DENTAL COMPOSITION

Abstract

Dental root canal filling composition comprising (a) one or more diepoxides; (b) one or more primary monoamines and/or disecondary diamines; (c) a particulate filler, wherein the one or more diepoxides are selected from compounds of the following formula (I) or a salt thereof:

##STR00001##

Claims

1. Dental root canal filling composition comprising (a) one or more diepoxides; (b) one or more primary monoamines and/or disecondary diamines; (c) a particulate filler, wherein the one or more diepoxides are selected from compounds of the following formula (I) or a salt thereof: ##STR00026## wherein R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group, a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms; L.sup.1 and L.sup.2 which may be the same or different when more than one of L.sup.1 and L.sup.2 is present, independently represent a divalent saturated C.sub.2-10 hydrocarbyl group or a polysiloxane group; a is an integer of at least 1; b is an integer of at least 2; m is an integer of from 1 to 3; and n is an integer of from 1 to 1000.

2. The dental root canal filling composition according to claim 1, wherein the compound of formula (I) or a salt thereof is obtainable by reacting one or more compounds of the following formula (II): ##STR00027## wherein R and m are as defined in claim 1, with an excess of one or more compounds of the following formula (III) ##STR00028## wherein L.sup.1 and a are as defined in claim 1.

3. The dental root canal filling composition according to claim 1, wherein the diepoxide is a compound of the following formula IA or a salt thereof: ##STR00029## wherein R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms; R.sup.1 and R.sup.2 which may be the same or different when more than one of R.sup.1 and R.sup.2 is present, represent a hydrogen atom or a C.sub.1-6 alkyl group; a is an integer of at least 1; b is an integer of at least 2; m is an integer of from 1 to 3; and n is an integer of from 1 to 1000.

4. The dental root canal filling composition according to claim 1, wherein m is 3.

5. The dental root canal filling composition according to claim 1, wherein R is a C.sub.1-6 alkoxy group or a C.sub.1-6 alkyl group.

6. The dental root canal filling composition according to claim 1, wherein the one or more diepoxides are selected from compounds of the following formula (IB) or a salt thereof: ##STR00030## wherein R.sup.a, R.sup.b, and R.sup.c independently represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two of R.sup.a, R.sup.b, and R.sup.c may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms; R.sup.1 and R.sup.2 which may be the same or different when more than one of R.sup.1 and R.sup.2 is present, represent a hydrogen atom or a C.sub.1-6 alkyl group; a is an integer of at least 1; b is an integer of at least 2; and n is an integer of from 1 to 1000.

7. The dental root canal filling composition according to claim 1, wherein the one or more diepoxides of component (a) have a dynamic viscosity at 23° C. of less than 10 Pa.Math.s.

8. The dental root canal filling composition according to claim 1, which has a gelation time of less than 20 hours.

9. The dental root canal filling composition according to claim 1, which further comprises an aliphatic polyamine selected among compounds of the following structures: ##STR00031## wherein R.sup.5 represents hydrogen or a substituted or unsubstituted C.sub.1 to C.sub.18 alkyl group, a substituted or unsubstituted C.sub.3 to C.sub.18 cycloalkyl group, or a substituted or unsubstituted C.sub.7 to C.sub.18 aralkyl group, R.sup.6 represents a difunctional substituted or unsubstituted C.sub.1 to C.sub.18 alkylene group, or a substituted or unsubstituted cycloalkylene group, A′ represents a moiety derived from a compound that is capable of an addition reaction with amines such as di- or polyepoxides, and c is an integer.

10. The dental root canal filling composition according to claim 1, wherein the particulate filler (c) comprises CaWO.sub.4.

11. A diepoxide of the following formula (I) or a salt thereof: ##STR00032## wherein R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms; R.sup.1 and R.sup.2 which may be the same or different when more than one of R.sup.1 and R.sup.2 is present, represent a hydrogen atom or a C.sub.1-6 alkyl group; a is an integer of at least 1; b is an integer of at least 2; m is an integer of from 1 to 3; and n is an integer of from 1 to 1000.

12. The diepoxide according to claim 11, for use in the treatment of endodontic disease.

13. A process for preparing a diepoxide of the following formula (I) or a salt thereof: ##STR00033## wherein R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms; R.sup.1 and R.sup.2 which may be the same or different when more than one of R.sup.1 and R.sup.2 is present, represent a hydrogen atom or a C.sub.1-6 alkyl group; a is an integer of at least 1; b is an integer of at least 2; m is an integer of from 1 to 3; and n is an integer of from 1 to 1000, which comprises reacting one or more compounds of the following formula (II): ##STR00034## wherein R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group, a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms and m is an integer of from 1 to 3, with an excess of one or more compounds of the following formula (III) ##STR00035## wherein R.sup.1 which may be the same or different when more than one R.sup.1 is present represent a hydrogen atom or a C.sub.1-6 alkyl group and a is an integer of at least 1.

