Formulations usable in additive manufacturing of a three-dimensional object made of a soft material

Patent metadata

Field	Value
Publication number	US-11939468-B2
Application number	US-202218076478-A
Country	US
Kind code	B2
Filing date	Dec 7, 2022
Priority date	Jul 28, 2017
Publication date	Mar 26, 2024
Grant date	Mar 26, 2024

Abstract

Modeling material formulations and formulation systems usable in additive manufacturing of a three-dimensional object, featuring, when hardened, a Shore A hardness lower than 10 and/or a Shore 00 hardness lower than 40, are provided. Additive manufacturing processes utilizing these formulations and formulation systems, and three-dimensional objects obtainable thereby, are also provided.

First claim

What is claimed is:

1. A method of additive manufacturing of a three-dimensional object featuring, in at least a portion thereof, a Shore A hardness lower than 10 or a Shore 00 hardness lower than 40, the method comprising sequentially forming a plurality of layers in a configured pattern corresponding to the shape of the object, thereby forming the object,
wherein the formation of each of at least a few of said layers comprises dispensing at least one modeling material formulation, and exposing the dispensed modeling material to curing energy to thereby form a cured modeling material,
said at least one modeling material formulation comprising:
a mono-functional curable material, in an amount of from 50 to 89 weight percent, the mono-functional curable material selected from the group consisting of ethoxylated nonylphenyl acrylate, isodecyl acrylate, lauryl acrylate and ethoxylated lauryl acrylate;
a non-curable polymeric material, in an amount ranging from 10 to 49 weight percent, the non-curable polymeric material selected from the group consisting of polypropylene glycol and block copolymers of polyethylene glycol and polypropylene glycol;
a multi-functional curable material, in an amount ranging from 1 to 10 weight percent, the multi-functional curable material selected from the group consisting of urethane diacrylate, aliphatic triacrylate and epoxy diacrylate,
wherein:
(i) said non-curable polymeric material features a molecular weight of at least 1000 Daltons; and/or
(ii) said non-curable polymeric material features a Tg lower than 0° C.; and/or
(iii) at least 80 weight percents of the total amount of said mono-functional and said multi-functional curable materials include curable materials having, when hardened, a Tg lower than 0° C.,
the curable formulation featuring, when hardened, a Shore A hardness lower than 10 or a Shore 00 hardness lower than 40.

2. The method of claim 1 , wherein a ratio of the total amount of said mono-functional and said multi-functional curable materials and the amount of said non-curable polymeric material ranges from 4:1 to 1.1:1, or from 3:1 to 2:1.

3. The method of claim 1 , wherein an amount of said mono-functional curable material ranges from 50 to 60 weight percent, or from 55 to 60 weight percent.

4. The method of claim 1 , wherein an amount of said multi-functional curable material ranges from 3 to 10 weight percent, or from 5 to 10 weight percent.

5. The method of claim 1 , wherein said non-curable polymeric material features a molecular weight of at least 1000 Daltons; and a Tg lower than 0° C.

6. The method of claim 1 , wherein:
said non-curable polymeric material comprises polypropylene glycol; and/or
said non-curable polymeric material is a block co-polymer that comprises at least one polypropylene glycol block; and/or
said non-curable polymeric material is a block co-polymer that comprises at least one polypropylene glycol block and at least one polyethylene glycol block, wherein a total amount of said polyethylene glycol in said block co-polymer is no more than 10 weight percent, wherein a ratio of polypropylene glycol blocks and said polyethylene glycol blocks in said block-copolymer is at least 2:1; and/or
said non-curable polymeric material comprises a polypropylene glycol and/or a block co-polymer comprising at least one polypropylene glycol block, each featuring a molecular weight of at least 2000 Daltons.

7. The method of claim 1 , wherein said mono-functional curable material features, when hardened, a Tg lower than −10° C.

8. The method of claim 1 , wherein said multi-functional curable material features, when hardened, a Tg lower than −10° C.

9. The method of claim 1 , wherein said at least one modeling formulation comprises:
a mono-functional amphiphilic acrylate that comprises a hydrophobic moiety, in an amount of 25-35 weight percent;
a mono-functional hydrophobic acrylate, in an amount of 25-30 weight percent;
a multi-functional acrylate, in an amount of 5-10 weight percent; and
a non-curable polymeric material featuring a molecular weight of at least 1000 Daltons; and a Tg lower than 0° C., in an amount of 30-35 weight percent.

10. The method of claim 9 , wherein said non-curable polymeric material comprises a polypropylene glycol and/or a block co-polymer comprises at least one polypropylene glycol block, each featuring a molecular weight of at least 2000 Daltons.

11. The method of claim 9 , wherein said multi-functional acrylate is a urethane diacrylate.

12. The method of claim 9 , wherein said mono-functional amphiphilic acrylate comprises a hydrocarbon chain of at least 6 carbon atoms and at least 2 alkylene glycol groups.

13. The method of claim 9 , wherein said mono-functional hydrophobic acrylate comprises a hydrocarbon chain of at least 8 carbon atoms.

14. The method of claim 1 , wherein said at least one modeling formulation is characterized, when hardened, by at least one of:
Tear Resistance of at least 150 N/m; and
Compression Modulus at least 0.01 MPa.

15. The method of claim 1 , wherein said at least one modeling formulation is devoid of a biological material.

16. The method of claim 1 , wherein said at least one modeling formulation comprises less than 10% by weight water.

17. The method of claim 1 , comprising dispensing at least two modeling material formulations, at least one of said modeling material formulations being said formulation featuring, when hardened, a Shore A hardness lower than 10 or a Shore 00 hardness lower than 40, and at least one of said modeling material formulations being an elastomeric curable formulation comprising at least one elastomeric curable material.

18. The method of claim 17 , wherein said elastomeric curable formulation further comprises silica particles.

19. The method of claim 1 , wherein said at least one modeling material formulation comprises a first modeling material formulation and a second modeling material formulation, said first modeling material formulation is said modeling material formulation featuring, when hardened, a Shore A hardness lower than 10 or a Shore 00 hardness lower than 40, wherein a Shore scale A hardness of said second modeling material formulation is higher than a Shore scale A hardness of said first modeling material formulation, and wherein said dispensing comprises forming voxel elements containing different building material formulations at interlaced locations over said layer, and wherein a ratio between a number of voxels occupied by said first modeling material formulation and a number of voxels occupied by said second modeling material formulation is from about 6 to about 9.

20. The method of claim 19 , wherein voxel elements containing said second modeling material formulation form a volumetric fibrous pattern in the object.

21. The method of claim 19 , further comprising forming from said second modeling material formulation a shell coating the object.

22. The method of claim 17 , further comprising forming from said elastomeric curable formulation a shell coating the object, and removing said shell following a completion of said additive manufacturing of said three-dimensional object.

23. A three-dimensional object prepared by the method of claim 1 , the object comprising at least one portion which features a Shore A hardness lower than 10 or a Shore 00 hardness lower than 40.

24. The object of claim 23 , featuring at least a shape, a mechanical property and a vis

Assignees

• Stratasys Ltd

Inventors

• Amiel-Levy Mazi
• Lupo Shiran
• Ely Tal
• Dikovsky Daniel

Classifications

• C08L71/02 Primary

  Polyalkylene oxides · CPC title

• B29C64/106

  using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material · CPC title

• B29C64/393

  for controlling or regulating additive manufacturing processes · CPC title

• B33Y40/00

  Auxiliary operations or equipment, e.g. for material handling · CPC title

• B33Y40/10

  Pre-treatment · CPC title