Compositions for endodontic procedures

Abstract

An adhesion promoter for endodontic sealant compositions for filling and sealing a root canal.

Claims

1. An endodontic composite sealant composition for filling and sealing a root canal comprising an adhesion promoter, wherein the adhesion promoter is characterized by the following formula (I):
R.sup.1R.sup.2WZR.sup.3R.sup.4(I) wherein ##STR00028## wherein R.sup.1 and R.sup.4 are independently Hydrogen, NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; R.sup.2 and R.sup.3 are independently a C.sub.1-10 alkyl group, NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.13 group such that R.sup.13 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 may be identical or different; and x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 1000, multiple groups of m may be identical or different.

2. The composition of claim 1, wherein a portion of the adhesion promoter includes a ring-opening functionality, a reactive-cyclic functionality, a free radical functionality, or any combination thereof.

3. The composition of claim 1, wherein the adhesion promoter includes a dentin binding functionality.

4. The composition of claim 3, wherein the dentin binding functionality includes a negative charge, a positive charge, an amphoteric charge, or a zwitterionic charge.

5. The composition of claim 4, wherein the negative or positive charge comprises carboxylic acid groups, sulfate groups, amine groups, phosphate groups, quaternary ammonium groups and sulfonate, betaine, phosphatidylcholine groups.

6. The composition of claim 1, wherein: i) R.sup.1 and R.sup.4 are independently an epoxide, a succunic anhydride, or a succinimide group; ii) R.sup.1 and R.sup.4 are independently NH.sub.2, OH, COOH, or SH group; or iii) at least one of R.sup.1 and R.sup.4 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group.

7. The composition of claim 1, wherein: i) R.sup.1 and R.sup.4 are independently an epoxide, a succunic anhydride, or a succinimide group; and ii) at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 is independently the C.sub.1-10R.sup.13 group such that R.sup.13 is independently the phosphate, the sulfate, the sulfonate, the betaine, the carboxylic acid, the amino acid, the diacids, the bisphosphate, or the phosphatidylcholine group.

8. The composition of claim 1, wherein: i) R.sup.1 and R.sup.4 are independently NH.sub.2, OH, COOH, or SH group; and ii) at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 is independently the C.sub.1-10R.sup.13 group such that R.sup.13 is independently the phosphate, the sulfate, the sulfonate, the betaine, the carboxylic acid, the amino acid, the diacids, the bisphosphate, or the phosphatidylcholine group.

9. The composition of claim 1, wherein: i) at least one of R.sup.1 and R.sup.4 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; and ii) at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 is independently the C.sub.1-10R.sup.13 group such that R.sup.13 is independently the NH.sub.2, OH, COOH, SH, epoxide, succunic anhydride, or succinimide group, whereas NH.sub.2, OH, COOH, or SH group is not present when the epoxide, the succunic anhydride, or the succinimide group is present.

10. The composition of claim 1, wherein R.sup.5, R.sup.6, R.sup.11, and R.sup.12 are independently a C.sub.1-10 alkyl group.

11. The composition of claim 1, wherein ##STR00029## and wherein R.sup.1 and R.sup.4 are independently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, provided at least one of R.sup.1 and R.sup.4 is not Hydrogen; R.sup.2 and R.sup.3 are independently a C.sub.1-10 alkyl group; and R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.13 group such that R.sup.13 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 may be identical or different, provided at least two of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 includes the C.sub.1-10R.sup.13 group.

12. The composition according to claim 11, wherein NH.sub.2, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.

13. The composition of claim 11, wherein at least two of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, and R.sup.12 includes the C.sub.1-10R.sup.13 group.

14. The composition of claim 11, wherein x ranges from 1-50, y ranges from 25-250, and m is 1.

15. An endodontic composite sealant composition for filling and sealing a root canal comprising an adhesion promoter, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (IIa):
R.sup.1R.sup.2WZR.sup.3R.sup.4(IIa); wherein R.sup.1 and R.sup.4 are independently NH.sub.2, OH, COOH, or SH; R.sup.2 and R.sup.3 are independently a C.sub.1-10 alkyl group; ##STR00030## R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.13 group such that R.sup.13 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 may be identical or different; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different; and b) the second component is characterized by the following formula (IIb):
R.sup.13R.sup.14WZR.sup.15R.sup.16(IIb); wherein R.sup.13 and R.sup.16 are independently an epoxide, a succunic anhydride, or a succinimide group; R.sup.14 and R.sup.15 are independently a C.sub.1-10 alkyl group; ##STR00031## R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, and R.sup.23 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.24 group such that R.sup.24 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, and R.sup.24 may be identical or different; q is an integer from 1 to 1000, multiple groups of q may be identical or different; r is an integer from 1 to 1000, multiple groups of r may be identical or different; and s is an integer from 1 to 10, multiple groups of s may be identical or different.

