Methods of using thermoplastic polyurethanes in fused deposition modeling and systems and articles thereof

Patent metadata

Field	Value
Publication number	US-2016333152-A1
Application number	US-201515111277-A
Country	US
Kind code	A1
Filing date	Jan 16, 2015
Priority date	Jan 17, 2014
Publication date	Nov 17, 2016
Grant date	—

Abstract

The present invention relates to systems and methods for solid freeform fabrication, especially fused deposition modeling, as well as various articles made using the same, where the systems and methods utilize certain thermoplastic polyurethanes which are particularly suited for such processing. The useful thermoplastic polyurethanes are derived from (a) a polyisocyanate component, (b) a polyol component, and (c) an optional chain extender component where the resulting thermoplastic polyurethane has a crystallization temperature above 80° C. and retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

First claim

1 . A system for solid freeform fabrication of a three-dimensional object, comprising: a solid freeform fabrication apparatus that deposits small beads of building materials in a controlled manner;
wherein said building materials comprises a thermoplastic polyurethane derived from (a) a polyisocyanate component, (b) a polyol component, and (c) an optional chain extender component; wherein the resulting thermoplastic polyurethane has a crystallization temperature above 80° C.; and wherein the resulting thermoplastic polyurethane retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

2 . A method of fabricating a three-dimensional object, comprising the step of: (I) operating a system for solid freeform fabrication of an object;
wherein said system comprises a solid freeform fabrication apparatus that deposits small beads of building materials in a controlled manner; so as to form the three-dimensional object; wherein said building materials comprises a thermoplastic polyurethane derived from (a) a polyisocyanate component, (b) a polyol component, and (c) an optional chain extender component; wherein the resulting thermoplastic polyurethane has a crystallization temperature above 80° C.; and wherein the resulting thermoplastic polyurethane retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

3 . An article of manufacturing, fabricated by a system for solid freeform fabrication of an object, comprising: a solid freeform fabrication apparatus that deposits small beads of building materials in a controlled manner;
wherein said building materials comprises a thermoplastic polyurethane derived from (a) a polyisocyanate component, (b) a polyol component, and (c) an optional chain extender component; wherein the resulting thermoplastic polyurethane has a crystallization temperature above 80° C.; and wherein the resulting thermoplastic polyurethane retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

4 . The system of claim 1 , wherein said solid freeform fabrication apparatus comprises (a) a plurality of dispensing heads; (b) a building material supply apparatus configured to supply a plurality of building materials to said fabrication apparatus; and (c) a control unit configured for controlling said fabrication apparatus and said building material supply apparatus, based on an operation mode selected from a plurality of predetermined operation modes;

5 . The system of claim 1 , wherein said solid freeform fabrication apparatus comprises a fused deposition modeling apparatus.

6 . The system of claim 1 , wherein the mole ratio of the chain extender to the polyol is greater than 1.5.

7 . The system of claim 1 , wherein the polyol has a number average molecular weight of at least 900.

8 . The system of claim 1 , wherein the polyisocyanate component comprises an aromatic diisocyanate.

9 . The system of claim 1 , wherein the polyisocyanate component comprises 4,4′-methylenebis(phenyl isocyanate).

10 . The system of claim 1 , wherein the polyol component comprises a polyether polyol, a polyester polyol, or a combination thereof.

11 . The system of claim 1 , wherein the polyol component comprises poly(tetramethylene ether glycol), polybutylene adipate, or a combination thereof.

12 . The system of claim 1 , wherein the chain extender component comprises a linear alkylene diol.

13 . The system of claim 1 , wherein the chain extender component comprises 1,4-butanediol.

14 . The system of claim 1 , wherein the thermoplastic polyurethane further comprises one or more colorants, antioxidants (including phenolics, phosphites, thioesters, and/or amines), antiozonants, stabilizers, inert fillers, lubricants, inhibitors, hydrolysis stabilizers, light stabilizers, hindered amines light stabilizers, benzotriazole UV absorber, heat stabilizers, stabilizers to prevent discoloration, dyes, pigments, inorganic and organic fillers, reinforcing agents, or any combinations thereof.

15 . The article of claim 3 wherein said article comprises cook and storage ware, furniture, automotive components, toys, sportswear, medical devices, personalized medical articles, replicated medical implants, dental articles, sterilization containers, drapes, gowns, filters, hygiene products, diapers, films, sheets, tubes, pipes, wire jacketing, cable jacketing, agricultural films, geomembranes, sporting equipment, cast film, blown film, profiles, boat and water craft components, crates, containers, packaging, labware, office floor mats, instrumentation sample holders, liquid storage containers, packaging material, medical tubing and valves, a footwear component, a sheet, a tape, a carpet, an adhesive, a wire sheath, a cable, a protective apparel, an automotive part, a coating, a foam laminate, an overmolded article, an automotive skin, an awning, a tarp, a leather article, a roofing construction article, a steering wheel, a powder coating, a powder slush molding, a consumer durable, a grip, a handle, a hose, a hose liner, a pipe, a pipe liner, a caster wheel, a skate wheel, a computer component, a belt, an applique, a footwear component, a conveyor or timing belt, a glove, a fiber, a fabric, or a garment.

16 . A medical device fabricated from a system for solid freeform fabrication, wherein the medical device is manufactured by a solid freeform fabrication apparatus that deposits small beads of building materials in a controlled manner; wherein the building materials comprise a thermoplastic polyurethane derived from (a) a polyisocyanate component, (b) a polyol component, and (c) an optional chain extender component; wherein the resulting thermoplastic polyurethane has a crystallization temperature above 80° C.; and wherein the resulting thermoplastic polyurethane retains more than 20% of its shear storage modulus at 100° C. relative to its shear storage modulus at 20° C.

Assignees

• Lubrizol Advanced Mat Inc

Inventors

• Cook John M
• Vontorcik Jr Joseph J
• Ault Edward W

Classifications

• C08L75/06 Primary

  from polyesters · CPC title

• C08L75/08

  from polyethers · CPC title

• B29K2075/00

  Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material · CPC title

• C08J2375/06

  from polyesters · CPC title

• C08L75/04 Primary

  Polyurethanes · CPC title