# US 11,897,189 B2 · Inks for 3D printing having low polymerization shrinkage > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,897,189 B2 - Document ID: US11897189B2 - Status: Granted - Kind: B2 - Application number: 17/825,396 - Filed: 2022-05-26 - Published: 2022-09-08 - Granted: 2024-02-13 - Earliest claimed: 2018-11-30 - Assignees: 3D Systems, Inc. - Applicants: 3D Systems, Inc. - Inventors: Khalil Moussa - Web page: https://patentgrep.com/patent/US11897189B2 ## CPC - B29C 64/124: using layers of liquid which are selectively solidified - B22F 10/12: by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP] - 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 - C08F 20/28: containing no aromatic rings in the alcohol moiety - C08F 20/36: containing oxygen in addition to the carboxy oxygen {, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate} - C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing - C09D 11/104: Polyesters - G03F 7/0037: {Production of three-dimensional images} - G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) - B22F 10/40: Structures for supporting workpieces or articles during manufacture and removed afterwards - B22F 12/63: Rollers - B33Y 70/00: Materials specially adapted for additive manufacturing - B33Y 80/00: Products made by additive manufacturing - C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators} - Y02P 10/25: Process efficiency - 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) - B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER - 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 - 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) - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract In one aspect, inks for use with a three-dimensional (3D) printing system are described herein. In some embodiments, an ink described herein comprises 20-60 wt. % oligomeric curable material; 10-50 wt. % cyclocarbonate (meth)acrylate monomer; and 0.1-5 wt. % photoinitiator, based on the total weight of the ink. Additionally, in some cases, the ink further comprises one or more additional curable materials differing from the oligomeric curable material and the cyclocarbonate (meth)acrylate monomer. An ink described herein, in some embodiments, also comprises one or more additional component that are non-curable. ## Claims ### Claim 1 A method of printing a three-dimensional article comprising: selectively depositing layers of an ink in a fluid state onto a substrate to form the three-dimensional article, wherein the ink comprises: 20-60 wt. % oligomeric curable material; 15-50 wt. % cyclocarbonate (meth)acrylate monomer; and 0.1-5 wt. % photoinitiator, based on the total weight of the ink, wherein the oligomeric curable material comprises one or more ethylenically unsaturated species having a weight average molecular weight of 500-6,000; wherein the cyclocarbonate (meth)acrylate monomer has the structure of Formula (A1): wherein R1 is selected from the group consisting of a linear or branched C1-C4 alkylene moiety; R2 is H or CH3; and wherein the ink, when cured, exhibits a tear strength of 30 to 200 kN/m when measured according to ASTM D624. ### Claim 2 (depends on 1) The method of claim 1, wherein the oligomeric curable material comprises one or more ethylenically unsaturated species having a dynamic viscosity of 1,000 to 200,000 cP at 50° C., when measured according to ASTM D2983. ### Claim 3 (depends on 1) The method of claim 1, wherein the oligomeric curable material comprises one or more aliphatic urethane (meth)acrylates. ### Claim 4 (depends on 1) The method of claim 1, wherein the oligomeric curable material is present in the ink in an amount of 25-50 wt. %, based on the total weight of the ink. ### Claim 5 (depends on 1) The method of claim 1, wherein R2 is H. ### Claim 6 (depends on 1) The method of claim 1, wherein R1 is CH2 and R2 is H. ### Claim 7 (depends on 6) The method of claim 6, wherein the cyclocarbonate (meth)acrylate monomer is present in the ink in an amount of 20-30 wt. %, based on the total weight of the ink. ### Claim 8 (depends on 1) The method of claim 1, wherein the ink further comprises one or more additional curable materials differing from the oligomeric curable material and the cyclocarbonate (meth)acrylate monomer. ### Claim 9 (depends on 8) The method of claim 8, wherein the additional curable materials comprise an additional monomeric curable material. ### Claim 10 (depends on 8) The method of claim 8, wherein the additional curable materials comprise an additional oligomeric curable material. ### Claim 11 (depends on 1) The method of claim 1, wherein the ink further comprises at least one colorant or at least one filler. ### Claim 12 (depends on 1) The method of claim 1, wherein the ink further comprises at least one inhibitor, at least one stabilizing agent, or a combination thereof. ### Claim 13 (depends on 1) The method of claim 1, wherein the dynamic viscosity of the uncured ink is greater than 100 cP at 25° C., when measured according to ASTM D2983. ### Claim 14 (depends on 1) The method of claim 1, wherein the dynamic viscosity of the uncured ink is greater than 100 cP and less than 5000 cP at 25° C., when measured according to ASTM D2983. ### Claim 15 (depends on 1) The method of claim 1, wherein the ink, when cured, exhibits a volumetric polymerization shrinkage of no greater than 5% compared to the ink when uncured, wherein the volumetric polymerization shrinkage is measured according to ASTM D792. ### Claim 16 (depends on 1) The method of claim 1, wherein the ink, when cured, exhibits a notched Izod impact strength of 50 to 200 J/m when measured according to ASTM D256. ### Claim 17 (depends on 1) The method of claim 1 further comprising photocuring the ink. ### Claim 18 A method of printing a three-dimensional article comprising: retaining an ink in a fluid state in a container; selectively applying energy to the ink in the container to solidify at least a portion of a first fluid layer of the ink, thereby forming a first solidified layer that defines a first cross-section of the article; raising or lowering the first solidified layer to provide a second fluid layer of the ink at a surface of the fluid ink in the container; and selectively applying energy to the ink in the container to solidify at least a portion of the second fluid layer of the ink, thereby forming a second solidified layer that defines a second cross-section of the article, the first cross-section and the second cross-section being bonded to one another in a z-direction, wherein the ink comprises: 20-60 wt. % oligomeric curable material; 15-50 wt. % cyclocarbonate (meth)acrylate monomer; and 0.1-5 wt. % photoinitiator, based on the total weight of the ink, wherein the oligomeric curable material comprises one or more ethylenically unsaturated species having a weight average molecular weight of 500-6,000; wherein the cyclocarbonate (meth)acrylate monomer has the structure of Formula (A1): wherein R1 is selected from the group consisting of a linear or branched C1-C4 alkylene moiety; R2 is H or CH3; and wherein the ink, when cured, exhibits a tear strength of 30 to 200 kN/m when measured according to ASTM D624. ### Claim 19 (depends on 18) The method of claim 18, wherein selectively applying energy to the ink in the container comprises photocuring the ink. ### Claim 20 (depends on 18) The method of claim 18, wherein the method of printing has a print speed of 20-60 mm/hour.