Compositions and methods for selective deposition modeling

• US 6,406,531 B1
• Filed: 03/07/2000
• Issued: 06/18/2002
• Est. Priority Date: 02/25/1999
• Status: Expired due to Term

• Current Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Original Assignee: 3D Systems, Inc. (3D Systems Corporation)
• Inventors: Kwo, Kelly, Doan, Vu, Bui, Loc V.
• Primary Examiner(s): BRUNSMAN, DAVID M
• Application Number:
  US09/520,661
• Time in Patent Office: 833 Days
• Field of Search: 106/31.29, 106/31.3, 106/31.61, 106/31.62, 106/230, 106/270, 106/287.3, 106/287.35, 524/227
• US Class Current: 106/287.35
• CPC Class Codes: B29C 41/003 characterised by the choice of material
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: C09D 11/34 Hot-melt inks

Abstract

Phase change compositions that are solid at ambient temperature and liquid at an elevated temperature above ambient temperature are disclosed for advantageous use in selective deposition modeling methods for building three-dimensional objects. A phase change composition according to the disclosed invention is a semi-crystalline component mixture having a freezing point of at least about 68° C., a melting point of at least about 88° C. and a viscosity of about 13 centipoise at 135° C. The composition includes a plurality of waxes having a broad melting point range and molecular weight range. Three-dimensional objects having minimal curl, delamination and stress cracks can be produced at a faster rate than heretofore known by using selective deposition modeling techniques employing the disclosed compositions.

Claims

1. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of polar and non-polar components, the semi-crystalline mixture having a freezing point of at least about 68°

C., a melting point of at least about 88°

C., and a viscosity of about 13 centipoise at 135°

C.

2. The phase change composition according to claim 1, having a freezing point in the range of about 68°

C. to about 71°

C. and a melting point in the range of about 88°

C. to about 90°

C.

3. The phase change composition according to claim 1, having an elongation of at least about 14%.

4. The phase change composition according to claim 3, having an elongation in the range of about 14% to about 73%.

5. The phase change composition according to claim 1, wherein there are at least two waxes present which have melting points in the range selected from the group consisting of:

86°

C. to 90°

C., 91°

C. to 94°

C., or 90°

C. to 97°

C., and 104°

C. to 116°

C.

6. The phase change composition according to claim 1, wherein there are at least three waxes present which have melting points in the range selected from the group consisting of:

86°

C. to 90°

C., 91°

C. to 94°

C., 90°

C. to 97°

C., and 104°

C. to 116°

C.

7. The phase change composition according to claim 1, wherein there are four waxes present and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

49. The phase change composition according to any of claims 1, 8, 18, 24, 31, or 44, further comprising at least one antioxidant.

50. The phase change composition according to any of claims 1, 8, 18, 24, 31, or 44, further comprising a colorant.

8. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of components including a tetra-amide and a plurality of waxes, wherein each wax of the plurality of waxes has a different melting point than each other wax in the plurality of waxes, and each wax has a melting point within the range from about 80°

C. to about 135°

C.

9. The phase change composition according to claim 8, wherein each wax of the plurality of waxes has a different melting point within the range from about 85°

C. to about 130°

C.

10. The phase change composition according to claim 9, wherein the synthetic wax is selected from the group consisting of polyethylene wax and synthetic branched wax.

11. The phase change composition according to claim 10, wherein the synthetic branched wax is an ethylene-propylene copolymer wax.

12. The phase change composition according to claim 8, wherein the ratio of the combined weight percentages of the plurality of waxes to the weight percentage of the tetra-amide in the composition ranges from about 2:

1 to about 6;

1.

13. The phase change composition according to claim 8, wherein each wax of the plurality of waxes has a different molecular weight than each other wax of the plurality of waxes, and each wax has a molecular weight within the range from about 150 to about 5000.

14. The phase change composition according to claim 8, wherein each wax of the plurality of waxes is selected from the group consisting of mono-amide wax, petroleum wax and synthetic wax.

15. The phase change composition according to claim 8, wherein there are at least two waxes in the plurality of waxes which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

16. The phase change composition according to claim 8, wherein there are at least three waxes in the plurality of waxes which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

17. The phase change composition according to claim 8, wherein there are at least four waxes in the plurality of waxes and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

18. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of components including a tetra-amide, a mono-amide wax, at least one wax selected from the group consisting of petroleum waxes and synthetic waxes, and an ester tackifier.

19. The phase change composition according to claim 18, wherein the ester tackifier is a modified rosin ester.

20. The phase change composition according to claim 19, wherein the modified rosin ester is a glycerol tri-ester of hydrogenated abietic acid.

21. The phase change composition according to claim 18, wherein the ratio of the weight percentage of the ester tackifier to the weight percentage of the tetra-amide in the composition ranges from about 0.5:

1 to about 5;

1.

22. The phase change composition according to claim 18, wherein the ratio of the combined weight percentages of the tetra-amide and the mono-amide wax to the weight percentage of the ester tackifier in the composition ranges from about 1:

1 to about 3;

1.