16. The composition of claim 15, wherein i) at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12 includes the C.sub.1-10R.sup.13 group; and/or ii) at least one of R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, and R.sup.23 includes the C.sub.1-10R.sup.24 group.

17. The composition of claim 15, wherein i) at least one of R.sup.7 and R.sup.8 includes the C.sub.1-10R.sup.13 group; and/or ii) at least one of R.sup.18 and R.sup.19 includes the C.sub.1-10R.sup.24 group.

18. The composition of claim 15, wherein x ranges from 1-50, y ranges from 25-250, and m is 1 and wherein q ranges from 1-50, r ranges from 25-250, and s is 1.

19. An endodontic composite sealant composition for filling and sealing a root canal comprising an adhesion promoter, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (IIIa):
R.sup.1R.sup.2WZR.sup.3R.sup.4(IIIa); wherein R.sup.1 and R.sup.4 are independently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, provided at least one of R.sup.1 and R.sup.4 is not Hydrogen; R.sup.2 and R.sup.3 are independently a substituted or unsubstituted C.sub.1-10 alkyl group; ##STR00032## R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.13 group such that R.sup.13 is independently NH.sub.2, OH, COOH, SH, whereas multiple groups of R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 may be identical or different; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different; and b) the second component is characterized by the following formula (IIIb):
R.sup.13R.sup.14WZR.sup.15R.sup.16(IIIb); wherein R.sup.13 and R.sup.16 are independently Hydrogen, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, provided at least one of R.sup.1 and R.sup.4 is not Hydrogen; R.sup.14 and R.sup.15 are independently a substituted or unsubstituted C.sub.1-10 alkyl group; ##STR00033## R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, and R.sup.23 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.24 group such that R.sup.24 is independently an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, and R.sup.24 may be identical or different; q is an integer from 1 to 1000, multiple groups of q may be identical or different; r is an integer from 1 to 1000, multiple groups of r may be identical or different; and s is an integer from 1 to 10, multiple groups of s may be identical or different.

20. The composition of claim 19, wherein i) at least one of R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12 includes the C.sub.1-10R.sup.13 group; and/or ii) at least one of R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, R.sup.22, and R.sup.23 includes the C.sub.1-10R.sup.24 group.

21. The composition of claim 19, wherein x ranges from 1-50, y ranges from 25-250, and m is 1; and wherein q ranges from 1-50, r ranges from 25-250, and s is 1.

22. An endodontic composite sealant composition for filling and sealing a root canal comprising an adhesion promoter, wherein adhesion promoter is characterized by the following formula (IV):
R.sup.1WZR.sup.2(IV) wherein R.sup.1 and R.sup.2 are independently a substituted or unsubstituted C.sub.1-11alkyl group; ##STR00034## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.11 group such that R.sup.11 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, a succinimide group, a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; whereas multiple groups of R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 may be identical or different; provided that at least one of R.sup.3, R.sup.4 R.sup.5, R.sup.6, R.sup.7, and R.sup.8 includes the C.sub.1-10R.sup.11 group; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different.

23. The composition according to claim 22, wherein NH.sub.2, OH, COOH, or SH is not present when the epoxide, the succunic anhydride, or the succinimide group is present.

24. The composition of claim 22, wherein ##STR00035## and wherein R.sup.3, R.sup.4, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 include the C.sub.1-10 alkyl group; x ranges from 1-50; y ranges from 25-250; and m is 1.

25. An endodontic composite sealant composition for filling and sealing a root canal comprising an adhesion promoter, wherein the adhesion promoter includes a first component and a second component, a) the first component is characterized by the following formula (IVa):
R.sup.1WZR.sup.2(IVa) wherein R.sup.1 and R.sup.2 are independently a substituted or unsubstituted C.sub.1-11 alkyl group; ##STR00036## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.11 group such that R.sup.11 is independently NH.sub.2, OH, COOH, or SH; whereas multiple groups of R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, and R.sup.11 may be identical or different; provided that at least one of R.sup.3, R.sup.4 R.sup.5, R.sup.6, R.sup.7, and R.sup.8 includes the C.sub.1-10R.sup.11 group; x is an integer from 1 to 1000, multiple groups of x may be identical or different; y is an integer from 1 to 1000, multiple groups of y may be identical or different; and m is an integer from 1 to 10, multiple groups of m may be identical or different; and b) the second component is characterized by the following formula (IVb):
R.sup.12WZR.sup.13(IVb) wherein R.sup.12 and R.sup.13 are independently a substituted or unsubstituted C.sub.1-11 alkyl group; ##STR00037## wherein R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, and R.sup.21 are independently Hydrogen, a C.sub.1-10 alkyl group, or a C.sub.1-10R.sup.22 group such that R.sup.22 is independently an epoxide, a succunic anhydride, or a succinimide group; whereas multiple groups of R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21, and R.sup.22 may be identical or different; provided that at least one of R.sup.14, R.sup.15, R.sup.16, R.sup.17, R.sup.18, and R.sup.19 includes the C.sub.1-10R.sup.11 group; q is an integer from 1 to 1000, multiple groups of x may be identical or different; r is an integer from 1 to 1000, multiple groups of y may be identical or different; and s is an integer from 1 to 10, multiple groups of m may be identical or different.

