THREE-DIMENSIONAL OBJECTS PRODUCED FROM MATERIALS HAVING MULTIPLE MECHANISMS OF HARDENING

1 . A three dimensional object comprised of:

(a) a light polymerized first component; and

(b) a second solidified component different from said first component;

said object comprising a polymer blend formed from said first component and said second component, with said polymer blend comprising an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network;

subject to the proviso that: (i) said second component does not contain a cationic polymerization photoinitiator, and/or (ii) said three dimensional object is produced by the process of continuous liquid interface production.

2 . The object of claim 1 , wherein said second component is solidified (or further reacted, polymerized, or chain extended) on contacting to heat, water, water vapor, light at a different wavelength than that at which said first component is polymerized, catalysts, evaporation of a solvent from the polymerizable liquid, exposure to microwave irradiation, or combinations thereof.

3 . The object of claim 1 , wherein:

(i) said first component comprises the polymerization product of monomers and/or prepolymers polymerized by exposure to actinic radiation or light, said monomers and/or prepolymers comprising reactive end groups selected from the group consisting of acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.

4 . The object of claim 3 , wherein:

(ii) said second component comprises the solidified product of the polymerization of monomers and/or prepolymers comprising reactive end groups, said reactive end groups selected from the group consisting of: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate/hydroxyl, isocyanate/amine, isocyanate/carboxylic acid, cyanate ester, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si—H, Si—Cl/hydroxyl, Si—Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/azide, click chemistry reactive groups, alkene/sulfur, alkene/thiol, alkyne/thiol, hydroxyl/halide, isocyanate/water, Si—OH/hydroxyl, Si—OH/water, Si—OH/Si—H, Si—OH/Si—OH, perfluorovinyl, diene/dienophiles, olefin metathesis polymerization groups, olefin polymerization groups for Ziegler-Natta catalysis, and ring-opening polymerization groups, and mixtures thereof.

5 . The object of claim 1 , wherein said second solidified component comprises a thermoset polymer.

6 . The object of claim 5 , wherein said second solidified component comprises a polyurethane, polyurea, or copolymer thereof.

7 . The object of claim 1 , wherein said second solidified component comprises a thermoplastic polymer.

8 . The object of claim 7 , wherein said second solidified component comprises a polyurethane, polyurea, or copolymer thereof.

9 . The object of claim 1 , further comprising:

(a) a third solidified component different from said first and second component, with

said object having at least a first structural segment and a second structural segment covalently coupled to one another,

said first structural segment comprised of said second solidified component,

said second structural segment comprised of said third solidified component; and

both said first and second structural segments comprised of the same or different light polymerized first component.

10 . The object of claim 1 , subject to the proviso that: (i) said second component does not contain a cationic polymerization photoinitiator.

11 . The object of claim 1 , subject to the proviso that: (ii) said three dimensional object is produced by the process of continuous liquid interface production.

12 . The object of claim 1 , wherein said object comprises a sol-gel composition, a hydrophobic-hydrophilic polymer network, a phenolic resin, a polyimide, a conductive polymer, a natural product polymer network, a polyolefin, or a combination thereof.

13 . The object of claim 1 , wherein said object further comprises reacted photoinitator fragments, and/or unreacted photoinitiator.

14 . The object of claim 1 , wherein said object is rigid, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young's modulus of 800 to 3500 megapascals, has a tensile strength of 30 to 100 megapascals, and has a percent elongation at break of from 1 to 100.

15 . The object of claim 14 , wherein said object is a fastener, an electronic device housing, a gear, propeller, or impeller, a wheel, a mechanical device housing, or a tool.

16 . The object of claim 1 , wherein said object is rigid and flexible, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young's modulus of 300 to 2500 megapascals, has a tensile strength of from 20 to 70 megapascals, and has a percent elongation at break of from 40 to 300 or 600.

17 . The object of claim 16 , wherein said object is a structural element, a hinge, a boat or watercraft hull or deck, a wheel, a bottle, jar or other container, a pipe, a liquid tube, or a connector.

18 . The object of claim 1 , wherein said object is elastomeric, is comprised of polyurethane, polyurea, or copolymer thereof, has a Young's modulus of 0.5 to 40 megapascals, has a tensile strength of from 0.5 to 30 megapascals, and has a percent elongation at break of from 50 to 1000.

19 . The object of claim 18 , wherein said object is a foot-ware sole, heel, innersole or midsole; a bushing or gasket; a cushion, or an electronic device housing.

20 . The object of claim 1 , produced by the process comprising:

(a) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

(b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component different from said first component;

(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from said first component and also advancing said carrier away from said build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object and containing said second solidifiable component carried in said scaffold in unsolidified and/or uncured form; and

(d) concurrently with or subsequent to said irradiating step, solidifying and/or curing said second solidifiable component in said three-dimensional intermediate to form said three-dimensional object.

21 . The object of claim 20 , wherein said irradiating and/or said advancing steps are carried out while also concurrently:

(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and

(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer and in contact with each thereof, said gradient of polymerization zone comprising said first component in partially cured form.

22 . The object of claim 1 , wherein said object has a shape that cannot be formed by injection molding or casting.

23 . The object of claim 1 , wherein said object comprises:

(i) enclosed cavities, partially open cavities, repeating unit cells, open cell foams, closed cell foams, or combinations thereof;

(ii) a waveguide, prism, lens, or combination thereof; and/or

(iii) a wall, strut, beam, tie, or combination thereof.