Polymerizable conditioners for adhesive bonding to dentin and enamel

• US 6,187,838 B1
• Filed: 06/07/1999
• Issued: 02/13/2001
• Est. Priority Date: 01/13/1997
• Status: Expired due to Term

• Current Assignee: ADA Foundation
• Original Assignee: American Dental Association Health Foundation
• Inventors: Dickens, Sabine H.
• Primary Examiner(s): Szekely, Peter A.
• Application Number:
  US09/327,180
• Time in Patent Office: 617 Days
• Field of Search: 523/116, 523/118, 524/547, 524/559, 526/277, 526/278, 526/318.1, 433/228.1, 206/63.5
• US Class Current: 523/118
• 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 6/40 Primers for dental adhesives A61K6/30
• CPC Class Codes: A61K 6/887 Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• 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 use of polymerizable monomeric conditioning agents for treating the enamel and dentin of a tooth prior to application of a primer and subsequent application of a bonding resin, or a combination of a primer/bonding resin has been found to provide good shear bond strength on both moist and dry dentin. In addition, the contact angles provided by water on dentin conditioned with the polymerizable conditioners as compared to the non-polymerizable phosphoric acid are much lower, reflecting improved spreading over the surface of the tooth.

Claims

1. A kit for repairing teeth, the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin.

2. The kit of claim 1 further comprising a filled composite resin.

3. The kit of claim 1 wherein the polymerizable acidic monomer contains at least two polymerizable functionalities, such that upon polymerization a cross-linked polymer is formed.

4. The kit of claim 3 wherein the polymerizable functionalities are methacrylate functionalities.

5. The kit of claim 3 wherein the primer and the bonding resin are in a single formulation.

7. The kit of claim 3 further comprising:

a photoinitiator and a photoreductant.

8. The kit of claim 3 wherein the primer and the bonding resin are in a single formulation.

6. A kit for repairing teeth, the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin,

wherein the polymerizable acidic monomer contains at least two polymerizable functionalities, such that upon polymerization a cross-linked polymer is formed and

wherein the tooth conditioner further comprises;

vinyl phosphonic acid or vinylbenzylphosphonic acid.

9. A composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride.

10. The composition of claim 9, wherein the dianhydride or anhydride chloride is selected from the group consisting of pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic acid dianhydride), 3,4-dicarboxy-1,2,3,4-tetrahydro-1-napthalenesuccinic acid dianhydride, 3,4,9,10-perylene tetracraboxylic anhydride, bicyclo (2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic anhydride, 1,4,5,8-napthalene tetracarboxylic anhydride, 3,3′

,4,4′

-benzophenone tetracarboxylic anhydride, 3,4-3′

,4′

-biphenyl tetracarboxylic anhydride, 1,2,3,4-cyclobutane tetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic acid 1,2,3,4-dianhydride, tetrahydrofuran 2,3,4,5-tetracarboxylic anhydride, 3-methyl-3-cyclohexene-1,2-carboxylic anhydride-5-ylsuccinic anhydride, and trimellitic anhydride chloride.

11. A composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride, wherein the dihydroxylated dimethacrylate is 2,2-bis {p(2′

-hydroxy-3′

-methacryloxypropoxyl)phenylene}propane (Bis-GMA).

12. A composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride, wherein the dihydroxylated dimethacrylate is an oligomeric analog of 2,2-bis{p(2′

-hydroxy-3′

-methacryloxypropoxyl)phenylene}propane (Bis-GMA).

13. A composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride, wherein the dihydroxylated dimethacrylate is 2,2-bis {p(2-hydroxy-3′

-methacryloxypropoxyl)phenylene}propane (Bis-GMA) and the dianhydride is pyromellitic dianhydride.

14. The composition of claim 13, wherein a molar ratio of reactants ranges from 1:

2 to 2;

1.

15. A composition comprising pyromellitic 2,2 bis-{p(2′

-hydroxy-3′

-methacryloxypropoxy)phenylene}propane (PMBGA).

16. A kit for repairing teeth, the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin,

wherein said dianhydride or anhydride chloride is selected from the group consisting of pyromellitic dianhydride (1,2,4,5-benzene tetracarboxylic acid dianhydride), 3,4-dicarboxy-1,2,3,4-tetrahydro-1-napthalenesuccinic acid dianhydride, 3,4,9,10-perylene tetracraboxylic anhydride, bicyclo (2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic anhydride, 1,4,5,8-napthalene tetracarboxylic anhydride, 3,3′

,4,4′

-benzophenone tetracarboxylic anhydride, 3,4-3′

,4′

-biphenyl tetracarboxylic anhydride, 1,2,3,4-cyclobutane tetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic acid 1,2,3,4-dianhydride, tetrahydrofuran 2,3,4,5-tetracarboxylic anhydride, 3-methyl-3-cyclohexene-1,2-carboxylic anhydride-5-ylsuccinic anhydride, and trimellitic anhydride chloride.

17. The kit of claim 16 further comprising a filled composite resin.

18. The kit of claim 16, wherein said polymerizable acidic monomer contains at least two polymerizable functionalities, such that upon polymerization a cross-linked polymer is formed.

19. The of claim 18, wherein said polymerizable functionalities are methacrylate functionalities.

20. A kit for repairing teeth the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin,

wherein said dihydroxylated dimethacrylate comprises 2,2-bis {p(2′

-hydroxy-3′

-methacryloxypropoxyl)phenylene}propane (Bis-GMA).

21. A kit for repairing teeth, the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin,

wherein said dihydroxylated dimethacrylate comprises an oligomeric analog of 2,2-bis {p(2′

-hydroxy-3′

-methacryloxypropoxyl)phenylene}propane (Bis-GMA).

22. A kit for repairing teeth, the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin,

wherein said dihydroxylated dimethacrylate comprises 2,2-bis {p(2′

-hydroxy-3′

-methacryloxypropoxyl)phenylene}propane (Bis-GMA) and said dianhydride comprises pyromellitic dianhydride.

23. The kit of claim 22, wherein a molar ratio of said Bis-GMA to said pyromellitic dianhydride ranges from 1:

2 to 2;

1.

24. A kit for repairing teeth, the kit comprising:

a tooth conditioner comprising a polymerizable acidic monomer which contains at least two carboxylic acid moieties, wherein said monomer comprises a composition formed by reacting (a) a dihydroxylated dimethacrylate and (b) a dianhydride or anhydride chloride;

a primer; and

a bonding resin,

further comprising pyromellitic 2,2 bis-{p(2′

-hydroxy-3′

-methacryloxypropoxy)pheylene}propane.