26. The composition of claim 25, wherein i) at least one of R.sup.5, R.sup.6, R.sup.7, and R.sup.8 includes the C.sub.1-10R.sup.11 group; and ii) at least one of R.sup.16, R.sup.17, R.sup.18, and R.sup.19 includes the C.sub.1-10R.sup.22 group.

27. The composition of claim 25, wherein x ranges from 1-50, y ranges from 25-250, and m is 1; and wherein q ranges from 1-50, r ranges from 25-250, and s is 1.

28. The composition of claim 25, wherein i) at least one of R.sup.5, R.sup.6, R.sup.7, and R.sup.8 is independently a C.sub.1-10R.sup.23 group such that R.sup.23 is a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; whereas multiple groups of R.sup.5, R.sup.6, R.sup.7, and R.sup.8 may be identical or different; and/or ii) at least one of R.sup.16, R.sup.17, R.sup.18, and R.sup.19 is independently a C.sub.1-10R.sup.24 group such that R.sup.24 is a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group; whereas multiple groups of R.sup.16, R.sup.17, R.sup.18, and R.sup.19 may be identical or different.

29. The composition of claim 1, further comprising bioglass or a bioactive glass.

30. The composition of claim 15, wherein the first component, the second component or both further include bioglass or a bioactive glass.

31. The composition of claim 19, wherein the first component, the second component or both further include bioglass or a bioactive glass.

32. The composition of claim 22, further comprising bioglass or a bioactive glass.

33. The composition of claim 25, wherein the first component, the second component or both further include bioglass or a bioactive glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Desirably, the composite sealant composition includes a cross-linkable material, though not required.

(2) In general, the present invention is directed to an improved high strength composite sealant composition and processes of forming the composition. Advantageously, the composite sealant composition can be employed to form dental sealants with desirable high strength characteristics. This high strength material enables the preparation of root canals and may be useful for improved bonding (higher adhesion) to the tooth dentin and/or root canal points. Dental materials containing polymerizable resins and filler particles often are used to prepare the root canals. Such dental materials can be self (chemically)-curable, heat-curable, light-curable, or dual-curable. The dental materials are cured and hardened by different chemical mechanisms to form strong and durable materials for various dental applications.

(3) In one aspect, the invention solves the problem of the creation of a seal between the sealer and the gutta-percha AND a seal between the sealer and the dentin to prevent leakage of bacteria into the root canal. The invention uses rubber formulations cryogenically ground into a powder and mixed as a filler in various two part polymer systems. The ground rubber can be blended in either one or both parts of the polymer system. One or more types of ground rubber can be used. This will create a fluid(s) with a paste like viscosity.

(4) The technology to make this work may not be the grinding or the dispersion into the polymer system. It is believed that the formulation of the ground rubber in relation to the polymer system provides the one of the advantages of this invention.

(5) In another aspect the invention solves the problem of the creation of a seal between the obturation material and the dentine to prevent leakage of bacteria into the root canal. The invention is two ideal molecular additives which have been designed to bond to collagen AND hydroxyapatite.

(6) Dentin is composed of a collagen (hydrocarbon polymer) matrix holding together crystalline hydroxyapatite (CaP). The dentin binding molecules are designed to include three subcomponents in a tri block construction. For example, in a first portion, Block A, may be composed of phosphate group, in a second portion, Block B, may be composed of tris methacrylate and in a third portion, Block C, may be either a reactive group such as an amino methacrylate or a glycidal methacrylate. Block A is designed to bond to the hydroxyapatite. Block B is designed to be a compatibilizer. Block C is designed to cross link into the network during setting (amino/epoxy reaction). The molecular additives are dispersed into two dimethylsiloxanes; an amino functionalized and an epoxy functionalized (see the attached document for more detail).

(7) Polymerizable Materials

(8) The polymerizable material (e.g., a composite sealant composition) typically includes at least one polymerizable component and optionally without limitation, one or more of at least one filler (e.g., glass particles), an adhesion promoter, an initiator, a catalyst, an accelerator, an inhibitor, surfactant, additive, or combinations thereof or others.

(9) Polymerizable Compounds

(10) Turning now in greater detail to the individual components of the overall composition. The composite sealant composition herein may include at least one polymerizable material. Desirably, the composite sealant composition may include a first polymerizable material having at least one of a cyclic compound that is capable of undergoing a ring opening reaction (e.g., a succunic anhydride, a succinimide group, an epoxide, or otherwise) a ring opening nucleophile (e.g., OH, COOH, SH, an amine resin (e.g., NH.sub.2), or otherwise), urethane di-(meth)acrylate, multi(meth)acrylate derivatives of isocyanatomethyl cyclohexane, a polymerizable polysiloxane compound (e.g., an epoxy functionalized siloxane, an amino functionalized siloxane, or otherwise), or any combination thereof.

