# US 10,357,435 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 10,357,435 B2 - Document ID: US10357435B2 - Status: Granted - Kind: B2 - Application number: 14/262,495 - Filed: 2014-04-25 - Published: 2014-08-28 - Granted: 2019-07-23 - Earliest claimed: 2012-12-18 - Assignees: DENTCA, Inc. - Applicants: DENTCA, Inc. - Inventors: Jae Sik Lee - Web page: https://patentgrep.com/patent/US10357435B2 ## CPC - A61C 13/0013: {using stereolithographic techniques} - A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds - B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - 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) - 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) - 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 ## Abstract A composition includes a light-curable viscous mixture that includes: 0-50% by weight of a poly(methyl methacrylate)/methyl methacrylate solution; 5-20% by weight of at least one kind of multifunctional aliphatic (meth)acrylate; 5-40% by weight of at least one kind of aliphatic urethane (meth)acrylate oligomer; 25-65% by weight of at least one kind of difunctional bisphenol-A dimethacrylate; 0.1 to 5% by weight of at least one kind of a photoinitiator; 0.05 to 2% by weight of at least one kind of light stabilizer; and 0.1 to 3% by weight of color pigment based on the total weight of the composition. ## Claims ### Claim 1 A composition comprising: a light-curable mixture comprising: 0-50% by weight of a poly(methyl methacrylate)/methyl methacrylate; 5-20% by weight of at least one kind of multifunctional aliphatic (meth)acrylate; 5-40% by weight of at least one kind of aliphatic urethane (meth)acrylate oligomer; 25-65% by weight of at least one kind of difunctional bisphenol-A methacrylate; 0.1 to 5% by weight of at least one kind of a photoinitiator; 0.05 to 2% by weight of at least one kind of light stabilizer; and 0.1 to 3% by weight of color pigment based on the total weight of the composition, wherein viscosity of the composition is less than about 700 centipoise (cps) at 70° C. such that the composition is used in a three-dimensional printer, wherein flexural strength of specimens printed by the three-dimensional printer using the composition and post cured by a curing machine is greater than 50 MPa, wherein molecular weight of the poly(methyl methacrylate) is between about 10,000 to about 400,000 g/mol, and wherein the composition is used for manufacturing artificial teeth and dentures using the three-dimensional printer. ### Claim 2 (depends on 1) The composition of claim 1, wherein the viscosity of the composition is greater than about 100 centipoise (cps) at 70° C. ### Claim 3 (depends on 1) The composition of claim 1, wherein viscosity of the mixture of poly(methyl methacrylate)/methyl methacrylate is less than 10000 cps at 25° C. ### Claim 4 (depends on 1) The composition of claim 1, further comprising a light-photo-polymerization initiator, wherein the light-photo-polymerization initiator comprises acylphosphine oxide compounds. ### Claim 5 A composition comprising: a light-curable mixture comprising: 0-25% by weight of a poly(methyl methacrylate)/methyl methacrylate; 5-15% by weight of at least one kind of multifunctional aliphatic (meth)acrylate; 5-35% by weight of at least one kind of aliphatic urethane (meth)acrylate oligomer; 30-60% by weight of at least one kind of difunctional bisphenol-A methacrylate; 0.1 to 3.5% by weight of at least one kind of a photoinitiator; 0.05 to 1% by weight of at least one kind of light stabilizer; and 0.1 to 2% by weight of color pigment based on the total weight of the composition, wherein viscosity of the composition is less than about 700 centipoise (cps) at 70° C. such that the composition is used in a three-dimensional printer, wherein flexural strength of specimens printed by the three-dimensional printer using the composition and post cured by a curing machine is greater than 50 MPa, wherein molecular weight of the poly(methyl methacrylate) is between about 10,000 to about 400,000 g/mol, and wherein the composition is used for manufacturing artificial teeth and dentures using the three-dimensional printer. ### Claim 6 (depends on 5) The composition of claim 5, wherein the viscosity of the composition is greater than about 100 centipoise (cps) at 70° C. ### Claim 7 (depends on 5) The composition of claim 5, further comprising 2.5-12% by weight of at least one kind of surface modified silica-based fine particles. ### Claim 8 (depends on 7) The composition of claim 7, wherein the surface modified silica-based fine particles comprise non-reactive and reactive silica particles that are surface-modified by a surface modifying agent. ### Claim 9 (depends on 8) The composition of claim 8, wherein the surface modifying agent comprises compounds containing methacryloxy groups. ### Claim 10 (depends on 7) The composition of claim 7, wherein the surface modified silica-based fine particles have an average particle size that is less than 200 nm. ### Claim 11 (depends on 1) A method of printing a denture using the composition of claim 1, the method comprising: stacking layers of the light curable mixture; and curing the stacked layers one-by-one using the 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 12 (depends on 11) The method of claim 11, wherein the three-dimensional printer is operated according to a digital light processing method or a stereolithography method. ### Claim 13 (depends on 11) The method of claim 11, wherein: the stacked layers are cured based on computer generated information that is related to the denture; and the information comprises a digital model generated based on a dental impression of a patient's mouth and a Computer-Aided Design/Computer-Aided Manufacturing (CAD/CAM) design. ### Claim 14 (depends on 11) The method of claim 11, wherein the denture comprises a printed denture base portion and a printed artificial teeth portion formed as a single body. ### Claim 15 (depends on 11) The method of claim 11, further comprising assembling the denture base and the artificial teeth with dental adhesives after printing the denture base and the artificial teeth separately. ### Claim 16 (depends on 11) The method of claim 11, wherein the denture comprises a partial denture and a full denture. ### Claim 17 (depends on 5) A method of printing a denture using the composition of claim 5, the method comprising: stacking layers of the light curable mixture; and curing the stacked layers one-by-one using the 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 18 (depends on 1) The composition of claim 1, wherein flexural modulus of the composition is between about 1500 Mpas and 2450 Mpas. ### Claim 19 A composition comprising: a light-curable mixture comprising: 0-50% by weight of a poly(methyl methacrylate)/methyl methacrylate; 5-20% by weight of at least one kind of multifunctional aliphatic (meth)acrylate; 5-40% by weight of at least one kind of aliphatic urethane (meth)acrylate oligomer; 25-65% by weight of at least one kind of difunctional bisphenol-A methacrylate; 0.1 to 5% by weight of at least one kind of a photoinitiator; 0.05 to 2% by weight of at least one kind of light stabilizer; and 0.1 to 3% by weight of color pigment based on the total weight of the composition, wherein viscosity of the composition is less than about 700 centipoise (cps) at 70° C. such that the composition is used in a three-dimensional printer, wherein flexural strength of specimens printed by the three-dimensional printer using the composition and post cured by a curing machine is greater than 50 MPa, wherein molecular weight of the poly(methyl methacrylate) is between about 10,000 to about 400,000 g/mol, and wherein the viscosity of the composition is greater than about 100 centipoise (cps) at 70° C.