Dental composition and method

• US 5,367,002 A
• Filed: 02/06/1992
• Issued: 11/22/1994
• Est. Priority Date: 02/06/1992
• Status: Expired due to Fees

• Current Assignee: Dentsply Research & Development Corporation (Astrazeneca PLC)
• Original Assignee: Dentsply Research & Development Corporation (Astrazeneca PLC)
• Inventors: Hammesfahr, Paul D., Jefferies, Steven R., Huang, Chin-Teh
• Primary Examiner(s): Cain, Edward J.
• Application Number:
  US07/832,202
• Time in Patent Office: 1,020 Days
• Field of Search: 523/116, 523/115, 523/117, 523/118
• US Class Current: 523/116
• CPC Class Codes: A61K 6/20 Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• CPC Class Codes: A61K 6/30 Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• CPC Class Codes: A61K 6/889 Polycarboxylate cements; Glass ionomer cements
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Abstract

The invention provides dental composite compositions formed by mixing a curable liquid composition with a powder in preselected proportions. The composite compositions formed are useful as cement, liner, base, restorative, pit and fissure sealants, and/or core build-up material, etc. having improved adhesion to dentin. These composite compositions include polyalkenoic acid, filler which provides elutable cations which are reactive with the polyalkenoic acid and fluoride ion, water to provide for elution of cations reactive with polyalkenoic acid, polymerizable monomer and/or prepolymer composition, unsaturated organic acid having 1 or more polymerizable groups and a catalyst system for polymerization. Optionally the composites include inert reinforcing filler for strength, aesthetics, and radiopacity.

Claims

1. A dental composition, comprising:

a) polyalkenoic acid,

b) from about 10 to about 90 percent by weight elutable glass filler,

c) effectively partially neutralized acid functional polymerizable organic ester,

d) water,

e) polymerizable monomer and/or prepolymer, and

f) polymerization catalyst system,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic acid (a), and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler.

2. The composition of claim 1 wherein said acid ester compound (c) is an ethylenically unsaturated organic phosphate ester or phosphonate.

3. The composition of claim 2 wherein said ethylenically unsaturated organic phosphoric acid ester is from about 20 to about 40 equivalent weight percent neutralized.

4. The composition of claim 1 wherein said acid ester compound is a dipentaerythritol pentacrylate phosphoric acid ester, pentaerythritol trimethacrylate phosphoric acid ester, glyceryl phosphate dimethacrylate or BIS-GMA diphosphonate.

5. The composition of claim 1 further comprising polyacrylic acid, hydroxyethyl methacrylate, triethylene glycol, dimethacrylate, and water.

6. The composition according to claim 1 wherein said polymerization catalyst system comprises a redox polymerization system effective at room temperature.

7. The composition according to claim 1 wherein said polymerization catalyst system comprises a free radical producing peroxide and reducing agent.

8. The composition according to claim 7 wherein said peroxide is benzoyl peroxide and said reducing agent is a tertiary amine or an organic sulfinate.

9. The composition according to claim 1 wherein the catalyst system is adapted to provide photopolymerization.

10. The composition according to claim 1 wherein the catalyst system comprises a redox polymerization system effective at room temperature in combination with a photopolymerization system.

11. The composition of claim 1 wherein said catalyst system comprises camphorquinone and a reducing agent.

12. The composition of claim 1 wherein the catalyst system comprises camphorquinone, ethyl 4-dimethylamino benzoate and a peroxide.

13. The composition according to claim 1 further comprising non-reactive fillers.

14. The composition according to claim 13 wherein said non-reactive glass filler is silica, silicates, or aluminosilicate glasses.

15. The composition according to claim 1 wherein said reactive filler comprises glasses containing cations having a valence of 2 or more and adapted to be elutable in said composition.

16. The composition of claim 1 further comprising ethyl 4-dimethylaminobenzoate.

17. The composition of claim 1 wherein said acid ester is of the general formula:

##STR3## wherein R₁ is hydrogen, lower alkyl of from 1 to 5 carbons, halogen or CN radical;

n and m are independently integers of 1 or greater, Z is an aliphatic, cycloaliphatic or aryl radical, having a carbon chain comprising at least 2 carbon atoms and 0 or more oxygen or sulfur atoms and having a valency of m+n and containing at least 2 carbon atoms.

18. The composition of claim 1 wherein said acid functional polymerizable organic ester further comprises a mixture of compounds of the general formulas:

##STR4## wherein R₁ is hydrogen, lower alkyl of from 1 to 5 carbons, halogen or CN radical;

n and m are independently integers of 1 or greater, Z is an aliphatic, cycloaliphatic or aryl radical having a carbon chain comprising at least 2 carbon atoms and 0 or more oxygen or sulfur atoms and having a valency of m+n and M, M₁ and M₂ each is independently a cation.

19. The composition of claim 18 wherein from 20 to 40 equivalent weight percent of said mixture of compounds is neutralized by reaction with base.

20. The composition of claim 1 wherein said elutable filler comprises from about 10 to 90 percent by weight of said composition.

