Acid-reactive dental fillers, compositions, and methods Number:7,090,722 from the United States Patent and Trademark Office (PTO) owispatent Acid-reactive dental fillers, and methods of making and using such fillers, are disclosed. The acid-reactive dental fillers include a trivalent metal, oxygen, fluorine, an alkaline earth metal, and, optionally, silicon. The acid-reactive dental fillers are preferably nanostructured, for example, in the form of nanoparticles.<H compositions, reactive, Acid, reactive, d, 7090722.html, Patent, pto, 7090722

Title: Acid-reactive dental fillers, compositions, and methods

Abstract: Acid-reactive dental fillers, and methods of making and using such fillers, are disclosed. The acid-reactive dental fillers include a trivalent metal, oxygen, fluorine, an alkaline earth metal, and, optionally, silicon. The acid-reactive dental fillers are preferably nanostructured, for example, in the form of nanoparticles.

Patent Number: 7,090,722 Issued on 08/15/2006 to Budd, et al.

Inventors: Budd; Kenton D. (Woodbury, MN), Thalacker; Jason P. (Minneapolis, MN), Mitra; Sumita B. (West St. Paul, MN), Kolb; Brant U. (Afton, MN), Kangas; Lani S. (Woodbury, MN)
Assignee: 3M Innovative Properties Company (St Paul, MN)

Appl. No.: 10/847,805

Filed: May 17, 2004

Current U.S. Class: 106/35 ; 423/263; 423/464; 423/465; 501/151; 501/152; 523/113; 523/115; 523/116

Current International Class: A61F 2/00 (20060101); A61K 6/06 (20060101); A61K 6/08 (20060101); A61K 6/083 (20060101)

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Primary Examiner: Koslow; C. Melissa
Attorney, Agent or Firm: Edman; Sean J.

Claims

What is claimed is:

1. A composition comprising an oxyfluoride material; wherein the oxyfluoride material is acid-reactive, non-fused, and comprises a trivalent metal, oxygen, fluorine, and an alkaline earth metal; and wherein the composition is a dental filler.

2. The composition of claim 1 wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof.

3. A composition comprising an oxyfluoride material; wherein the oxyfluoride material is acid-reactive, non-fused, and comprises aluminum, oxygen, fluorine, and an alkaline earth metal; and wherein the composition is a dental filler.

4. The composition of claim 3 wherein at least 90% by weight of the oxyfluoride material is nanostructured.

5. The composition of claim 4 wherein at least 90% by weight of the oxyfluoride material is in the form of nanoparticles.

6. The composition of claim 5 wherein the nanoparticles are non-aggregated.

7. The composition of claim 5 wherein the nanoparticles are aggregated.

8. The composition of claim 5 wherein the nanoparticles have an average size of at most 100 nanometers.

9. The composition of claim 4 wherein the oxyfluoride material is in the form of a coating on a particle.

10. The composition of claim 9 wherein the particle is a nanoparticle.

11. The composition of claim 9 wherein the particle comprises a metal oxide.

12. The composition of claim 11 wherein the metal oxide is silica.

13. The composition of claim 4 wherein the oxyfluoride material is in the form of a coating on an aggregate of particles.

14. The composition of claim 13 wherein the particles comprise nanoparticles.

15. The composition of claim 13 wherein the particles comprise a metal oxide.

16. The composition of claim 15 wherein the metal oxide is silica.

17. The composition of claim 4 wherein the oxyfluoride material is infiltrated in a porous structure.

18. The composition of claim 17 wherein the porous structure comprises a porous particle.

19. The composition of claim 18 wherein the porous particle comprises a metal oxide.

20. The composition of claim 19 wherein the metal oxide is silica.

21. The composition of claim 17 wherein the porous structure comprises a porous aggregate of particles.

22. The composition of claim 21 wherein the particles are nanoparticles.

23. The composition of claim 21 wherein the particles comprise a metal oxide.

24. The composition of claim 23 wherein the metal oxide is silica.

25. The composition of claim 17 wherein the porous structure comprises a porous coating.

26. The composition of claim 3 wherein the oxyfluoride material further comprises silicon.

27. The composition of claim 3 wherein the oxyfluoride material further comprises a heavy metal.

28. The composition of claim 27 wherein the heavy metal is zirconium.

29. The composition of claim 3 wherein the molar ratio of aluminum to the alkaline earth metal in the oxyfluoride material is at least 50:50 and at most 95:5.

