Inks for 3D printing having low polymerization shrinkage

Patent metadata

Field	Value
Publication number	US-11370928-B2
Application number	US-201916691249-A
Country	US
Kind code	B2
Filing date	Nov 21, 2019
Priority date	Nov 30, 2018
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

Abstract

In one aspect, inks for use with a three-dimensional (3D) printing system are described herein. In some embodiments, an ink described herein comprises 20-60 wt. % oligomeric curable material; 10-50 wt. % cyclocarbonate (meth)acrylate monomer; and 0.1-5 wt. % photoinitiator, based on the total weight of the ink. Additionally, in some cases, the ink further comprises one or more additional curable materials differing from the oligomeric curable material and the cyclocarbonate (meth)acrylate monomer. An ink described herein, in some embodiments, also comprises one or more additional component that are non-curable.

First claim

The invention claimed is:

1. An ink for use in three-dimensional printing, the ink comprising:
20-60 wt. % oligomeric curable material;
15-50 wt. % cyclocarbonate (meth)acrylate monomer; and
0.1-5 wt. % photoinitiator, based on the total weight of the ink,
wherein the oligomeric curable material comprises one or more ethylenically unsaturated species having a weight average molecular weight of 500-6,000;
wherein the cyclocarbonate (meth)acrylate monomer has the structure of Formula (A1):

wherein R 1 is selected from the group consisting of a linear or branched C1-C6 alkylene moiety, an alkylene-carbonate moiety, an alkylene-ester moiety, and an alkylene-amide moiety and
R 2 is H or CH 3 ; and
wherein the amounts of at least the oligomeric material, the cyclocarbonate, and the photoinitiator are selected such that the ink, when cured, exhibits a tear strength of 30 to 200 kN/m when measured according to ASTM D624.

2. The ink of claim 1 , wherein the oligomeric curable material comprises one or more ethylenically unsaturated species having a dynamic viscosity of 1,000 to 250,000 cP at 50° C., when measured according to ASTM D2983.

3. The ink of claim 2 , wherein the oligomeric curable material comprises one or more ethylenically unsaturated species having a dynamic viscosity of 1,000 to 200,000 cP at 50° C., when measured according to ASTM D2983.

4. The ink of claim 1 , wherein the oligomeric curable material comprises one or more aliphatic urethane (meth)acrylates.

5. The ink of claim 1 , wherein the oligomeric curable material is present in the ink in an amount of 25-50 wt. %, based on the total weight of the ink.

6. The ink of claim 1 , wherein R 1 is a linear or branched C1-C4 alkylene moiety.

7. The ink of claim 1 , wherein R 2 is H.

8. The ink of claim 1 , wherein R 1 is CH 2 and R 2 is H.

9. The ink of claim 1 , wherein the cyclocarbonate (meth)acrylate monomer is present in the ink in an amount of 20-30 wt. %, based on the total weight of the ink.

10. The ink of claim 1 , wherein the ink further comprises one or more additional curable materials differing from the oligomeric curable material and the cyclocarbonate (meth)acrylate monomer.

11. The ink of claim 10 , wherein the additional curable materials comprise an additional monomeric curable material.

12. The ink of claim 10 , wherein the additional curable materials comprise an additional oligomeric curable material.

13. The ink of claim 1 , further comprising at least one colorant.

14. The ink of claim 1 , further comprising at least one filler.

15. The ink of claim 1 , further comprising at least one inhibitor, at least one stabilizing agent, or a combination thereof.

16. The ink of claim 1 , wherein the dynamic viscosity of the uncured ink is greater than 100 cP at 25° C., when measured according to ASTM D2983.

17. The ink of claim 16 , wherein the dynamic viscosity of the uncured ink is greater than 100 cP and less than 5000 cP at 25° C., when measured according to ASTM D2983.

18. The ink of claim 1 , wherein the ink, when cured, exhibits a volumetric polymerization shrinkage of no greater than 5% compared to the ink when uncured, wherein the volumetric polymerization shrinkage is measured according to ASTM D792.

19. The ink of claim 1 , wherein the ink, when cured, exhibits a notched Izod impact strength of 50 to 200 J/m when measured according to ASTM D256.

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

21. The method of claim 20 further comprising photocuring the ink.

22. A method of printing a three-dimensional article comprising:
retaining an ink in a fluid state in a container;
selectively applying energy to the ink in the container to solidify at least a portion of a first fluid layer of the ink, thereby forming a first solidified layer that defines a first cross-section of the article;
raising or lowering the first solidified layer to provide a second fluid layer of the ink at a surface of the fluid ink in the container; and
selectively applying energy to the ink in the container to solidify at least a portion of the second fluid layer of the ink, thereby forming a second solidified layer that defines a second cross-section of the article, the first cross-section and the second cross-section being bonded to one another in a z-direction,
wherein the ink comprises the ink of claim 1 .

23. The method of claim 22 , wherein selectively applying energy to the ink in the container comprises photocuring the ink.

24. The method of claim 22 , wherein the method of printing has a print speed of 20-60 mm/hour.

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

26. The ink of claim 1 , wherein the ink, when cured, exhibits a tear strength of 80 to 200 kN/m when measured according to ASTM D624.

27. The ink of claim 1 , wherein the ink, when cured, is at least 70% cross-linked.

Assignees

• 3D Systems Incorporated
• 3D Systems Inc

Inventors

• Moussa Khalil

Classifications

• B33Y70/10 Primary

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• B29C64/124 Primary

  using layers of liquid which are selectively solidified · CPC title

• B22F10/40

  Structures for supporting workpieces or articles during manufacture and removed afterwards · CPC title

• B22F12/63

  Rollers · CPC title

• B22F10/12

  by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP] · CPC title