IP Library Granted Patent US 10,323,156
Granted Patent B2
US 10,323,156 · App. 15/664,952 · Granted Jun 18, 2019

Method of three-dimensional printing

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Quick Facts
Patent No.
US 10,323,156
App. No.
15/664,952
Granted
Jun 18, 2019
Kind
B2
Abstract

A sustainable material suitable for three-dimensional printing is disclosed. The sustainable material comprises a resin derived from a bio-based diacid monomer and a bio-based glycol monomer. The resulting sustainable material provides a much more robust 3-D printing material with different properties than conventional materials.

Claims (39)

1. A method of printing comprising

providing a thermoplastic filament, wherein the thermoplastic filament further comprises

a sustainable resin derived from a bio-based diacid monomer and bio-based glycol monomer, wherein the bio-based diacid monomer is selected from the group consisting of succinic acid, 2,5-furandicarboxylic acid , itaconic acid and mixtures thereof, and the bio-based glycol monomer is selected from the group consisting of 1,4-butane-diol, 1,3-propane-diol and 1,2-propanediol and mixtures thereof; wherein the sustainable resin has a viscosity of from about 500 centipoise to about 2,000 centipoise at 100° C. to about 200 ° C.;

a colorant, and

an optional additive;

heating the thermoplastic filament to its melting point;

extruding the melted thermoplastic filament layer by layer; and

forming a three-dimensional object from the layers of melted thermoplastic filament.

2. The method of claim 1 , wherein the heating step is conducted at a temperature of from about 160 to about 260° C.

3. The method of claim 1 , further comprising cooling and solidifying the formed three-dimensional object.

4. The method of claim 1 , wherein the bio-based diacid monomer comprises succinic acid.

5. The method of claim 1 , wherein the bio-based diacid monomer comprises 2,5-furandicarboxylic acid.

6. The method of claim 1 , wherein the bio-based diacid monomer comprises itaconic acid.

7. The method of claim 1 , wherein the sustainable resin is derived from about 48 to about 52 percent by mole equivalent of bio-based diacid monomer, and from about 48 to about 52 percent by mole equivalent of the bio-based glycol monomer, provided that the sum of both is 100 percent.

8. The method of claim 1 , wherein the sustainable resin is selected from the group consisting of poly-(butylene-succinate), poly-(butylene-2,5-furanate), poly-(butylene-itaconate), poly-(propylene-succinate), poly-(propylene-2,5-furanate), poly-(propylene-itaconate), and mixtures thereof.

9. The method of claim 1 , wherein the weight average molecular weight of the sustainable resin is from about 10,000 grams/mole to about 500,000 grams/mole.

10. The method of claim 1 , wherein the sustainable resin has a softening point of from about 120 ° C. to about 200 ° C.

11. The method of claim 1 , wherein the sustainable resin has a freezing point of from about 20° C. to about 60° C.

12. The method of claim 1 , wherein the sustainable resin has a melting point of from about 75° C. to about 150° C.

13. The method of claim 1 , wherein the sustainable resin has a Young's Modulus of from about 0.5 to about 5 gigapascals.

14. The method of claim 1 , wherein the sustainable resin has a Yield Stress of from about 10 to about 100 megapascals.

15. The method of claim 1 , wherein the sustainable resin is present in the thermoplastic filament in an amount of from about 85% to about 100% by weight.

16. A method of printing comprising

providing a thermoplastic filament, wherein the thermoplastic filament further comprises

a sustainable resin derived from a bio-based succinic acid and 1,4-butane-diol, wherein the sustainable resin is poly-(butylene-succinate) having a weight average molecular weight of from about 10,000 grams/mole to about 500,000 grams/mole; wherein the sustainable resin has a viscosity of from about 500 centipoise to about 2,000 centipoise at 100° C. to about 200 ° C.;

a colorant, and

an optional additive;

heating the thermoplastic filament to its melting point;

extruding the melted thermoplastic filament layer by layer; and

forming a three-dimensional object from the layers of melted thermoplastic filament.

17. The method of claim 16 , wherein the sustainable resin has a Young's Modulus of from about 0.5 to about 5 gigapascals and a Yield Stress of from about 10 to about 100 megapascals.

18. A method of printing comprising

providing a thermoplastic filament, wherein the thermoplastic filament further comprises

a sustainable resin derived from a bio-based succinic acid and 1,4-butane-diol; wherein the sustainable resin is poly-(butylene-succinate) having a weight average molecular weight of from about 10,000 grams/mole to about 500,000 grams/mole; wherein the sustainable resin has a Yield Stress of from about 20 to about 80 megapascals; wherein the sustainable resin has a viscosity of from about 500 centipoise to about 2,000 centipoise at 100° C. to about 200 ° C.; wherein the sustainable resin has a Tg of from about 50° C. to about 120° C.;

a colorant; and

an optional additive;

heating the thermoplastic filament to its melting point;

extruding the melted thermoplastic filament layer by layer; and

forming a three-dimensional object from the layers of melted thermoplastic filament.

Assignments (9)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 6, 2025
From: XEROX CORPORATION
To: GENESEE VALLEY INNOVATIONS, LLC
Reel/Frame 073842/0479 →
SECOND LIEN NOTES PATENT SECURITY AGREEMENT Recorded Jul 2, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 071785/0550 →
FIRST LIEN NOTES PATENT SECURITY AGREEMENT Recorded Apr 11, 2025
From: XEROX CORPORATION
To: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, AS COLLATERAL AGENT
Reel/Frame 070824/0001 →
SECURITY INTEREST Recorded Feb 13, 2024
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 066741/0001 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS RECORDED AT RF 064760/0389 Recorded Feb 13, 2024
From: CITIBANK, N.A., AS COLLATERAL AGENT
To: XEROX CORPORATION
Reel/Frame 068261/0001 →
SECURITY INTEREST Recorded Nov 20, 2023
From: XEROX CORPORATION
To: JEFFERIES FINANCE LLC, AS COLLATERAL AGENT
Reel/Frame 065628/0019 →
SECURITY INTEREST Recorded Jun 22, 2023
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 064760/0389 →
RELEASE OF SECURITY INTEREST IN PATENTS AT R/F 062740/0214 Recorded May 18, 2023
From: CITIBANK, N.A., AS AGENT
To: XEROX CORPORATION
Reel/Frame 063694/0122 →
SECURITY INTEREST Recorded Nov 10, 2022
From: XEROX CORPORATION
To: CITIBANK, N.A., AS AGENT
Reel/Frame 062740/0214 →