Production of light-transmissive objects by additive manufacturing

Abstract

Provided herein is a method of making a clear or translucent object by additive manufacturing, comprising (a) providing a clear or translucent light polymerizable resin, the resin comprising: (i) light-polymerizable monomers, prepolymers, or a combination thereof; (ii) a photoinitiator; and (iii) a polysubstituted linear polyacene ultraviolet light absorbing compound which compound is polysubstituted with bromo, chloro, —Se—R′, —S—R′ or combinations thereof, where each R′ is independently selected from alkyl, aryl, and arylalkyl; and then (b) producing by stereolithography with ultraviolet light a clear or translucent object from said light polymerizable resin.

We claim: 
     
         1 . A method of making a clear or translucent object by additive manufacturing, comprising:
 (a) providing a clear or translucent light polymerizable resin, said resin comprising:
 (i) light-polymerizable monomers, prepolymers, or a combination thereof; 
 (ii) a photoinitiator; and 
 (iii) a polysubstituted linear polyacene ultraviolet light absorbing compound that is polysubstituted with substituents independently selected from the group consisting of: bromo, chloro, —Se—R′, and —S—R′, where each R′ is independently selected from alkyl, aryl, and arylalkyl; and then 
   (b) producing by stereolithography with ultraviolet light a clear or translucent object from said light polymerizable resin.   
     
     
         2 . The method of  claim 1 , wherein said polyacene is selected from the group consisting of naphthalene, anthracene, tetracene, pentacene, and hexacene. 
     
     
         3 . The method of  claim 1 , wherein said polysubstituted linear polyacene ultraviolet light absorbing compound has a structure of Formula I: 
       
         
           
           
               
               
           
         
         wherein:
 m is 0, 1, 2, 3, 4 or 5; 
 n is from 2 to 4, 6 or 8; and 
 each R is independently selected from the group consisting of: bromo, chloro, —Se—R′, and —S—R′, where each R′ is independently selected from alkyl, aryl, and arylalkyl. 
 
       
     
     
         4 . The method of  claim 3 , wherein each R is bromo. 
     
     
         5 . The method of  claim 4 , herein said compound of Formula I is selected from the group consisting of 9,10-dibromoanthracene, 3,9,10-tetrabromoanthracene, and 5,11-dibromotetracene. 
     
     
         6 . The method of  claim 4 , wherein said compound of Formula I is: 
       
         
           
           
               
               
           
         
       
     
     
         7 . The method of  claim 1 , wherein said producing step is carried out by bottom-up stereolithography. 
     
     
         8 . The method of  claim 1 , wherein said light-polymerizable monomers, prepolymers, or combination thereof are free-radical polymerizable, optionally wherein said resin further comprises a reactive diluent. 
     
     
         9 . The method of  claim 1 , wherein said resin comprises a dual cure resin. 
     
     
         10 . The method of  claim 1 , wherein said resin has a light absorption coefficient, alpha, of from 0.0005 to 0.05. 
     
     
         11 . The method of  claim 1 , further comprising:
 (c) washing said object; and then   (d) further curing said object (e.g., by baking).   
     
     
         12 . The method of  claim 1 , wherein said object comprises a dental aligner, lens, lens cover, or window. 
     
     
         13 . An object produced by a method of  claim 1 . 
     
     
         14 . A clear or translucent light polymerizable resin, comprising:
 (a) light-polymerizable monomers, prepolymers, or a combination thereof;   (b) a photoinitiator; and   (c) a polysubstituted linear polyacene ultraviolet light absorbing compound that is polysubstituted with substituents independently selected from the group consisting of: bromo, chloro, —Se—R′, and —S—R′, where each R′ is independently selected from alkyl, aryl, and arylalkyl.   
     
     
         15 . The resin of  claim 14 , wherein said polyacene is selected from the group consisting of naphthalene, anthracene, tetracene, pentacene, and hexacene. 
     
     
         16 . The resin of  claim 14 , wherein said polysubstituted linear polyacene ultraviolet light absorbing compound has a structure of Formula I: 
       
         
           
           
               
               
           
         
         wherein:
 m is 0, 1, 2, 3, 4 or 5; 
 n is from 2 to 4, 6 or 8; and 
 each R is independently selected from the group consisting of: bromo, chloro, —Se—R′, and —S—R′ where each R′ is independently selected from alkyl, aryl, and arylalkyl. 
 
       
     
     
         17 . The resin of  claim 16 , wherein each R is bromo. 
     
     
         18 . The resin of  claim 17 , wherein said compound of Formula I is selected from the group consisting of 9,10-dibromoanthracene, 2,3,9,10-tetrabromoanthracene, and 5,11-dibromotetracene. 
     
     
         19 . The resin of  claim 17 , wherein said compound of Formula I is: 
       
         
           
           
               
               
           
         
       
     
     
         20 . The resin of  claim 14 , wherein said light-polymerizable monomers, prepolymers, or a combination thereof are free-radical polymerizable, optionally wherein said resin further comprises a reactive diluent. 
     
     
         21 . The resin of  claim 14 , wherein said resin has a light absorption coefficient, alpha, of from 0.0005 to 0.05.