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US-12624161-B2 - Water dispersible polymer for use in additive manufacturing

US12624161B2US 12624161 B2US12624161 B2US 12624161B2US-12624161-B2

Abstract

A water dispersible sulfopolymer for use as a material in the layer-wise additive manufacture of a 3D part made of a non water dispersible polymer wherein the water dispersible polymer is a reaction product of a metal sulfo monomer, the water dispersible sulfo-polymer being dispersible in water resulting in separation of the water dispersible polymer from the 3D part made of the non water dispersible polymer.

Inventors

  • William R. Priedeman, Jr.

Assignees

  • STRATASYS, INC.

Dates

Publication Date
20260512
Application Date
20211118

Claims (20)

  1. 1 . A water dispersible sulfo-polymer configured for use as a consumable feedstock in an additive manufacture of a part comprising a non water dispersible polyamide based polymer having a glass transition temperature ranging from 185° C. and 225° C., wherein the water dispersible sulfo-polymer is a reaction product of a sulfo monomer and the reaction product is a sulfo-polyamide with approximately 18 to 35% sulfoisophthalic monomer wherein the water dispersible sulfo-polymer has a glass transition temperature within ±20° C. of the glass transition temperature of the non water dispersible polyamide based polymer, the water dispersible sulfo-polymer being dispersible in water resulting in separation of the water dispersible polymer from the three-dimensional part comprising the non water dispersible polymer, wherein the consumable feedstock comprises a filament form or a powder having a charge control agent.
  2. 2 . The water dispersible polymer of claim 1 wherein the reaction product is a condensation reaction.
  3. 3 . The water dispersible polymer of claim 1 comprising approximately 20 to 35% sulfoisophthalic monomer.
  4. 4 . The water dispersible polymer of claim 1 comprising approximately 25 to 35% sulfoisophthalic monomer.
  5. 5 . The water dispersible polymer of claim 1 wherein the water dispersible polymer is substantially amorphous.
  6. 6 . The water dispersible polymer of claim 1 wherein the water dispersible polymer is at least semi-crystalline.
  7. 7 . The water dispersible polymer of claim 1 wherein the water dispersible polymer has a charge density of at least about 0.4 meq./g, suitable to exhibit water solubility or water dispersibility without the aid of any other solubility or dispersibility adjuvant.
  8. 8 . The water dispersible polymer of claim 1 wherein a sulfonated aromatic diacid or diol monomer is used in the formation of the reaction product.
  9. 9 . A water dispersible sulfo polymer configured for use as a consumable material in an additive manufacture of a non water dispersible polyamide based polymer part comprising: a non water dispersible polyamide based polymer, wherein the water dispersible polymer is a reaction product of a metal sulfo monomer, the reaction product is a sulfo-polyamide with approximately 18 to 35% sulfoisophthalic monomer, the water dispersible sulfopolymer being dispersible in water resulting in separation of the water dispersible polymer from the part comprising the non water dispersible polyamide based polymer, wherein the non water dispersible polyamide based polymer has a glass transition temperature ranging from 185° C. and 225° C. and the water dispersible sulfo polymer has a glass transition temperature of ±20° C. of the glass transition temperature of the non water dispersible polyamide based polymer, wherein the consumable feedstock comprises a filament form or a powder having a charge control agent.
  10. 10 . The water dispersible sulfopolymer of claim 9 wherein the reaction product is a condensation reaction.
  11. 11 . The water dispersible sulfo polymer of claim 9 comprising approximately 20 to 35% sulfoisophthalic monomer.
  12. 12 . The water dispersible sulfo polymer of claim 9 comprising approximately 25 to 35% sulfoisophthalic monomer.
  13. 13 . The water dispersible sulfo polymer of claim 9 wherein the water dispersible polymer is substantially amorphous.
  14. 14 . The water dispersible sulfo polymer of claim 9 wherein the water dispersible polymer is at least semi-crystalline.
  15. 15 . The water dispersible sulfo polymer of claim 9 wherein the water dispersible polymer has a charge density of at least about 0.4 meq./g, suitable to exhibit water solubility or water dispersibility without the aid of any other solubility or dispersibility adjuvant.
  16. 16 . A consumable feedstock material for use in an additive manufacturing system, the consumable feedstock material comprising: a water dispersible sulfo polymer comprising a reaction product of a sulfur monomer and the reaction product is a sulfo-polyamide with approximately 18 to 35% sulfoisophthalic monomer, wherein the consumable feedstock comprises a filament form or a powder having a charge control agent wherein the water dispersible sulfo polymer has a glass transition temperature within ±20° C. of the glass transition temperature of a non water soluble polyamide based part material having a glass transition temperature ranging from 185° C. and 225° C.
  17. 17 . The consumable feedstock material of claim 16 , wherein the reaction product includes approximately 20 to 35% sulfoisophthalic monomer.
  18. 18 . The consumable feedstock material of claim 16 , wherein the reaction product includes approximately 25 to 35% sulfoisophthalic monomer.
  19. 19 . The consumable feedstock material of claim 16 , wherein the water dispersible sulfo polymer is substantially amorphous.
  20. 20 . The consumable feedstock material of claim 16 , wherein the water dispersible sulfo polymer is at least semi-crystalline.

