# US 10,864,673 B2 · Additive manufacturing using polyurea materials > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,864,673 B2 - Document ID: US10864673B2 - Status: Granted - Kind: B2 - Application number: 16/423,474 - Filed: 2019-05-28 - Published: 2019-09-19 - Granted: 2020-12-15 - Earliest claimed: 2017-08-18 - Assignees: PPG Industries Ohio, Inc. - Applicants: PPG Industries Ohio, Inc. - Inventors: David Robert Fenn; Kurt G. Olson; Reza M. Rock; Cynthia Kutchko; Susan Donaldson; Anthony J. Fogl - Web page: https://patentgrep.com/patent/US10864673B2 ## CPC - B29C 64/112: using individual droplets, e.g. from jetting heads - 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 - C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step - C08G 18/3234: {cycloaliphatic} - C08G 18/325: {containing secondary or tertiary amino groups (C08G18/3228, C08G18/3234, C08G18/3246 take precedence)} - C08G 18/3821: {Carboxylic acids; Esters thereof with monohydroxyl compounds} - C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate} - C08G 59/66: Mercaptans - C08G 75/045: from mercapto compounds and unsaturated compounds - C08G 75/14: Polysulfides - C09D 175/02: Polyureas - C09D 175/04: Polyurethanes - C08G 18/3855: {having sulfur} - C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group} - C08G 18/5024: {containing primary and/or secondary amino groups} - C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates} - C08G 2150/50: Compositions for coatings applied by spraying at least two streams of reaction components - C08K 3/046: {Carbon nanorods, nanowires, nanoplatelets or nanofibres} - C08K 3/36: Silica - 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) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract Methods of additive manufacture using coreactive components are disclosed. Thermosetting compositions for additive manufacturing are also disclosed. ## Claims ### Claim 1 A reactive additive manufacturing composition, comprising: a first component comprising a polyisocyanate and having a first viscosity; and a second component comprising a polyamine and having a second viscosity, wherein the reactive additive manufacturing composition is characterized by a tack free time of greater than 3 minutes, and wherein the first viscosity is within ±20% of the second viscosity; wherein the viscosity is measured using an Anton Paar MCR 301 or 302 rheometer with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C. ### Claim 2 (depends on 1) The composition of claim 1, wherein, the polyisocyanate comprises a polyisocyanate monomer, a polyisocyanate prepolymer, or a combination thereof; and the polyamine comprises a polyamine monomer, a polyamine prepolymer, or a combination thereof. ### Claim 3 (depends on 2) The composition of claim 2, wherein, each of the polyisocyanate monomer and the polyamine monomer independently has a molecular weight less than 600 Daltons; and each of the polyisocyanate prepolymer and the polyamine prepolymer independently has a molecular weight from 1,000 Daltons to 20,000 Daltons. ### Claim 4 (depends on 1) The composition of claim 1, wherein the reactive additive manufacturing composition comprises a polymeric rheology modifier. ### Claim 5 (depends on 4) The composition of claim 4, wherein the polymeric rheology modifier comprises a reactive polymeric rheology modifier. ### Claim 6 (depends on 4) The composition of claim 4, wherein the polymeric rheology modifier is selected from a polyethylene, a polyethylene/ethylene copolymer, a polypropylene/ethylene copolymer, and a combination of any of the foregoing. ### Claim 7 (depends on 4) The composition of claim 4, wherein each of the first component and the second component independently comprises from 1 wt % to 20 wt % of the polymeric rheology modifier, wherein wt % is based on the total weight of the first component or the second component. ### Claim 8 (depends on 1) The composition of claim 1, wherein the reactive additive manufacturing composition comprises from 0.1 wt % to 40 wt % of a filler, wherein wt % is based on the total weight of the reactive additive manufacturing composition. ### Claim 9 (depends on 8) The composition of claim 8, wherein the filler comprises an inorganic filler, an organic filler, a low-density filler, an electrically conductive filler, magnetic filler, or a combination of any of the foregoing. ### Claim 10 (depends on 1) An object formed using the reactive additive manufacturing composition of claim 1. ### Claim 11 (depends on 10) The object of claim 10, wherein the object comprises a plurality of layers, wherein adjacent layers forming the object are covalently bonded. ### Claim 12 A method of reactive additive manufacturing using a reactive additive manufacturing composition, wherein, the reactive additive manufacturing composition comprises: a first component comprising a polyisocyanate and having a first viscosity; and a second component comprising a polyamine and having a second viscosity, wherein the reactive additive manufacturing composition is characterized by a tack free time of greater than 3 minutes; and the method comprises: providing the first component into a first pump; providing the second component into a second pump, wherein the second prepolymer is reactive with the first prepolymer; pumping the first component from the first pump, and the second component from the second pump through a mixer to provide a reactive additive manufacturing composition; and depositing the reactive additive manufacturing composition through a nozzle connected to the mixer. ### Claim 13 (depends on 12) The method of claim 12, wherein each of the first pump and the second pump independently comprises a syringe pump, a peristaltic pump, or a progressive cavity pump. ### Claim 14 (depends on 12) The method of claim 12, wherein the mixer comprises a static mixer, a dynamic mixer, or a combination thereof. ### Claim 15 (depends on 12) The method of claim 12, wherein depositing comprises extruding the reactive additive manufacturing composition. ### Claim 16 (depends on 12) The method of claim 12, wherein pumping comprises extruding each of the first component and the second component into the mixer. ### Claim 17 (depends on 12) The method of claim 12, wherein, the method comprises extruding the reactive additive manufacturing composition to form an extrudate; and a cross-sectional profile of the extrudate is characterized by a variable ratio of the first component to the second component. ### Claim 18 (depends on 17) The method of claim 17, wherein the ratio refers to the mol % ratio of the coreactive components in the extrudate. ### Claim 19 (depends on 17) The method of claim 17, wherein the ratio refers to the equivalents ratio of the functional groups in the extrudate. ### Claim 20 (depends on 17) The method of claim 17, wherein the ratio refers to the wt % ratio of the coreactive components in the extrudate. ### Claim 21 (depends on 17) The method of claim 17, wherein a surface of the extrudate has an excess of one or more functional groups. ### Claim 22 (depends on 12) The method of claim 12, wherein depositing comprises depositing the reactive additive manufacturing composition from a single nozzle. ### Claim 23 (depends on 12) The method of claim 12, wherein depositing comprises spraying the reactive additive manufacturing composition. ### Claim 24 (depends on 12) An object fabricated using the method of claim 12. ### Claim 25 A reactive additive manufacturing composition, comprising: a first component comprising a polyisocyanate and having a first viscosity; and a second component comprising a polyamine and having a second viscosity, wherein the reactive additive manufacturing composition is characterized by a tack free time of greater than 3 minutes, and wherein the reactive additive manufacturing composition comprises a polymeric rheology modifier. ### Claim 26 (depends on 25) The composition of claim 25, wherein the polymeric rheology modifier is selected from a polyethylene, a polyethylene/ethylene copolymer, a polypropylene/ethylene copolymer, and a combination of any of the foregoing. ### Claim 27 (depends on 25) The composition of claim 25, wherein each of the first component and the second component independently comprises from 1 wt % to 20 wt % of the polymeric rheology modifier, wherein wt % is based on the total weight of the first component or the second component. ### Claim 28 (depends on 25) The composition of claim 25, wherein the reactive additive manufacturing composition comprises from 0.1 wt % to 40 wt % of a filler, wherein wt % is based on the total weight of the reactive additive manufacturing composition. ### Claim 29 (depends on 28) The composition of claim 28, wherein the filler comprises an inorganic filler, an organic filler, a low-density filler, an electrically conductive filler, magnetic filler, or a combination of any of the foregoing. ### Claim 30 (depends on 25) An object formed using the reactive additive manufacturing composition of claim 25. ### Claim 31 (depends on 30) The object of claim 30, wherein the object comprises a plurality of layers, wherein adjacent layers forming the object are covalently bonded. ### Claim 32 An object formed from a reactive additive manufacturing composition, wherein the reactive additive manufacturing composition comprises: a first component comprising a polyisocyanate and having a first viscosity; and a second component comprising a polyamine and having a second viscosity, wherein the reactive additive manufacturing composition is characterized by a tack free time of greater than 3 minutes, and wherein the object comprises a plurality of layers, wherein adjacent layers forming the object are covalently bonded. ### Claim 33 (depends on 32) The object of claim 32, wherein the first viscosity is within ±20% of the second viscosity; wherein the viscosity is measured using an Anton Paar MCR 301 or 302 rheometer with a 25 mm-diameter parallel plate spindle, an oscillation frequency of 1 Hz and amplitude of 0.3%, and with a rheometer plate temperature of 25° C. ### Claim 34 (depends on 33) The object of claim 33, wherein the reactive additive manufacturing composition comprises a polymeric rheology modifier.