(11) The first polymerizable material may typically be present in an amount of at least about 1%, preferably at least about 5%, and more preferable at least about 10% by wt the composite sealant composition. Furthermore, it is appreciated that the first polymerizable material may typically be present in an amount of less than about 99%, preferably less than about 75% and preferably less than about 50% by wt the overall composite sealant composition. For example, the first polymerizable material may typically be present in an amount ranging from about 1% to about 99%, preferably from about 5% to about 75%, and more preferably from about 10% to about 50% by wt the overall composite sealant composition. In one specific embodiment, the first polymerizable material is the polymerizable polysiloxane compound.

(12) Examples of polymerizable polysiloxane compounds (e.g., polydimethylsiloxane copolymers) that may be used in the composition of this invention, include, but are not limited to, cyclic compounds that are capable of undergoing a ring opening reaction such as epoxy modified polysiloxane compounds (e.g., difunctional and multifunctional epoxy silicones) and ring opening nucleophiles such as amine modified polysiloxane compounds (e.g., aminoalkyl functional silicones). One preferred epoxy modified polysiloxane is sold under the Tradename EMS 622 and is commercially available from Gelest, Inc. One preferred amine modified polysiloxane is sold under the Tradename AMS 162 and is commercially available from Gelest, Inc.

(13) The first polymerizable material may include a first component (e.g., a cyclic compound that is capable of undergoing a ring opening reaction) and a second component (e.g., ring opening nucleophile) capable of polymerization. For example, the polysiloxane compound may include a first polysiloxane component having an epoxy modified polysiloxane or a second polysiloxane component having an amine modified polysiloxane. The epoxy modified polysiloxane may be present in an amount of at least about 1%, preferably at least about 3%, and more preferable at least about 5% by wt the overall composite sealant composition. Furthermore, the epoxy modified polysiloxane may be present in an amount of less than about 50%, preferably less than about 40% and preferably less than about 25% by wt the overall composite sealant composition. For example, the epoxy modified polysiloxane may be present in an amount ranging from about 1% to about 50%, preferably from about 3% to about 40%, and more preferably from about 5% to about 25% by wt the overall composite sealant composition. An example of the first polysiloxane component having the epoxy modified polysiloxane may be present as formula (I).

(14) ##STR00017## wherein x is 1-1000, and y is 1-1000.

(15) Alternatively or in addition to the first polysiloxane component having an epoxy modified polysiloxane, the polysiloxane component may include a second polysiloxane component having an amine modified polysiloxane. The amine modified polysiloxane may be present in an amount of at least about 1%, preferably at least about 3%, and more preferable at least about 5% by wt the overall composite sealant composition. Furthermore, the amine modified polysiloxane may be present in an amount of less than about 50%, preferably less than about 40% and preferably less than about 25% by wt the overall composite sealant composition. For example, the amine modified polysiloxane may be present in an amount ranging from about 1% to about 50%, preferably from about 3% to about 40%, and more preferably from about 5% to about 25% by wt the overall composite sealant composition.

(16) An example of the second polysiloxane component having the amine modified polysiloxane may be present as formula (II).

(17) ##STR00018## wherein n is 1-1000, and m is 1-1000.

(18) Curing Agent

(19) The composite sealant composition herein may include at least one initiating component (e.g., catalyst) to effectuate curing of the material. The initiating component may be present in an amount of at least about 0.0005%, preferably at least about 0.005%, and more preferably at least about 0.05% by wt the overall composite sealant composition. The overall composite sealant composition may include less than about 3.0%, preferably less than about 1.5%, and more preferably less than about 1% wt of the initiating component. For example, the initiating component may be present in a range of about 0.0005% to about 3%, preferably from about 0.005% to about 1.5%, and more preferably from about 0.05% to about 1% wt of the overall composite sealant composition.

(20) One preferred initiating component includes an alkanol amine. Examples of suitable alkanol amines include, but are not limited to ethanolamine, 2-amino-1-butanol, 4-amino-1-butanol, 2-aminoethanthiol, 2-amino-1-hexanol, 2-amino-3-methyl-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 5-amino-1-pentanol, 2-(methylamino) ethanol, 2-(propylamino)ethanol, tris(hydroxymethyl)aminomethane, 2-amino-1-propanol, 2-amino-1-pentanol, ethanolamine, 2-hydroxyethylhydoradine, 3-amino-1-propanol, DL-2-amino-1-propanol, DL-1-amino-2-propanol, DL-2-amino-1-pentanol, DL-2-Amino-1-hexanol, 6-amino-1-hexanol, 2-(2-aminoethoxy) ethanol, or otherwise and combinations thereof. Other catalysts are appreciated such as salts (e.g., platinum, palladium, or otherwise).

