3d printing ink containing a cyclopolymerizable monomer

Abstract

In one aspect, inks for use with a three-dimensional (3D) printing system are described herein. In some embodiments, an ink described herein comprise 10-70 wt. % or 20-40 wt. % of a cyclopolymerizable monomer, based on the total weight of the ink. The cyclopolymerizable monomer comprises an acrylate moiety and an ethenyl or ethynyl moiety, and the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety may have a 1,5-, 1,6-, 1,7-, or 1,8-relationship. Additionally, an ink described herein can have a viscosity of 1600 centipoise (cP) or less at 30° C., or of 500 cP or less at 30° C. and can be used to print a desired 3D article having mechanical properties similar to those of articles formed from thermoplastic materials.

That which is claimed: 
     
         1 . An ink for use in a three-dimensional printing system comprising:
 10-70 wt. % cyclopolymerizable monomer, based on the total weight of the ink; and   40-80 wt. % oligomeric curable material, based on total weight of the ink,   wherein the cyclopolymerizable monomer comprises an acrylate moiety and an ethenyl or ethynyl moiety, and   wherein the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety have a 1,5-, 1,6-, 1,7-, or 1,8-relationship, and   wherein the ink, in a cured state, has a tensile strength of 40-70 MPa and an impact resistance of 1-4 ft·lb/in.   
     
     
         2 . The ink of  claim 1 , wherein the cyclopolymerizable monomer is present in the ink in an amount of 10-50 wt. %, based on the total weight of the ink. 
     
     
         3 . The ink of  claim 1 , wherein the cyclopolymerizable monomer is present in the ink in an amount of 20-40 wt. %, based on the total weight of the ink. 
     
     
         4 . The ink of  claim 1 , wherein the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety have a 1,5-relationship. 
     
     
         5 . The ink of  claim 1 , wherein the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety have a 1,6-relationship. 
     
     
         6 . The ink of  claim 1 , wherein the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety have a 1,7-relationship. 
     
     
         7 . The ink of  claim 1 , wherein the α-carbon of the acrylate moiety and the α-carbon of the ethenyl or ethynyl moiety have a 1,8-relationship. 
     
     
         8 . The ink of  claim 1 , wherein the cyclopolymerizable monomer has the structure of Formula (I): 
       
         
           
           
               
               
           
         
         wherein X is O, S, NH, NR 5 , or CR 5 R 6 ; 
         R 1  is H or a hydrocarbon group having 1-10 carbon atoms; 
         R 2  is a hydrocarbon group having 1-4 carbon atoms; 
         R 3  is a hydrocarbon group having 1-4 carbon atoms; 
         or R 4  is HC═CH 2  or C≡CH; 
         R 5  is a hydrocarbon group having 1-4 carbon atoms; 
         R 6  is a hydrocarbon group having 1-4 carbon atoms; and 
         the total number of carbon atoms of R 2  and R 3  does not exceed 5. 
       
     
     
         9 . The ink of  claim 8 , wherein X is O. 
     
     
         10 . The ink of  claim 8 , wherein X is S, NH, NR 5 , or CR 5 R 6 . 
     
     
         11 . The ink of  claim 8 , wherein the total number of carbon atoms of R 2  and R 3  does not exceed 4. 
     
     
         12 . The ink of  claim 8 , wherein the total number of carbon atoms of R 2  and R 3  does not exceed 3. 
     
     
         13 . The ink of  claim 8 , wherein the total number of carbon atoms of R 2  and R 3  is 2. 
     
     
         14 . The ink of  claim 8 , wherein the cyclopolymerizable monomer has the structure of Formula (II): 
       
         
           
           
               
               
           
         
       
     
     
         15 . The ink of  claim 1 , wherein the weight average molecular weight of the oligomeric curable material is from 400 to 10,000. 
     
     
         16 . The ink of  claim 1  further comprising:
 up to 80 wt. % additional monomeric curable material, based on the total weight of the ink. 
 
     
     
         17 . The ink of  claim 1  further comprising at least one photoinitiator. 
     
     
         18 . The ink of  claim 1  further comprising at least one colorant or one or more additives selected from the group consisting of inhibitors and stabilizing agents. 
     
     
         19 . The ink of  claim 1 , wherein the viscosity of the ink is 1,600 centipoise (cP) or less at 30° C.