Additively manufactured dental attachment placement devices using curable compositions

Abstract

Disclosed herein are dental attachment placement devices generated from curable compositions by additive manufacturing. The curable compositions contain a high crosslinker content, and after curing, yield tough and color neutral materials suitable for dental attachment placement devices.

What is claimed is: 
     
         1 . A dental attachment placement device generated from a curable composition by additive manufacturing, the curable composition comprising:
 at least one first crosslinker having a rigid backbone between a plurality of first polymerizable functional groups;   at least one second crosslinker having a flexible backbone between a plurality of second polymerizable functional groups; and   a photoinitiator,   wherein a polymeric material formed from the curable composition has a tensible strength of about 50 MPa or greater, a modulus strength of 1200 MPa or greater, and a strain at break of about 4% or greater.   
     
     
         2 . The dental attachment placement device of  claim 1 , wherein the at least one first crosslinker has the following structure (I):
   Y 1 —X 1 -L 1 -A-L 2 -X 2 —Y 2 ,   (I)
   
       wherein:
 A is a cycloalkylene, alkylenecycloalkylene, alkylenecycloalkylenealkylene heterocycloalkylene, arylene, heteroarylene, alkylenearylene or alkylenearylenealkylene group; 
 L 1  and L 2  are independently an amide, ether, ester, carbonate, urethane or urea linkage; 
 X 1  and X 2  are independently an alkylene or heteroalkene linker; and 
 Y 1  and Y 2  are independently a polymerizable functional group. 
 
     
     
         3 . The dental attachment placement device of  claim 2 , wherein A has one of the following structures: 
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2  and R 3  are independently H or alkyl. 
     
     
         4 . The dental attachment placement device of  claim 2 , wherein X 1  and X 2  independently have one of the following structures: 
       
         
           
           
               
               
           
         
       
       wherein n is an integer from 1 to 20. 
     
     
         5 . The dental attachment placement device of  claim 2 , wherein Y 1  and Y 2  independently have one of the following structures: 
       
         
           
           
               
               
           
         
       
       wherein R 4  is H or alkyl. 
     
     
         6 . The dental attachment placement device of  claim 1 , wherein the at least one second crosslinker has the following structure (II):
   Y 3 —X 3 -L 3 -B-L 4 -X 4 —Y 3 ,   (II)
   
       wherein:
 B is a linear or branched alkylene or heteroalkylene group; 
 L 3  and L 4  are independently an optional amide, ether, ester, carbonate, urethane or urea linkage; 
 X 3  and X 4  are independently an optional alkylene or heteroalkene linker; and 
 Y 3  and Y 4  are independently a polymerizable functional group. 
 
     
     
         7 . The dental attachment placement device of  claim 6 , wherein B has one of the following structures: 
       
         
           
           
               
               
           
         
       
       wherein m is an integer from 1 to 20. 
     
     
         8 . The dental attachment placement device of  claim 6 , wherein X 3  and X 4  independently have one of the following structures: 
       
         
           
           
               
               
           
         
       
       wherein n is an integer from 1 to 20. 
     
     
         9 . The dental attachment placement device of  claim 6 , wherein Y 3  and Y 4  independently have one of the following structures: 
       
         
           
           
               
               
           
         
       
       wherein R 4  is H or alkyl. 
     
     
         10 . The dental attachment placement device of  claim 1 , wherein the photoinitiator comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide (BAPO) and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl) phenyl]. 
     
     
         11 . The dental attachment placement device of  claim 1 , wherein the dental attachment placement device comprises:
 a body;   one or more additively manufactured dental attachments shaped to attach to a person's dentition at corresponding locations, wherein the one or more additively manufactured dental attachments are shaped to engage with corresponding one or more attachment wells of an aligner, and when, engaged with the one or more attachment wells, impart one or more forces to the person's dentition; and   one or more additively manufactured supports to removably couple the one or more additively manufactured attachments to the body.   
     
     
         12 . A dental attachment placement device generated from a curable composition by additive manufacturing,
 wherein the curable composition comprises:
 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; and 
 
   wherein the dental attachment placement device comprises:
 a body; 
 one or more additively manufactured dental attachments shaped to attach to a person's dentition at corresponding locations, wherein the one or more additively manufactured dental attachments are shaped to engage with corresponding one or more attachment wells of an aligner, and when, engaged with the one or more attachment wells, impart one or more forces to the person's dentition; and 
 one or more additively manufactured supports to removably couple the one or more additively manufactured attachments to the body. 
   
     
     
         13 . The dental attachment placement device of  claim 12 , 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. 
     
     
         14 . The dental attachment placement device of  claim 12 , wherein the alkylene backbone is unsubstituted or 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. 
     
     
         15 . The dental attachment placement device of  claim 12 , wherein the curable composition further comprising a third crosslinker, the 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.   
     
     
         16 . The dental attachment placement device of  claim 15 , wherein the first, the second, and the third crosslinkers differ in molecular weight by at least 200 Daltons (Da). 
     
     
         17 . A dental attachment placement device generated from a curable composition by additive manufacturing,
 wherein the curable composition comprises:
 a plurality of polymerizable monomers, which polymerizable monomers comprise at least 80 wt % of a crosslinker; and 
 at least 10 wt % of a filler material; and 
   wherein the dental attachment placement device comprises:
 a body; 
 one or more additively manufactured dental attachments shaped to attach to a person's dentition at corresponding locations, wherein the one or more additively manufactured dental attachments are shaped to engage with corresponding one or more attachment wells of an aligner, and when, engaged with the one or more attachment wells, impart one or more forces to the person's dentition; and 
 one or more additively manufactured supports to removably couple the one or more additively manufactured attachments to the body. 
   
     
     
         18 . The dental attachment placement device of  claim 17 , wherein the crosslinker comprises a plurality of crosslinkers with different molecular weights. 
     
     
         19 . The dental attachment placement device of  claim 17 , wherein the crosslinker comprises an alkane backbone, an alkane diol backbone, an oligoethylene glycol backbone, a bisphenyl backbone, a glycidyl backbone, a urethane backbone, or a combination thereof. 
     
     
         20 . The dental attachment placement device of  claim 17 , wherein the filler material comprises a silica, a glass, a radiopaque material, a ceramic, a metal, a metal oxide, a crystal, a pre-polymerized species or any combination thereof.