21. The composition of claim 1 wherein said elutable filler comprises from about 20 to 90 percent by weight of said composition.

22. The composition of claim 1 wherein said composition comprising polyacrylic acid, hydroxyethyl methacrylate, water, triethyleneglycoldimethacrylate, dipentaerythritolpentacrylate phosphoric acid ester, camphorquinone, and ethyl 4-dimethylaminobenzoate.

23. The composition of claim 1 wherein said dental composition comprises

(a) from 0.5 to 30 percent weight polyalkenoic acid,

(b) from 10 to 90 percent by weight elutable glass filler,

(c) from 1 to 60 percent by weight an acid functional polymerizable organic ester, and said acid functional polymerizable organic ester comprises a mixture of compounds of the general formulas:

##STR5## wherein R₁ is hydrogen, lower alkyl of from 1 to 5 carbons, halogen or CN radical;

n and m are independently integers of 1 or greater, Z is an aliphatic, cycloaliphatic or aryl radical having a carbon chain comprising at least 2 carbon atoms and 0 or more oxygen or sulfur atoms and having a valency of m+n and M, M₁ and M₂ each is independently a cation, said mixture of compounds of general formulas I, II and III being formed by mixing from 20 to 40 equivalent weight percent of a base and said compounds at about pH 1,

(d) from 0.5 to 30 percent by weight water,

(e) from 1 to 60 percent by weight polymerizable monomer and/or prepolymer, and

(f) from 0.01 to 10 percent by weight polymerization catalyst system,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic acid (a), and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler, said composition being adapted to form a substantially radiopaque polymeric product.

24. The composition of claim 23 wherein said dental composition comprises

(a) from 0.5 to 20 percent weight polyalkenoic acid,

(b) from 20 to 90 percent by weight elutable glass filler,

(c) from 2 to 50 percent by weight of an acid functional polymerizable organic ester which is partially neutralized by addition of from 20 to 40 equivalent weight percent base,

(d) from 0.5 to 20 percent by weight water,

(e) from 2 to 50 percent by weight polymerizable monomer and/or prepolymer, and

(f) from 0.01 to 5 percent by weight polymerization catalyst system,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic acid (a), and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler, said composition being adapted to form a substantially radiopaque polymeric product.

25. The composition of claim 23 wherein said composition comprises from 1 to 60 percent by weight non-reactive filler.

26. The composition of claim 24 wherein said composition comprises from 4 to 40 percent by weight non-reactive filler.

27. The composition of claim 1 wherein said dental composition comprises

(a) from 0.5 to 10 percent weight polyalkenoic acid,

(b) from 30 to 90 percent by weight elutable glass filler,

(c) from 2 to 40 percent by weight an acid functional polymerizable organic esters, which are from 20 to 40 equivalent weight percent neutralized by mixing with a base,

(d) from 0.5 to 10 percent by weight water,

(e) from 5 to 40 percent by weight polymerizable monomer and/or prepolymer,

(f) from 0.01 to 4 percent by weight polymerization catalyst system, and

(g) from 4 to 30 percent by weight non-reactive filler,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic acid (a), and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler, said composition being adapted to form a substantially radiopaque polymeric product.

28. The composition of claim 27 wherein said acid functional polymerizable organic ester comprises from about 1 to 60 percent by weight of dipentaerythritol pentacrylate phosphoric acid of said composition.

29. A dental composition comprising

(a) a polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000,

(b) a fluoroaluminosilicate glass powder having an average particle size of 0.02 to 50 μ

m and a specific gravity of 2.0 to 4.0 and capable of reacting with said polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000,

(c) a polymerizable monomer and/or prepolymer,

(d) a polymerization catalyst,

(e) water,

(f) ethylenically unsaturated organic acid, 20 to 40 equivalent weight percent salts of said ethylenically unsaturated organic acid, and

(g) a reducing agent,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic acid (a), a substantial portion of said cations being strontium cations and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler, said composition being adapted to form a substantially radiopaque polymeric product.

30. The composition of claim 29 further comprising at least one non-reactive filler.

31. A dental composition according to claim 29 wherein said non-reactive glass is further characterized by not forming a hardened coherent mass within 10 hours when combined with said α

-β

unsaturated polycarboxylic acid.

32. A dental composition according to claim 29 wherein said polymerizable monomer and/or prepolymer is further characterized as not forming a hardened coherent mass within 10 hours when combined with said non-reactive glass.

33. A dental composition comprising:

(a) 0.5 to 30 parts by weight of a polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000,

(b) 10 to 90 parts by weight of a fluoroalumino-silicate glass powder having an average particle size of 0.02 to 50 μ

m and a specific gravity of 2.0 to 4.0 and capable of reacting with said polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000,

(c) 1 to 60 parts by weight of a polymerizable monomer or prepolymer,

(d) 0.5 to 30 parts by weight of water,

(e) 1 to 60 parts by weight of ethylenically unsaturated organic acid and salts of said ethylenically unsaturated organic acid, said salts being 20 to 40 equivalent weight percent of said acid,

(f) 0.01 to 5 parts by weight of a polymerization catalyst, and

(g) 0.001 to 5 parts by weight of a reducing agent,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic acid (a), a substantial portion of said cations being strontium cations and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler, said composition being adapted to form a substantially radiopaque polymeric product.

