Thiol-ene inks for 3D printing

Patent metadata

Field	Value
Publication number	US-11826925-B2
Application number	US-202117403338-A
Country	US
Kind code	B2
Filing date	Aug 16, 2021
Priority date	Apr 7, 2016
Publication date	Nov 28, 2023
Grant date	Nov 28, 2023

Abstract

In one aspect, inks for use with a three-dimensional printing system are described herein. In some embodiments, an ink described herein comprises a thiol monomer component and an ene monomer component. Moreover, in some cases, an ink described herein further comprises an additional (meth)acrylate monomer component differing from the ene monomer component. In some such cases, the additional (meth)acrylate monomer component can be polymerized separately from the thiol and ene monomers of the ink.

First claim

That which is claimed:

1. An ink for use in a three-dimensional printing system comprising:
up to 30 wt. % thiol monomer, the thiol monomer comprising a secondary thiol monomer; and
up to 90 wt. % of at least one of an ene monomer and an ene oligomer, based on the total weight of the ink,
wherein the thiol monomer is present in at least a detectable amount.

2. The ink of claim 1 , further comprising 0.1-5 wt. % photoinitiator, based on the total weight of the ink.

3. The ink of claim 1 , wherein the thiol monomer comprises pentaerythritol tetrakis(3-mercaptobutylate).

4. The ink of claim 1 , wherein the thiol monomer comprises a plurality of differing thiol-containing species.

5. The ink of claim 1 , further comprising a (meth)acrylate monomer that differs from the at least one of an ene monomer and an ene oligomer.

6. The ink of claim 1 , comprising up to 20 wt. % thiol monomer.

7. The ink of claim 1 , further comprising an inhibitor and/or a stabilizing agent.

8. A kit for use in a three-dimensional printing system, the kit comprising:
a first ink comprising up to 30 wt. % thiol monomer, the thiol monomer comprising pentaerythritol tetrakis(3-mercaptobutylate); and
a second ink comprising at least one of an ene monomer and an ene oligomer, the ene monomer or ene oligomer comprising a ethylenically unsaturated moiety; wherein
the thiol monomer and the ene monomer are not combined prior to printing.

9. The kit of claim 8 , wherein the second ink comprises a (meth)acrylate monomer that differs from the at least one ene monomer and ene oligomer.

10. The kit of claim 8 , wherein the first ink comprises a plurality of differing thiol-containing species.

11. The kit of claim 8 , wherein at least one of the first ink and the second ink comprise 0.1-5 wt. % photoinitiator, based on the total weight of the first ink and the second ink.

12. The kit of claim 8 , wherein at least one of the first ink and the second ink comprise an inhibitor and/or a stabilizing agent.

13. The kit of claim 8 , wherein the first ink comprises a plurality of thiol moieties.

14. A printed three-dimensional article formed from the ink of claim 1 .

15. A method of printing a three-dimensional article comprising:
Selectively depositing layers of an ink in a fluid state onto a substrate, wherein the ink comprises the ink of claim 1 .

16. The method of claim 15 , wherein the layers are deposited according to an image of the three-dimensional article in a computer readable format.

17. The method of claim 15 , wherein the ink comprises a (meth)acrylate monomer differing from the at least one ene monomer and ene oligomer, and the method comprises further UV curing the (meth)acrylate monomer.

18. The method of claim 15 , wherein the thiol monomer comprises pentaerythritol tetrakis(3-mercaptobutylate).

19. The method of claim 15 , further comprising thermally curing the thiol monomer and the at least one ene monomer and ene oligomer.

Assignees

• 3D Systems Incorporated
• 3D Systems Inc

Inventors

• Fong John
• Xu Pingyong

Classifications

• B28B1/001 Primary

  Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material (selective deposition modelling of metallic powder B22F10/00; rapid manufacturing of 3D objects in general and in particular of plastics B29C64/00) · CPC title

• B29C64/00

  Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering · CPC title

• B29C64/386

  Data acquisition or data processing for additive manufacturing · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title

• B33Y30/00

  Apparatus for additive manufacturing; Details thereof or accessories therefor · CPC title