Claims
- 1. A polymerizable composition comprising:
(a) a cationically active functional group; (b) an initiation system capable of initiating cationic polymerization of said cationically active functional group; and (c) a filler composition comprising a radiopacifying filler selected from the group consisting of metal oxides, metal halides, metal borates, metal phosphates, metal silicates, metal carbonates, metal germanates, metal tetrafluoroborates, metal hexafluorophosphates, and combinations thereof, in an amount sufficient to render said polymerizable composition radiopaque, wherein components (a), (b), and (c) are selected such that said polymerizable composition polymerizes to form a polymerized composition having a Barcol hardness, measured using a GYZJ-935 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.
- 2. A polymerizable composition according to claim 1 wherein said polymerizable composition polymerizes to form a polymerized composition having a Barcol hardness, measured using a GYZJ-934-1 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.
- 3. A polymerizable composition according to claim 1 wherein cationic polymerization of said cationically active functional group forms a polymerized composition having a Barcol hardness, measured using a GYZJ-935 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.
- 4. A polymerizable composition according to claim 1 wherein said filler composition is selected such that when the amount of said radiopacifying filler is at least 50% by weight of said polymerizable composition, said radiopacifying filler has an isoelectric point, measured according to Test Procedure B, of no greater than 7.
- 5. A polymerizable composition according to claim 1 wherein said filler composition is selected such that when the amount of said filler composition is 70% by weight of said polymerizable composition, a test polymerizable composition defined in Test Procedure C that includes said filler composition has an adsorption value of no greater than about 20 micromoles/g filler, as determined by surface area titration according to Test Procedure C.
- 6. A polymerizable composition according to claim 1 wherein said filler composition is selected such that when the amount of said filler composition is 50% by weight of said polymerizable composition, a test polymerizable composition defined in Test Procedure C that includes said filler composition has an adsorption value of no greater than about 80 micromoles/g filler, as determined by surface area titration according to Test Procedure C.
- 7. A polymerizable composition according to claim 1 wherein said filler composition is selected such that when the amount of said filler composition is 70% by weight of said polymerizable composition, said filler composition causes a change in conductivity of a test solution of no greater than 60 mV, determined according to Test Procedure D.
- 8. A polymerizable composition according to claim 1 wherein said filler composition is selected such that when the amount of said filler composition is 50% by weight of said polymerizable composition, said filler composition causes a change in conductivity of a test solution of no greater than 125 mV, determined according to Test Procedure D.
- 9. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises an element having an atomic number of at least 30.
- 10. A polymerizable composition according to claim 9 wherein said element is selected from the group consisting of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, molybdenum, tin, zinc, lanthanide elements, and combinations thereof.
- 11. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises:
(a) an oxide selected from the group consisting of lanthanum oxide, zinc oxide, tantalum oxide, tin oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, and combinations thereof; and (b) an oxide selected from the group consisting of aluminum oxide, boron oxide, silicon oxide, and combinations thereof.
- 12. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 13. A polymerizable composition according to claim 10 wherein said filler composition is selected such that said filler composition has a relative peak height of greater than 80% as determined by Fourier transform infrared spectroscopy according to Test Procedure E.
- 14. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises a melt-derived filler.
- 15. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight lanthanum oxide and 45% to 99% by weight silicon oxide.
- 16. A polymerizable composition according to claim 15 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 17. A polymerizable composition according to claim 15 wherein said radiopacifying filler is semi-crystalline.
- 18. A polymerizable composition according to claim 15 wherein said radiopacifying filler comprises a melt-derived filler.
- 19. A polymerizable composition according to claim 15 wherein said radiopacifying filler is amorphous.
- 20. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight lanthanum oxide, 0.5% to 50% by weight aluminum oxide, and 0.5% to 90% by weight silicon oxide.
- 21. A polymerizable composition according to claim 20 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 22. A polymerizable composition according to claim 20 wherein said radiopacifying filler comprises a melt-derived filler.
- 23. A polymerizable composition according to claim 20 wherein said radiopacifying filler is semi-crystalline.
- 24. A polymerizable composition according to claim 20 wherein said radiopacifying filler is amorphous.
- 25. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight lanthanum oxide, 0.1% to 55% by weight aluminum oxide, 0.01% to 80% by weight boron oxide, and 1% to 90% by weight silicon oxide.
