Photosensitive Resin and Manufacturing Method Thereof

Abstract

Various embodiments disclosed relate to photopolymerizable compositions that are suitable for making three-dimensional structures when exposed to laser light.

What is claimed is: 
     
         1 . A composition comprising:
 at least one monomer or oligomer comprising urethane acrylate;   at least one monomer comprising pentaerythritol acrylate;   at least one polyester acrylate resin;   at least one photo initiator; and   the polyester acrylate resin comprises one or more thiol groups.   
     
     
         2 . The composition of  claim 1 , wherein the urethane acrylate comprises a urethane diacrylate. 
     
     
         3 . The composition of  claim 2 , wherein the urethane diacrylate is an aliphatic urethane diacrylate. 
     
     
         4 . The composition of  claim 1 , wherein the urethane acrylate is present in an amount of about 30 wt % to about 70 wt %. 
     
     
         5 . The composition of  claim 1 , wherein the pentaerythritol acrylate comprises a pentaerythritol tetraacrylate. 
     
     
         6 . The composition of  claim 5 , wherein the pentaerythritol tetraacrylate is ethoxylated. 
     
     
         7 . The composition of  claim 1 , wherein the pentaerythritol acrylate is present in an amount of about 30 wt % to about 70 wt %. 
     
     
         8 . The composition of  claim 1 , wherein the polyester acrylate resin is present in an amount of about 10 wt % to about 30 wt %. 
     
     
         9 . The composition of  claim 1 , wherein the photo initiator has the formula I 
       
         
           
           
               
               
           
         
         wherein, 
         M is a transition metal; and 
         L 1 , L 2 , L 3 , and L 4  are each independently alkyl, aryl, alkylaryl, or heteroaryl, each of which is substituted or unsubstituted. 
       
     
     
         10 . The composition of  claim 9 , wherein L 1  is substituted or unsubstituted cyclopentadienyl. 
     
     
         11 . The composition of  claim 10 , wherein L 1  is cyclopentadienyl. 
     
     
         12 . The composition of  claim 9 , wherein L 3  is substituted aryl. 
     
     
         13 . The composition of  claim 12 , wherein L 3  has the structure 
       
         
           
           
               
               
           
         
       
     
     
         14 . The composition of  claim 9 , wherein the photo initiator has the structure 
       
         
           
           
               
               
           
         
       
     
     
         15 . The composition of  claim 1 , wherein the photo initiator is present in an amount of from about 0.01 wt % to about 1 wt %. 
     
     
         16 . A method of polymerizing a composition, comprising exposing the composition of  claim 1  to laser light. 
     
     
         17 . A composition comprising:
 about 40 wt % of a monomer comprising aliphatic urethane diacrylate;   about 40 wt % of monomer comprising ethoxylated pentaerythritol tetraacrylate;   about 20 wt % of a thiol substituted polyester acrylate resin; and   at least one photo initiator having the structure   
       
         
           
           
               
               
           
         
       
     
     
         18 . A method of making a polymerizable composition, comprising:
 combining at least one monomer comprising urethane acrylate, at least one monomer comprising pentaerythritol acrylate, and at least one polyester acrylate resin to form a homogenous mixture;   combining the homogenous mixture with a photo initiator to form an initial mixture; and   stirring the initial mixture at a temperature greater than about 30° C.,   wherein the polyester acrylate resin comprises one or more thiol groups.   
     
     
         19 . The method of  claim 18 , wherein initial mixture is stirred at about 40° C. 
     
     
         20 . A composition comprising:
 at least one monomer or oligomer comprising urethane acrylate;   at least one monomer comprising pentaerythritol acrylate;   at least one polyester acrylate resin; and   at least one photo initiator,   wherein:
 the photo initiator has the formula I 
   
       
         
           
           
               
               
           
         
         
           M is a transition metal; 
           L 1 , L 2 , and L 4  are each independently alkyl, aryl, alkylaryl, or heteroaryl, each of which is substituted or unsubstituted; and 
           L 3  has the structure 
         
       
       
         
           
           
               
               
           
         
       
     
     
         21 . The composition of  claim 20 , wherein the urethane acrylate comprises a urethane diacrylate. 
     
     
         22 . The composition of  claim 21 , wherein the urethane diacrylate is an aliphatic urethane diacrylate. 
     
     
         23 . The composition of  claim 20 , wherein the urethane acrylate is present in an amount of about 30 wt % to about 70 wt %. 
     
     
         24 . The composition of  claim 20 , wherein the pentaerythritol acrylate comprises a pentaerythritol tetraacrylate. 
     
     
         25 . The composition of  claim 24 , wherein the pentaerythritol tetraacrylate is ethoxylated. 
     
     
         26 . The composition of  claim 20 , wherein the pentaerythritol acrylate is present in an amount of about 30 wt % to about 70 wt %. 
     
     
         27 . The composition of  claim 20 , wherein the polyester acrylate resin comprises one or more thiol groups. 
     
     
         28 . The composition of  claim 20 , wherein the polyester acrylate resin is present in an amount of about 10 wt % to about 30 wt %. 
     
     
         29 . The composition of  claim 20 , wherein L 1  is substituted or unsubstituted cyclopentadienyl. 
     
     
         30 . The composition of  claim 30 , wherein L 1  is cyclopentadienyl. 
     
     
         31 . The composition of  claim 20 , wherein the photo initiator has the structure 
       
         
           
           
               
               
           
         
       
     
     
         32 . The composition of  claim 20 , wherein the photo initiator is present in an amount of from about 0.01 wt % to about 1 wt %. 
     
     
         33 . A method of polymerizing a composition, comprising:
 exposing the composition of  claim 20  to laser light.