14. The process according to claim 12, wherein the compound of formula (II) is 3,4,5-trimethoxy aniline.

15. Storage-stable two-pack dental root canal filling composition comprising a first paste and a second paste, which pastes each having a dynamic viscosity at 23° C. which differ by less than 20 Pa.Math.s, wherein the dental root canal filling composition is a composition as defined by claim 1.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0047] FIG. 1 shows the synthesis of epoxide-functional prepolymers (Pre-TMA-PPO) and monitoring of viscosity.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0048] The present invention relates to a dental root canal filling composition comprising a specific diepoxide compound. A dental root canal filling in accordance with the invention is adapted to form epoxide-amine addition polymers. Furthermore, the present invention relates to a specific diepoxide and to the use of the specific diepoxide compound in the treatment of endodontic disease. Moreover, the present invention relates to a process for preparing a specific diepoxide compound. Finally, the present invention relates to a storage-stable two-pack dental root canal filling composition, wherein the two packs each have a dynamic viscosity at 23° C. which differ by less than 20 Pa.Math.s.

[0049] The terms “polymerization” and “polymerizable” relate to the combining by covalent bonding of a large number of smaller molecules, such as monomers, to form larger molecules, that is, macromolecules or polymers. The monomers may be combined to form only linear macromolecules or they may be combined to form three-dimensional macromolecules, commonly referred to as crosslinked polymers. For example, difunctional monomers form linear polymers, whereas monomers having at least three functional groups form crosslinked polymers also known as networks. In case of a higher conversion rate of the polymerizable monomer, the amount of multifunctional monomers may be reduced or the leaching problem may be alleviated.

[0050] The term “curing” means the polymerization of functional polymerizable compounds such as monomers, oligomers or even polymers, into a polymer network, preferably a crosslinked polymer network.

[0051] The “working time” is the time between the beginning of the setting reaction when the polymer and modified particulate reactive filler are combined in the presence of water, and the time the setting reaction proceeds to the point when it is no longer practical to perform further physical work upon the system, e.g. spatulate it or reshape it, for its intended dental or medical application.

[0052] The “setting time” is the time measured from the beginning of the setting reaction in a restoration to the time sufficient hardening has occurred to allow subsequent clinical or surgical procedures to be performed on the surface of the restoration. In a setting reaction, due to the presence of polymerizable groups, a polymerization reaction takes place. In addition to the polymerization reaction, in a glass ionomer cement, the setting reaction additionally involves neutralization of acid groups, for example of polymerizable compounds, by a base in the form of a reactive particulate glass.

[0053] The term “storage stability” as used herein means that the dental composition keeps its characteristics, in particular its working time and setting time, even after a long storage time of for example about 2 years.

[0054] The One or More Diepoxides

[0055] The dental root canal filling composition according to the present invention comprises one or more diepoxides, wherein the one or more diepoxides are selected from compounds of the following formula (I) or a salt thereof:

##STR00006##

[0056] wherein

[0057] R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms;

[0058] L.sup.1 and L.sup.2 which may be the same or different when more than one of L.sup.1 and L.sup.2 is present, independently represent a divalent saturated C.sub.2-10 hydrocarbyl group or a polysiloxane group:

[0059] a is an integer of at least 1;

[0060] b is an integer of at least 2;

[0061] m is an integer of from 1 to 3; and

[0062] n is an integer of from 1 to 1000.

[0063] The diepoxide is a compound of formula (I) or a salt thereof, preferably the diepoxide is a compound of formula (I).

[0064] In a compound of formula (I), R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group, a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms.

[0065] Preferably, R is a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, more preferably R is a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group, or a di-C.sub.1-6-alkylamino group, even more preferable R is a C.sub.1-6 alkyl group, or a C.sub.1-6 alkoxy group, in particular R is a C.sub.1-6 alkoxy group.

[0066] In a particularly preferred embodiment, R is a C.sub.1-3 alkoxy group, and even more preferred R is a methoxy group.

[0067] In a compound of formula (I), L.sup.1 and L.sup.2 which may be the same or different when more than one of L.sup.1 and L.sup.2 is present, independently represent a divalent saturated C.sub.2-10 hydrocarbyl group or a polysiloxane group.

[0068] Preferably, L.sup.1 and L.sup.2 independently represent a divalent saturated C.sub.2-10 hydrocarbyl group.