- 26. A polymerizable composition according to claim 25 wherein said radiopacifying filler comprises a melt-derived filler.
- 27. A polymerizable composition according to claim 25 wherein said radiopacifying filler is amorphous.
- 28. A polymerizable composition according to claim 25 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 29. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight lanthanum oxide, 0.01% to 80% by weight boron oxide, and 1% to 90% by weight silicon oxide.
- 30. A polymerizable composition according to claim 29 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 31. A polymerizable composition according to claim 29 wherein said radiopacifying filler comprises a melt-derived filler.
- 32. A polymerizable composition according to claim 29 wherein said radiopacifying filler is semi-crystalline.
- 33. A polymerizable composition according to claim 29 wherein said radiopacifying filler is amorphous.
- 34. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight zinc oxide, 0.5% to 55% by weight lanthanum oxide, 0.1% to 40% by weight aluminum oxide, 0.01% to 80% by weight boron oxide, and 1% to 80% by weight silicon oxide.
- 35. A polymerizable composition according to claim 34 wherein said radiopacifying filler comprises a melt-derived filler.
- 36. A polymerizable composition according to claim 34 wherein said radiopacifying filler is amorphous.
- 37. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises colloidally derived zirconium oxide.
- 38. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight zirconium oxide and 45% to 99% by weight silicon oxide.
- 39. A polymerizable composition according to claim 38 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 40. A polymerizable composition according to claim 38 wherein said radiopacifying filler is semi-crystalline.
- 41. A polymerizable composition according to claim 38 wherein said radiopacifying filler is amorphous.
- 42. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight zirconium oxide, 0.01% to 40% by weight boron oxide, and 1% to 90% by weight silicon oxide.
- 43. A polymerizable composition according to claim 42 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 44. A polymerizable composition according to claim 42 wherein said radiopacifying filler is semi-crystalline.
- 45. A polymerizable composition according to claim 42 wherein said radiopacifying filler is amorphous.
- 46. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight yttrium oxide and 1% to 90% by weight silicon oxide.
- 47. A polymerizable composition according to claim 46 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 48. A polymerizable composition according to claim 46 wherein said radiopacifying filler is semi-crystalline.
- 49. A polymerizable composition according to claim 46 wherein said radiopacifying filler is amorphous.
- 50. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight yttrium oxide, 0.1% to 50% by weight aluminum oxide, and 1% to 90% by weight silicon oxide.
- 51. A polymerizable composition according to claim 50 wherein said radiopacifying filler comprises a sol-gel-derived filler.
- 52. A polymerizable composition according to claim 50 wherein said radiopacifying filler comprises a melt-derived filler.
- 53. A polymerizable composition according to claim 50 wherein said radiopacifying filler is semi-crystalline.
- 54. A polymerizable composition according to claim 50 wherein said radiopacifying filler is amorphous.
- 55. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight barium oxide, 0.1% to 40% by weight aluminum oxide, 0.01% to 80% by weight boron oxide, and 1% to 90% by weight silicon oxide.
- 56. A polymerizable composition according to claim 55 wherein said radiopacifying filler comprises a melt-derived filler.
- 57. A polymerizable composition according to claim 55 wherein said radiopacifying filler is amorphous.
- 58. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises 0.5% to 55% by weight strontium oxide, 0.1% to 40% by weight aluminum oxide, 0.01% to 80% by weight boron oxide, and 1% to 90% by weight silicon oxide.
- 59. A polymerizable composition according to claim 58 wherein said radiopacifying filler comprises a melt-derived filler.
- 60. A polymerizable composition according to claim 58 wherein said radiopacifying filler is amorphous.
- 61. A polymerizable composition according to claim 1 wherein said radiopacifying filler is selected from the group consisting of yttrium fluoride, zinc fluoride, tin fluoride, lanthanide fluorides, and combinations thereof.
- 62. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises a core having a first chemical composition and a coating on the surface of said core having a second chemical composition different from said first chemical composition.
- 63. A polymerizable composition according to claim 62 wherein said core is selected from the group consisting of quartz, fused quartz, silicate glass, zirconium oxide-silicon oxide, zirconium oxide-boron oxide-silicon oxide, and combinations thereof.