30. The composition of claim 3 wherein the molar ratio of oxygen to fluorine in the oxyfluoride material is at least 50:50 and at most 95:5.

31. The composition of claim 3 wherein the alkaline earth metal is selected from the group consisting of strontium, calcium, barium, and combinations thereof.

32. A composition comprising an oxyfluoride material; wherein the oxyfluoride material is acid-reactive and comprises a trivalent metal, oxygen, fluorine, and an alkaline earth metal, with the proviso that the oxyfluoride material comprises at most 25 mole % silicon based on the total moles of silicon, the trivalent metal, the alkaline earth metal, and any additional cations; and wherein the material is a dental filler.

33. The composition of claim 32 wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof.

34. The composition of claim 32 wherein the trivalent metal is aluminum.

35. The composition of claim 34, with the proviso that the oyxfluoride material comprises at most 20 mole % silicon, based on the total moles of silicon, aluminum, and the alkaline earth metal.

36. A dental filler prepared by a method comprising: combining a first liquid composition comprising a source of a trivalent metal and a source of an alkaline earth metal with a second liquid composition comprising a source of fluorine to provide an acid-reactive oxyfluoride material, wherein the oxyfluoride material comprises the trivalent metal, oxygen, fluorine, and the alkaline earth metal; and separating the oxyfluoride material from the combined liquid compositions to provide the dental filler.

37. The dental filler of claim 36 wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof.

38. The dental filler of claim 36 wherein the trivalent metal is aluminum.

39. A method of preparing a dental filler comprising: combining a first liquid composition comprising a source of a trivalent metal and a source of an alkaline earth metal with a second liquid composition comprising a source of fluorine to provide an acid-reactive oxyfluoride material, wherein the oxyfluoride material comprises the trivalent metal, oxygen, fluorine, and the alkaline earth metal; and separating the oxyfluoride material from the combined liquid compositions to provide the dental filler.

40. The method of claim 39 wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof.

41. A method of preparing a dental filler comprising: combining a first liquid composition comprising a source of aluminum and a source of an alkaline earth metal with a second liquid composition comprising a source of fluorine to provide an acid-reactive oxyfluoride material, wherein the oxyfluoride material comprises aluminum, oxygen, fluorine, and the alkaline earth metal; and separating the oxyfluoride material from the combined liquid compositions to provide the dental filler.

42. The method of claim 41 wherein the oxyfluoride material is nanostructured.

43. The method of claim 41 wherein at least one of the liquid compositions further comprises a source of hydroxide as a source of oxygen.

44. The method of claim 43 wherein the source of hydroxide is selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and combinations thereof.

45. The method of claim 41 wherein at least one of the liquid compositions is an aqueous composition having a pH greater than 7.

46. The method of claim 41 further comprising drying the separated oxyfluoride material at a temperature of at most 350.degree. C.

47. The method of claim 46 wherein drying is at a temperature of at most 250.degree. C.

48. The method of claim 47 wherein drying is at a temperature of at most 150.degree. C.

49. The method of claim 41 wherein combining provides an oxyfluoride material in a form selected from the group consisting of a precipitate, a coating on a particle, a coating on an aggregate of particles, a material infiltrated in a porous structure, and combinations thereof.

50. The method of claim 41 wherein separating the oxyfluoride material comprises filtering the oxyfluoride material.

51. The method of claim 41 wherein the source of aluminum is selected from the group consisting of aluminum nitrates and basic or oxy salts thereof, aluminum carboxylates and basic or oxy salts thereof, aluminum halides and basic or oxy salts thereof, and combinations thereof.

52. The method of claim 41 wherein the source of aluminum comprises an aluminum alkoxide.

53. The method of claim 52 wherein the aluminum alkoxide is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, and combinations thereof.

54. The method of claim 41 wherein the source of fluorine is selected from the group consisting of ammonium fluoride, ammonium hydrogen difluoride, hexafluorosilicic acid and salts thereof, and combinations thereof.

55. The method of claim 41 wherein the source of the alkaline earth metal comprises strontium nitrates, strontium carboxylates, strontium halides, calcium nitrates, calcium carboxylates, calcium halides, and combinations thereof.

