Hardenable self-supporting structures and methods

1. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.; and

wherein the crystalline resin component is a polymeric material having crystallizable pendant moieties and the following general formula:

wherein R is hydrogen or a (C 1 -C 4 )alkyl group, X is —CH 2 —, —C(O)O—, —O—C(O)—, —C(O)—NH—, —HN—C(O)—, —O—, —NH—, —O—C(O)—NH—, —HN—C(O)—O—, —HN—C(O)—NH—, or —Si(CH 3 ) 2 —, m is the number of repeating units in the polymer, and n is great enough to provide sufficient side chain length and conformation to form polymers containing crystalline domains or regions;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.

2. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.; and

wherein the filler system comprises an inorganic material comprising nanoscopic particles;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.

3. The dental product of claim 2 wherein the inorganic material comprises surface hydroxyl groups.

4. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

a surfactant system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.

5. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.; and

wherein the hardenable composition has a G′ value of about 100 kPa to about 50,000 kPa at a frequency of about 0.005 Hz;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.

6. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.; and

wherein the crystalline resin component has a dendritic, hyperbranched, or a star-shaped structure;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.

7. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

a filler system comprising inorganic nanoscopic particles having an average primary particle size of no greater than about 50 nm;

a surfactant system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape.

8. The dental product of claim 7 which is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

9. The dental product of claim 7 which is a filling material.

10. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition;

wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint; and

wherein the crystalline resin component comprises polyesters, polyethers, polyolefins, polythioethers, polyarylalkylenes, polysilanes, polyamides, polyurethanes, or combinations thereof.

11. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.; and

wherein the crystalline resin component comprises polyesters, polyethers, polyolefins, polythioethers, polyarylalkylenes, polysilanes, polyamides, polyurethanes, or combinations thereof;

with the proviso that if the filler system comprises fibers, the fibers are present m an amount of less than 20 wt-%, based on the total weight of the composition.

12. The dental product of claim 7 wherein the filler system is present in an amount greater than 50 wt-%, based on the total weight of the composition.

13. The dental product of claim 7 wherein the hardenable self-supporting structure having a first shape has sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.

14. The dental product of claim 13 wherein the hardenable self-supporting structure having a first shape has sufficient malleability to be formed into a second shape substantially similar to the first shape.

15. The dental product of claim 7 wherein if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition.

16. The dental product of claim 7 wherein the resin system further comprises a noncrystalline resin component.

17. The dental product of claim 7 wherein the crystalline resin component has a dendritic, hyperbranched, or a star-shaped structure.

18. The dental product of claim 7 wherein upon hardening the structure in the second shape, the hardened structure has a flexural strength of at least about 25 MPa.

19. The dental product of claim 10 wherein the hardenable composition has a sufficient malleability to be formed into a second shape at room temperature.

20. The dental product of claim 10 wherein the filler system is greater than 70 wt-%.

21. The dental product of claim 10 wherein at least a portion of the filler system comprises particulate filler.

22. The dental product of claim 10 wherein upon hardening the structure in the second shape, the hardened structure has a flexural strength of at least about 25 MPa.

23. The dental product of claim 10 wherein the crystalline resin component comprises a reactive group.

24. The dental product of claim 11 wherein upon hardening the structure in the second shape, the hardened structure does not require an additional veneering material for the hardened dental product.

25. The dental product of claim 24 wherein the crystalline resin component comprises saturated, linear, aliphatic polyester polyols containing primary hydroxyl end groups.

26. The dental product of claim 25 wherein the hydroxyl end groups are modified to introduce polymerizable unsaturated functional groups.

27. A dental impression tray comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

a filler system comprising inorganic nanoscopic particles having an average primary particle size of no greater than about 50 nm;

a surfactant system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape.

28. The dental impression tray of claim 27 wherein the self-supporting structure has at least one structured surface.

29. The dental impression tray of claim 28 wherein the structured surface is formed by a porous substrate.

30. The dental impression tray of claim 28 wherein the structured surface is a microreplicated surface.

31. A preformed dental crown comprising a composition comprising a resin system, a filler system, and an imtiator system;

wherein the resin system comprises a crystalline resin component;

wherein the composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape; and

wherein the hardenable self-supporting structure having a first shape has sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.

