Three-dimensional inkjet printing of a thermally stable object

Patent metadata

Field	Value
Publication number	US-11235511-B2
Application number	US-201917280956-A
Country	US
Kind code	B2
Filing date	Sep 27, 2019
Priority date	Sep 28, 2018
Publication date	Feb 1, 2022
Grant date	Feb 1, 2022

Abstract

A formulation system usable in additive manufacturing of a three-dimensional object that comprises, in at least a portion thereof, a cyanate ester-containing polymeric network, and additive manufacturing processes employing the formulation system are provided. Also provided are objects obtainable by the additive manufacturing and kits containing the formulation system. The formulation system includes a first modeling material formulation which includes a first curable material which is a thermally-curable cyanate ester and a second modeling material formulation which comprises an activating agent for promoting polymerization of the cyanate ester and is devoid of the first curable material, and further includes a second curable material which is different from the first curable material, and optionally an agent for promoting hardening of the second curable material.

First claim

What is claimed is:

1. A method of fabricating a three-dimensional object by three-dimensional inkjet printing, the object comprising, in at least a portion thereof, a cyanate ester-containing polymeric network, the method comprising sequentially forming a plurality of layers in a configured pattern corresponding to the shape of the object, thereby fabricating the object,
wherein a formation of at least a portion of said layers comprises dispensing a first modeling material formulation which comprises a first curable material being a thermally-curable cyanate ester and a second modeling material formulation which comprises an activating agent for promoting polymerization of said cyanate ester and is devoid of said first curable material, said at least two modeling material formulations further comprise a second curable material being different from said first curable material, and optionally an agent for promoting hardening of said second curable material,
thereby fabricating the three-dimensional object.

2. The method of claim 1 , further comprising exposing each of said layers to a first curing condition for effecting hardening of said second curable material.

3. The method of claim 2 , wherein said first curable material and said first curing condition are such that a degree of polymerization of said cyanate ester is no more than 20%.

4. The method of claim 1 , further comprising exposing said layers to a second curing condition to thereby effect polymerization of said thermally-curable cyanate ester, said second curing condition comprising heat energy.

5. The method of claim 4 , wherein a formation of said at least a portion of said layers comprises:
repeating said dispensing of said at least two modeling material formulations, and said exposing of each of said layers to said first curing condition; and
collectively exposing said plurality of layers to said second curing condition.

6. The method of claim 1 , wherein said second curable material is a photocurable material, said first curing condition comprises irradiation, and said agent for promoting hardening of said second curable material is a photoinitiator.

7. The method of claim 6 , wherein said photocurable material features, when hardened, Tg of at least 150° C.

8. The method of claim 1 , wherein said second curable material is or comprises an acrylic material.

9. The method of claim 1 , wherein said agent for promoting polymerization of said cyanate ester is activatable upon said exposing to said first curing condition and/or to said second curing condition.

10. The method of claim 1 , wherein said agent for promoting polymerization of said cyanate ester is inactive or is partially active towards promoting polymerization of said cyanate ester prior to said exposing to said first curing condition and/or to said second curing condition, and wherein said at least two formulations further comprise an agent that activates said agent for promoting polymerization of said cyanate ester, said agent activates said agent for promoting polymerization of said cyanate ester upon exposure to said first curing condition and/or to said second curing condition.

11. The method of claim 1 , wherein said agent for promoting polymerization of said cyanate ester comprises a nucleophilic group.

12. The method of claim 11 , wherein said nucleophilic group is thiol or amine.

13. The method of claim 12 , wherein said amine is selected from a primary amine, a secondary amine and a combination thereof.

14. The method of claim 12 , wherein said agent for promoting polymerization of said cyanate ester is an aromatic amine.

15. The method of claim 1 , wherein said second formulation further comprises a metal species that promotes polymerization of said cyanate ester.

16. The method of claim 1 , wherein said at least two modeling material formulations further comprise an additional curable material which is capable of interacting with said cyanate ester to thereby form a co-polymeric network.

17. The method of claim 16 , wherein said additional curable material is or comprises an epoxy-containing curable material.

18. The method of claim 16 , wherein said additional curable material features a viscosity lower than 1,000, or lower than 500, centipoises, at room temperature.

19. The method of claim 1 , wherein a weight ratio of said first and said second modeling material formulations in each of said layers ranges from 50:50 to 70:30.

20. The method of claim 1 , wherein said first formulation comprises said first curable material and a photoinitiator and said second formulation comprises a multi-functional acrylic material that features, when hardened, a Tg of at least 150° C., and an aromatic amine.

21. The method of claim 20 , wherein a total amount of said multi-functional acrylic material ranges from 20 to 40, or from 20 to 30, or from 25 to 30, % by weight, of the total weight of said first and second formulations.

22. The method of claim 20 , wherein an amount of said aromatic amine ranges from 2 to 4, % by weight of the total weight of said first and second formulations.

23. The method of claim 20 , wherein an amount of said photoinitiator ranges from 0.5 to 1.5%, by weight, of the total weight of said first and second formulations.

24. The method of claim 20 , wherein said at least two formulations further comprise an additional curable material that is capable of interacting with said cyanate ester.

25. The method of claim 24 , wherein said additional curable material is included in the second modeling material formulation.

26. The method of claim 24 , wherein a total amount of said first curable material and said additional curable material, if present, ranges from 50 to 80, or from 60 to 80, or from 60 to 70, %, by weight, of the total weight of said at least two formulations.

27. The method of claim 1 , wherein forming said plurality of layers further comprises dispensing a third modeling material, said dispensing being configured such that said at least two formulations form an inner region and said third formulation forms an outer region enveloping at least a portion of said inner region.

28. The method of claim 27 , wherein said third modeling material formulation comprises a third curable material which is curable upon exposure to said first curing condition.

Assignees

• Stratasys Ltd

Inventors

• Kuno Lev

Classifications

• C09D11/38

  characterised by non-macromolecular additives other than solvents, pigments or dyes · CPC title

• C09D11/36

  based on non-aqueous solvents · CPC title

• C09D11/101

  Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title

• B29C64/112 Primary

  using individual droplets, e.g. from jetting heads · CPC title