56. The method of claim 41 wherein the second liquid composition further comprises a source of silicon.

57. The method of claim 56 wherein the source of silicon comprises sodium silicate, hexafluorosilicic acid and salts thereof, silicon alkoxides, and combinations thereof.

58. The method of claim 41 wherein at least one of the first and second liquid compositions further comprises water.

59. The method of claim 41 further comprising dispersing the separated oxyfluoride material in a liquid medium.

60. The method of claim 59 wherein the liquid medium comprises water.

61. The method of claim 59 further comprising coating the dispersed oxyfluoride material on a particle, coating the dispersed oxyfluoride material on an aggregate of particles, infiltrating the dispersed oxyfluoride material in a porous structure, or combinations thereof.

62. A method of preparing a dental filler comprising: providing a porous structure; infiltrating a first liquid composition comprising a source of a trivalent metal and a source of an alkaline earth metal in the porous structure; and infiltrating a second liquid composition comprising a source of fluorine in the porous structure to provide a porous structure infiltrated with an acid-reactive oxyfluoride material, wherein the acid-reactive oxyfluoride material comprises the trivalent metal, oxygen, fluorine, and the alkaline earth metal.

63. The method of claim 62 wherein the trivalent metal is selected from the group consisting of aluminum, lanthanum, and combinations thereof.

64. A method of preparing a dental filler comprising: providing a porous structure; infiltrating a first liquid composition comprising a source of aluminum and a source of an alkaline earth metal in the porous structure; and infiltrating a second liquid composition comprising a source of fluorine in the porous structure to provide a porous structure infiltrated with an acid-reactive oxyfluoride material, wherein the acid-reactive oxyfluoride material comprises aluminum, oxygen, fluorine, and the alkaline earth metal.

65. The method of claim 64 further comprising drying the porous structure infiltrated with the acid-reactive oxyfluoride material at a temperature of at most 350.degree. C.

66. The method of claim 64 wherein infiltrating the first liquid composition is carried out before infiltrating the second liquid composition.

67. The method of claim 64 wherein infiltrating the first liquid composition is carried out after infiltrating the second liquid composition.

68. The method of claim 64 wherein the second liquid composition further comprises a component selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, and combinations thereof.

69. The method of claim 64 wherein the second liquid composition further comprises a source of silicon.

70. The method of claim 64 wherein at least one of the first and second liquid compositions further comprises water.

71. The method of claim 64 wherein the porous structure is selected from the group consisting of porous particles, porous aggregates of particles, and combinations thereof.

72. A dental composition comprising a hardenable resin and a dental filler according to claim 1.

73. A dental composition comprising a hardenable resin and a dental filler according to claim 3.

74. The dental composition of claim 73 wherein the hardenable resin comprises a polymerizable ethylenically unsaturated compound.

75. The dental composition of claim 74 wherein the hardenable resin further comprises an acid.

76. The dental composition of claim 73 wherein the composition is in the form of a single-part dental composition.

77. The dental composition of claim 73 wherein the composition is in the form of a multi-part dental composition.

78. The dental composition of claim 77 wherein the multi-part composition comprises a first part and a second part, and wherein each part is independently selected from the group consisting of a liquid, paste, gel, or powder.

79. The dental composition of claim 77 wherein the multi-part composition is selected from the group consisting of a paste-paste composition, a paste-liquid composition, a paste-powder composition, and a powder-liquid composition.

80. The dental composition of claim 73 wherein the composition is selected from the group consisting of dental adhesives, cavity liners, cements, coatings, orthodontic adhesives, restoratives, sealants, and combinations thereof.

81. The dental composition of claim 73 wherein at least 90% by weight of the oxyfluoride material is nanostructured.

82. The dental composition of claim 81 further comprising a non acid-reactive filler.

83. The dental composition of claim 82 wherein at least 75% by weight of the total filler in the dental composition is nanofiller.

84. The dental composition of claim 82 wherein at least 90% by weight of the total filler in the dental composition is nanofiller.

