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

Patent metadata

Field	Value
Publication number	US-11549012-B2
Application number	US-201816634173-A
Country	US
Kind code	B2
Filing date	Jul 27, 2018
Priority date	Jul 28, 2017
Publication date	Jan 10, 2023
Grant date	Jan 10, 2023

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 50 to 89 weight percents, 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 percents, 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 1 to 10 weight percents, 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 has a molecular weight of at least 1000 Daltons; and/or
(ii) said non-curable polymeric material has a Tg lower than 0; 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 having, when hardened, a Shore A hardness lower than 0 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, or from 3:1 to 2:1.

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

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

5. The curable formulation of claim 1 , wherein said non-curable polymeric material features a molecular weight of at least 1000, or at least 1500 or at least 2000 Daltons; and a Tg lower than 0, or lower than −10, or lower than −20, ° 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 percents, 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, or lower than −20° C.

8. The curable formulation of claim 1 , wherein said multi-functional curable material features, when hardened, a Tg lower than −10, or lower than −20° C.

9. The curable formulation of claim 1 , comprising:
a mono-functional amphiphilic acrylate that comprises a hydrophobic moiety, in an amount of 25-35 weight percents;
a mono-functional hydrophobic acrylate, in an amount of 25-30 weight percents;
a multi-functional acrylate, in an amount of 5-10 weight percents; and
a non-curable polymeric material featuring a molecular weight of at least 1000, or at least 1500 or at least 2000 Daltons; and a Tg lower than 0, or lower than −10, or lower than −20, ° C., in an amount of 30-35 weight percents.

10. The curable formulation 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 curable formulation of claim 9 , wherein said multi-functional acrylate is a urethane diacrylate.

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

14. 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.

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

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

17. A formulation system comprising:
the curable formulation of claim 1 ; and
an elastomeric curable formulation comprising at least one elastomeric curable material.

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

19. A kit comprising the formulation system of claim 17 , wherein each of said formulations is packaged individually within the kit.

Assignees

• Stratasys Ltd

Inventors

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

Classifications

• G03F7/0037 Primary

  Production of three-dimensional images · CPC title

• G03F7/032

  with binders · CPC title

• G03F7/027

  Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence) · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B29K2071/02

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