Radiopaque fluoride releasing VLC dental composites and the use of specific fillers therein

• US 5,304,586 A
• Filed: 08/02/1991
• Issued: 04/19/1994
• Est. Priority Date: 01/30/1989
• Status: Expired due to Term

• Current Assignee: Dentsply Research & Development Corporation (Astrazeneca PLC)
• Original Assignee: Dentsply Research & Development Corporation (Astrazeneca PLC)
• Inventors: Campbell, Robert C., Danielson, Paul S., Hammesfahr, Paul D.
• Primary Examiner(s): Page, Thurman K.
• Assistant Examiner(s): Hulina, Amy
• Application Number:
  US07/739,946
• Time in Patent Office: 991 Days
• Field of Search: 424/52, 523/116, 523/117, 501/59
• US Class Current: 523/117
• CPC Class Codes: A61K 6/77 Glass
• CPC Class Codes: A61K 6/893 Polyurethanes
• CPC Class Codes: C08L 75/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10S 522/908 Dental utility

Abstract

One component, visible light-cured dental restorative compositions having fluoride release properties for the purpose of reducing the chances of secondary caries are provided. The compositions include inorganic particulate fluoride leachable glass.

Claims

1. A dental composite composition comprising;

photoactivated resin suitable for a dental restorative and translucent, phase separated, fluoride-containing glass wherein the phase separated droplets do not exceed about 1400 angstrom in size and wherein upon exposure to an aqueous environment, fluoride ions will be released therefrom at a controlled, relatively constant rate over a substantial period of time, but with essentially no development of porosity or other physical breakdown effect, and which can be melted and formed with relatively low volatilization of fluorine, said glass being essentially free of alkali metal oxides and heavy toxic metals and consisting essentially, expressed in terms of weight percent of;

SiO₂ ;

40-56;

BaO;

15-35;

Al₂ O₃ ;

4-12;

B₂ O₃ ;

5-12;

F;

2-20;

ZrO;

0-7;

SrO;

0-18.

4. The composition of claim 1 wherein said resin and glass comprises a matrix wherein said resin is chemically bonded to said inorganic filler, and wherein said matrix is adapted to slowly release fluoride ion when said matrix is in the oral cavity without significantly reducing the strength and physical integrity of said matrix.

5. The composition of claim 1 wherein said inorganic filler is essentially free of alkali metal oxides and heavy toxic metals and consists essentially of by weight 41.4-55.9% SiO₂, 24.7-33.6% BaO, 5.6-11% Al₂ O₃, 6.5-10.3% B₂ O₃, and 3-6% F.

6. The composition of claim 1 wherein said glass comprises 4-8% Al₂ O₃.

7. The composition of claim 1 wherein said fluoride is provided in said glass by the presence of SrF₂, AlF₃, or BaF₂, or a mixture thereof in the materials used in the preparation of said glass.

8. The composition of claim 1 wherein said resin is hardenable by free radical polymerization and comprises:

(a) binder resin comprising the reaction product of at least one vinyl ester of a polyglycidyl ether having secondary hydroxyl groups and at least one isocyanate reactant, said isocyanate reactant and said vinyl ester reacting through said secondary hydroxyl groups;

(b) a polymerizable acrylic diluent monomer; and

(c) a free radical polymerization catalyst, said diluent being present in an amount such that said composition has a viscosity suitable for use in dental applications.

9. The composition of claim 1 wherein said resin comprises isocyanate having ethylenic unsaturation.

10. The composition of claim 1 wherein said resin comprises a photosensitive catalyst system.

11. The composition of claim 1 which comprises from about 20% to about 90% by weight of said glass.

12. The composition of claim 1 wherein said resin comprises Bis-GMA.

13. The composition of claim 1 wherein said resin comprises isocyanatoethyl methacrylate.

14. The composition of claim 1 wherein said resin comprises triethyleneglycol diemthacrylate, 1,6-Hexanediol dimethacrylate, or ethoxylated bisphenol-A-dimethacrylate.

15. The composition of claim 1 wherein said resin component comprises the reaction product of a vinyl ester of a polyglycidyl ether having secondary hydroxyl groups, a first isocyanate reactant containing ethylenic unsaturation and a second isocyanate reactant which is diisocyanate, said vinyl ester and said first and second isocyanate reactants being reacted through said secondary hydroxyl groups.

16. The composition of claim 1 wherein said resin comprises Bis-GMA, isocyanathoetyhl methacrylate or trimethylhexamethylene diisocyanate.

17. The composition of claim 1 wherein said resin comprises the reaction product of a second vinyl ester of a polyglycidyl ether having secondary hydroxyl groups and a diisocyanate reacted through said secondary hydroxyl groups.

