Dental compositions comprising semi-crystalline resin and nanocluster filler

1. A preformed semi-finished dental article comprising an uncured dental restoration composition comprising:

a resin system comprising a free-radically polymerizable semi-crystalline resin having a molecular weight no greater than 3000 g/mole; and

at least 50 wt-% of nanocluster filler wherein the nanocluster filler comprises primary particles having an average diameter of less than 100 nm;

wherein the uncured dental restoration composition has a first shape that is sufficiently malleable to be formed into a second shape.

2. A method of making a dental article comprising:

providing a preformed semi-finished uncured dental article having a first shape wherein the uncured dental article comprises:

a resin system comprising a free-radically polymerizable semi-crystalline resin having a molecular weight no greater than 3000 g/mole;

at least 50 wt-% of nanocluster filler wherein the nanocluster filler comprises primary particles having an average diameter of less than 100 nm; and

one more additional nanoscopic particulate filler present in an amount ranging from 15 wt-% to 30 wt-%;

forming the semi-finished uncured dental article into a second shape; and

hardening the semi-finished uncured dental article by curing.

3. A curable dental restoration composition comprising:

a resin system comprising a free-radically polymerizable semi-crystalline resin having a molecular weight no greater than 3000 g/mole;

at least 50 wt-% of nanocluster filler wherein the nanocluster filler comprises primary particles having an average diameter of less than 100 nm; and

one more additional nanoscopic particulate filler present in an amount ranging from 15 wt-% to 30 wt-%.

4. The article of claim 1 wherein the semi-crystalline resin comprises polycaprolactone units.

5. The article of claim 1 wherein the semi-crystalline resin is a reaction product of a polycarprolactone diol and a hydroxyl reactive (meth)acrylate.

6. The article of claim 1 wherein the semi-crystalline resin is present in amount ranging from 1 wt-% to 15 wt-%.

7. The article of claim 1 wherein the resin system comprises at least one multi-(meth)acrylate aromatic monomer.

8. The article of claim 7 wherein the multi-(meth)acrylate aromatic monomer is a low shrinkage resin derived from bisphenol A.

9. The article of claim 8 wherein the low shrinkage resin is present in an amount ranging from 3 wt-% to 15 wt-% of the dental composition.

10. The article of claim 8 wherein the low shrinkage resin is present in an amount of at least 5 wt-% or 10 wt-%.

11. The article of claim 8 wherein the low shrinkage resin is BisGMA

12. The article of claim 8 wherein the resin system further comprises other polymerizable resins in addition to the low shrinkage resin in an amount of less than 20 wt-% of the total dental restoration composition.

13. The article of claim 12 wherein the other polymerizable resins are present in an amount no greater than 5 wt % of the dental composition.

14. The article of claim 1 wherein the composition further comprises one or more additional nanoscopic particulate fillers.

15. The article of claim 14 wherein the one or more additional nanoscopic particulate fillers are present in an amount ranging from 15 wt-% to 30 wt-%.

16. The article of claim 14 wherein the one or more additional nanoscopic particulate fillers comprise silica.

17. The article of claim 14 wherein the one or more additional nanoscopic particulate fillers comprise fumed silica.

18. The method of claim 2 wherein the semi-crystalline resin comprises polycaprolactone units.

19. The method of claim 2 wherein the semi-crystalline resin is a reaction product of a polycarprolactone diol and a hydroxyl reactive (meth)acrylate.

20. The method of claim 2 wherein the semi-crystalline resin is present in amount ranging from 1 wt-% to 15 wt-%.

21. The method of claim 2 wherein the resin system comprises at least one multi-(meth)acrylate aromatic monomer.

22. The method of claim 21 wherein the multi- (meth)acrylate aromatic monomer is a low shrinkage resin derived from bisphenol A.

23. The method of claim 22 wherein the low shrinkage resin is present in an amount ranging from 3 wt-% to 15 wt-% of the dental composition.

24. The method of claim 22 wherein the low shrinkage resin is present in an amount of at least 5 wt-% or 10 wt-%.

25. The method of claim 22 wherein the low shrinkage resin is BisGMA

26. The method of claim 22 wherein the resin system further comprises other polymerizable resins in addition to the low shrinkage resin in an amount of less than 20 wt-% of the total dental restoration composition.

27. The method of claim 26 wherein the other polymerizable resins are present in an amount no greater than 5 wt-% of the dental composition.

28. The method of claim 2 wherein the composition further comprises one or more additional nanoscopic particulate fillers.

29. The method of claim 28 wherein the one or more additional nanoscopic particulate fillers are present in an amount ranging from 15 wt-% to 30 wt-%.

30. The method of claim 28 wherein the one or more additional nanoscopic particulate fillers comprise silica.

31. The method of claim 28 wherein the one or more additional nanoscopic particulate fillers comprise fumed silica.

32. The curable dental restoration composition of claim 3 wherein the semi-crystalline resin comprises polycaprolactone units.

33. The curable dental restoration composition of claim 3 wherein the semi-crystalline resin is a reaction product of a polycarprolactone diol and a hydroxyl reactive (meth)acrylate.

34. The curable dental restoration composition of claim 3 wherein the semi-crystalline resin is present in amount ranging from 1 wt-% to 15 wt-%.

35. The curable dental restoration composition of claim 3 wherein the resin system comprises at least one multi- (meth)acrylate aromatic monomer.

36. The curable dental restoration composition of claim 35 wherein the multi-(meth)acrylate aromatic monomer is a low shrinkage resin derived from bisphenol A.

37. The curable dental restoration composition of claim 36 wherein the low shrinkage resin is present in an amount ranging from 3 wt-% to 15 wt-% of the dental composition.

38. The curable dental restoration composition of claim 36 wherein the low shrinkage resin is present in an amount of at least 5 wt-% or 10 wt-%.

39. The curable dental restoration composition of claim 36 wherein the low shrinkage resin is BisGMA

40. The curable dental restoration composition of claim 36 wherein the resin system further comprises other polymerizable resins in addition to the low shrinkage resin in an amount of less than 20 wt-% of the total dental restoration composition.

41. The curable dental restoration composition of claim 40 wherein the other polymerizable resins are present in an amount no greater than 5 wt-% of the dental composition.

42. The curable dental restoration composition of claim 3 wherein the composition further comprises one or more additional nanoscopic particulate fillers.

43. The method of claim 42 wherein the one or more additional nanoscopic particulate fillers are present in an amount ranging from 15 wt-% to 30 wt-%.

44. The method of claim 42 wherein the one or more additional nanoscopic particulate fillers comprise silica.

45. The method of claim 42 wherein the one or more additional nanoscopic particulate fillers comprise fumed silica.