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

Patent metadata

Field	Value
Publication number	US-12202971-B2
Application number	US-202418592619-A
Country	US
Kind code	B2
Filing date	Mar 1, 2024
Priority date	Jul 28, 2017
Publication date	Jan 21, 2025
Grant date	Jan 21, 2025

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 curable formulation comprising:
a mono-functional curable material, in an amount of from about 50 to about 89 weight percent, the mono-functional curable material being 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 about 10 to about 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; and
a multi-functional curable material, in an amount ranging from about 1 to about 10 weight percent, the multi-functional curable material selected from the group consisting of urethane diacrylate, aliphatic triacrylate and epoxy diacrylate,
the formulation featuring, when hardened, a Shore A hardness lower than 10 or a Shore 00 hardness lower than 40.

2. The curable formulation 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.

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

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

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

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

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

9. The curable formulation of claim 1 , wherein at least 80 weight percent of the total amount of said mono-functional and said multi-functional curable materials include curable materials featuring, when hardened, a Tg lower than 0° C.

10. The curable formulation of claim 1 , comprising:
a mono-functional amphiphilic acrylate that comprises a hydrophobic moiety, in an amount of from about 25 to about 35 weight percent;
a mono-functional hydrophobic acrylate, in an amount of from about 25 to about 30 weight percent;
a multi-functional acrylate, in an amount of from about 5 to about 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 from about 30 to about 35 weight percent.

11. The curable formulation of claim 10 , 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.

12. The curable formulation of claim 10 , wherein said multi-functional acrylate is a urethane diacrylate.

13. The curable formulation of claim 10 , wherein said mono-functional amphiphilic acrylate comprises a hydrocarbon chain of at least 6 carbon atoms and at least 2 alkylene glycol groups.

14. The curable formulation of claim 10 , wherein said mono-functional hydrophobic acrylate comprises a hydrocarbon chain of at least 8 carbon atoms.

15. The curable formulation of claim 1 , characterized, when hardened, by at least one of:
Tear Resistance of at least 150 N/m; and
Compression Modulus at least 0.01 MPa.

16. The curable formulation of claim 1 , being devoid of a biological material.

17. The curable formulation of claim 1 , comprising less than 10% by weight water.

18. A kit comprising the curable formulation of claim 1 ; and an elastomeric curable formulation comprising at least one elastomeric curable material, wherein each of said formulations is packaged individually within the kit.

19. The kit of claim 18 , wherein said elastomeric curable formulation further comprises silica particles.

20. 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 the curable formulation of claim 1 .

Assignees

• Stratasys Ltd

Inventors

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

Classifications

• B33Y40/10

  Pre-treatment · CPC title

• B33Y40/00

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

• C08K3/36

  Silica · CPC title

• B29K2105/0085

  Copolymers · CPC title

• B29K2071/02

  Polyalkylene oxides, e.g. PEO, i.e. polyethylene oxide, or derivatives thereof · CPC title