Method of three-dimensional printing

• US 10,323,156 B2
• Filed: 07/31/2017
• Issued: 06/18/2019
• Est. Priority Date: 11/10/2014
• Status: Active Grant

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Sacripante, Guerino G., Zhou, Ke
• Primary Examiner(s): Tentoni, Leo B
• Application Number:
  US15/664,952
• Publication Number:
  US 20170327704A1
• Time in Patent Office: 687 Days
• Field of Search: 264237, 264308, 26433121
• CPC Class Codes: B29C 2948/92695 Viscosity; Melt flow index [MFI]; Molecular weight
• CPC Class Codes: B29C 2948/92704 Temperature
• CPC Class Codes: B29C 48/001 Combinations of extrusion moulding with other shaping operations
• CPC Class Codes: B29C 48/022 characterised by the choice of material
• CPC Class Codes: B29C 48/05 Filamentary, e.g. strands
• CPC Class Codes: B29C 48/78 Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
• CPC Class Codes: B29C 48/911 Cooling
• CPC Class Codes: B29C 48/92 Measuring, controlling or regulating
• 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 64/30 Auxiliary operations or equipment
• CPC Class Codes: B29K 2067/00 Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2067/04 Polyesters derived from hydroxycarboxylic acids
• CPC Class Codes: B29K 2995/002 Coloured
• CPC Class Codes: B29K 2995/006 Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
• CPC Class Codes: B29L 2009/00 Layered products
• 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: B33Y 80/00 Products made by additive manufacturing
• CPC Class Codes: C09D 11/104 Polyesters

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

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.