# US 2019/0168449 A1 · Fabrication of solid materials or films from a polymerizable liquid > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2019/0168449 A1 - Document ID: US20190168449A1 - Status: Published application - Kind: A1 - Application number: 16/268,096 - Filed: 2019-02-05 - Published: 2019-06-06 - Earliest claimed: 2017-04-11 - Assignees: Molecule CORP - Applicants: Molecule CORP - Inventors: Nick Talken; Austin Wyatt Levy; Zack Kisner; Ken Kisner - Web page: https://patentgrep.com/patent/US20190168449A1 ## CPC - C08F 222/1065: {of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates} - B29C 64/00: 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 - B29C 64/124: using layers of liquid which are selectively solidified - B29C 64/135: the energy source being concentrated, e.g. scanning lasers or focused light sources - B29C 64/386: Data acquisition or data processing for additive manufacturing - B29C 64/40: Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof - B33Y 70/00: Materials specially adapted for additive manufacturing - C08F 2/48: by ultraviolet or visible light - C08F 2/50: with sensitising agents - C08F 212/08: Styrene - C08F 220/06: Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof - C08F 220/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} - C08F 220/343: {in the form of urethane links} - C08F 220/56: Acrylamide; Methacrylamide - C08F 220/58: containing oxygen in addition to the carbonamido oxygen {, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine} - C08F 222/1006: {of polyhydric alcohols or polyhydric phenols} - C08F 226/10: N-Vinyl-pyrrolidone - C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof - C08F 290/067: {Polyurethanes; Polyureas} - C08F 299/065: {from polyurethanes with side or terminal unsaturations} - C08G 69/14: Lactams - C09D 11/322: Pigment inks - C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - B33Y 80/00: Products made by additive manufacturing - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - 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 - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - 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) ## Abstract The disclosure describes a polymerizable liquid that includes a reactive oligomer and a reactive monomer. The polymerizable liquid is an energy polymerizable liquid hardenable by a single reaction mechanism forming a photoplastic material. The disclosure further describes a method of producing the photoplastic material and articles that can be made from the photoplastic material. ## Claims ### Claim 1 A method of forming a three-dimensional object from an energy polymerizable liquid, the method comprising: mixing together: a reactive oligomer, the reactive oligomer being a multi-functional oligomer; and a reactive monofunctional monomer, wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 5:1; and hardening the energy polymerizable liquid to a photoplastic material. ### Claim 2 (depends on 1) The method of claim 1, wherein the three-dimensional object is a medical device, a part of footwear or part of soft robotics. ### Claim 3 (depends on 1) The method of claim 1, wherein the three-dimensional object is a hydrogel. ### Claim 4 (depends on 1) The method of claim 1, further comprising polymerizing by pixel or voxel polymerization to produce different physical properties by altering the energy polymerization conditions. ### Claim 5 (depends on 1) The method of claim 1, further comprising mixing in a photoinitiator in an amount from about 0.01 percent to about 15 percent by weight. ### Claim 6 (depends on 1) The method of claim 1, further comprising irradiating the polymerizable liquid with patterned irradiation. ### Claim 7 (depends on 1) The method of claim 1, wherein mixing includes mixing in an amount from about 0.001 percent to about 10 percent by weight at least one of a non-reactive light absorbing pigment, a hindered amine light stabilizer, a filler, a polymerization inhibitor, and a polymerization catalyst. ### Claim 8 (depends on 1) The method of claim 1, wherein the mixing includes mixing at least one of a reactive or non-reactive plasticizer in an amount from about 1 to about 30 percent by weight. ### Claim 9 (depends on 1) The method of claim 1, wherein the formation of a three-dimensional object from an energy polymerizable liquid occurs with supplied heat. ### Claim 10 (depends on 1) The method of claim 1, wherein the oligomer and the monomer react by a same polymerization mechanism and have different reaction rates. ### Claim 11 (depends on 1) The method of claim 1, wherein a solubility of the monomer and oligomer change during polymerization to assist homopolymerization of either the monomeric or oligomeric species. ### Claim 12 (depends on 1) The method of claim 1, wherein polymerization creates a material with more than one glass transition temperature. ### Claim 13 (depends on 1) The method of claim 1, wherein the molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 10:1. ### Claim 14 (depends on 13) The method of claim 13, wherein the molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 20:1. ### Claim 15 (depends on 1) The method of claim 1, wherein the three-dimensional object reaches prescribed mechanical properties without supplied heat. ### Claim 16 (depends on 1) The method of claim 1, wherein the three-dimensional object reaches prescribed mechanical properties with supplied heat. ### Claim 17 (depends on 1) The method of claim 1, wherein the polymerizable liquid is non-toxic. ### Claim 18 (depends on 1) The method of claim 1, wherein the three-dimensional object is non-toxic and biocompatible in accordance with ISO 10933 or 20795 standards or both. ### Claim 19 (depends on 1) The method of claim 1, wherein the three-dimensional object is a medical appliance. ### Claim 20 (depends on 1) The method of claim 1, wherein the three-dimensional object is a dental appliance. ### Claim 21 (depends on 20) The method of claim 20, wherein the dental appliance is a dental prosthesis, orthodontic splint, aligner, retainer, implant, mold, crown, bridge, tooth, indirect bonding tray, mouth guard, bite plane, veneer, night guard, snoring appliance, repositioner, denture base, denture try-in, or denture. ### Claim 22 A method of forming a three-dimensional object from an energy polymerizable liquid, the method comprising: mixing together: a reactive oligomer, the reactive oligomer being at least one of (i) a multi-functional methacrylate oligomer, and (ii) a multi-functional acrylate oligomer; and a reactive monofunctional monomer, the reactive monofunctional monomer being at least one of (i) a monofunctional N-vinyl monomer, (ii) a monofunctional vinyl ether monomer, (iii) a monofunctional vinyl ester monomer, (iv) a monofunctional vinylamide monomer, (v) a styrene monomer, (vi) a monofunctional (meth)acrylamide monomer, (vii) a monofunctional (meth)acrylate monomer, (viii) a cyanoacrylate monomer, (ix) a monofunctional vinyl carbonate monomer, (x) a monofunctional acryloyl monomer, (xi) a monofunctional maleimide monomer, (xii) a monofunctional acrylonitrile monomer, (xiii) a monofunctional 1,3-diene monomer, and (xiv) a monofunctional vinyl carbamate monomer, wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 5:1; and hardening the energy polymerizable liquid to a photoplastic material. ### Claim 23 A method of forming a three-dimensional object from an energy polymerizable liquid, the method comprising: mixing together: a reactive oligomer, the reactive oligomer being at least one of (i) a multi-functional methacrylate oligomer, and (ii) a multi-functional acrylate oligomer; and a reactive monofunctional monomer, the reactive monofunctional monomer being at least one of (i) a monofunctional N-vinyl monomer, (ii) a monofunctional vinyl ether monomer, (iii) a monofunctional vinyl ester monomer, (iv) a monofunctional vinylamide monomer, (v) a styrene monomer, (vi) a monofunctional (meth)acrylamide monomer, (vii) a monofunctional (meth)acrylate monomer, (viii) a cyanoacrylate monomer, (ix) a monofunctional vinyl carbonate monomer, (x) a monofunctional acryloyl monomer, (xi) a monofunctional maleimide monomer, (xii) a monofunctional acrylonitrile monomer, (xiii) a monofunctional 1,3-diene monomer, and (xiv) a monofunctional vinyl carbamate monomer, wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 5:1; and hardening the energy polymerizable liquid by a single reaction mechanism to a photoplastic material by an apparatus for bottom-up or top-down three dimensional fabrication. ### Claim 24 (depends on 23) The method of claim 23, wherein the bottom or top-down three dimensional fabrication is selected from the group consisting of stereolithography (SLA) and digital light processing (DLP).