 17 (depends on 13) The method of claim 13, further comprising the step of adding one or more additives to the solvent, to the solution or gel of the polymer, or to the ink. ### Claim 18 (depends on 13) The method of claim 13, further comprising the step of packaging the ink in a 3D printer ink cartridge. ### Claim 19 (depends on 1) A method of using the solvent-cast 3D printing ink of claim 1 for manufacturing a solvent-cast 3D printed material, the method comprising the steps of: a) providing the solvent-cast 3D printing ink claim 1; b) using a 3D printer, extruding the ink through a needle into a controlled pattern; and c) allowing solvent evaporation, thereby providing the solvent-cast 3D printed material. ### Claim 20 A solvent-cast 3D printed material shaped into a controlled pattern made of a composite comprising a polymer and carbon nanotubes dispersed in a matrix of the polymer, the carbon nanotubes being present in a carbon nanotubes:polymer weight ratio between about 20:80 and about 40:60.