Three-dimensional inkjet printing of a thermally stable object

Patent metadata

Field	Value
Publication number	US-12208567-B2
Application number	US-202318126512-A
Country	US
Kind code	B2
Filing date	Mar 27, 2023
Priority date	Sep 28, 2018
Publication date	Jan 28, 2025
Grant date	Jan 28, 2025

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, a second modeling material formulation and a third modeling material formulation, said dispensing being configured such that said first and second modeling material formulations form an inner region and said third modeling material formulation forms an outer region enveloping at least a portion of said inner region,
the method further comprising exposing each of said layers to a first curing condition, said first curing condition comprising irradiation; and
collectively exposing said plurality of layers to a second curing condition which comprises heat energy,
wherein:
said first modeling material formulation comprises a first curable material being a thermally-curable cyanate ester and a photoinitiator;
said second modeling material formulation comprises an activating agent for promoting polymerization of said cyanate ester, said activating agent being an aromatic amine, and a second curable material being a photocurable material comprising at least one multi-functional acrylic material that features, when hardened, a Tg of at least 150° C., and is devoid of said first curable material; and
said third modeling material formulation comprises a third curable material which is curable upon exposure to said first curing condition,
thereby fabricating the three-dimensional object.

2. The method of claim 1 , wherein said agent for promoting polymerization of said cyanate ester is selected from an aromatic primary amine, an aromatic secondary amine and a combination thereof.

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

4. 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.

5. The method of claim 1 , 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 modeling material formulations.

6. The method of claim 1 , wherein an amount of said aromatic amine ranges from 2 to 4, % by weight of the total weight of said first and second modeling material formulations.

7. The method of claim 1 , wherein an amount of said photoinitiator ranges from 0.5 to 1.5%, by weight, of the total weight of said first and second modeling material formulations.

8. The method of claim 1 , wherein a total amount of said first curable material ranges from 50 to 80, or from 60 to 80, or from 60 to 70, %, by weight, of the total weight of said first and second modeling material formulations.

9. The method of claim 1 , wherein upon exposure to said first curing condition, a change in a hardening parameter of the third modeling material formulation is higher than a change in a hardening parameter of the first and second modeling material formulations.

10. The method of claim 1 , wherein said third modeling material formulation comprises at least one UV-curable material and a photoinitiator.

11. The method of claim 1 , wherein a thickness of said outer region ranges from 0.1 to 2 mm.

12. The method of claim 1 , wherein at least one of said first modeling material formulation, said second modeling material formulation and said third modeling material formulation comprises at least one non-curable material selected from a surface active agent, an inhibitor, an antioxidant, a filler, a pigment, a dye and a dispersant.

13. A kit comprising at least a first modeling material formulation, a second modeling material formulation and a third modeling material formulation, said at least first, second and third modeling material formulations being for use in additive manufacturing of a three-dimensional object that comprises, in at least a portion thereof, a cyanate ester-containing polymeric network, wherein:
said first modeling material formulation comprises a first curable material being a thermally-curable cyanate ester and a photoinitiator;
said second modeling material formulation comprises an activating agent for promoting polymerization of said cyanate ester, said activating agent being an aromatic amine, and a second curable material, said second curable material comprising at least one multi-functional acrylic material that features, when hardened, a Tg of at least 150° C., and is devoid of said first curable material; and
said third modeling material formulation comprises a third curable material which is curable upon exposure to irradiation.

14. The kit of claim 13 , wherein said first, said second and said third modeling material formulations are separately packaged within the kit.

15. The kit of claim 13 , wherein said agent for promoting polymerization of said cyanate ester is selected from an aromatic primary amine, an aromatic secondary amine, and a combination thereof.

16. The kit of claim 13 , wherein said second modeling material formulation further comprises a metal species that promotes polymerization of said cyanate ester.

17. The kit of claim 13 , 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 modeling material formulations.

18. The kit of claim 13 , wherein an amount of said aromatic amine ranges from 2 to 4, % by weight of the total weight of said first and second modeling material formulations.

19. The kit of claim 13 , wherein an amount of said photoinitiator ranges from 0.5 to 1.5%, by weight, of the total weight of said first and second modeling material formulations.

20. The kit of claim 13 , wherein a total amount of said first curable material ranges from 50 to 80, or from 60 to 80, or from 60 to 70, %, by weight, of the total weight of said first and second modeling material formulations.

21. The kit of claim 13 , wherein said third modeling material formulation and said first and second modeling material formulations are selected such that upon exposure to irradiation, a change in a hardening parameter of the third modeling material formulation is higher than a change in a hardening parameter of the first and second modeling material formulations.

22. The kit of claim 13 , wherein said third modeling material formulation comprises at least one UV-curable material and a photoinitiator.

23. The kit of claim 13 , wherein at least one of said first modeling material formulation, said second modeling material formulation and said third modeling material formulation comprises at least one non-curable material selected from a surface active agent, an inhibitor, an antioxidant, a filler, a pigment, a dye and a dispersant.

Assignees

• Stratasys Ltd

Inventors

• Kuno Lev

Classifications

• C09D11/38

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

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B33Y10/00

  Processes of additive manufacturing · CPC title