32. The preformed dental crown of claim 31 wherein the filler system is present in an amount greater than 60 wt-%, based on the total weight of the composition.

33. The preformed dental crown of claim 31 wherein the filler system is present in an amount greater than 70 wt-%, based on the total weight of the composition.

34. The preformed dental crown of claim 31 wherein upon forming the second shape and hardening the structure in the second shape, the hardened structure does not need an additional veneering material.

35. The preformed dental crown of claim 31 which is in packaging.

36. The preformed dental crown of claim 35 wherein the packaging is light-blocking packaging sufficient to protect the preformed dental crown from conditions that would activate the initiator system and cause premature hardening.

37. The preformed dental crown of claim 31 further comprising a resin material lining the crown.

38. The preformed dental crown of claim 31 wherein the resin system comprises a compound of the formula:

wherein each Q independently comprises polyester segments, polyamide segments, polyurethane segments, polyether segments, or combinations thereof.

39. The dental product of claim 10 wherein the crystalline resin component comprises saturated, linear, aliphatic polyester polyols containing primary hydroxyl end groups.

40. The dental product of claim 39 wherein the hydroxyl end groups are modified to introduce polymerizable unsaturated functional groups.

41. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition;

wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint; and

wherein the crystalline resin component is a polymeric material having crystallizable pendant moieties and the following general formula:

wherein R is hydrogen or a (C 1 -C 4 )alkyl group, X is —CH 2 —, —C(O)O—, —O—C(O)—, —C(O)—NH—, —HN—C(O)—, —O—, —NH—, —O—C(O)—NH—, —HN—C(O)—O—, —HN—C(O)—NH—, or —Si(CH 3 ) 2 —, m is the number of repeating units in the polymer, and n is great enough to provide sufficient side chain length and conformation to form polymers containing crystalline domains or regions.

42. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition;

wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint; and

wherein the filler system comprises an inorganic material comprising nanoscopic particles.

43. The dental product of claim 42 wherein the inorganic material comprises surface hydroxyl groups.

44. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition;

wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint; and

wherein the hardenable composition further comprises a surfactant system.

45. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition;

wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint; and

wherein the hardenable composition has a G′ value of about 100 kPa to about 50,000 kPa at a frequency of about 0.005 Hz.

46. A dental product comprising a hardenable composition, wherein the hardenable composition comprises:

a resin system comprising a crystalline resin component;

greater than 60 wt-% of a filler system; and

an initiator system;

wherein the hardenable composition is in the form of a hardenable self-supporting structure having a first shape and sufficient malleability to be formed into a second shape at a temperature of about 15° C. to 38° C.;

with the proviso that if the filler system comprises fibers, the fibers are present in an amount of less than 20 wt-%, based on the total weight of the composition;

wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint; and

wherein the crystalline resin component has a dendritic, hyperbranched, or a star-shaped structure.

47. The dental product of claim 24 wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

48. The dental product of claim 24 which is a filling material.

49. The dental product of claim 24 which is a dental impression tray.

50. The dental product of claim 1 wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

51. The dental product of claim 1 which is a filling material.

52. The dental product of claim 1 which is a dental impression tray.

53. The dental product of claim 2 wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

54. The dental product of claim 2 which is a filling material.

55. The dental product of claim 2 which is a dental impression tray.

56. The dental product of claim 4 wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

57. The dental product of claim 4 which is a filling material.

58. The dental product of claim 4 which is a dental impression tray.

59. The dental product of claim 5 wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

60. The dental product of claim 5 which is a filling material.

61. The dental product of claim 5 which is a dental impression tray.

62. The dental product of claim 6 wherein the dental product is a preformed crown, a preformed inlay, a preformed onlay, a preformed bridge, a preformed veneer, a preformed orthodontic appliance, a preformed maxillofacial prosthesis, a preformed tooth facsimile, or a preformed tooth splint.

63. The dental product of claim 6 which is a filling material.

64. The dental product of claim 6 which is a dental impression tray.