Three dimensional printing material system and method using peroxide cure

• US 7,905,951 B2
• Filed: 12/07/2007
• Issued: 03/15/2011
• Est. Priority Date: 12/08/2006
• Status: Active Grant

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: Z CORPORATION (A Holdings Corp.)
• Inventors: Williams, Derek X.
• Primary Examiner(s): Wu; David
• Assistant Examiner(s): NGUYEN, VU ANH
• Application Number:
  US11/952,727
• Publication Number:
  US 20080138515A1
• Time in Patent Office: 1,194 Days
• Field of Search: 106/31.13, 106/31.6, 106/31.9, 106/400
• US Class Current: 106/400
• CPC Class Codes: B29C 64/165 using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• 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

Abstract

A materials system and methods are provided to enable the formation of articles by Three Dimensional Printing. The materials system includes a transition metal catalyst that facilitates the reaction of an acrylate-containing binder with a particulate material.

Claims

1. A kit comprising:

a substantially dry particulate material comprising;

an insoluble filler;

a soluble filler; and

a transition metal catalyst, and

a fluid binder comprising;

a (meth)acrylate monomer;

at least one of an allyl ether functional monomer or an allyl ether functional oligomer; and

organic hydroperoxide,

wherein the insoluble filler is insoluble in the fluid binder and the soluble filler is soluble in the fluid binder.

2. The kit of claim 1, wherein the fluid binder comprises about 40%-95% by weight of the (meth)acrylate monomer, about 5-25% by weight of the allyl ether functional monomer/oligomer, and about 0.5-5% by weight of the organic hydroperoxide.

3. The kit of claim 1, wherein a contact angle of the fluid binder is less than 25°

when in contact with the particulate material.

4. The kit of claim 1, wherein a 1 mm penetration hardening rate of the substantially dry particulate material upon application of the fluid binder ranges from 0.01/min to 1.0/min.

5. The kit of claim 1, wherein the fluid binder further comprises a (meth)acrylate oligomer.

6. The kit of claim 5, wherein the fluid binder comprises about 10-40% by weight of the (meth)acrylate oligomer.

7. The kit of claim 1, wherein the fluid binder further comprises a surfactant.

8. The kit of claim 1, wherein the dry particulate material further comprises at least one of a pigment or a processing aid.

9. The kit of claim 1, wherein the dry particulate material is suitable for use in three dimensional printing to form an article comprised of a plurality of layers, the layers including a reaction product of the particulate material and the fluid binder that contacts the particulate material during three dimensional printing.

10. The kit of claim 1, wherein an internal angle of friction of the particulate material has a value ranging from 40°

to 70°

.

11. The kit of claim 1, wherein a critical surface tension of the particulate material is greater than 20 dynes/cm.

12. The kit of claim 1, wherein the particulate material comprises about 50%-90% by weight of the insoluble filler, about 10-50% by weight of the soluble filler, and about 0.01-0.5% by weight of the transition metal catalyst.

13. The kit of claim 1, wherein the insoluble filler is selected from the group consisting of solid glass spheres, hollow glass spheres, solid ceramic spheres, hollow ceramic spheres, potato starch, tabular alumina, calcium sulfate hemihydrate, calcium sulfate dehydrate, calcium carbonate, ultra-high molecular weight polyethylene, polyamide, poly-cyclic-olefins, polyurethane, polypropylene and combinations thereof.

14. The kit of claim 1, wherein the soluble filler is selected from the group consisting of methyl methacrylate polymers, ethyl methacrylate polymers, butyl methacrylate polymers, polyvinylbutyral, and combinations thereof.

15. The kit of claim 14, wherein the soluble filler has a weight-average molecular weight selected from a range of 100,000 g/mol to 500,000 g/mol.

16. The kit of claim 1, wherein the transition metal catalyst is selected from the group consisting of cobalt (II) octoate, cobalt (II) naphthenate, vanadium (II) octoate, manganese naphthenate and combinations thereof.

17. The kit of claim 8, wherein the particulate material comprises the pigment.

18. The kit of claim 17, wherein the particulate material comprises about 0.5-5% by weight of the pigment.

19. The kit of claim 17, wherein the pigment is selected from the group consisting of zinc oxide, zinc sulfide, barium sulfate, titanium dioxide, zirconium silicate, lead carbonate, and hollow borosilicate glass spheres.

20. The kit of claim 8, wherein the particulate material comprises the processing aid.

21. The kit of claim 20, wherein the particulate material comprises about 0.01-2.0% by weight of the processing aid.

22. The kit of claim 20, wherein the processing aid is selected from the group consisting of mineral oil, propylene glycol di(caprylate/caprate), petroleum jelly, propylene glycol, di-isobutyl phthalate, di-isononyl phthalate, polyalkyleneoxide modified heptamethyltrisiloxanes, polyalkyleneoxide modified polydimethylsiloxanes, secondary alcohol ethoxylated hydrocarbons, hydrogenated hydrocarbon resins, and combinations thereof.