Filament for material extrusion 3D printer molding and production method of molded body

Patent metadata

Field	Value
Publication number	US-11268214-B2
Application number	US-201715789536-A
Country	US
Kind code	B2
Filing date	Oct 20, 2017
Priority date	Apr 20, 2015
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

The present invention provides a filament for material extrusion 3D printer molding, which affords a molded article having soft texture and excellent heat resistance and among others, exhibits good moldability in molding by a material extrusion 3D printer. The present invention relates to a filament for material extrusion 3D printer molding, including a thermoplastic elastomer which contains at least a specific block copolymer and in which the ratio between storage modulus and loss modulus measured at 200° C. and 100 Hz by dynamic viscoelasticity measurement is in a specific range.

First claim

The invention claimed is:

1. A filament for material extrusion 3D printer molding, comprising:
a thermoplastic elastomer comprising at least one block copolymer selected from the group consisting of a first block copolymer comprising a polymer block P including 50% by weight or more of a structural unit derived from a vinyl aromatic compound and a polymer block Q including 50% by weight or more of a structural unit derived from conjugated diene and/or isobutylene, and a second block copolymer obtained by hydrogenating the first block copolymer,
wherein a ratio tan δ=Gδ[200° C., 100 Hz]/G′[200° C., 100 Hz] between storage modulus G′[200° C., 100 Hz] and loss modulus G″[200° C., 100 Hz] of the thermoplastic elastomer measured at 200° C. and 100 Hz by dynamic viscoelasticity measurement is from 0.50 to 2.50.

2. The filament according to claim 1 , wherein the thermoplastic elastomer further comprises
a softening agent capable of softening the thermoplastic elastomer.

3. The filament according to claim 2 , wherein the softening agent is included in an amount of from 30 to 400 parts by weight per 100 parts by weight of the at least one block copolymer.

4. The filament according to claim 1 , wherein the thermoplastic elastomer further comprises
a polyolefin resin.

5. The filament according to claim 4 , wherein the polyolefin resin comprises a polypropylene resin.

6. The filament according to claim 4 , wherein the polyolefin resin is included in an amount of from 10 to 300 parts by weight per 100 parts by weight of the at least one block copolymer.

7. The filament according to claim 1 , wherein the filament has a diameter of from 1.0 to 5.0 mm.

8. The filament according to claim 1 , wherein storage modulus G′[30° C., 1 Hz] of the thermoplastic elastomer measured at 30° C. and 1 Hz by dynamic viscoelasticity measurement is from 1×10 4 to 5×10 7 Pa.

9. The filament according to claim 8 , wherein storage modulus G′[200° C., 1 Hz] of the thermoplastic elastomer measured at 200° C. and 1 Hz by dynamic viscoelasticity measurement is 2×10 4 Pa or less.

10. The filament according to claim 9 , wherein G′[30° C., 1 Hz]/G′[200° C., 1 Hz] of the thermoplastic elastomer is from 5×10 −1 to 5×10 6 .

11. The filament according to claim 1 , wherein a melt flow rate (MFR) of the thermoplastic elastomer at 190° C. under a load of 1.20 kgf based on ISO 1133 is from 1 to 400 g/10 min.

12. The filament according to claim 1 , wherein a durometer A hardness of the thermoplastic elastomer is 90 or less.

13. A roll of the filament according to claim 1 .

14. A cartridge for material extrusion 3D printer molding, comprising:
a container in which the filament according to claim 1 is housed.

15. A method for producing a molded article, the method comprising:
molding the filament according to claim 1 with a material extrusion 3D printer.

16. A method for producing a molded article, the method comprising:
molding the filament according to claim 2 with a material extrusion 3D printer.

17. A method for producing a molded article, the method comprising:
molding the filament according to claim 3 with a material extrusion 3D printer.

18. A method for producing a molded article, the method comprising:
molding the filament according to claim 4 with a material extrusion 3D printer.

19. A method for producing a molded article, the method comprising:
molding the filament according to claim 5 with a material extrusion 3D printer.

20. A method for producing a molded article, the method comprising:
molding the filament according to claim 6 with a material extrusion 3D printer.

21. The method according to claim 15 , wherein the filament has a diameter of from 1.0 to 5.0 mm.

22. A method for producing a molded article, the method comprising:
molding the filament according to claim 8 with a material extrusion 3D printer.

23. A method for producing a molded article, the method comprising:
molding the filament according to claim 9 with a material extrusion 3D printer.

24. A method for producing a molded article, the method comprising:
molding the filament according to claim 10 with a material extrusion 3D printer.

25. A method for producing a molded article, the method comprising:
molding the filament according to claim 11 with a material extrusion 3D printer.

26. A method for producing a molded article, the method comprising:
molding the filament according to claim 12 with a material extrusion 3D printer.

27. The method according to claim 15 , wherein the filament is molded such that a temperature of a molten resin discharged from an extrusion head of the material extrusion 3D printer is from 180 to 250° C.

28. The method according to claim 15 , wherein the molding by the material extrusion 3D printer is based on a fused deposition modeling method.

29. The method according to claim 15 , wherein the molding by the material extrusion 3D printer is performed by discharging a molten resin from an extrusion head in a strand shape with a diameter of 0.01 to 1 mm.

30. The filament according to claim 1 , wherein the at least one block copolymer comprises a hydrogenated styrene-butadiene-styrene block copolymer.

Assignees

• Mcpp Innovation Llc
• Mitsubishi Chem Corp

Inventors

• Sano Jiro
• Ishihara Toshihisa
• Furomoto Shigeyuki

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08L23/02

  not modified by chemical after-treatment · CPC title

• D01F6/46

  of polyolefins · CPC title

• B29K2023/12

  PP, i.e. polypropylene · CPC title

• C08L53/02

  of vinyl-aromatic monomers and conjugated dienes · CPC title