(21) As shown in Table 1, an example of acceleration effects for curing various composite sealant compositions of the two-component systems with different catalysts:

(22) TABLE-US-00001 TABLE 1 I.D. 712A11 712B11 712C11 712D11 712 E11 712U11 AMS 162 50.3% 49.5% 49.3% 49.4% 49.0% 85.8% EMS 622 49.7% 49.5% 49.7% 49.5% 50.0% 14.2% 2-amino-3methyl-butanol 0.0% 1.0% 0.0% 0.0% 0.0% 0.0% dl-2-amino-1-pentanol 0.0% 0.0% 1.0% 0.0% 0.0% 0.0% dl-2-amino-1-hexanol 0.0% 0.0% 0.0% 1.0% 0.0% 0.0% 6-amino-1-hexanol 0.0% 0.0% 0.0% 0.0% 1.0% 0.0% Total Mass (g) 10.1 10.1 10.1 10.1 10.3 10.0 Time after mixing to 5 3 3 3 5 Not Set, >15 full cure (days)

(23) Filler

(24) The composite sealant compositions may include one or more fillers. Fillers having radiopacity useful in accordance with the invention, without limitation, include inorganic fillers such as Ag, TiO.sub.2, La.sub.2O.sub.3, ZrO.sub.2, BaSO.sub.4, CaWO.sub.4, BaWO.sub.4, Fe.sub.2O.sub.3 and Bi.sub.2O.sub.3, CeO.sub.2, ZrO.sub.2, MgO, lanthanide salts, polymer granulates, barium or strontium-containing glass. The glass may contain fluoride for fluoride release in vivo. When included, the radiopacifier may be present in an amount of at least about 20%, preferably at least about 30%, and more preferable at least about 40% by wt the overall composite sealant composition. Furthermore, the radiopacifier may be present in an amount of less than about 80%, preferably less than about 70% and preferably less than about 60% by wt the overall composite sealant composition. For example, the radiopacifier may be present in an amount ranging from about 20% to about 80%, preferably from about 30% to about 70%, and more preferably from about 40% to about 60% by wt the overall composite sealant composition.

(25) Other fillers that may be employed include, but are not limited to silicas, aluminas, magnesias, titanias, inorganic salts, metallic oxides, (e.g., zinc oxides, calcium hydroxide, or otherwise) and glasses. In one desired embodiment, precipitated silica (e.g., Hi-Sil 233) may be included as a filler. In another desired embodiment, fumed silica (e.g., Aerosil 200) may be included as a filler. The filler material may be present in an amount of at least about 0.1%, preferably at least about 1%, and more preferably at least about 5% by wt the overall composite sealant composition. Furthermore, the filler material may be present in an amount of less than about 25%, preferably less than about 20% and more preferably less than about 15% by wt the overall composite sealant composition. For example, the filler material may be present in an amount ranging from about 0.1% to about 25%, preferably from about 1% to about 20%, and more preferably from about 5% to about 15% by wt the overall composite sealant composition.

(26) In a preferred embodiment, the composite sealant composition may further include a cross-linked material (e.g., cross-linked rubber such as polyisoprene or otherwise). A desirable example of a cross-linked material may include a cross-linked cis-polyisoprene-based material such as a cis-1,4-polyisoprene-based material. As shown in Tables 2 and 3, the cross-linked material may include the following compositions as described in U.S. Ser. No. 13/045,744, filed Mar. 11, 2011, which is herein incorporated by reference for all purposes:

(27) TABLE-US-00002 TABLE 2 Component Weight % 1-4, Polyisoprene 10 to 40 Curing Agent 0.1 to 30 Curing Co agent 0.01 to 30 Zinc Oxide 0 to 80 Radiopacifier 0 to 40 Reinforcing Fillers 0 to 50 Carbon Nanotubes 0 to 50 Fibers 0 to 50 Colorant 0 to 10

(28) TABLE-US-00003 TABLE 3 Component Weight % Cross-Linkable Material 10 to 40 Rubber 0.5 to 15 Curing Agent 0.1 to 30 Curing Co agent 0.01 to 15 Antimicrobial 0.01 to 50 Radiopacifier 5.0 to 60 Reinforcing Fillers 0.5 to 30 Fibers 0.5 to 30 Colorant 0.01 to 25 Anti Oxidant 0 to 10 Processing Aid 0 to 10

(29) The cross-linked material may be present in an amount of at least about 3%, preferably at least about 5%, and more preferably at least about 10% by wt the overall composite sealant composition. Furthermore, the cross-linked material may be present in an amount of less than about 50%, preferably less than about 40% and more preferably less than about 30% by wt the overall composite sealant composition. For example, the cross-linked material may be present in an amount ranging from about 3% to about 50%, preferably from about 5% to about 40%, and more preferably from about 10% to about 30% by wt the overall composite sealant composition.

