Compositions and methods for use in three dimensional model printing

• US 8,883,392 B2
• Filed: 06/13/2013
• Issued: 11/11/2014
• Est. Priority Date: 03/13/2000
• Status: Expired due to Fees

• Current Assignee: Stratasys Incorporated
• Original Assignee: Stratasys Incorporated
• Inventors: Napadensky, Eduardo, Brusilovsky, David
• Primary Examiner(s): Nutter, Nathan M
• Application Number:
  US13/917,111
• Publication Number:
  US 20130273376A1
• Time in Patent Office: 516 Days
• Field of Search: 430/269, 522/83, 522/96, 522/148, 522/167, 522/180, 522/182
• US Class Current: 430/263
• CPC Class Codes: B29C 64/112 using individual droplets, e.g. from jetting heads
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B33Y 70/00 Materials specially adapted for additive manufacturing
• CPC Class Codes: B33Y 70/10 Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• CPC Class Codes: B41M 3/006 Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
• CPC Class Codes: C08F 22/10 Esters
• CPC Class Codes: C08L 33/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C08L 35/02 Homopolymers or copolymers of esters C08L35/06, C08L35/08 take precedence
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: Y10T 428/31554 Next to second layer of polyamidoester

Abstract

A radiation curing composition suitable for building a three-dimensional object by a solid freeform method is disclosed. The composition includes one or more mono-functional monomers where a respective polymer has a Glass Transition Temperature higher than about 60° C., one or more di-functional oligomers where a respective polymer has a Glass Transition Temperature lower than about 40° C. and a phase separation inducing component. The phase separation may be induced during curing, resulting in a non-clear cured material having an improved impact strength and higher elongation, when compared to similar compositions without a phase separation inducing component.

Claims

1. A composition suitable for building a three dimensional object by three-dimensional printing, the composition comprising:

one or more mono-functional monomers; and

one or more di-functional oligomers,

wherein functional groups of the one or more monomers and one or more oligomers are meth(acrylic), the composition has a viscosity of about 50-500 cps at ambient temperature, the concentration of said one or more mono-functional monomers is at least 20% by weight and the concentration of said one or more di-functional oligomers is at least 20% by weight.

2. The composition of claim 1, where a respective polymer of the one or more mono-functional monomers has a Glass Transition Temperature higher than about 60°

C. and a respective polymer of the one or more di-functional oligomers has a Glass Transition Temperature lower than about 40°

C.

3. The composition of claim 1, wherein the composition has a viscosity lower than 20 cps at a temperature higher than the ambient temperature and after curing, the composition results in a solid form.

4. The composition of claim 1, further comprising a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.

5. The composition of claim 1, further comprising a photo-initiator.

6. The composition of claim 5, further wherein the photo-initiator is a free radical photo-initiator, a cationic photo-initiator or any combination thereof.

7. The composition of to claim 1, further comprising a surface-active agent and a stabilizer.

18. A solid composition formed by curing the composition of claim 1.

19. A layer formed by the solid composition of claim 18.

8. A method for the preparation of a three-dimensional object by three-dimensional printing, the method comprising:

dispensing from a printing head a composition that comprises one or more mono-functional monomers and one or more di-functional oligomers, wherein functional groups of the one or more monomers and one or more oligomers are meth(acrylic), the composition has a viscosity of about 50-500 cps at ambient temperature, the concentration of said one or more mono-functional monomers is at least 20% by weight and the concentration of said one or more di-functional oligomers is at least 20% by weight; and

curing the composition.

9. The method of claim 8, where a respective polymer of the one or more mono-functional monomers in the composition has a Glass Transition Temperature higher than about 60°

C. and a respective polymer of the one or more di-functional oligomers in the composition has a Glass Transition Temperature lower than about 40°

C.

10. The method of claim 8, wherein the composition has a viscosity lower than 20 cps at a temperature higher than the ambient temperature and after curing, the composition results in a solid form.

11. The method of claim 8, wherein the composition further comprises at least one of a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.

12. A three-dimensional object comprising:

a multiplicity of construction layers formed by curing a composition that comprises one or more mono-functional monomers and one or more di-functional oligomers, wherein functional groups of the one or more monomers and one or more oligomers are meth(acrylic), the composition has a viscosity of about 50-500 cps at ambient temperature, the concentration of said one or more mono-functional monomers is at least 20% by weight and the concentration of said one or more di-functional oligomers is at least 20% by weight, wherein after curing, the composition results in a solid material.

13. The three-dimensional object of claim 12, where a respective polymer of the one or more mono-functional monomers in the composition has a Glass Transition Temperature higher than about 60°

C. and a respective polymer of the one or more di-functional oligomers in the composition has a Glass Transition Temperature lower than about 40°

C.

14. The three-dimensional object of claim 12, wherein the composition has a viscosity lower than 20 cps at a temperature higher than the ambient temperature and after curing, the composition results in a solid form.

15. The three-dimensional object of claim 12, wherein the composition comprises a photo-initiator, a surface-active agent and a stabilizer.

16. The three-dimensional object of claim 12, wherein the composition further comprises at least one of a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.

17. The three-dimensional object of claim 12, wherein the composition further comprises at least one pigment and at least one dispersant.