IP Library Granted Patent US 11,396,136
Granted Patent B2
US 11,396,136 · App. 17/097,032 · Granted Jul 26, 2022

3D printing support structures incorporating sacrificial materials

Inventors: Carolyn P. Moorlag (Mississauga, CA); Nan-Xing Hu (Oakville, CA); Valerie M. Farrugia (Oakville, CA)
Assignee: Xerox Corporation
B29C64/40B29K2069/00B33Y40/00B33Y70/00
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Quick Facts
Patent No.
US 11,396,136
App. No.
17/097,032
Granted
Jul 26, 2022
Kind
B2
Abstract

The present teachings according to various embodiments provides a support material for 3D printing. The support material includes poly(alkylene carbonate) having a decomposition temperature of from 100° C. to about 300° C.

Claims (29)

1. A method of printing a three-dimensional article, the method comprising;

printing a build material;

printing a support material, wherein the support material comprises poly(alkylene carbonate), wherein the support material supports the build material, wherein the support material comprises particles having a size of from 3 to 250 microns, wherein the particles include a core comprising an inert material of from 5 weight percent to about 50 weight percent of the support material, and wherein the balance of the support material includes a poly(alkylene carbonate) having a tunable decomposition temperature of from 100° C. to about 300° C.; and

heating the support material to a temperature above the decomposition temperature of the support material wherein the support material decomposes.

2. The method according to claim 1 , wherein the poly(alkylene carbonate) is selected from the group consisting of: poly(propylene carbonate), poly(ethylene carbonate), poly(butylene carbonate) and poly(cyclohexene carbonate), poly(norbornene carbonate), and poly(cyclohexene propylene carbonate).

3. The method according to claim 1 , wherein the inert material is selected from the group consisting of: silica, titania, alumina, carbon, glass, metal, cellulose, and a synthetic polymer.

4. The method according to claim 1 , wherein the support material further comprises an additive selected from a group consisting of: a cyclodextrin, an organic acid, a photo acid generator, a photo base generator, a thermal acid generator, and a thermal base generator.

5. The method according to claim 4 , wherein a concentration of the additive is about 0.1 to about 5 weight percent based on the weight of the poly(alkylene carbonate).

6. The method according to claim 4 , wherein the organic acid comprises a carboxylic acid containing from about 5 to about 30 carbon atoms.

7. The method according to claim 4 , wherein the photo acid generator or the thermal acid generator comprises a diphenyliodonium salt, a benzyl sulfonate ester, an imino sulfonate ester, and a spiropyran-based sulfonic acid.

8. The method according to claim 4 , wherein the photo base generator comprises 2-(9-oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene salt or 1,5,7 e triaza-bicyclo [4.4.0]dec-5-ene tetraphenylborate.

9. The method to claim 1 , wherein the poly(alkylene carbonate) has a molecular weight (Mw) ranging from about 10,000 to about 500,000.

10. A method of printing a three-dimensional article, the method comprising;

printing a build material;

printing a support material, wherein the support material comprises poly(alkylene carbonate), wherein the support material supports the build material, wherein the support material comprises poly(alkylene carbonate) filaments having a diameter of from 0.5 millimeters to 15 millimeters, wherein the poly(alkylene carbonate) filaments comprise an inert material of from 5 weight percent to about 50 weight percent of the support material, and wherein the balance of the support material includes a poly(alkylene carbonate) having a tunable decomposition temperature of from 100° C. to about 300° C.; and

heating the support material to a temperature above the decomposition temperature of the support material wherein the support material decomposes.

11. The method according to claim 10 , wherein the poly(alkylene carbonate) filaments are selected from the group consisting of: poly(propylene carbonate), poly(ethylene carbonate), poly(butylene carbonate) and poly(cyclohexene carbonate), poly(norbornene carbonate), and poly(cyclohexene propylene carbonate).

12. The method according to claim 10 , wherein the inert material is selected from the group consisting of: silica, titania, alumina, carbon, glass, metal, cellulose, and a synthetic polymer.

13. The method according to claim 10 , wherein the poly(alkylene carbonate) filaments further comprises an additive selected from a group consisting of: a cyclodextrin, an organic acid, a photo acid generator, a photo base generator, a thermal acid generator, and a thermal base generator.

14. The method according to claim 13 , wherein a concentration of the additive is about 0.1 to about 5 weight percent based on the weight of the poly(alkylene carbonate).

15. The method according to claim 13 , wherein the organic acid comprises a carboxylic acid containing from about 5 to about 30 carbon atoms.

16. The method according to claim 13 , wherein the photo acid generator or the thermal acid generator comprises a diphenyliodonium salt, a benzyl sulfonate ester, an imino sulfonate ester, and a spiropyran-based sulfonic acid.

17. The method according to claim 13 , wherein the photo base generator comprises 2-(9-oxoxanthen-2-yl)propionic Acid 1,5,7-Triazabicyclo[4.4.0]dec-5-ene salt or 1,5,7 e triaza-bicyclo [4.4.0]dec-5-ene tetraphenylborate.

18. The method to claim 10 , wherein the poly(alkylene carbonate) has a molecular weight (Mw) ranging from about 10,000 to about 500,000.

19. A method of printing a three-dimensional article, the method comprising;

printing a build material;

printing a support material, wherein the support material comprises particles having a size of from 3 to 250 microns, wherein the particles include a core comprising an inert material of from 5 weight percent to about 50 weight percent of the support material, wherein the balance of the support material includes a poly(alkylene carbonate) having a tunable decomposition temperature of from 100° C. to about 300° C. and an additive selected from a group consisting of: a cyclodextrin, an organic acid, a photo acid generator, a photo base generator, a thermal acid generator, and a thermal base generator, wherein the support material supports the build material; and

heating the support material to a temperature above the decomposition temperature of the poly(alkylene carbonate) wherein the poly(alkylene carbonate) decomposes.

20. The method according to claim 19 , wherein the poly(alkylene carbonate) is selected from the group consisting of: poly(propylene carbonate), poly(ethylene carbonate), poly(butylene carbonate) and poly(cyclohexene carbonate), poly(norbornene carbonate), and poly(cyclohexene propylene carbonate).

Assignments (10)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 14, 2025
From: XEROX CORPORATION
To: GENESEE VALLEY INNOVATIONS, LLC
Reel/Frame 073562/0677 →
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 →
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 Feb 13, 2024
From: XEROX CORPORATION
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 066741/0001 →
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 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 13, 2020
From: MOORLAG, CAROLYN P.; HU, NAN-XING; FARRUGIA, VALERIE M.
To: XEROX CORPORATION
Reel/Frame 054356/0738 →
Continuity (2)
Division 16123625 · Sep 6, 2018
Related Publication 20210060867A1 · Mar 4, 2021