(30) Desirably, the cross-linked material may be provided as a powder (e.g., from a grinding or chopping process of the cross-linked material). The cross-linked material may include a particle size of at least about 5, preferably at least about 10 and more preferably at least about 25 microns. Furthermore, the cross-linked material may include a particle size of less than about 500, preferably less than about 400, and more preferably less than about 300 microns. For example, the cross-linked material may include a particle size ranging from about 5 to about 500, preferably from about 10 to about 300, and more preferably from about 25 to about 150 microns (e.g., from about 50 microns to about 100 microns or from about 125 microns to about 200 microns).

(31) As shown in Table 4, one specific example of the two component composite sealant composition containing a cross-linked material:

(32) TABLE-US-00004 TABLE 4 Component A Weight % Component B Weight % Reactive-cyclic-based 5.0 to 50 Ring-opening-based 5.0 to 50 Polymerizable Polymerizable Compound Compound Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier 20 to 80 Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers 0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50

(33) Desirably, the cyclic-based polymerizable compound includes epoxy functionality, while the ring-opening-based polymerizable compound includes amine functionality, though not required.

(34) The composite sealant composition may further include additives, pharmaceutical active ingredients, dyes or pigments (e.g., iron oxides) waxes, oils (e.g., silicone oil and paraffin oil), surfactants, fatty acids (e.g., stearic acid), anti-oxidants, preservatives (e.g., nanosilver), or mixtures thereof.

(35) Adhesion Promoter

(36) The composite sealant composition may further include at least one adhesion promoter. In one aspect, the adhesion promoter (e.g., second polymerizable material) may be present in addition to the polymerizable compound (e.g., second polymerizable material). In another aspect the adhesion promoter may be the polymerizable compound.

(37) Without intending to be bound by theory, it is believed that the adhesion promoter herein makes advantageous employment of a particular molecular structure by which at least a portion of the molecule may include cyclic compounds that are capable of undergoing a ring opening reaction functionality (e.g., epoxy group, a succunic anhydride group, a succinimide group, or otherwise) and/or ring opening nucleophile functionality (e.g., OH, COOH, SH amine group, such as diepoxide or diamine group, or otherwise), which is capable of cross-linking the composite sealant composition. The adhesion promoter molecular structure may include hydrophobic functionality such as a hydrocarbon, a silicone (e.g., it is silanated such as SiO, SiO.sub.2, SiH.sub.4, or SiC), or otherwise, which is capable of being a thickener and/or may be provided as a dispersion carrier for the cross-linked material discussed herein. In one specific embodiment, the silicone functionality includes a Tris(trimethylsiloxy)silyl group such as [tris(trimethylsilyloxy)silyl]propyl methacrylate). Furthermore, the adhesion promoter molecular structure may include a dentin binding functionality, such as an phosphate, sulfate, sulfonate, betaine, carboxylic acids, amino acid, diacids, bisphosphate, or phosphatidylcholine functionality, which is capable of improving the linkage with the tooth dentin such as through the molecular network of the composite sealant composition.

(38) The adhesion promoter may be a one component material or a two component material. Examples of the adhesion promoter include but are not limited to:

(39) ##STR00019##

(40) wherein

(41) R.sup.1 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas R.sup.1 may be identical or different, (preferably R.sup.1 is a ring opening nucleophile such as NH.sub.2, OH, COOH, SH or otherwise);

(42) x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x may be identical or different; and

(43) y is an integer from 1 to 1000, multiple groups of y may be identical or different.

(44) ##STR00020##

(45) wherein

(46) R.sup.2 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.2 may be identical or different, (preferably R.sup.2 is a ring opening nucleophile such as NH.sub.2, OH, COOH, SH or otherwise);

(47) x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x may be identical or different;

(48) y is an integer from 1 to 10, multiple groups of y may be identical or different;

(49) A is an integer from 1 to 1000 (e.g., 1 to 100, preferably 1 to 10), multiple groups of A may be identical or different; and

(50) B is an integer from 0 to 1000 (e.g., 1 to 100, preferably 45 to 65), multiple groups of B may be identical or different.

(51) ##STR00021##

(52) wherein

(53) R.sup.3 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas R.sup.3 may be identical or different, (preferably R.sup.3 is a cyclic compound that may undergo ring polymerization such as an epoxide, a succunic anhydride, a succinimide group, or otherwise);

(54) x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x may be identical or different; and

(55) y is an integer from 1 to 1000, multiple groups of y may be identical or different.