- 64. A polymerizable composition according to claim 62 wherein said coating is selected from the group consisting of silicate, boron oxide, colloidally derived silicon oxide, colloidally derived zirconium oxide, and combinations thereof.
- 65. A polymerizable composition according to claim 62 wherein said coating comprises a polymer.
- 66. A polymerizable composition according to claim 1 wherein said radiopacifying filler comprises one or more inorganic radiopacifying particles dispersed in a polymer matrix.
- 67. A polymerizable composition according to claim 1 wherein the amount of said filler composition is at least 50% by weight based upon the total weight of the polymerizable composition.
- 68. A polymerizable composition according to claim 1 wherein the amount of said filler composition is at least 70% by weight based upon the total weight of the polymerizable composition.
- 69. A polymerizable composition according to claim 1 wherein said filler composition further comprises a non-radiopacifying filler.
- 70. A polymerizable composition according to claim 1 wherein said initiator system comprises a photoinitiator system.
- 71. A polymerizable composition according to claim 70 wherein said polymerizable composition polymerizes to form a polymerized composition having a depth of cure of at least 2 mm within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 37□ C.
- 72. A polymerizable composition according to claim 70 wherein said polymerizable composition polymerizes to form a polymerized composition having a depth of cure of at least 6 mm within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 37□ C.
- 73. A polymerizable composition according to claim 1 wherein said initiator system comprises a salt selected from the group consisting of iodonium salts, sulfonium salts, organometallic complex salts, and combinations thereof.
- 74. A polymerizable composition according to claim 1 wherein said polymerizable composition comprises an epoxy resin comprising a cationically active functional groups.
- 75. A polymerizable composition according to claim 1 wherein said polymerizable composition comprises a vinyl ether comprising a cationically active functional group.
- 76. A polymerizable composition according to claim 1 wherein said polymerizable composition further comprises a free radically active functional group and an initiator system capable of initiating free radical polymerization of said free radically active functional group.
- 77. A polymerizable composition according to claim 76 wherein said polymerizable composition comprises an initiator system capable of initiating cationic polymerization of said cationically active functional group and free radical polymerization of said free radically active functional group.
- 78. A polymerizable composition according to claim 1 wherein said polymerizable composition comprises a dental composite.
- 79. A polymerizable composition according to claim 1 wherein said polymerizable composition comprises an orthodontic bracket adhesive.
- 80. A polymerizable composition according to claim 1 wherein said polymerizable composition comprises an orthodontic band cement.
- 81. A photopolymerizable dental composite comprising:
(a) a cationically active functional group; (b) a photoinitiation system capable of initiating cationic polymerization of said cationically active functional group upon exposure to visible light; and (c) a filler composition comprising a radiopacifying filler in an amount sufficient to render said photopolymerizable composite radiopaque, wherein components (a), (b), and (c) are selected such that upon exposure to visible light, said photopolymerizable composite polymerizes to form a polymerized composite having a Barcol hardness, measured using a GYZJ-935 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.
- 82. A photopolymerizable dental composite according to claim 81 wherein upon exposure to visible light, said composite polymerizes to form a polymerized composite having a Barcol hardness, measured using a GYZJ-934-1 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.
- 83. A photopolymerizable dental composite according to claim 81 wherein the amount of said filler composition is at least 50% by weight based upon the total weight of the polymerizable composite.
- 84. A photopolymerizable dental composite according to claim 81 further comprising an ethylenically unsaturated reactant comprising a free radically active functional group selected from the group consisting of an acrylic acid ester, a methacrylic acid ester, and combinations thereof.
- 85. A photopolymerizable dental composite according to claim 81 wherein upon exposure to visible light, said photopolymerizable composite polymerizes to form a polymerized composite having a depth of cure of at least 2 mm within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 37° C.
- 86. A polymerizable composition comprising:
(a) a cationically active functional group; (b) an initiation system capable of initiating cationic polymerization of said cationically active functional group; and (c) a filler composition comprising a radiopacifying filler other than a sulfate in an amount sufficient to render said polymerizable composition radiopaque, wherein components (a), (b), and (c) are selected such that said polymerizable composition polymerizes to form a polymerized composition having a Barcol hardness, measured using a GYZJ-935 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.