34. The composition of claim 33 further comprising 1 to 60 parts non-reactive glass powder.

35. A dental composition as claimed in claim 33 wherein said "polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000" is a co- or homopolymer containing at least one selected from the group consisting of acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid and citraconic acid.

36. A dental composition as claimed in claim 33 wherein said "polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000", is a co- or homopolymer containing acrylic and maleic acids.

37. A dental composition as claimed in claim 33 wherein said polymerizable unsaturated organic compound having at least one CH₂ ═

C(R1)--COO group wherein R1 is H or CH₃ is an ester of acrylic or methacrylic acid.

38. A dental composition as claimed in claim 33 wherein said fluoroaluminosilicate glass powder having an average particle size of 0.02 to 50 μ

m and a specific gravity of 2.0 to 4.0 and capable of reacting with said "polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000", contains Al³⁺, Si⁴⁺, F^- and O^2-, as elutable cations and including further Sr²⁺ and/or Ca²⁺.

39. A dental composition as claimed in claim 33 wherein said "polymerization catalyst" is a photopolymerization catalyst.

40. A dental composition as claimed in claim 33 wherein said aluminosilicate glass powder having an average particle size of 0.02 to 50 μ

m and a specific gravity of 2.0 to 4.0 and capable of reacting with said polymer of an α

-β

unsaturated carboxylic acid having a weight average molecular weight of 5,000 to 500,000 is a fluoroaluminosilicate glass powder which is coated on its surface with an organic compound.

41. A two-paste dental composition comprising a first and a second paste, said first paste comprising a polyalkenoic acid, an acid functional polymerizable organic ester, and a non-reactive filler;

said second paste, comprising a polymerizable monomer and/or prepolymer, cation elutable glass filler, and water, at least one of said first and second paste comprising a catalyst.

42. A method of treating a tooth consisting of dental compositions, comprising mixing a powder and polymerizable liquid in preselected proportions to form at least two dental compositions selected from the group consisting of cement, liner, base, restorative, core build-up, and pit and fissure sealant, and applying them to at least one tooth whereupon they are caused to harden wherein said dental compositions comprise

a) polyalkenoic acid,

b) elutable glass filler,

c) an acid functional polymerizable organic ester, 20 to 40 equivalent weight percent salts of said acid functional polymerizable organic ester,

d) water,

e) polymerizable monomer and/or prepolymer, and

f) polymerization catalyst system,

said elutable glass filler (b) being adapted to elute strontium and fluoride cations which are reactive with said polyalkenoic acid (a) to form a substantially radiopaque polymeric product, and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler.

43. The method of claim 42 wherein said powder comprises a glass-containing elutable cations of valence of 2 or more.

44. The method of claim 42 wherein said polymerizable liquid comprises polymerizable monomer and an acid ester compound.

45. The method of claim 42 wherein said polymerizable liquid comprises dipentaerythritol pentacrylate phosphoric acid ester.

46. The method of claim 42 wherein said powder and liquid are mixed in a ratio of from 0.5 to 6 parts by weight powder to 1 part by weight liquid.

47. A dental composition comprising a powder and liquid wherein said powder comprises

(a) about 70-85 percent by weight strontium fluoroaluminosilicate glass,

(b) about 0.7-0.9 percent by weight ethyl 4-dimethylaminobenzoate, and

(c) about 15-30 percent by weight barium alumino borosilicate glass;

and said liquid comprises

(a) about 6-8 percent by weight polyacrylic acid,

(b) about 6-8 percent by weight water,

(c) about 26-32 percent by weight hydroxyethylmethacrylate,

(d) about 26-32 percent by weight tetraethylene glycol dimethacrylate,

(e) about 26-30 percent by weight dipentaerythritol pentacrylate phosphoric acid, dipentaerythritol pentacrylate phosphoric acid salts, said salts being 20 to 40 equivalent weight percent of said acid and

(f) about 0.1-0.5 percent by weight camphorquinone,

said elutable glass filler (b) being adapted to elute cations which are reactive with said polyalkenoic (a), a substantial portion of said cations being strontium and said monomer and/or prepolymer (e) being non-reactive with cations from the elutable glass filler, said composition being adapted to form a substantially radiopaque polymeric product.

48. A polymerizable liquid dental composition, comprising:

14.2 parts by weight polyacrylic acid;

28.5 parts by weight hydroxyethyl methacrylate;

0.1 parts by weight butylate hydroxytoluene;

28.5 parts by weight triethylene-glycol dimethacrylate;

28.5 parts by weight partially neutralized dipentaerythritol pentacrylate phosphoric acid ester and

0.2 parts by weight camphorquinone.