85. The dental composition of claim 73 wherein the composition is in the form of a paste.

86. A dental composition comprising a hardenable resin and a dental filler according to claim 32.

87. The dental composition of claim 86 wherein the composition is in the form of a paste.

88. A dental composition comprising at most 15% by weight of a dental filler according to claim 1, with the proviso that the dental filler provides at least 2 square meters of surface area per gram of the dental composition.

89. A dental composition comprising: at most 10% by weight of a dental filler according to claim 1, based on the total weight of the dental composition; and at least 40% by weight of additional fillers, based on the total weight of the dental composition.

90. A method of preparing a dental composition comprising combining a dental filler according to claim 1 and a hardenable resin.

91. A method of preparing a dental composition comprising combining a dental filler according to claim 3 and a hardenable resin.

92. A method of preparing a dental composition comprising combining a dental filler according to claim 32 and a hardenable resin.

93. A dental composition comprising: a dental filler according to claim 1; a polyacid; and water.

94. A dental composition comprising: a dental filler according to claim 3; a polyacid; and water.

95. A multi-part dental composition comprising: a part A comprising a dental filler according to claim 1; and a part B comprising a polyacid.

96. A multi-part dental composition comprising: a part A comprising a dental filler according to claim 3; and a part B comprising a polyacid.

97. The multi-part dental composition of claim 96, wherein at least 90% by weight of the oxyfluoride material is nanostructured.

98. The multi-part dental composition of claim 96 wherein at least one of part A or part B further comprises an additional acid reactive filler.

99. The multi-part dental composition of claim 96 wherein at least one of part A or part B is in the form of a liquid or a paste.

100. The multi-part dental composition of claim 99 wherein part A and part B are provided in a unit-dose capsule.

101. The multi-part dental composition of claim 99 wherein part A and part B are each independently in the form of a liquid or a paste.

102. The multi-part dental composition of claim 101 further comprising a dual barrel syringe having a first barrel and a second barrel, wherein the part A resides in the first barrel and the part B resides in the second barrel.

103. The multi-part dental composition of claim 101 wherein part A and part B can be mixed in a static mixer.

104. The multi-part dental composition of claim 96 further comprising water residing in at least one of part A or part B.

105. The multi-part dental composition of claim 96 further comprising a polymerizable component residing in at least one of part A or part B.

106. The multi-part dental composition of claim 105 wherein the polyacid and the polymerizable component are the same.

107. The multi-part dental composition of claim 105 wherein the polyacid and the polymerizable component are different.

108. The multi-part dental composition of claim 96 further comprising a non acid-reactive dental filler residing in at least one of part A or part B.

109. The multi-part dental composition of claim 108 wherein at least 90% by weight of the non acid-reactive dental filler is in the form of nanoparticles.

110. The multi-part dental composition of claim 108 wherein the non acid-reactive dental filler comprises a metal oxide.

111. The multi-part dental composition of claim 110 wherein the metal oxide is silica.

112. A multi-part dental composition comprising: a part A comprising an acid-reactive dental filler according to claim 32; and a part B comprising at least one polyacid.

113. A method of using a multi-part dental composition according to claim 95 comprising: mixing a quantity of part A and a quantity of part B to form a dental composition; and applying the dental composition to a surface.

114. A method of preparing a dental article comprising: combining a dental filler according to claim 1 and a hardenable resin to form a dental composition; and hardening the composition to fabricate a dental article selected from the group consisting of crowns, fillings, mill blanks, orthodontic devices, and prostheses.

115. A method of preparing a dental article comprising: combining a dental filler according to claim 3 and a hardenable resin to form a dental composition; and hardening the composition to fabricate a dental article selected from the group consisting of crowns, fillings, mill blanks, orthodontic devices, and prostheses.

116. A method of preparing a dental article comprising: combing a dental filler according to claim 32 and a hardenable resin to form a dental composition; and hardening the composition to fabricate a dental article selected from the group consisting of crowns, fillings, mill blanks, orthodontic devices, and prostheses.

Description

BACKGROUND

Acid-reactive fillers have been widely used in dental compositions. Acid-reactive fillers include, for example, metal oxides, metal salts, and glasses. An example of an acid-reactive glass is fluoroaluminosilicate (FAS) glass, which is a known fluoride releasing material. FAS glass particles are typically prepared by a melt fusion process, which effectively limits available particle sizes to particles typically having an average size of at least 0.5 micrometers.

