Non-Isocyanate Polyurethane Inks for 3D Printing

• US 20170260418A1
• Filed: 03/08/2017
• Published: 09/14/2017
• Est. Priority Date: 03/08/2016
• Status: Active Grant

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Inventors: Wu, Bo, Banning, Jeffery, Xu, Pingyong
• Granted Patent: US 10,316,214 B2
• Time in Patent Office: Days
• CPC Class Codes: B29C 64/112 using individual droplets, e.g. from jetting heads
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2105/0058 Liquid or visquous
• 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: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: C09D 11/10 based on artificial resins
• CPC Class Codes: C09D 11/101 Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• CPC Class Codes: C09D 11/54 Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
• CPC Class Codes: C09D 175/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• CPC Class Codes: C09D 4/00 Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Abstract

In one aspect, inks for use with a 3D printer are described herein. In some embodiments, an ink described herein comprises a cyclic carbonate monomer and an amine monomer. Further, in some instances, an ink described herein also comprises an ethylenically unsaturated monomer such as a (meth)acrylate. Additionally, an ink described herein, in some cases, further comprises a colorant, such as a molecular dye, a particulate inorganic pigment, or a particulate organic colorant. An ink described herein may also comprise one or more additives selected from the group consisting of inhibitors, stabilizing agents, photoinitiators, and photosensitizers.

Claims

1. An ink for use in a three-dimensional printing system comprising:

a cyclic carbonate monomer; and

an amine monomer.

2. The ink of claim 1, wherein the cyclic carbonate monomer comprises two cyclic carbonate moieties.

3. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A1), Formula (A2), Formula (A3), or Formula (A4):

4. The ink of claim 3, wherein the cyclic carbonate monomer has the structure of Formula (A6):

5. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A9):

6. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A10), Formula (A11), Formula (A12), or Formula (A13):

7. The ink of claim 1, wherein the cyclic carbonate monomer comprises one or more (meth)acrylate moieties.

8. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A14) or Formula (A15):

9. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A17) or Formula (A18):

10. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A20):

11. The ink of claim 1, wherein the cyclic carbonate monomer has the structure of Formula (A21):

12. The ink of claim 1, wherein the amine monomer comprises two amine moieties.

13. The ink of claim 1, wherein the amine monomer has the structure of Formula (B1):

H₂N—

R₁₀—

NH₂ 

 

(B1),

wherein R₁₀ is a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

14. The ink of claim 1, wherein the amine monomer comprises at least one secondary or tertiary amine moiety.

15. The ink of claim 1 further comprising a (meth)acrylate.

16. 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.

17. The method of claim 16, wherein the ink comprises one or more (meth)acrylates and the method further comprises curing the (meth)acrylates with UV light and thermally curing the cyclic carbonate monomer and the amine monomer.

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

19. The article of claim 18, wherein:

the cyclic carbonate monomer and the amine monomer, when cured, together form a polyurethane;

the ink comprises one or more (meth)acrylates;

the one or more (meth)acrylates, when cured, forms a poly(meth)acrylate; and

the polyurethane and the poly(meth)acrylate together form an interpenetrating polymer network.