(56) ##STR00022##

(57) wherein

(58) R.sup.4 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.4 may be identical or different, (preferably R.sup.4 is a cyclic compound that may undergo ring polymerization such as an epoxide, a succunic anhydride, a succinimide group, or otherwise);

(59) x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x may be identical or different;

(60) y is an integer from 1 to 10, multiple groups of y may be identical or different;

(61) A is an integer from 1 to 1000, multiple groups of A may be identical or different; and

(62) B is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of B may be identical or different.

(63) ##STR00023##

(64) wherein

(65) R.sup.5 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.5 may be identical or different;

(66) R.sup.6 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R.sup.6 may be identical or different;

(67) x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x may be identical or different;

(68) y is an integer from 1 to 10, multiple groups of y may be identical or different;

(69) A is an integer from 1 to 1000, multiple groups of A may be identical or different; and

(70) B is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of B may be identical or different; and

(71) wherein R.sup.5 and R.sup.6 can change positions.

(72) The adhesion promoter may be a one component material or a two component material. Examples of the adhesion promoter include but are not limited to:

(73) ##STR00024##

(74) wherein

(75) R.sup.9 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.9 may be identical or different;

(76) R.sup.10 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R.sup.10 may be identical or different;

(77) x is an integer from 0 to 10 (e.g., 1 to 10), multiple groups of x may be identical or different;

(78) y is an integer from 1 to 10, multiple groups of y may be identical or different;

(79) z is an integer from 1 to 10, multiple groups of z may be identical or different;

(80) A is an integer from 1 to 1000, multiple groups of A may be identical or different; and

(81) B is an integer from 1 to 1000, multiple groups of B may be identical or different; and

(82) C is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of C may be identical or different; and

(83) wherein R.sup.9 and R.sup.10 can change positions.

(84) In a desired embodiment, each functional portion is present thereby forming a ter-polymer adhesion promoter.

(85) ##STR00025##

(86) wherein

(87) R.sup.13 is independently a phosphate, a sulfate, a sulfonate, a betaine, a carboxylic acid, an amino acid, a diacids, a bisphosphate, or a phosphatidylcholine group, whereas multiple groups of R.sup.13 may be identical or different;

(88) R.sup.14 is independently a hydrophobic group such as a hydrocarbon, a silicone (e.g., it is silanated), or otherwise, (preferably the silicone includes a Tris(trimethylsiloxy)silyl group such as [tris(trimethylsilyloxy)silyl]propyl methacrylate), whereas multiple groups of R.sup.14 may be identical or different;

(89) R.sup.15 is independently NH.sub.2, OH, COOH, SH, an epoxide, a succunic anhydride, or a succinimide group, whereas multiple groups of R.sup.15 may be identical or different;

(90) n is an integer from 1 to 1000, multiple groups of x may be identical or different;

(91) m is an integer from 0 to 1000 (e.g., 1 to 1000), multiple groups of y may be identical or different;

(92) p is an integer from 1 to 1000, multiple groups of z may be identical or different; and

(93) wherein R.sup.13, R.sup.14, and R.sup.15 can change positions.

(94) It is appreciated that a two component adhesion promoter may include a first component of the formula i)-vii) having a cyclic compound that may undergo ring polymerization such as an epoxide, a succunic anhydride, a succinimide group, or otherwise and a second component of the formula i)-vii) having a ring opening nucleophile such as NH.sub.2, OH, COOH, SH or otherwise. When included, polymerization may occur by mixing the first and second components to form the adhesion promoter.

(95) The adhesion promoter may be synthesized by various processes. Desirably, the ter-polymer adhesion promoter may be formed by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization to form a two component system. For example, the first component (having a cyclic compound that may undergo ring polymerization) may be formed by the following RAFT polymerization:

(96) ##STR00026##

(97) The second component (having a ring opening nucleophile) may be formed by the following RAFT polymerization:

(98) ##STR00027##

(99) These specific examples i)-vii) of possible adhesion promoters should not be construed as limiting examples.

(100) In a composite sealant composition that includes at least one polymerizable compound and at least one adhesion promoter (Examples from Tables 4-7), the adhesion promoter may be present in an amount of at least about 3%, preferably at least about 5%, and more preferably at least about 10% by wt the overall composite sealant composition. Furthermore, the adhesion promoter may be present in an amount of less than about 50%, preferably less than about 40% and more preferably less than about 30% by wt the overall composite sealant composition. For example, the adhesion promoter may be present in an amount ranging from about 3% to about 50%, preferably from about 5% to about 40%, and more preferably from about 10% to about 30% by wt the overall composite sealant composition.

