Fabrication of solid materials or films from a polymerizable liquid

Abstract

The disclosure describes a polymerizable liquid that includes a reactive oligomer and a reactive monomer. The polymerizable liquid is an energy polymerizable liquid hardenable by a single reaction mechanism forming a photoplastic material. The disclosure further describes a method of producing the photoplastic material and articles that can be made from the photoplastic material.

What is claimed is: 
     
         1 . A method of forming a three-dimensional object from an energy polymerizable liquid, the method comprising:
 mixing together
 a reactive oligomer, the reactive oligomer being a multi-functional oligomer; and 
 a reactive monofunctional monomer, wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 5:1; and 
   hardening the energy polymerizable liquid to a photoplastic material.   
     
     
         2 . The method of  claim 1 , wherein the three-dimensional object is a medical device, a part of footwear or part of soft robotics. 
     
     
         3 . The method of  claim 1 , wherein the three-dimensional object is a hydrogel. 
     
     
         4 . The method of  claim 1 , further comprising polymerizing by pixel or voxel polymerization to produce different physical properties by altering the energy polymerization conditions. 
     
     
         5 . The method of  claim 1 , further comprising mixing in a photoinitiator in an amount from about 0.01 percent to about 15 percent by weight. 
     
     
         6 . The method of  claim 1 , further comprising irradiating the polymerizable liquid with patterned irradiation. 
     
     
         7 . The method of  claim 1 , wherein mixing includes mixing in an amount from about 0.001 percent to about 10 percent by weight at least one of a non-reactive light absorbing pigment, a hindered amine light stabilizer, a filler, a polymerization inhibitor, and a polymerization catalyst. 
     
     
         8 . The method of  claim 1 , wherein the mixing includes mixing at least one of a reactive or non-reactive plasticizer in an amount from about 1 to about 30 percent by weight. 
     
     
         9 . The method of  claim 1 , wherein the formation of a three-dimensional object from an energy polymerizable liquid occurs with supplied heat. 
     
     
         10 . The method of  claim 1 , wherein the oligomer and the monomer react by a same polymerization mechanism and have different reaction rates. 
     
     
         11 . The method of  claim 1 , wherein a solubility of the monomer and oligomer change during polymerization to assist homopolymerization of either the monomeric or oligomeric species. 
     
     
         12 . The method of  claim 1 , wherein polymerization creates a material with more than one glass transition temperature. 
     
     
         13 . The method of  claim 1 , wherein the molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 10:1. 
     
     
         14 . The method of  claim 13 , wherein the molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 20:1. 
     
     
         15 . The method of  claim 1 , wherein the three-dimensional object reaches prescribed mechanical properties without supplied heat. 
     
     
         16 . The method of  claim 1 , wherein the three-dimensional object reaches prescribed mechanical properties with supplied heat. 
     
     
         17 . The method of  claim 1 , wherein the polymerizable liquid is non-toxic. 
     
     
         18 . The method of  claim 1 , wherein the three-dimensional object is non-toxic and biocompatible in accordance with ISO 10933 or 20795 standards or both. 
     
     
         19 . The method of  claim 1 , wherein the three-dimensional object is a medical appliance. 
     
     
         20 . The method of  claim 1 , wherein the three-dimensional object is a dental appliance. 
     
     
         21 . The method of  claim 20 , wherein the dental appliance is a dental prosthesis, orthodontic splint, aligner, retainer, implant, mold, crown, bridge, tooth, indirect bonding tray, mouth guard, bite plane, veneer, night guard, snoring appliance, repositioner, denture base, denture try-in, or denture. 
     
     
         22 . A method of forming a three-dimensional object from an energy polymerizable liquid, the method comprising:
 mixing together
 a reactive oligomer, the reactive oligomer being at least one of (i) a multi-functional methacrylate oligomer, and (ii) a multi-functional acrylate oligomer; and 
 a reactive monofunctional monomer, the reactive monofunctional monomer being at least one of (i) a monofunctional N-vinyl monomer, (ii) a monofunctional vinyl ether monomer, (iii) a monofunctional vinyl ester monomer, (iv) a monofunctional vinylamide monomer, (v) a styrene monomer, (vi) a monofunctional (meth)acrylamide monomer, (vii) a monofunctional (meth)acrylate monomer, (viii) a cyanoacrylate monomer, (ix) a monofunctional vinyl carbonate monomer, (x) a monofunctional acryloyl monomer, (xi) a monofunctional maleimide monomer, (xii) a monofunctional acrylonitrile monomer, (xiii) a monofunctional 1,3-diene monomer, and (xiv) a monofunctional vinyl carbamate monomer, wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 5:1; and 
   hardening the energy polymerizable liquid to a photoplastic material.   
     
     
         23 . A method of forming a three-dimensional object from an energy polymerizable liquid, the method comprising:
 mixing together
 a reactive oligomer, the reactive oligomer being at least one of (i) a multi-functional methacrylate oligomer, and (ii) a multi-functional acrylate oligomer; and 
 a reactive monofunctional monomer, the reactive monofunctional monomer being at least one of (i) a monofunctional N-vinyl monomer, (ii) a monofunctional vinyl ether monomer, (iii) a monofunctional vinyl ester monomer, (iv) a monofunctional vinylamide monomer, (v) a styrene monomer, (vi) a monofunctional (meth)acrylamide monomer, (vii) a monofunctional (meth)acrylate monomer, (viii) a cyanoacrylate monomer, (ix) a monofunctional vinyl carbonate monomer, (x) a monofunctional acryloyl monomer, (xi) a monofunctional maleimide monomer, (xii) a monofunctional acrylonitrile monomer, (xiii) a monofunctional 1,3-diene monomer, and (xiv) a monofunctional vinyl carbamate monomer, wherein a molar bond ratio of the reactive ethylenically unsaturated groups of the reactive monofunctional species to the reactive ethylenically unsaturated groups of the reactive multi-functional species is at least 5:1; and 
   hardening the energy polymerizable liquid by a single reaction mechanism to a photoplastic material by an apparatus for bottom-up or top-down three dimensional fabrication.   
     
     
         24 . The method of  claim 23 , wherein the bottom or top-down three dimensional fabrication is selected from the group consisting of stereolithography (SLA) and digital light processing (DLP).