18. The composition of claim 1 wherein said resin comprises Bis-GMA and a diisocyanate selected from the group consisting of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and phenylene diisocyanate.

19. The composition of claim 1 wherein said resin comprises a diisocyanate.

20. The composition of claim 1 wherein said resin comprises trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and phenylene diisocyanate.

21. The composition of claim 1 wherein said inorganic filler comprises, by weight, from about 35 to about 64% of silanated barium glass having a mean particle size of from about 5 to about 9 microns, from about 20 to about 50% of a silanated barium glass having a mean particle size of from about 2 to about 5 microns, and from about 5 to about 15% of a silanated submicron silica.

22. The composition of claim 1 wherein said glass is present in said composition in an amount of from about 50% to about 80% by weight.

23. The composition according to claim 1 wherein up to one-half on a molar basis of BaO is replaced with SrO.

24. The composition according to claim 1 wherein up to one-third on a molar basis of BaO is replaced with ZnO.

25. The composition according to claim 1 wherein said heavy toxic metals are selected from the group consisting of arsenic, cadmium, lead and mercury.

26. The composition according to claim 1 wherein said fluoride is included in the composition through the use of a batch material selected from the group of AlF₃ and BaF₂.

2. A method of making a dental composite restorative composition, comprising:

providing a resin suitable for use in a dental restorative and an inorganic filler comprising nonalkali, radiopaque glass containing extractable fluoride, said glass being translucent, phase separated, fluoride-containing glass wherein the phase separated droplets do not exceed about 1400 angstrom in size and wherein upon exposure to an aqueous environment, fluoride ions will be released therefrom at a controlled, relatively constant rate over a substantial period of time, but with essentially no development of porosity or other physical breakdown effect, and which can be melted and formed with relatively low volatilization of fluorine, said glass being essentially free of alkali metal oxides and heavy toxic metals and consisting essentially, expressed in terms of weight percent of;

SiO₂ ;

41.4-55.9;

BaO;

24.7-33.6;

Al₂ O₃ ;

5.6-11;

B₂ O₃ ;

6.5-10.3;

F;

3-6 and

forming said composition into a dental composite restorative adapted to provide at least 0.5 ppm of fluoride through leaching into a static aqueous medium at about 37°

C. replaced weekly over a 30 week period.

3. A method of extracting fluoride form a dental composite restorative composition, comprising:

providing a blend of at least 10% by weight of polymerizable resin suitable for use in a dental restorative and from 20 and 90% by weight of an inorganic filer comprising nonalkali, silantable, radiopaque glass containing BaO and fluoride, said glass being translucent, phase separated, fluoride-containing glass wherein the phase separated droplets do not exceed about 1400 angstrom in size and wherein upon exposure to an aqueous environment, fluoride ions will be released therefrom at a controlled, relatively constant rate over a substantial period of time, but with essentially no development of porosity or other physical breakdown effect, and which can be melted and formed with relatively low volatilization of fluorine, said glass being essentially free of alkali metal oxides and heavy toxic metals and consisting essentially, expressed in terms of weight percent of;

SiO₂ ;

41.4-55.9;

BaO;

24.7-33.6;

Al₂ O₃ ;

5.6-11;

B₂ O₃ ;

6.5-10.3;

F;

3-6 and

forming said composition into a dental composite restorative adapted to provide at least 0.5 ppm of fluoride through leaching into a static aqueous medium at about 37°

C. at a rate sufficient to maintain from about 0.5 to about 2.0 ppm fluoride in said medium over a 20 week period during which said medium is replaced weekly.

27. A dental composite restorative composition comprising

(a) a resin suitable for use in a dental restorative, and

(b) an inorganic filler particle having a mean particle size less than 9 microns comprising a non alkali, silantable, radiopaque glass containing extractable fluoride, said fluoride comprising from about 1 to about 20 percent by weight of said composition said glass being translucent, phase separated, fluoride-containing glass wherein the phase separated droplets do not exceed about 1400 angstrom in size and wherein upon exposure to an aqueous environment, fluoride ions will be released therefrom at a controlled, relatively constant rate over a substantial period of time, but with essentially no development of porosity or other physical breakdown effect, and which can be melted and formed with relatively low volatilization of fluorine, said glass being essentially free of alkali metal oxides and heavy toxic metals and consisting essentially, expressed in terms of weight percent of:

SiO₂ ;

41.4-55.9;

BaO;

24.7-33.6;

Al₂ O₃ ;

5.6-11;

B₂ O₃ ;

6.5-10.3;

F;

3-6;

28. The composition of claim 27 wherein said fluoride comprises from about 2 to about 15 percent by weight of said composition.

29. The composition of claim 27 wherein said fluoride comprises from about 2 to about 7 percent by weight of said composition.