(101) TABLE-US-00005 TABLE 4 Component A Weight % Component B Weight % Reactive-Cyclic-based 5.0 to 25 Ring-opening-based 5.0 to 25 Polymerizable Polymerizable Compound Compound Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier 20 to 80 Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers 0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50 Reactive-Cyclic-based 5.0 to 25 Ring-opening-based 5.0 to 25 Adhesion Promoter Adhesion Promoter

(102) TABLE-US-00006 TABLE 5 Component A Weight % Component B Weight % Reactive-Cyclic-based 5.0 to 50 Ring-opening-based 0 Polymerizable Polymerizable Compound Compound Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier 20 to 80 Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers 0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50 Reactive-Cyclic-based 0 Ring-opening-based 5.0 to 50 Adhesion Promoter Adhesion Promoter

(103) TABLE-US-00007 TABLE 6 Component A Weight % Component B Weight % Reactive-Cyclic-based 0 Ring-opening-based 5.0 to 50 Polymerizable Polymerizable Compound Compound Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier 20 to 80 Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers 0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50 Reactive-Cyclic-based 5.0 to 50 Ring-opening-based 0 Adhesion Promoter Adhesion Promoter

(104) Desirably, the cyclic-based polymerizable compound and the cyclic-based adhesion promoter include epoxy functionality, while the ring opening-based polymerizable compound and the ring opening-based adhesion promoter include amine functionality, though not required. It is appreciated that in a composite sealant composition that includes an adhesion promoter as the polymerizable compound (Example of Table 7), the adhesion promoter may in an amount of at least about 1%, preferably at least about 5%, and more preferably at least about 10% by wt the overall composite sealant composition. Furthermore, it is appreciated that the adhesion promoter may be present in an amount of less than about 90%, preferably less than about 70% and preferably less than about 50% by wt the overall composite sealant composition. For example, the adhesion promoter may be present in an amount ranging from about 1% to about 90%, preferably from about 5% to about 70%, and more preferably from about 10% to about 50% by wt the overall composite sealant composition.

(105) TABLE-US-00008 TABLE 7 Component A Weight % Component B Weight % Reactive-Cyclic-based 5.0 to 50 Ring-opening-based 5.0 to 50 Adhesion Promoter Adhesion Promoter Catalyst 0 Catalyst 0.001 to 5.0 Radiopacifier 20 to 80 Radiopacifier 20 to 80 Reinforcing Fillers 0.1 to 25 Reinforcing Fillers 0.1 to 25 Cross-linked Rubber 0.1 to 50 Cross-linked Rubber 0.1 to 50

(106) Desirably, the cyclic-based adhesion promoter includes epoxy functionality, while the ring opening-based adhesion promoter includes amine functionality, though not required.

(107) In one specific two-component example, the product may comprise of a putty formulation, which includes ground cross-linked material (e.g., ground cross-lined endodontic carriers), silica, polymer, catalyst and bismuth oxide. The formulation mixes into a firm putty which can be delivered with an amalgum delivery device or with pluggers and spreaders. It has the consistency of a putty and can be rolled into any desired shaped prior to placing into the canal. Once the canal is filled, a gutta-percha point or a cross-linked endodontic carrier can be inserted into the canal to facilitate a 3-d fill and prevent leakage out the apex.

(108) In another specific example, the composite sealant composition may comprise of an injectable formulation which includes ground cross-linked material, silica, polymer, catalyst, and bismuth oxide. The formulation mixes in a static mixer connected on the end of a dual syringe. The material is directly injected into the canal. Once the canal is filled, a cross-linked endodontic carrier or gutta-percha-point can be inserted into the canal to facilitate a 3-d fill and prevent leakage out the apex.

(109) It is appreciated that the gutta-percha point/cross-linked carrier choice can left up to the clinician (they are interchangeable).

(110) It is further appreciated that in the composite sealant composition systems, different types can be used. The sealant material according to the invention can be present as single-component systems or as multi-component systems, preferably as two-component systems, as a function of the polymer system, in each instance. The curable polymer systems and their additional components, such as catalysts and/or initiators, are known to a person skilled in the art as such.

(111) Preferably, one-component dental sealant materials are used that are cured by means of UV radiation and/or heat. Aside from the curable polymer system as well as the surfactant mixture used according to the invention, photoinitiators are usually contained in them

(112) It will be further appreciated that functions or structures of a plurality of components or steps may be combined into a single component or step, or the functions or structures of one-step or component may be split among plural steps or components. The present invention contemplates all of these combinations. Unless stated otherwise, dimensions and geometries of the various structures depicted herein are not intended to be restrictive of the invention, and other dimensions or geometries are possible. In addition, while a feature of the present invention may have been described in the context of only one of the illustrated embodiments, such feature may be combined with one or more other features of other embodiments, for any given application. It will also be appreciated from the above that the fabrication of the unique structures herein and the operation thereof also constitute methods in accordance with the present invention. The present invention also encompasses intermediate and end products resulting from the practice of the methods herein. The use of comprising or including also contemplates embodiments that consist essentially of or consist of the recited feature.

(113) The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. Those skilled in the art may adapt and apply the invention in its numerous forms, as may be best suited to the requirements of a particular use. Accordingly, the specific embodiments of the present invention as set forth are not intended as being exhaustive or limiting of the invention. The scope of the invention should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes.