High-temperature soluble support material for additive manufacturing

• US 10,675,853 B2
• Filed: 05/13/2015
• Issued: 06/09/2020
• Est. Priority Date: 05/16/2014
• Status: Active Grant

• Current Assignee: Stratasys Incorporated
• Original Assignee: Stratasys Incorporated
• Inventors: Pawloski, Adam R., Zhu, Jiayi, Kaske, Kent, Rodgers, Luke M. B., Sherar, Theresa
• Primary Examiner(s): Yi, Stella K
• Application Number:
  US15/311,719
• Publication Number:
  US 20170087774A1
• Time in Patent Office: 1,854 Days
• 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: B29K 2025/08 Copolymers of styrene, e.g. AS or SAN, i.e. acrylonitrile styrene B29K2055/02 takes precedence
• CPC Class Codes: B29K 2033/08 Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
• CPC Class Codes: B29K 2105/0085 Copolymers
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 2438/02 Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]

Abstract

A support material for use in an additive manufacturing system, which includes a thermoplastic copolymer polymerized from monomers comprising acid-functional monomers having carboxylic acid groups, and one or more non-acid-functional monomers, where a portion of the carboxylic acid groups are neutralized with a base having an alkali metal cation. The thermoplastic copolymer has a high glass transition temperature and melt processing temperature, and is thermally stable at its melt processing temperature. The neutralized thermoplastic copolymer is soluble in an alkaline aqueous solution.

Claims

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

printing the three-dimensional part with a part material with a glass transition temperature greater than 160°

C., and a support structure with a support material wherein the glass transition temperature of the support material is higher than about 150°

C. and within about 10°

C. of the glass transition temperature of the part material, the melt processing temperature is greater than about 220°

C. and wherein the support material comprises a thermoplastic copolymer comprising carboxylic acid groups wherein a portion of the carboxylic acid groups are neutralized to form carboxylic acid salt groups wherein the amount of carboxylic acid salt groups in the thermoplastic copolymer of the support material is controlled to control the glass transition temperature of the support material.

2. The method of claim 1, further comprising disintegrating at least a portion of the support structure in an alkaline aqueous solution.

3. The method of claim 1, wherein the carboxylic acid groups are neutralized by basic substances selected from the group consisting of potassium bicarbonate, potassium hydroxide, sodium hydroxide and lithium hydroxide.

4. The method of claim 1, wherein the carboxylic acid salt groups comprise a cation selected from the group consisting of potassium ions, sodium ions and lithium ions.

5. The method of claim 1, wherein the neutralization of the carboxyl acid groups is performed by melt processing.

6. The method of claim 1, wherein the melt processing temperature of the thermoplastic copolymer with the carboxylic acid salt groups is greater than the melt processing temperature of the thermoplastic copolymer prior to being neutralized.

7. The method of claim 1, wherein the thermoplastic copolymer is polymerized from monomers comprising one or more acid-functional monomers comprising one or more (meth)acrylic acid monomers and from monomers comprising one or more non-acid-functional monomers comprising one or more ethylenically-unsaturated aromatic monomers.

8. The method of claim 1, wherein the thermoplastic copolymer further comprises one or more second acid-functional monomers having carboxyl acid groups and one or more second additional, non-acid monomers functional monomers.

9. The method of claim 1, wherein the thermoplastic copolymer further comprises one or more additives selected from the group consisting of impact modifiers, heat stabilizers, antioxidants, and combinations thereof.

10. The method of claim 1, wherein the thermoplastic copolymer has a glass transition temperature greater than about 160°

C. and a melt processing temperature greater than about 250°

C.

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

printing the three-dimensional part by extruding a part material in a plurality of layers comprising a plurality of roads, wherein the part material has a glass transition temperature greater than about 160°

C., and

printing a support structure by extruding a support material in a plurality of layers, wherein the support structure provides support for the three-dimensional part as the part is being printed, wherein the glass transition temperature of the support material is higher than about 150°

C., the melt processing temperature is greater than about 220°

C. and wherein the support material comprises a thermoplastic copolymer comprising carboxylic acid groups wherein a portion of the carboxylic acid groups are neutralized to form carboxylic acid salt groups, wherein a concentration of carboxylic acid salt groups is utilized to control the glass transition temperature of the support material.

12. The method of claim 11, further comprising disintegrating at least a portion of the support structure in an alkaline aqueous solution.

13. The method of claim 11, wherein the carboxylic acid groups are neutralized by basic substances selected from the group consisting of potassium bicarbonate, potassium hydroxide, sodium hydroxide and lithium hydroxide.

14. The method of claim 11, wherein the carboxylic acid salt groups comprise a cation selected from the group consisting of potassium ions, sodium ions and lithium ions.

15. The method of claim 11, wherein the thermoplastic copolymer is polymerized from monomers comprising one or more acid-functional monomers comprising one or more (meth)acrylic acid monomers and from monomers comprising one or more non-acid-functional monomers comprising one or more ethylenically-unsaturated aromatic monomers.

16. The method of claim 11, wherein the thermoplastic copolymer further comprises one or more second acid-functional monomers having carboxyl acid groups and one or more second additional, non-acid monomers functional monomers.

17. The method of claim 11, wherein the thermoplastic copolymer further comprises one or more additives selected from the group consisting of impact modifiers, heat stabilizers, antioxidants, and combinations thereof.

18. The method of claim 11, wherein the thermoplastic copolymer has a glass transition temperature greater than about 160°

C. and a melt processing temperature greater than about 250°

C.