Curable compositions with crosslinkers for additive manufacturing

Abstract

Disclosed herein are curable compositions containing an initiator and two or more crosslinkers for additive manufacturing. The curable compositions comprise high-crosslinker content, and yield tough, lightweight polymeric materials suitable for dental appliances, including but not limited to aligners, attachment placement devices, incremental palatal expanders, dentures, crowns, etc.

What is claimed is: 
     
         1 . A curable composition for additive manufacturing, the curable composition comprising:
 an initiator to initiate a reaction;   a first crosslinker comprising:
 a first plurality of polymerizable functional groups, and 
 an arylene or a heteroarylene group disposed between at least two polymerizable functional groups of the first plurality of polymerizable functional groups; and 
   a second crosslinker comprising:
 a second plurality of polymerizable functional groups, and 
 an alkylene or heteroalkylene group disposed between at least two polymerizable functional groups of the second plurality of polymerizable functional groups. 
   
     
     
         2 . The curable composition of  claim 1 , wherein the first and the second pluralities of polymerizable functional groups are each pluralities of ethylenically unsaturated functional groups. 
     
     
         3 . The curable composition of  claim 1 , wherein the first and the second pluralities of polymerizable functional groups each comprise two polymerizable functional groups. 
     
     
         4 . The curable composition of  claim 1 , wherein the second crosslinker comprises a carbamate, a glycol, or a combination thereof disposed between at least two polymerizable functional groups of the second plurality of polymerizable functional groups. 
     
     
         5 . The curable composition of  claim 1 , wherein the first and the second pluralities of polymerizable functional groups are pluralities of acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl ether groups, styryl groups, epoxy groups or a combination thereof. 
     
     
         6 . The curable composition of  claim 1 , wherein the first and the second pluralities of polymerizable functional groups are pluralities of acrylate groups, methacrylate groups, or a combination thereof. 
     
     
         7 . The curable composition of  claim 1 , wherein the at least two polymerizable functional groups of the first plurality of polymerizable functional groups are spaced by at least 14 atoms. 
     
     
         8 . The curable composition of  claim 1 , wherein the at least two polymerizable functional groups of the second plurality of polymerizable functional groups are spaced by at least 14 atoms. 
     
     
         9 . The curable composition of  claim 1 , wherein the first and the second crosslinker differ in molecular weight by at least 200 Daltons (Da). 
     
     
         10 . The curable composition of  claim 1 , wherein the alkylene backbone is substituted with a functional group selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, alkoxyl, hydroxyl, amine, thiol, cyano, aryl, heteroaryl, ester, amide, carbamate, carbonate, and combinations thereof. 
     
     
         11 . The curable composition of  claim 1 , wherein the alkylene backbone is unsubstituted. 
     
     
         12 . The curable composition of  claim 1 , further comprising a third crosslinker comprising:
 a third plurality of polymerizable functional groups, and   an alkylene backbone connecting at least two polymerizable functional groups of the third plurality of polymerizable functional groups.   
     
     
         13 . The curable composition of  claim 12 , wherein the at least two polymerizable functional groups of the third plurality of functional groups are separated by 6 to 15 carbons of the alkylene backbone. 
     
     
         14 . The curable composition of  claim 12 , wherein the third plurality of polymerizable functional groups comprises two polymerizable functional groups. 
     
     
         15 . The curable composition of  claim 12 , wherein the third plurality of polymerizable functional groups is a plurality of ethylenically unsaturated functional groups. 
     
     
         16 . The curable composition of  claim 12 , wherein the third plurality of polymerizable functional groups is a plurality of acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl ether groups, styryl groups, epoxy groups or a combination thereof. 
     
     
         17 . The curable composition of  claim 12 , wherein the third plurality of polymerizable functional groups is a plurality of acrylate groups, methacrylate groups, or a combination thereof. 
     
     
         18 . The curable composition of  claim 12 , wherein the at least two polymerizable functional groups of the third plurality of polymerizable functional groups are spaced by at least 6 atoms. 
     
     
         19 . The curable composition of  claim 13 , wherein the first, the second, and the third crosslinkers differ in molecular weight by at least 200 Daltons (Da). 
     
     
         20 . The curable composition of  claim 19 , wherein at least 90% of polymerizable functional groups of the curable composition are disposed within crosslinkers. 
     
     
         21 . The curable composition of  claim 1 , wherein the curable composition is photocurable, chemically curable, thermocurable, or any combination thereof. 
     
     
         22 . The curable composition of  claim 1 , wherein the curable composition is photocurable. 
     
     
         23 . The curable composition of  claim 1 , further comprising a filler material. 
     
     
         24 . The curable composition of  claim 23 , wherein the filler material comprises a silica, a glass, a radiopaque material, a ceramic, a metal, a metal oxide, a crystal, or any combination thereof. 
     
     
         25 . The curable composition of  claim 23 , wherein the curable composition comprises between 0.05 and 60 wt % of the filler material. 
     
     
         26 . The curable composition of  claim 23 , wherein the curable composition comprises between 1 and 20 wt % of the filler material. 
     
     
         27 . The curable composition of  claim 1 , wherein the curable composition comprises between 60 wt % and 90 wt % polymerizable species. 
     
     
         28 . The curable composition of  claim 1 , further comprising a wetting agent. 
     
     
         29 . The curable composition of  claim 28 , wherein the wetting agent comprises a siloxane. 
     
     
         30 . The curable composition of  claim 1 , further comprising a pigment. 
     
     
         31 . The curable composition of  claim 30 , wherein the pigment is inorganic or organometallic. 
     
     
         32 . The curable composition of  claim 1 , wherein the initiator comprises a photoinitiator. 
     
     
         33 . The curable composition of  claim 32 , wherein the photoinitiator comprises an oligomer or a polymer. 
     
     
         34 . The curable composition of  claim 1 , wherein the curable composition is configured to develop a color defined by an L* value between 70 and 95, an a* value of between −11 and 1, and a b* value of between 2 and 22 upon curing. 
     
     
         35 . The curable composition of  claim 1 , wherein the curable composition is configured to develop a color defined by an L* value between 78 and 87, an a* value of between −7 and −3, and a b* value of between 8 and 16 upon curing.