Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base

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 1,000-5,200 cps at room temperature and has a low viscosity of 50-500 cps at 70° C. 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.

What is claimed is: 
     
         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 1000-5,200 centipoise (cps) at room temperature or 25° C. 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.   
     
     
         2 . The composition of  claim 1 , wherein the viscosity is from 1,100-4,000 cps at the room temperature. 
     
     
         3 . The composition of  claim 1 , wherein the light-photo-polymerization initiator comprises acylphosphine oxide compounds. 
     
     
         4 . The composition of  claim 1 , wherein the silica-based fine particles comprise reactive silica particles that are surface-modified by a surface modifying agent. 
     
     
         5 . The composition of  claim 4 , wherein the surface modifying agent comprises compounds containing methacryloxy groups. 
     
     
         6 . The composition of  claim 4 , wherein the surface modified silica-based fine particles have an average particle size less than 200 nm. 
     
     
         7 . 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.   
     
     
         8 . The method of  claim 7 , wherein the three-dimensional printer is operated according to an ink-jet printing method or a digital light processing method. 
     
     
         9 . The method of  claim 7 , wherein the information comprises a digital model generated based on a dental impression of a patent's mouth and a CAD/CAM design. 
     
     
         10 . The method of  claim 7 , further comprising performing post-treatment to the printed denture to improve surface quality of the denture. 
     
     
         11 . The method of  claim 7 , further comprising performing a post-curing operation on the printed denture at about 30 to about 160° C. 
     
     
         12 . The method of  claim 7 , wherein the denture comprises a partial denture and a full denture. 
     
     
         13 . The method of  claim 7 , wherein the denture comprises a printed denture base portion and a printed artificial tooth portion formed as a single body. 
     
     
         14 . The method of  claim 7 , further comprising assembling a denture base portion and an artificial tooth portion with dental adhesives after using the three-dimensional printer to separately print the denture base portion and the artificial tooth portion. 
     
     
         15 . 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 1,000-5,200 centipoise (cps) at room temperature or 25° C. and from 50 to 500 cps at 70° C.,   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,   wherein 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 1,000-5,200 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.   
     
     
         16 . The method of  claim 15 , wherein:
 the viscosity of the first liquid state mixture is from 1,000-4,000 cps at the room temperature; and   the viscosity of the second liquid state mixture is from 1,100-4,000 cps at the room temperature.   
     
     
         17 . 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 1000-5200 centipoise (cps) at room temperature or 25° C. 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.   
     
     
         18 . The composition of  claim 17 , wherein the viscosity is from 1,100-4,000 cps at the room temperature.