IP Library Granted Patent US 11,390,771
Granted Patent B2
US 11,390,771 · App. 16/340,749 · Granted Jul 19, 2022

Filaments comprising ionomers and use in fused filament fabrication

Inventor: Lynda Kaye Johnson (Wilmington, DE)
Assignee: Dow Global Technologies LLC
C09D123/0876B29C64/118B33Y10/00B33Y70/00C08F210/02B29K2023/08B29K2033/00B29K2995/0077C08F2800/20C08F2810/50
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Quick Facts
Patent No.
US 11,390,771
App. No.
16/340,749
Granted
Jul 19, 2022
Kind
B2
Abstract

The disclosure generally relates to 3D printed articles prepared from filaments comprising an ionomer (A) prepared from a base resin (B); wherein: base resin (B) is prepared from ethylene and at least one C 3 to C 8 α,β ethylenically unsaturated carboxylic acid monomer; the carboxylic acid moieties of base resin (B) are 10 to 99.5 percent neutralized by zinc or lithium; the at least one C 3 to C 8 α,β ethylenically unsaturated carboxylic acid is present from about 2 weight percent to about 30 weight percent, based on the weight of base resin (B).

Claims (27)

1. A 3D printed article prepared from a conditioned or unconditioned filament, said filament comprising an ionomer (A), said ionomer (A) prepared from a base resin (B);

wherein:

base resin (B) is prepared from ethylene and at least one C 3 to C 8 α, β ethylenically unsaturated carboxylic acid monomer;

the carboxylic acid moieties of base resin (B) are 10 to 99.5 percent neutralized by zinc or lithium;

the at least one C 3 to C 8 α, β ethylenically unsaturated carboxylic acid is present from about 2 weight percent to about 30 weight percent, based on the weight of base resin (B).

2. The 3D printed article of claim 1 wherein base resin (B) has a melt index of 20 to 250 g/10 minutes or less when measured according to ASTM D1238-13 using a 2.16 kg. weight.

3. The 3D printed article of claim 1 wherein ionomer (A) has a relative percent neutralization of 8 or less.

4. The 3D printed article of claim 1 wherein ionomer (A) has a relative percent neutralization of 7 or less.

5. The 3D printed article of claims 1 and 2 wherein the C 3 to C 8 α, β ethylenically unsaturated carboxylic acid is present from 2 weight percent to 18 weight percent.

6. The 3D printed article of claim 1 wherein ionomer (A) has a melt index of at least about 1 to 20 g/10 minutes using a 2.16 kg weight measured according to ASTM D1238-13.

7. The 3D printed article of claim 1 which, when in the shape of ISO 527-2 test bars, exhibits a vertical relative strength of greater than 2.

8. The 3D printed article of claim 1 which, when in the shape of ISO 527-2 test bars, exhibits a vertical relative strength of greater than 3.

9. The 3D printed article of claim 1 which, when in the shape of ISO 527-2 test bars, exhibits a vertical relative strength which is at least 50 percent greater than the vertical relative strength of an identical 3D printed article but wherein the ionomer is neutralized with sodium ions or magnesium ions.

10. The 3D printed article of claim 1 which, when in the shape of ISO 527-2 test bars, exhibits a nominal strain at break of greater than 20 percent.

11. The 3D printed article of claim 1 which, when in the shape of a hollow single-wall cylinder and tested according to the Temperature Range Test, exhibits a temperature range greater than 60.

12. The 3D printed article of claim 1 wherein the filament is unconditioned.

13. The 3D printed article of claim 1 which, when in the shape of a hollow single-wall cylinder and tested according to the Temperature Range Test, exhibits a temperature range greater than 20.

14. The 3D printed article of claim 2 which, when in the shape of a hollow single-wall cylinder and tested according to the Temperature Range Test, exhibits no macroscopic bubbles at one or more temperatures greater than 170° C.

15. The 3D printed article of claim 1 in which the filament diameter ranges from 1.5 to 3.1 mm.

16. The 3D printed article of claim 1 prepared by the deposition of one or more lines by fused filament deposition.

17. A process for making a 3D printed article from a conditioned or unconditioned filament, said process comprising the step of depositing a plurality of layers using a 3D printer to form said 3D printed article wherein said filament comprises an ionomer (A) prepared from a base resin (B);

wherein:

base resin (B) is prepared from ethylene and at least one C 3 to C 8 α, β ethylenically unsaturated carboxylic acid monomer;

the carboxylic acid moieties of base resin (B) are 10 to 99.5 percent neutralized by zinc or lithium;

the at least one C 3 to C 8 α, β ethylenically unsaturated carboxylic acid is present from about 2 weight percent to about 30 weight percent, based on the weight of base resin (B).

18. The process of claim 17 wherein base resin (B) has a melt index of 20 to 250 g/10 minutes or less when measured according to ASTM D1238-13 using a 2.16 kg. weight.

19. The process of claim 17 wherein ionomer (A) has a relative percent neutralization of about 8 or less.

Assignments (5)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 14, 2021
From: PERFORMANCE MATERIALS NA, INC.
To: THE DOW CHEMICAL COMPANY
Reel/Frame 057813/0792 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 14, 2021
From: THE DOW CHEMICAL COMPANY
To: DOW GLOBAL TECHNOLOGIES LLC
Reel/Frame 057813/0928 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 10, 2021
From: JOHNSON, LYNDA KAYE
To: E I DU PONT DE NEMOURS AND COMPANY
Reel/Frame 056812/0549 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 10, 2021
From: DUPONT POLYMERS, INC.
To: PERFORMANCE MATERIALS NA, INC.
Reel/Frame 056812/0551 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 10, 2021
From: E. I. DU PONT DE NEMOURS AND COMPANY
To: DUPONT POLYMERS, INC.
Reel/Frame 056821/0413 →
Cited By (1)
US 12,663,241