Polyglycolic acid support material for additive manufacturing systems

• US 9,714,318 B2
• Filed: 07/26/2013
• Issued: 07/25/2017
• Est. Priority Date: 07/26/2013
• Status: Active Grant

• Current Assignee: Stratasys Incorporated
• Original Assignee: Stratasys Incorporated
• Inventors: Graley, Christopher Scott, Jaker, Vittorio L., Orrock, James E.
• Primary Examiner(s): BUTTNER, DAVID J
• Application Number:
  US13/951,629
• Publication Number:
  US 20150028523A1
• Time in Patent Office: 1,460 Days
• CPC Class Codes: B29B 2009/125 Micropellets, microgranules, microparticles
• CPC Class Codes: B29B 9/12 characterised by structure or composition
• CPC Class Codes: B29B 9/16 Auxiliary treatment of granules
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/118 using filamentary material being melted, e.g. fused deposition modelling [FDM]
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: C08G 63/06 derived from hydroxycarboxylic acids
• CPC Class Codes: C08G 63/912 derived from hydroxycarboxylic acids
• CPC Class Codes: C08G 81/00 Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers involving only carbon-to-carbon unsaturated bond reactions C08F299/00 ; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42
• CPC Class Codes: C08K 3/04 Carbon
• CPC Class Codes: C08K 3/40 Glass
• CPC Class Codes: G03G 15/224 Machines for forming tactile or three dimensional images by electrographic means, e.g. braille, 3d printing
• CPC Class Codes: G03G 15/225 using contact-printing

Abstract

A support material for use in an additive manufacturing system, which compositionally includes a polyglycolic acid polymer, which is at least partially soluble in an aqueous solution, and which is configured for use in the additive manufacturing system for printing a support structure in coordination with printing of a three-dimensional part.

Claims

1. A support material for use in an additive manufacturing system, the support material comprising:

a composition in a filament form or a powder form and comprising a polyglycolic acid polymer wherein the polyglycolic acid polymer comprises about 80% or more by weight of the composition, the polyglycolic acid polymer having at least one extension bonded to the PGA polymer, wherein the extension comprises;

a linkage group bonded to the PGA polymer wherein the linkage group is selected from the group consisting of an epoxy group, an isocyanate group, and an anhydride group prior to bonding with the PGA polymer wherein the linkage group comprises about 0.1% by weight to about 5% by weight of the composition; and

a terminal group bonded to the linkage group, wherein the terminal group comprises a polymer chain wherein the terminal group comprises about 1% by weight to less than about 20% by weight of the composition wherein the polymer chain of the terminal group is derived from a thermoplastic material selected from the group consisting of polyethersulfone polysulfone, polyphenylsulfone, polycarbonate, polyamide, and mixtures thereof;

wherein the support material is configured for use in the additive manufacturing system for printing a support structure from the support material in coordination with printing of a three-dimensional part and wherein the support material has a heat deflection temperature ranging from about 150°

C. to less than about 220°

C.; and

wherein the composition is at least partially soluble in an aqueous solution.

2. The support material of claim 1, wherein the linkage group is bonded to the PGA polymer at a terminal location of the PGA polymer.

3. The support material of claim 1, wherein the linkage group is bonded to a non-terminal monomer unit of the PGA polymer.

4. The support material of claim 1, wherein the composition has a heat deflection temperature ranging from about 160°

C. to about 175°

C.

5. The support material of claim 1, wherein the powder form has a particle size in the range of about 15 micrometers to about 125 micrometers.

6. The support material of claim 1, wherein the polyglycolic acid polymer comprises between about 85% and 95% by weight of the composition.

7. The support material of claim 1, wherein the linkage group comprises between about 0.2% and about 2.5% by weight of the composition.

8. The support material of claim 1, wherein the terminal group comprises between about 5% and about 15% by weight of the composition.

9. A support material for use in an additive manufacturing system, the support material comprising:

a composition in a filament form or a powder form and comprising a polyglycolic acid polymer filled with carbon or glass, wherein the polyglycolic acid polymer comprises about 80% or more by weight of the composition, the polyglycolic acid polymer having at least one extension bonded to the PGA polymer, wherein the extension comprises;

a linkage group bonded to the PGA polymer wherein the linkage group is selected from the group consisting of an epoxy group, an isocyanate group, and an anhydride group prior to bonding with the PGA polymer wherein the linkage group comprises about 0.1% by weight to about 5% by weight of the composition; and

a terminal group bonded to the linkage group, wherein the terminal group comprises a polymer chain wherein the terminal group comprises about 1% by weight to less than about 20% by weight of the composition;

wherein the support material is configured for use in the additive manufacturing system for printing a support structure from the support material in coordination with printing of a three-dimensional part and wherein the support material has a heat deflection temperature ranging from about 150°

C. to less than about 220°

C.; and

wherein the composition is at least partially soluble in an aqueous solution.

10. The support material of claim 9, wherein the linkage group is bonded to the PGA polymer at a terminal location of the PGA polymer.

11. The support material of claim 9, wherein the linkage group is bonded to a non-terminal monomer unit of the PGA polymer.

12. The support material of claim 9, wherein the polymer chain of the terminal group is derived from a thermoplastic material selected from the group consisting of polyethersulfone polysulfone, polyphenylsulfone, polycarbonate, polyamide, and mixtures thereof.

13. The support material of claim 9, wherein the composition has a heat deflection temperature ranging from about 160°

C. to about 175°

C.

14. The support material of claim 9, wherein the powder form has a particle size in the range of about 15 micrometers to about 125 micrometers.

15. The support material of claim 9, wherein the polyglycolic acid polymer comprises between about 85% and 95% by weight of the composition.

16. The support material of claim 9, wherein the linkage group comprises between about 0.2% and about 2.5% by weight of the composition.

17. The support material of claim 9, wherein the terminal group comprises between about 5% and about 15% by weight of the composition.

18. A method for printing a three-dimensional part with an additive manufacturing system, the method comprising:

providing a support material in filament or powder form wherein the support material has a heat deflection temperature ranging from about 150°

C. to less than about 220°

C. and wherein the support material comprising a polyglycolic acid (PGA) polymer wherein the polyglycolic acid polymer comprises about 80% or more by weight of the composition, wherein at least a portion of the PGA polymer has monomer units with a structure;

19. The method of claim 18, wherein the support material has a heat deflection temperature ranging from about 160°

C. to about 175°

C.

20. The method of claim 18, wherein the part material comprises a thermoplastic polymer selected from the group consisting of polyethersulfone polysulfone, polyphenylsulfone, polyetherimide, and mixtures thereof.

21. The method of claim 18, wherein printing the layers of a support structure comprises:

feeding the support material to a print head;

melting the fed support material in the print head; and

extruding the molten support material from the print head.

22. The method of claim 18, wherein printing the layers of a support structure comprises:

developing the layers with an electrophotography engine;

transferring the developed layers to a layer transfusion assembly; and

transfusing the transferred layers to previously-transfused layers.

23. The method of claim 18, wherein the PGA polymer further comprises the chain extension bonded to a terminal location of the PGA polymer.

24. The method of claim 18, wherein the terminal group comprises a polymer chain derived from a terminal compound that is substantially miscible with the part material.

25. The method of claim 18, wherein the PGA polymer further comprises a branched extension grafted to a non-terminal monomer unit of the PGA polymer.