# US 12,006,444 B2 · Water-breakable resin formulation > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,006,444 B2 - Document ID: US12006444B2 - Status: Granted - Kind: B2 - Application number: 17/569,070 - Filed: 2022-01-05 - Published: 2022-07-07 - Granted: 2024-06-11 - Earliest claimed: 2021-01-05 - Assignees: Formlabs, Inc. - Applicants: Formlabs, Inc. - Inventors: Cheying Kuo - Web page: https://patentgrep.com/patent/US12006444B2 ## CPC - B29C 64/40: Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof - C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} - B29C 64/118: using filamentary material being melted, e.g. fused deposition modelling [FDM] - B29C 64/124: using layers of liquid which are selectively solidified - B33Y 10/00: Processes of additive manufacturing - B33Y 70/00: Materials specially adapted for additive manufacturing - C08F 220/343: {in the form of urethane links} - C08F 222/1065: {of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates} - C08K 3/36: Silica - C09D 7/61: inorganic - C09D 7/68: {Particle size between 100-1000 nm} - C09D 7/69: {Particle size larger than 1000 nm} - C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen - C08F 2800/20: as weight or mass percentages - C08F 2810/20: leading to a crosslinking, either explicitly or inherently - C08K 2201/005: Additives being defined by their particle size in general - C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen - 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) - 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) - 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 - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract A resin formulation that may be used for additive manufacturing, for example, to provide a water-breakable object is generally described. ## Claims ### Claim 1 A resin for additive manufacturing, the resin comprising: an ionic component in an amount between greater than or equal to 20 wt. % and less than or equal to 95 wt. % based on the total weight of the resin, wherein the ionic component comprises a vinyl, acrylate, methacrylate, or acrylamide moiety; an oligomer in an amount between greater than or equal to 1 wt. % and less than or equal to 45 wt. % based on the total weight of the resin; a monomer in an amount between greater than or equal to 1 wt. % and less than or equal to 45 wt. % based on the total weight of the resin; and a crosslinking agent in an amount between greater than or equal to 1 wt. % and less than or equal to 30 wt. % based on the total weight of the resin. ### Claim 2 (depends on 1) The resin of claim 1, wherein the ionic component comprises a positively charged ion. ### Claim 3 (depends on 1) The resin of claim 1, wherein the ionic component comprises a choline moiety. ### Claim 4 (depends on 1) The resin of claim 1, wherein the ionic component is methacroylcholine chloride. ### Claim 5 (depends on 1) The resin of claim 1, wherein the oligomer is water-dilutable but not water-soluble. ### Claim 6 (depends on 1) The resin of claim 1, wherein the oligomer is a urethane (meth)acrylate oligomer. ### Claim 7 (depends on 1) The resin of claim 1, wherein the monomer is a urethane (meth)acrylate monomer. ### Claim 8 (depends on 1) The resin of claim 1, wherein the crosslinking agent comprises an anhydride moiety and the resin comprises the crosslinking agent in an amount between greater than or equal to 5 wt. % and less than or equal to 15 wt. % based on the total weight of the resin. ### Claim 9 (depends on 8) The resin of claim 8, wherein the crosslinking agent is methacrylic anhydride. ### Claim 10 (depends on 1) The resin of claim 1, wherein the crosslinking agent comprises a silane moiety and the resin comprises the crosslinking agent in an amount between greater than or equal to 1 wt. % and less than or equal to 20 wt. % based on the total weight of the resin. ### Claim 11 (depends on 10) The resin of claim 10, wherein the crosslinking agent comprises an alkoxy silane moiety. ### Claim 12 (depends on 10) The resin of claim 10, further comprising an initiator. ### Claim 13 (depends on 12) The resin of claim 12, wherein the composition comprises the initiator in an amount greater than or equal to 0.1 wt. % and less than or equal to 2 wt. % based on the total weight of the resin. ### Claim 14 (depends on 12) The resin of claim 12, wherein the initiator is or comprises a bisacrylphosphine oxide (BAPO) and/or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO). ### Claim 15 (depends on 1) The resin of claim 1, wherein the crosslinking agent comprises a multi-functional (meth)acrylate and the resin comprises the crosslinking agent in an amount between greater than or equal to 3 wt. % and less than or equal to 30 wt. % based on the total weight of the resin. ### Claim 16 (depends on 15) The resin of claim 15, wherein the crosslinking agent is trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate, glycerol propoxylate (1PO/OH) triacrylate, and/or alkoxylated derivatives thereof. ### Claim 17 (depends on 1) The resin of claim 1, further comprising a filler. ### Claim 18 (depends on 17) The resin of claim 17, wherein the filler comprises silica particles having an average characteristic dimension between less than or equal to 10 micrometers and greater than or equal to 0.5 micrometers. ### Claim 19 A method of additive manufacturing, the method comprising: providing a resin comprising: an ionic component in an amount between greater than or equal to 20 wt.% and less than or equal to 95 wt.% based on the total weight of the resin, wherein the ionic component comprises a vinyl, acrylate, methacrylate, or acrylamide moiety; an oligomer in an amount between greater than or equal to 1 wt.% and less than or equal to 45 wt.% based on the total weight of the resin; a monomer in an amount between greater than or equal to 1 wt.% and less than or equal to 45 wt.% based on the total weight of the resin; and a crosslinking agent in an amount between greater than or equal to 1 wt.% and less than or equal to 30 wt.% based on the total weight of the resin; and forming a three-dimensional object from the resin by additive manufacturing. ### Claim 20 (depends on 19) The method of claim 19, wherein the three-dimensional object is water-breakable. ### Claim 21 (depends on 19) The method of claim 19, wherein additive manufacturing comprises stereolithography or fused deposition modeling. ### Claim 22 (depends on 19) The method of claim 19, wherein the three-dimensional object comprises ionic interactions between the ionic component, the oligomer, and/or the monomer, and wherein at least a portion of the ionic interactions are breakable upon exposure of the three-dimensional material to water. ### Claim 23 (depends on 19) The method of claim 19, wherein the three-dimensional object comprises covalent interactions between the ionic component, the oligomer, the monomer, and/or the crosslinking agent, and wherein at least a portion of the covalent interactions are breakable upon exposure of the three-dimensional material to water. ### Claim 24 (depends on 19) The method of claim 19, wherein the three-dimensional object is a support, and the method further comprises forming a second three-dimensional object on the support. ### Claim 25 (depends on 19) The method of claim 19, further comprising exposing the three-dimensional object to water.