Radiation curable resin composition and rapid three dimensional imaging process using the same

Abstract

The invention relates to a radiation curable resin composition comprising a cationically polymerizable component, a cationic photoinitiator, a hydroxy component, and an impact modifier. The resin composition can preferably be used in the preparation of three dimensional objects.

1 - 32 . (canceled) 
     
     
         41 . A radiation curable resin composition comprising:
 a) a cationically polymerizable component comprising at least one epoxy group;   b) a cationic photoinitiator;   c) a hydroxy component; and   d) 1 to 30 wt %. of an impact modifier selected from the group consisting of elastomers based on copolymers of ethylene and one or more C2 to C12 α-olefin monomers, elastomers based on copolymers of propylene and one or more C2 to C12 α-olefin monomers, styrene/butadiene random copolymer, styrene/isoprene random copolymer, ethylene/acrylate random copolymers, acrylic block copolymers, styrene/butadiene/(meth)acrylate block copolymers, styrene/butadiene block copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer.   
     
     
         42 . The radiation curable resin composition of  claim 41  wherein the impact modifier comprises a styrene/butadiene/(meth)acrylate block copolymer. 
     
     
         43 . The radiation curable resin composition of  claim 41  wherein the impact modifier comprises an acrylic block copolymer. 
     
     
         44 . The radiation curable resin composition according to  claim 41 , wherein the elastomers are modified to contain reactive groups comprising epoxy, oxetane, carboxyl or hydroxyl. 
     
     
         45 . The radiation curable resin composition of  claim 41  wherein the cationically polymerizable/hydroxy ratio of the composition is in the range of from 2 to 5. 
     
     
         46 . The radiation curable resin composition of  claim 41  wherein the cationically polymerizable/radically polymerizable ratio is in the range of from 4.5 to 15. 
     
     
         47 . The radiation curable resin composition of  claim 41  wherein, the cationically polymerizable/hydroxy ratio of the composition is in the range of from 2.2 to 4.75. 
     
     
         48 . The radiation curable resin composition of  claim 47  wherein the cationically polymerizable/radically polymerizable ratio is in the range of from 5 to 10. 
     
     
         49 . The radiation curable resin composition of  claim 41  wherein the cationically polymerizable/hydroxy ratio of the composition is in the range of from 2.4 to 4.5. 
     
     
         50 . The radiation curable resin composition of  claim 41  wherein the resin composition after full cure has a tensile modulus of >2 GPa; a yield stress <70 MPa; and a Ki C  value >1.3 MPa·(m) 172  or an Izod value >0.45 J/cm. 
     
     
         51 . The radiation curable resin composition of  claim 41 , wherein the hydroxy component is selected from the group consisting of polyoxyethylene glycols of molecular weights from about 200 to about 10,000; polyoxypropylene glycols of molecular weights from about 200 to about 10,000; triols of molecular weights from about 200 to about 10,000; polytetramethylene glycols; poly(oxyethylene-oxybutylene) random copolymer; poly(oxyethylene-oxybutylene) block copolymers; hydroxy-terminated polyesters; hydroxy-terminated polylactones; hydroxy-functionalized polyalkadienes; aliphatic polycarbonate polyols; hydroxy-terminated polyethers; and a chemical of the following structure: 
       
         
           
           
               
               
           
         
         wherein R3=—CH 2 —, —C(CH 3 J 2 -, —C(CF 3 ) 2 —, —CCl 2 —, —O—, —S—, and R4=—CH 2 CH 2 — or —CH 2 CH(CH 3 )—, and n and m are 1 through 10. 
       
     
     
         52 . The radiation curable resin composition of  claim 41 , wherein the composition contains 1-30 wt % of a radically polymerizable compound and 0.1-15 wt % of a free radical photoinitiator. 
     
     
         53 . The radiation curable resin composition of  claim 52 , wherein the radically polymerizable compound comprises a polyfunctional acrylate. 
     
     
         54 . The composition according to  claim 41 , wherein the composition comprises 1-15 wt % of a component having at least one epoxy group and at least one (meth)acrylate group. 
     
     
         55 . The radiation curable resin composition of  claim 41 , wherein the composition comprises a aromatic/cycloaliphatic content between 0.2 and 0.6. 
     
     
         56 . The radiation curable resin composition of  claim 41 , wherein the composition contains a filler. 
     
     
         57 . A three-dimensional article formed from the radiation 
     
     
         58 . A process for making three dimensional articles comprising the steps of
 (1) coating a thin layer of a composition onto a surface;   (2) exposing said thin layer imagewise to actinic radiation to form an imaged cross-section, wherein the radiation is of sufficient intensity and time to cause substantial curing of the thin layer in the exposed areas;   (3) coating an additional thin layer of the composition onto the imaged cross-section;   (4) exposing said additional thin layer from step (3) imagewise to actinic radiation to form a new imaged cross-section, wherein the radiation is of sufficient intensity and time to cause substantial curing of the additional thin layer in the exposed areas and to cause adhesion of the new imaged cross-section to the imaged cross-section, wherein the new imaged cross-section becomes part of the imaged cross-section;   (5) repeating steps (3) and (4) a sufficient number of times in order to build up the three-dimensional article, wherein the composition is defined according to  claim 41 .   
     
     
         59 . A radiation curable resin composition comprising:
 a) a cationically polymerizable component comprising at least one epoxy group;   b) a cationic photoinitiator;   c) a hydroxy component; and   d) an impact modifier selected from the group consisting of a SBM block copolymer, a SBS block copolymer, a SEBS block copolymer, a SIS block copolymer, a SEPS block copolymer, an ethyl/acrylate random copolymer, a glycidyl methacrylate modified random ethylene/acrylate copolymer, and a maleic anhydride modified random ethylene/acrylate copolymer.   
     
     
         60 . A three-dimensional article formed from the radiation curable resin of  claim 59 .