Stabilized matrix-filled liquid radiation curable resin compositions for additive fabrication

Abstract

Matrix-filled liquid radiation curable resin compositions for additive fabrication are described and claimed. Such resins include a cationically polymerizable component that is an aliphatic epoxide, a multifunctional (meth)acrylate component, a cationic photoinitiator, a free-radical photo initiator, and a matrix of inorganic fillers, wherein the matrix further constitutes prescribed ratios of at least one microparticle constituent and at least one nanoparticle constituent. Also described and claimed is a process for using the matrix-filled liquid radiation curable resins for additive fabrication to create three dimensional parts, and the three-dimensional parts made from the liquid radiation curable resins for additive fabrication.

1 - 26 . (canceled) 
     
     
         27 . A liquid radiation curable composition for additive fabrication comprising:
 a cationically polymerizable component;   a (meth)acrylate component;   a cationic photoinitiator;   a free-radical photoinitiator; and   a filled matrix; the filled matrix comprising
 a microparticle constituent consisting of microparticles having a particle size from about 1 to about 10 microns; and 
 a nanoparticle constituent consisting of nanoparticles having a particle size from about 20 to about 200 nm; 
   wherein a ratio of the average particle size of the microparticle constituent to the average particle size of the nanoparticle constituent is from about 6.46:1 to less than 200:1; and   wherein a ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 1:1 to about 12:1.   
     
     
         28 . The liquid radiation curable composition for additive fabrication of  claim 27 , wherein the average particle size of the microparticle constituent is from 2 microns to 8 microns; and
 the average particle size of the nanoparticle constituent is from 50 nm to 200 nm.   
     
     
         29 . The liquid radiation curable composition for additive fabrication of  claim 28 , wherein the filled matrix comprises a second nanoparticle constituent, wherein the second nanoparticle constituent possesses an average particle size from about 20 nm to about 100 nm. 
     
     
         30 . The liquid radiation curable composition for additive fabrication of  claim 29 , wherein the ratio of the average particle size of the microparticle constituent to the average particle size of the nanoparticle constituent is from about 6.46:1 to less than 100:1. 
     
     
         31 . The liquid radiation curable composition for additive fabrication of  claim 30 , wherein the particle size of the microparticles, the particle size of the nanoparticles, the average particle size of the microparticle constituent, the average particle size of the nanoparticle constituent, and the average particle size of the second nanoparticle constituent is determined using an image analyzer of a microphotograph from a scanning electron microscope (SEM). 
     
     
         32 . The liquid radiation curable composition for additive fabrication of  claim 30 , wherein the particle size of the microparticles, the particle size of the nanoparticles, the average particle size of the microparticle constituent, the average particle size of the nanoparticle constituent, and the average particle size of the second nanoparticle constituent is determined via laser diffraction particle size analysis in accordance with ISO13320:2009. 
     
     
         33 . The liquid radiation curable composition for additive fabrication of  claim 30 , wherein the microparticle constituent consists essentially of inorganic microparticles; the nanoparticle constituent consists essentially of inorganic nanoparticles; and the second nanoparticle constituent consists essentially of inorganic nanoparticles. 
     
     
         34 . The liquid radiation curable composition for additive fabrication of  claim 33 , wherein the microparticle constituent consists of greater than 85 wt. %, or greater than 95 wt. % of silica microparticles;
 and the nanoparticle constituent and/or the second nanoparticle constituent consist of greater than 85 wt. %, or greater than 95 wt. % of silica nanoparticles.   
     
     
         35 . The liquid radiation curable composition for additive fabrication of  claim 34 , wherein the microparticle constituent comprises silica microparticles having a sphericity of 0.80 or greater; and the nanoparticle constituent and/or the second nanoparticle constituent comprises silica nanoparticles having a sphericity of 0.80 or greater, wherein sphericity is determined using an image analyzer of an SEM microphotograph. 
     
     
         36 . The liquid radiation curable composition for additive fabrication of  claim 33 , wherein the microparticle constituent consists essentially of surface treated microparticles; and the nanoparticle constituent and/or the second nanoparticle constituent consists essentially of surface treated nanoparticles. 
     
     
         37 . The liquid radiation curable composition for additive fabrication of  claim 36 , wherein the surface treated microparticles and the surface treated nanoparticles are surface treated with a silane coupling agent. 
     
     
         38 . The liquid radiation curable composition for additive fabrication of  claim 33 , wherein the filled matrix comprises a second microparticle constituent. 
     
     
         39 . The liquid radiation curable composition for additive fabrication of  claim 29 , wherein, relative to the weight of the entire composition:
 the cationically polymerizable component is present from about 20 to about 65 wt. %;   the (meth)acrylate component is present from about 2 to about 20 wt. %;   the cationic photoinitiator is present from 0.05 to 5 wt. %;   the free-radical photoinitiator is present from 0.1 to 6 wt. %; and   the filled matrix is present from 30 to 70 wt. %.   
     
     
         40 . The liquid radiation curable composition for additive fabrication of  claim 39 , wherein the cationically polymerizable component consists of cycloaliphatic epoxides, oxetanes, and diglycidyl ether epoxides. 
     
     
         41 . The liquid radiation curable composition for additive fabrication of  claim 40 , wherein the (meth)acrylate component comprises triacrylate compounds. 
     
     
         42 . The liquid radiation curable composition for additive fabrication of  claim 41 , wherein the free-radical photoinitiator consists of 1-hydroxycyclohexyl phenyl ketone; and/or the cationic photoinitiator consists of aromatic sulfonium salts. 
     
     
         43 . The liquid radiation curable composition for additive fabrication of  claim 42 , wherein the composition further comprises additives, wherein the additives include one or more than one of a stabilizer, a wetting agent, a dye and/or a pigment. 
     
     
         44 . The liquid radiation curable composition for additive fabrication of  claim 43 , wherein the composition possesses a viscosity, when measured at 30 degrees Celsius at a shear rate of 50 s −1 , of between 200 cPs and 2000 cPs. 
     
     
         45 . The liquid radiation curable composition for additive fabrication of  claim 44 , wherein a ratio of the average particle size of the microparticle constituent to the average particle size of the nanoparticle constituent is from about 6.46:1 to about 100:1; and wherein a ratio by weight of the microparticle constituent to the nanoparticle constituent is from about 4:1 to about 8:1. 
     
     
         46 . The liquid radiation curable composition for additive fabrication of  claim 45 , wherein the particle size of the microparticles, the particle size of the nanoparticles, the average particle size of the microparticle constituent, the average particle size of the nanoparticle constituent, and the average particle size of the second nanoparticle constituent is determined using an image analyzer of an SEM microphotograph.