For applications in which the acid-reactive filler is dispersed in a hardenable resin to form a dental composition (e.g., a dental paste), the reactivity of the acid-reactive filler in the composition is generally limited by the available surface area of the acid-reactive filler. Thus, high loadings (e.g., greater than 50% by weight) of acid-reactive filler are often used to achieve compositions with the desired level of reactivity. However, high loadings of acid-reactive fillers sometimes restrict the flexibility to incorporate additional fillers (e.g., non acid-reactive fillers) in the composition.

As such, there remains a need for acid-reactive dental fillers with improved properties including, for example, higher surface areas.

SUMMARY

In one aspect, the present invention provides a composition that is a dental filler, and methods of making and using such dental fillers. In one embodiment, the dental filler includes an oxyfluoride material that is acid-reactive, non-fused, and includes a trivalent metal, oxygen, fluorine, and an alkaline earth metal. Preferably the trivalent metal includes aluminum and/or lanthanum, and in more preferred embodiments the trivalent metal is aluminum. In some embodiments, the oxyfluoride material optionally includes silicon and/or a heavy metal. Preferably at least a portion of the oxyfluoride material is nanostructured.

In another embodiment, the dental filler includes an oxyfluoride material that is acid-reactive, and includes a trivalent metal, oxygen, fluorine, and an alkaline earth metal, with the proviso that the oxyfluoride material includes at most 25 mole %, and preferably at most 20 mole % silicon, based on the total moles of silicon, trivalent metal, alkaline earth metal, and any additional cations.

In another aspect, the present invention provides dental compositions, and methods of making and using dental compositions, wherein the dental composition includes a dental filler of the present invention and a hardenable resin (e.g., a polymerizable ethylenically unsaturated compound and/or an acid). The dental composition may be a single-part or a multi-part dental composition. In addition to the dental filler of the present invention, such dental compositions can include additional acid-reactive or non acid-reactive fillers including, for example, nanofillers. The dental compositions of the invention may be dental adhesives, cavity liners, cements, coating, orthodontic adhesives, restoratives, sealants, and combinations thereof. Dental compositions of the present invention can be hardened to prepare dental articles including, for example, crowns, fillings, mill blanks, orthodontic devices, and prostheses.

Preferably, by incorporating acid-reactive fillers of the present invention in resins, dental compositions (e.g., dental restoratives) can be prepared that exhibit improvements in one or more properties including, for example, strength, polish, polish retention, fluoride release, abrasion resistance, aesthetics, and radiopacity.

Definitions

As used herein, a "non-fused" material means that the material was not formed from a melted state. Non-fused materials may be formed by methods including, for example, chemical syntheses, precipitations, and combinations thereof.

As used herein, a "dental filler" is a particulate material suitable for use in the oral environment. Dental fillers generally have an average particle size of at most 100 micrometers.

As used herein, the term "paste" refers to a soft, viscous mass of solids dispersed in a liquid.

As used herein, the term "non-fused" refers to a material that has not been prepared by a melt fusion process.

As used herein, an "acid-reactive" dental filler is a filler that chemically reacts in the presence of an acidic component.

As used herein, an "alkaline earth metal" is an element selected from the group consisting of Be, Mg, Ca, Sr, and Ba.

As used herein an oxyfluoride is a material in which atoms of oxygen and fluorine are bonded to the same atom (e.g., aluminum in an aluminum oxyfluoride). Generally, at least 50% of the fluorine atoms are bonded to an atom bearing an oxygen atom in an oxyfluoride material.

As used herein, a "nanostructured" material refers to a material in a form having at least one dimension that is, on average, at most 200 nanometers (e.g., nanosized particles). Thus, nanostructured materials refer to materials including, for example, nanoparticles as defined herein below; aggregates of nanoparticles; materials coated on particles, wherein the coatings have an average thickness of at most 200 nanometers; materials coated on aggregates of particles, wherein the coatings have an average thickness of at most 200 nanometers; materials infiltrated in porous structures having an average pore size of at most 200 nanometers; and combinations thereof. Porous structures include, for example, porous particles, porous aggregates of particles, porous coatings, and combinations thereof.

