# US 9,456,963 B2 · Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,456,963 B2 - Document ID: US9456963B2 - Status: Granted - Kind: B2 - Application number: 13/865,907 - Filed: 2013-04-18 - Published: 2014-06-19 - Granted: 2016-10-04 - Earliest claimed: 2012-12-18 - Assignees: DENTCA, Inc. - Applicants: DENTCA, Inc. - Inventors: Jae Sik Lee - Web page: https://patentgrep.com/patent/US9456963B2 ## CPC - A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds - A61C 13/0013: {using stereolithographic techniques} - 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 - A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D) - A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00) - 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 ## Abstract Photo-curable compositions for artificial teeth and denture base and a method for manufacturing denture by a three-dimensional printing system are provided. The compositions include photo-curable organic compounds, surface modified nano-sized inorganic filler, photo-initiator, colorant, and stabilizer. The composition is in a viscous liquid state having 1500-5000 cps at ambient temperature and has a low viscosity of 50-500 cps at jetting temperature or dispensing temperature. The composition also has an excellent curing rate for three-dimensional printing. Using the compositions, denture having a distinctive denture base and a set of artificial teeth can be manufactured via an inkjet type or digital light process type three-dimensional printing according to Computer Aided Design (CAD) data. ## Claims ### Claim 1 A composition comprising: about 50 to about 75 weight % of at least one kind of ethoxylated difunctional bisphenol A dimethacrylate; about 5 to about 15 weight % of at least one kind of multifunctional methacrylate having two or more methacryloxy groups; about 15 to about 35 weight % of at least one kind of urethane dimethacrylate; about 5 to about 35 weight % of at least one kind of silica-based fine particles having methacrylate functionalization layers and having an average particle size of less than about 200 nm; about 0.2 to about 5.0 weight % of at least one kind of ultraviolet/visible (UV/Vis) light-photo-polymerization initiator; at least one colorant; and at least one stabilizer, wherein viscosity of a liquid state mixture, including the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer, is from 2000-5200 centipoise (cps) at room temperature and from 50 to 500 cps at 70° C., and wherein the viscosity is adjusted by controlling a ratio of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer in the mixture. ### Claim 2 A composition comprising: about 40 to about 60 weight % of at least one kind of ethoxylated difunctional bisphenol A dimethacrylate; about 5 to about 20 weight % of at least one kind of multifunctional methacrylate; about 20 to about 45 weight % of at least one kind of urethane dimethacrylate; about 0 to about 15 weight % of at least one kind of silica-based fine particles having methacrylate functionalization layers and having an average particle size of less than about 200 nm; about 0.2 to about 5.0 weight % of at least one kind of ultraviolet/visible (UV/Vis) light-photo-polymerization initiator; at least one colorant; and at least one stabilizer, wherein viscosity of a liquid state mixture, including the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer, is from 2000-5200 centipoise (cps) at room temperature and from 50 to 500 cps at 70° C., and wherein the viscosity is adjusted by controlling a ratio of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer in the mixture. ### Claim 3 (depends on 1) The composition of claim 1, wherein the light-photo-polymerization initiator comprises acylphosphine oxide compounds. ### Claim 4 (depends on 1) The composition of claim 1, wherein the silica-based fine particles comprise reactive silica particles that are surface-modified by a surface modifying agent. ### Claim 5 (depends on 4) The composition of claim 4, wherein the surface modifying agent comprises compounds containing methacryloxy groups. ### Claim 6 (depends on 1) A method of printing a denture using the composition of claim 1, the method comprising: stacking layers of the mixture and curing the stacked layers one-by-one using a three-dimensional printer based on Computer-Aided Design/Computer-Aided Manufacturing (CAD/CAM) generated information that is related to the denture to be manufactured. ### Claim 7 (depends on 6) The method of claim 6, wherein the three-dimensional printer is operated according to an ink-jet printing method or a digital light processing method. ### Claim 8 (depends on 6) The method of claim 6, wherein the information comprises a digital model generated based on a dental impression of a patent's mouth and a CAD/CAM design. ### Claim 9 (depends on 6) The method of claim 6, further comprising performing post-treatment to the printed denture to improve surface quality of the denture. ### Claim 10 (depends on 6) The method of claim 6, further comprising performing a post-curing operation on the printed denture at about 30 to about 160° C. ### Claim 11 (depends on 6) The method of claim 6, wherein the denture comprises a printed denture base portion and a printed artificial tooth portion formed as a single body. ### Claim 12 (depends on 6) The method of claim 6, further comprising assembling a denture base and artificial teeth with dental adhesives after using the three-dimensional printer to separately print the denture base and the artificial teeth. ### Claim 13 (depends on 6) The method of claim 6, wherein the denture comprises a partial denture and a full denture. ### Claim 14 A method for manufacturing a denture using a three-dimensional printer and light-curable materials based on denture information, the method comprising: manufacturing a denture base from a first composition; and manufacturing at least one artificial tooth from a second composition that is different from the first composition, wherein: the first composition comprises: about 40 to about 60 weight % of at least one kind of ethoxylated difunctional bisphenol A dimethacrylate; about 5 to about 20 weight % of at least one kind of multifunctional methacrylate; about 20 to about 45 weight % of at least one kind of urethane dimethacrylate; about 0 to about 15 weight % of at least one kind of a silica-based fine particles having methacrylate functionalization layers and having an average particle size of less than about 200 nm; about 0.2 to about 5.0 weight % of at least one kind of ultraviolet/visible (UV/Vis) light-photo-polymerization initiator; at least one colorant; and at least one stabilizer, wherein viscosity of a first liquid state mixture, including the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer, is from 2000-5200 centipoise (cps) at room temperature and from 50 to 500 cps at 70° C., and wherein the viscosity of the first liquid state mixture is adjusted by controlling a ratio of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer in the mixture; and the second composition comprises: about 50 to about 75 weight % of at least one kind of ethoxylated difunctional bisphenol A dimethacrylate; about 5 to about 15 weight % of at least one kind of multifunctional methacrylate having two or more methacryloxy groups; about 15 to about 35 weight % of at least one kind of urethane dimethacrylate; about 5 to about 35 weight % of at least one kind of a silica-based fine particles having or methacrylate functionalization layers and having an average particle size of less than about 200 nm; about 0.2 to about 5.0 weight % of at least one kind of ultraviolet/visible (UV/Vis) light-photo-polymerization initiator; at least one colorant; and at least one stabilizer, wherein viscosity of a second liquid state mixture, including the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer, is from 2000-5200 centipoise (cps) at room temperature and from 50 to 500 cps at 70° C., and wherein the viscosity of the second liquid state mixture is adjusted by controlling a ratio of the at least one kind of ethoxylated difunctional bisphenol A dimethacrylate, the at least one kind of multifunctional methacrylate, the at least one kind of urethane dimethacrylate, the at least one kind of silica-based fine particles, the at least one kind of UV/Vis light-photo-polymerization initiator, the at least one colorant, and the at least one stabilizer in the mixture.