Dual-cure resins and related methods

• US 10,316,213 B1
• Filed: 05/01/2017
• Issued: 06/11/2019
• Est. Priority Date: 05/01/2017
• Status: Active Grant

• Current Assignee: Formlabs Incorporated
• Original Assignee: Formlabs Incorporated
• Inventors: Arndt, Eric, Lyon, Gayla, Zguris, Zachary
• Primary Examiner(s): Harlan, Robert D.
• Application Number:
  US15/583,083
• Time in Patent Office: 771 Days
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08G 18/089 Reaction retarding agents
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/2081 containing at least two non-condensed heterocyclic rings
• CPC Class Codes: C08G 18/246 containing also tin-carbon bonds
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/3281 containing three hydroxy groups
• CPC Class Codes: C08G 18/3838 containing cyano groups
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group
• CPC Class Codes: C09D 175/02 Polyureas
• CPC Class Codes: C09D 175/04 Polyurethanes

Abstract

The present disclosure relates generally to curable resins, in particular dual-cure resins, and related methods for use in an additive fabrication (e.g., 3-dimensional printing) device.

Claims

1. A dual-cure resin for use in additive manufacturing, comprising:

a photo-curable component configured to cure when subjected to an effective amount of actinic radiation; and

a secondary component comprising a plurality of encapsulants containing a first secondary precursor species, wherein the plurality of encapsulants are configured to degrade, when subjected to a degrading event, and release the first secondary precursor species for secondary curing.

2. The dual-cure resin of claim 1, wherein the degrading event comprises application of an effective amount of heat.

3. The dual-cure resin of claim 1, wherein the degrading event comprises application of an effective mechanical force.

4. The dual-cure resin of claim 3, wherein the effective mechanical force comprises a vibrational force.

5. The dual-cure resin of claim 1, wherein the degrading event comprises introduction of a chemical species comprising at least one of a solvent or a catalyst.

6. The dual-cure resin of claim 1, wherein the encapsulant comprises a wax or polymer shell.

7. The dual-cure resin of claim 1, wherein the secondary component comprises a second secondary precursor species configured to react with the released secondary precursor species to produce a secondary polymer.

8. The dual-cure resin of claim 7, wherein the first secondary precursor species comprises at least one chain extender species.

9. The dual-cure resin of claim 8, wherein the at least one chain extender species comprises at least one of a polyamine species or a polyol species.

10. The dual-cure resin of claim 7, wherein the second secondary precursor species comprises a diisocyanate species.

11. The dual-cure resin of claim 1, wherein the secondary component is configured to produce a secondary polymer selected from the group consisting of polyurethane and polyurea.

12. The dual-cure resin of claim 1, wherein the dual-cure resin is configured to have a shelf-life of at least six months.

13. The dual-cure resin of claim 1, wherein the dual-cure resin is configured to have a viscosity of between 1 cP and 10,000 cP at 30°

C.

14. A method of producing an additively-manufactured article, comprising:

providing a dual-cure resin comprising a photo-curable component and a secondary component, the secondary component comprising a plurality of encapsulants containing a first secondary precursor species, the secondary component further comprising a second secondary precursor species;

subjecting the photo-curable component to actinic radiation to produce a photo-cured polymer;

subjecting the secondary component to a degrading event to degrade the plurality of encapsulants and release the first heat-curable precursor species; and

reacting the first secondary precursor species with the second secondary precursor species to produce a secondary polymer,

wherein the photo-cured polymer and the secondary polymer form an additively-manufactured article.

15. The method of claim 14, wherein subjecting the secondary component to a degrading event comprises applying an effective amount of heat.

16. The method of claim 14, wherein subjecting the secondary component to a degrading event comprises applying an effective vibrational force.

17. The method of claim 14, wherein subjecting the secondary component to a degrading event comprises introducing a chemical species comprising at least one of a solvent or a catalyst.

18. The method of claim 14, wherein the step of subjecting the photo-curable component to actinic radiation to produce the photo-cured polymer comprises forming successive layers of the photo-cured polymer to produce a green article comprising the secondary component.

19. The method of claim 18, wherein the step of subjecting the secondary component to the degrading event comprises subjecting the green article to the degrading event to degrade the plurality of encapsulants within the green article and release the first secondary precursor species within the green article.

20. The method of claim 19, wherein the step of reacting the first secondary precursor species with the second secondary precursor species comprises reacting the first secondary precursor species with the second secondary precursor species in the green article to produce the additively-manufactured article.