Description

CROSS-REFERENCE TO RELATED APPLICATION This Application is a divisional of U.S. Ser. No. 15/737,579, filed Dec. 18, 2017, which is a Section 371 National Stage Application of International Application No. PCT/US2016/038140, filed Jun. 17, 2016 and published as WO/2016/205690 on Dec. 22, 2016, which claims priority to U.S. Patent Application No. 62/182,159, filed Jun. 19, 2015, the contents of each of which are hereby incorporated by reference in their entireties. BACKGROUND The present disclosure relates to additive manufacturing systems for printing three-dimensional (3D) parts and support structures. In particular, the present disclosure relates to support and build materials for use in additive manufacturing systems, and methods of using the support and build materials as consumables in additive manufacturing systems to print printed items. Additive manufacturing is generally a process in which a three-dimensional (3D) object is manufactured utilizing a computer model of the objects. The basic operation of an additive manufacturing system consists of slicing a three-dimensional computer model into thin cross sections, translating the result into two-dimensional position data, and feeding the data to control equipment which manufacture a three-dimensional structure in a layerwise manner using one or more additive manufacturing techniques. Additive manufacturing entails many different approaches to the method of fabrication, including fused deposition modeling, ink jetting, selective laser sintering, powder/binder jetting, electron-beam melting, electrophotographic imaging, and stereolithographic processes. In a fused deposition modeling additive manufacturing system, a 3D part of model may be printed from a digital representation of the 3D part in a layer-by-layer manner by extruding a flowable part material along toolpaths. The part material is extruded through an extrusion tip carried by a print head of the system, and is deposited as a sequence of roads on a substrate in an x-y plane. The extruded part material fuses to previously deposited part material, and solidifies upon a drop in temperature. The position of the print head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane) after each layer is formed, and the process is then repeated to form a printed item resembling the digital representation. In an electrophotographic 3D printing process, each slice of the digital representation of the 3D part and its support structure is printed or developed using an electrophotographic engine. The electrophotographic engine generally operates in accordance with 2D electrophotographic printing processes, but with a polymeric toner. The electrophotographic engine typically uses a conductive support drum that is coated with a photoconductive material layer, where latent electrostatic images are formed by electrostatic charging, followed by image-wise exposure of the photoconductive layer by an optical source. The latent electrostatic images are then moved to a developing station where the polymeric toner is applied to charged areas, or alternatively to discharged areas of the photoconductive insulator to form the layer of the polymeric toner representing a slice of the 3D part. The developed layer is transferred to a transfer medium, from which the layer is transfused to previously printed layers with heat and/or pressure to build the 3D part. In fabricating printed items by depositing layers of a part material, supporting layers or structures are typically built underneath overhanging portions or in cavities of printed items under construction, which are not supported by the part material itself. A support structure may be built utilizing the same deposition techniques by which the part material is deposited. A host computer generates additional geometry acting as a support structure for the overhanging or free-space segments of the 3D part being formed. The support material adheres to the part material during fabrication, and is removable from the completed printed item when the printing process is complete. Prior art methods of removing support structure have included simply breaking the support structure off of the part material and then smoothing out any residual rough areas, or dissolving away soluble supports using a water-based solution. It is desirable to have a support structure that can be removed without special tool or solutions, and with minimal labor. A more easily removable support structure reduces time of manufacture of the part in addition to making the process of removing the support structure easier. SUMMARY A water dispersible sulfopolymer for use as a sacrificial support material in the layer-wise additive manufacture of a printed part made of a non water dispersible polymer, wherein the water dispersible polymer is a reaction product of a sulfo monomer, the water dispersible sulfopolymer being dispersible in water resulting in separation of the wat