Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening

Patent metadata

Field	Value
Publication number	US-10968307-B2
Application number	US-201816133890-A
Country	US
Kind code	B2
Filing date	Sep 18, 2018
Priority date	Jun 23, 2014
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

A method of forming a three-dimensional object is carried out by: (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, the polymerizable liquid including a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid polymer scaffold from the first component and also advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

First claim

We claim:

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 mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component, wherein said second solidifiable component comprises monomers and/or prepolymers polymerizable by ring-opening polymerization and/or comprises monomers and/or prepolymers polymerizable by reaction of amine and ester groups;
(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) subsequent to said irradiating step, heating, microwave irradiating, or both heating and microwave irradiating, said second solidifiable component in said three-dimensional intermediate to form said three-dimensional object.

2. The method of claim 1 , wherein said second component comprises a polymerizable liquid solubilized in or suspended in said first component.

3. The method of claim 1 , wherein said second component comprises:
(i) a polymerizable solid suspended in said first component;
(ii) a polymerizable solid solubilized in said first component; or
(iii) a polymer solubilized in said first component.

4. The method of claim 1 , wherein said three-dimensional intermediate is collapsible or compressible.

5. The method of claim 1 , wherein said three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network formed from said first component and said second component.

6. The method of claim 1 , wherein said polymerizable liquid comprises:
from 1 percent by weight to 30 percent by weight of said first component; and
from 70 percent by weight to 99 percent by weight of said second component.

7. The method of claim 1 , wherein step (d) is carried out by heating said second component.

8. The method of claim 1 , wherein: said second component comprises the precursors to a polyurethane, polyurea, or copolymer thereof, and step (d) is carried out by heating.

9. The method of claim 1 , wherein said monomers and/or prepolymers polymerizable by ring-opening polymerization in said second component comprise lactams, lactones, siloxanes, epoxides, cyclic ethers, imines, or cyclic acetals, and step (d) is carried out by heating.

10. The method of claim 1 , said first component comprising 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.

11. The method of claim 1 , wherein said three-dimensional object comprises an interpenetrating polymer network (IPN).

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

13. The method of claim 1 , wherein said three-dimensional 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.

14. The method of claim 1 , wherein the object is produced by bottom-up stereolithography.

15. 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 mixture of (i) a light polymerizable liquid first component, said first component comprising monomers and/or prepolymers comprising reactive end groups selected from the group consisting of acrylates and methacrylates, and (ii) a second solidifiable component that is different from said first component, wherein said second solidifiable component comprises monomers and/or prepolymers polymerizable by ring-opening polymerization and/or comprises monomers and/or prepolymers polymerizable by reaction of amine and ester groups;
(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) subsequent to said irradiating step, heating second solidifiable component in said three-dimensional intermediate to form said three-dimensional object.

16. The method of claim 15 , wherein said monomers and/or prepolymers polymerizable by ring-opening polymerization comprises lactams, lactones, siloxanes, epoxides, cyclic ethers, imines, or cyclic acetals.

17. The method of claim 15 , wherein said three-dimensional object comprises an interpenetrating polymer network (IPN).

18. The method of claim 15 , wherein the object is produced by bottom-up stereolithography.

Assignees

• Carbon Inc

Inventors

• Rolland Jason P
• Chen Kai
• Poelma Justin
• Goodrich James
• Pinschmidt Robert
• Desimone Joseph M
• Robeson Lloyd M

Classifications

• B29K2105/251

  Particles, powder or granules (expandable particles B29K2105/046) · CPC title

• B29K2105/0091

  IPN, i.e. interpenetrating polymer networks · CPC title

• B29K2105/0073

  Solution · CPC title

• B29C64/286

  Optical filters, e.g. masks · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title