- 87. A method of preparing a polymerized composition comprising:
(a)providing a polymerizable composition comprising:
(i) a cationically active functional group; (ii) an initiation system capable of initiating cationic polymerization of said cationically active functional group; and (iii) a filler composition comprising a radiopacifying filler selected from the group consisting of metal oxides, metal halides, metal borates, metal phosphates, metal silicates, metal carbonates, metal germanates, metal tetrafluoroborates, metal hexafluorophosphates, and combinations thereof, in an amount sufficient to render said composition radiopaque, components (i), (ii), and (iii) being selected such that said polymerizable composition is capable of polymerizing to form a polymerized composition having a Barcol hardness, measured using a GYZJ-935 meter, of at least 10 within 30 minutes following initiation of said cationically active functional group at a reaction temperature of 25° C.; and (b) initiating polymerization of said cationically active functional group to form said polymerized composition.
- 88. A method according to claim 87 comprising initiating polymerization of said cationically active functional group at a reaction temperature of 37° C. or less.
- 89. A method according to claim 87 wherein said initiation system comprises a photoinitiation system,
said method comprising exposing said polymerizable composition to actinic radiation to initiate polymerization of said cationically active functional group.
- 90. A method according to claim 87 wherein said photoinitiation system comprises a visible light sensitizer,
said method comprising exposing said polymerizable composition to visible radiation to initiate polymerization of said cationically active functional group.
- 91. A method according to claim 87 wherein said initiation system comprises a thermal initiation system,
said method comprising exposing said composition to thermal radiation to initiate polymerization of said cationically active functional group.
- 92. A method according to claim 87 wherein said polymerized product comprises a dental composite.
- 93. A melt-derived filler comprising 5-25% by weight aluminum oxide, 10-35% by weight boron oxide, 15-50% by weight lanthanum oxide, and 20-50% by weight silicon oxide.
- 94. A melt-derived filler comprising 10-30% by weight aluminum oxide, 10-40% by weight boron oxide, 20-50% by weight silicon oxide, and 15-40% by weight tantalum oxide.
- 95. A melt-derived filler comprising 5-30% by weight aluminum oxide, 5-40% by weight boron oxide, 0-15% by weight lanthanum oxide, 25-55% by weight silicon oxide, and 10-40% by weight zinc oxide.
- 96. A melt-derived filler comprising 15-30% by weight aluminum oxide, 15-30% by weight boron oxide, 20-50% by weight silicon oxide, and 15-40% by weight ytterbium oxide.
- 97. Non vitreous microparticles prepared by a sol-gel method in which an aqueous or organic dispersion or sol of amorphous silicon oxide is mixed with an aqueous or organic dispersion, sol, or solution of a radiopacifying metal oxide, or precursor organic or inorganic compound,
said microparticles being substantially free of crystalline microregions or inhomogeneities detectable via powder x-ray diffraction.
- 98. Non vitreous microparticles prepared by a sol-gel method in which an aqueous or organic dispersion or sol of amorphous silicon oxide is mixed with an aqueous or organic dispersion, sol, or solution of a radiopacifying metal oxide, or precursor organic or inorganic compound,
said microparticles comprising:
(i) a plurality of amorphous microregions comprising oxygen and silicon, (ii) a plurality of semicrystalline radiopacifying, metal oxide microregions, and (iii) no greater than about 40% by weight of B2O3 or P2O5, said plurality of amorphous microregions being substantially uniformly interspersed with said plurality of semicrystalline microregions, said microparticles being substantially free of crystalline microregions or inhomogeneities having diameters greater than 0.4 micrometers.
- 99. Non vitreous microparticles according to claim 98 comprising 20-40% by weight zirconium oxide, 0.01-20% by weight boron oxide, and 1-90% by weight silicon oxide.
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. patent application Ser. No. 09/898,219, filed Jul. 3, 2001, which is a division of U.S. patent application Ser. No. 09/168,051, filed Oct. 7, 1998, now U.S. Pat. No. 6,306,926.
Divisions (2)
|
Number |
Date |
Country |
Parent |
09898219 |
Jul 2001 |
US |
Child |
10269131 |
Oct 2002 |
US |
Parent |
09168051 |
Oct 1998 |
US |
Child |
09898219 |
Jul 2001 |
US |