As used herein, "nanoparticles" is used synonymously with "nanosized particles," and refers to particles having an average size of at most 200 nanometers. As used herein for a spherical particle, "size" refers to the diameter of the particle. As used herein for a non-spherical particle, "size" refers to the longest dimension of the particle.

As used herein, "agglomerated" is descriptive of a weak association of primary particles usually held together by charge or polarity. Agglomerated particles can typically be broken down into smaller entities by, for example, shearing forces encountered during dispersion of the agglomerated particles in a liquid.

In general, "aggregated" and "aggregates" are descriptive of a strong association of primary particles often bound together by, for example, residual chemical treatment, covalent chemical bonds, or ionic chemical bonds. Further breakdown of the aggregates into smaller entities is very difficult to achieve. Typically, aggregated particles are not broken down into smaller entities by, for example, shearing forces encountered during dispersion of the aggregated particles in a liquid.

As used herein, "aggregated silica" is descriptive of an association of primary silica particles often bound together by, for example, residual chemical treatment, covalent chemical bonds, or ionic chemical bonds. Although complete breakdown of aggregated silica into smaller entities may be difficult to achieve, limited or incomplete breakdown may be observed under conditions including, for example, shearing forces encountered during dispersion of the aggregated silica in a liquid. As used herein, a "silica cluster" or "silica-zirconia cluster" refers to aggregated silica or silica-zirconia in which a substantial amount of the aggregated primary silica or zirconia particles are loosely bound. "Loosely bound" refers to the nature of the association among the particles present in the silica or silica-zirconia cluster. Typically, the particles are associated by relatively weak intermolecular forces that cause the particles to clump together. Preferably, many of the clusters remain intact during dispersion into a hardenable resin for a dental material, even though some clusters may be fractured into smaller structures during the dispersion process. Thus, silica clusters and silica-zirconia clusters are typically referred to as "loosely bound aggregated silica" or "loosely bound aggregated silica-zirconia." The clusters disclosed in the present application are preferably substantially spherical and preferably not fully densified. The term "fully dense," as used herein, is descriptive of a particle that is near theoretical density, having substantially no open porosity detectable by standard analytical techniques such as the B.E.T. nitrogen technique (based upon adsorption of N.sub.2 molecules from a gas with which a specimen is contacted). Such measurements yield data on the surface area per unit weight of a sample (e.g. m.sup.2/g), which can be compared to the surface area per unit weight for a mass of perfect microspheres of the same size to detect open porosity. The term "not fully densified" as used herein, is descriptive of a particle that is less than theoretical density, and therefore, has porosity. For porous particles with open porosity, (e.g., clusters of primary particles), the measured surface area is greater than the surface area calculated for solid particles of the same size. Such measurements may be made on a Quantasorb apparatus made by Quantachrome Corporation of Syossett, N.Y. Density measurements may be made using an air, helium or water pycnometer.

As used herein, "particle size" refers to the longest dimension (e.g., diameter) of a particle.

Silica clusters disclosed in the present application may be manufactured in a process that includes drying and optionally heat treating and/or calcining. The ratio of the surface area after heat treatment compared to the surface area before heat treatment is preferably greater than 50%, more preferably greater than 80%. Preferably the change in surface area after heating is at most 10% and more preferably at most 5%.

As used herein, a "shelf-stable" composition refers to a composition that has a shelf-life of at least one year, and preferably at least 2 years, at room temperature. Shelf-life of an adhesive composition is typically measured by determining if the aged composition provides acceptable bond strengths when the aged composition is bonded to a dental structure surface.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention provides a dental filler that includes an acid-reactive oxyfluoride material, and methods of making and using the dental filler. As used herein an oxyfluoride is a material in which atoms of oxygen and fluorine are bonded to the same atom (e.g., aluminum in an aluminum oxyfluoride). In some embodiments, at least 50%, sometimes at least 70%, and in other embodiments at least 80%, of the fluorine atoms are bonded to or coordinated by an atom bearing or coordinated by an oxygen atom in an oxyfluoride material. Single- and multi-part dental compositions can include, in addition to a dental filler of the present invention, a hardenable resin and/or a hardenable polyacid. Such dental compositions are useful as, for example, dental adhesives, artificial crowns, anterior fillings, posterior fillings, casting materials, cavity liners, cements, coating compositions, mill blanks, orthodontic devices, orthodontic adh