23. The phase change composition according to claim 18, wherein there are four waxes present and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

24. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of components including a tetra-amide, an ester tackifier and a hydrocarbon resin tackifier.

25. The phase change composition according to claim 24, wherein the ester tackifier is a modified rosin ester and the hydrocarbon resin tackifier is a hydrocarbon based aromatic resin.

26. The phase change composition according to claim 25, wherein the modified rosin ester is a glycerol tri-ester of hydrogenated abietic acid.

27. The phase change composition according to claim 24, wherein the ratio of the weight percentage of the ester tackifier to the weight percentage of the tetra-amide in the composition ranges from about 0.5:

1 to about 5;

1.

28. The phase change composition according to claim 24, further comprising a plurality of waxes wherein at least two waxes in the plurality of waxes have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

29. The phase change composition according to claim 24, wherein there are at least three waxes in the plurality of waxes which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

30. The phase change composition according to claim 24, wherein there are four waxes in the plurality of waxes and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

31. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of components including a tetra-amide, a mono-amide wax and at least one ester component for hydrogen-bonding with the tetra-amide and the mono-amide wax.

32. The phase change composition according to claim 31, wherein the at least one ester component is selected from the group consisting of ester tackifiers and ester plasticizers.

33. The phase change composition according to claim 32, wherein the ester tackifier is a modified rosin ester.

34. The phase change composition according to claim 33, wherein the modified rosin ester is a glycerol tri-ester of hydrogenaced abietic acid.

35. The phase change composition according to claim 31, wherein the ester plasticizer is an alkyl benzene phthalate.

36. The phase change composition according to claim 35, wherein the ester component comprises an ester tackifier and an ester plasticizer.

37. The phase change composition according to claim 36, wherein the ester tackifier is a modified rosin ester and the ester plasticizer is an alkyl benzene phthalate.

38. The phase change composition according to claim 37, wherein the modified rosin ester is a glycerol tri-ester of hydrogenated abietic acid.

39. The phase change composition according to claim 31, wherein the ratio of the combined weight percentages of the tetra-amide and the mono-amide wax to the weight percentage of the ester component in the composition ranges from about 0.75:

1 to about 2.5;

1.

40. The phase change composition according to claim 31, wherein the ratio of the combined weight percentages of the tetra-amide and the mono-amide wax to the weight percentage of the ester tackifier in the composition ranges from about 1:

1 to about 3;

1.

41. The phase change composition according to claim 31, wherein there are at least two waxes present which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 94°

C., and 104°

C. to 116°

C.

42. The phase change composition according to claim 31, wherein there are at least three waxes present which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

43. The phase change composition according to claim 31, wherein there are four waxes in the plurality of waxes and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

44. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of components including a tetra-amide, a mono-amide wax, at least one wax selected from the group consisting of petroleum waxes and synthetic waxes.

45. The phase change composition according to claim 44, further comprising a plasticizer.

46. The phase change composition according to claim 44, wherein there are at least two waxes present which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C. and 90°

C. to 97°

C., and 104°

C. to 116°

C.

47. The phase change composition according to claim 44, wherein there are at least three waxes present which have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

48. The phase change composition according to claim 44, wherein there are four waxes present and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

51. A phase change composition that is a solid at ambient temperature and a liquid at an elevated temperature above ambient temperature, adapted for use in selective deposition modeling to form a three-dimensional object, comprising a semi-crystalline mixture of components including a tetra-amide, a mono-amide wax, a petroleum wax, a polyethylene wax, an ethylene-propylene copolymer wax, a modified rosin ester, a hydrocarbon based aromatic resin, an alkyl benzene phthalate, at least one antioxidant and at least one colorant.

52. The phase change composition according to claim 51, wherein the tetra-amide is present in an amount of about 5% to about 30% by weight, the mono-amide wax is present in an amount of about 15% to about 40% by weight, the petroleum wax is present in an amount of about 5% to about 25% by weight, the polyethylene wax is present in an amount of up to about 15% by weight, the ethylene-propylene copolymer wax is present in an amount of up to about 10% by weight, the tri-ester is present in an amount of about 10% to about 40% by weight, the aromatic resin is present in an amount of up to about 15% by weight, the alkyl benzene phthalate is present in an amount of up to about 10% by weight, each antioxidant is present in an amount of less than about 1% by weight. and the colorant is present in an amount of no greater than about 2% by weight, all weight percentages being based on the total weight of the composition.

53. The phase change composition according to claim 51, wherein at least two waxes present have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.

54. The phase change composition according to claim 51, wherein at least three waxes present have melting points in the range of 86°

C. to 90°

C., and 91°

C. to 94°

C. and 90°

C. to 97°

C., and 104°

C. to 116°

C.

55. The phase change composition according to claim 51, wherein there are four waxes present and the melt points of the waxes are in the ranges of 86°

C. to 90°

C., and 91°

C. to 94°

C., and 90°

C. to 97°

C., and 104°

C. to 116°

C.