초록 ▼

Provided is a method of forming a three-dimensional object, which may include the steps of: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable li

Provided is a method of forming a three-dimensional object, which may include the steps of: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid that comprises a reactive blocked monomer and/or prepolymer comprising a self-polymerizing monomer and/or prepolymer blocked with a light-polymerizable blocking group; (c) irradiating the build region with light through said optically transparent member to form a solid polymer scaffold from the reactive blocked monomer and/or prepolymer and also advancing the carrier away from the build surface to form a three-dimensional intermediate; and then (d) heating and/or microwave irradiating, the three-dimensional intermediate sufficiently to degrade the scaffold and regenerate the monomer and/or prepolymer in de-blocked form, which monomer and/or prepolymer in turn self-polymerize, to form said three-dimensional object.

대표청구항 ▼

1. A method of forming a three-dimensional object, 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 li

1. A method of forming a three-dimensional object, 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 reactive blocked monomer and/or prepolymer, said reactive blocked monomer and/or prepolymer comprising a self-polymerizing monomer and/or prepolymer blocked with a light-polymerizable blocking group;(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from said reactive blocked monomer and/or prepolymer 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 then(d) heating, microwave irradiating, or both heating and microwave irradiating, said three-dimensional intermediate sufficiently to degrade said scaffold and regenerate said monomer and/or prepolymer in de-blocked form, which monomer and/or prepolymer in turn self-polymerize, to form said three-dimensional object,wherein said reactive blocked monomer and/or prepolymer comprises a reactive blocked polyisocyanate, and said monomer and/or prepolymer in de-blocked form self-polymerizes by trimerization of said polyisocyanate, andwherein said polymerizable liquid further comprises an isocyanate trimerization catalyst. 2. The method of claim 1, wherein said light-polymerizable blocking group is 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, vinyl ethers, and combinations thereof. 3. The method of claim 1, wherein said light-polymerizable blocking group is selected from the group consisting of acrylates, methacrylates, and combinations thereof. 4. The method of claim 1, wherein said polymerizable liquid further comprises at least one photoinitiator. 5. The method of claim 1, wherein said polymerizable liquid further comprises at least one photoinitiator in an amount of from 0.1 to 5 percent by weight. 6. The method of claim 1, wherein said polymerizable liquid further comprises at least light-absorbing pigment one dye. 7. The method of claim 1, wherein said polymerizable liquid further comprises at least light-absorbing pigment one dye in an amount of from 0.001 to 5 percent by weight. 8. The method of claim 1, wherein said polymerizable liquid further comprises at least one filler. 9. The method of claim 1, wherein said polymerizable liquid further comprises at least one filler in an amount of from 0.01 to 50 percent by weight. 10. The method of claim 1, wherein said isocyanate trimerization catalyst is present in an amount of from 0.1 percent by weight to 6 percent by weight of the polymerizable liquid. 11. The method of claim 1, wherein said isocyanate trimerization catalyst comprises potassium acetate, a tertiary amine, cesium fluoride, a metal salt of a carboxylic acid, or a mixture of two or more thereof. 12. The method of claim 1, wherein said isocyanate trimerization catalyst comprises a tertiary amine. 13. The method of claim 1, wherein said three-dimensional object comprises a polymer blend, an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network. 14. The method of claim 1, wherein said three-dimensional object comprises a polymer blend, an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network of said degraded scaffold in combination with the product of said self-polymerization. 15. The method of claim 1, wherein said irradiating and/or said advancing steps are carried out while also concurrently: (i) continuously maintaining a dead zone of said 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 scaffold and in contact with each thereof, said gradient of polymerization zone comprising said reactive blocked monomer and/or prepolymer in partially-cured form. 16. The method of claim 15, wherein said optically transparent member comprises a semipermeable member, and said continuously maintaining said dead zone is carried out by feeding an inhibitor of polymerization through said optically transparent member, thereby creating a gradient of inhibitor in said dead zone and optionally in at least a portion of said gradient of polymerization zone. 17. The method of claim 16, wherein said inhibitor of polymerization is oxygen. 18. The method of claim 16, wherein said optically transparent member comprises a fluoropolymer. 19. A three-dimensional object produced by the method of claim 1. 20. The three-dimensional object of claim 19, wherein said object comprises a three-dimensional lattice structure.