[0069] The divalent saturated C.sub.2-10 hydrocarbyl group according to L.sup.1 and L.sup.2 may be an C.sub.2-10 hydrocarbyl group which contains up to 5 heteroatoms selected from the group of O, S and N. The divalent saturated C.sub.2-10 hydrocarbyl group according to L.sup.1 and L.sup.2 may be an C.sub.2-10 aliphatic group or a C.sub.3-10 cycloaliphatic group.

[0070] In a preferred embodiment, the divalent saturated C.sub.2-10 hydrocarbyl group according to L.sup.1 and L.sup.2 is a C.sub.2-10 aliphatic group, more preferably a C.sub.2-6 aliphatic group, even more preferably a C.sub.2-4 aliphatic group, still more preferably a C.sub.2-3 aliphatic group, and most preferably a C.sub.3 aliphatic group.

[0071] In a particularly preferred embodiment, the divalent saturated C.sub.2-10 hydrocarbyl group according to L.sup.1 and L.sup.2 is the following group:

##STR00007##

[0072] In a preferred embodiment, the divalent saturated C.sub.2-10 hydrocarbyl group according to L.sup.1 and L.sup.2 is a C.sub.3-10 cycloaliphatic group, more preferably a C.sub.3-6 cycloaliphatic group, even more preferably a C.sub.4-6 cycloaliphatic group, and in particular a C.sub.6 cycloaliphatic group.

[0073] In a preferred embodiment, the divalent saturated C.sub.2-10 hydrocarbyl group according to L.sup.1 and L.sup.2 is a polysiloxane group. Preferably, the polysiloxane group according to L.sup.1 and L.sup.2 is a group of the formula [—OSiR′.sub.2].sub.2, wherein R′ represents a C.sub.1-4 alkyl group and z is an integer of from 2 to 20, preferably z is an integer of from 2 to 10, more preferably an integer of from 2 to 6.

[0074] In a compound of formula (I), a is an integer of at least 1, preferably a is an integer of from 1 to 20, more preferably a is an integer of from 1 to 10, even more preferably a is an integer of from 5 to 10, in particular a is 9.

[0075] In a compound of formula (I), b is an integer of at least 2, preferably b is an integer of from 2 to 20, more preferably b is an integer of from 2 to 10, even more preferably b is an integer of from 5 to 10, in particular b is 9.

[0076] In a compound of formula (I), m is an integer of from 1 to 3, preferably m is an integer of from 2 to 3, more preferably m is 3.

[0077] In a compound of formula (I), n is an integer of from 1 to 1000, preferably n is an integer of from 1 to 500, more preferably n is an integer of from 1 to 100, even more preferably n is an integer of from 1 to 50, in particular n is an integer of from 1 to 10.

[0078] In an embodiment of the present invention, the one or more diepoxides are a salt of the compound of formula (I). The salt of the compound of formula (I) may be any salt, which is suitable for dental applications.

[0079] Furthermore, the present invention provides a dental root canal filling composition, wherein the compound of formula (I) or a salt thereof is obtainable by reacting one or more compounds of the following formula (II):

##STR00008##

wherein R and m are as defined as in formula (I), with an excess of one or more compounds of the following formula (III)

##STR00009##

[0080] wherein L.sup.1 and a are as defined as in formula (I).

[0081] If a salt of the compound of formula (I) is synthesized by the process described above, after reacting the compound of formula (II) and the compound of formula (III), subsequently an acid is added to form a salt of the compound of formula (I).

[0082] Moreover, the present invention provides a dental root canal filling composition, wherein the diepoxide is a compound of the following formula IA or a salt thereof:

##STR00010##

[0083] wherein

[0084] R which may be the same or different when more than one R is present, represents a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, or a C.sub.6-10 aryl group, or two R may be linked together and form with the carbon atoms to which they are bonded a 5- to 7-membered ring which may contain 1 or 2 heteroatoms selected from oxygen atoms and sulfur atoms;

[0085] R.sup.1 and R.sup.2 which may be the same or different when more than one of R.sup.1 and R.sup.2 is present, represent a hydrogen atom or a C.sub.1-6 alkyl group;

[0086] a is an integer of at least 1;

[0087] b is an integer of at least 2;

[0088] m is an integer of from 1 to 3; and

[0089] n is an integer of from 1 to 1000.

[0090] In one embodiment of the present invention, the diepoxide is a compound of formula (IA) or a salt thereof, preferably the diepoxide is a compound of formula (IA).

[0091] In a compound of formula (IA), R is defined according to the definition of R in formula (I).

[0092] In a compound of formula (IA). R.sup.1 and R.sup.2 which may be the same or different when more than one of R.sup.1 and R.sup.2 is present, represent a hydrogen atom or a C.sub.1-6 alkyl group. Preferably, R.sup.1 and R.sup.2 represent a hydrogen atom or a C.sub.1-3 alkyl group, more preferably R.sup.1 and R.sup.2 represent a hydrogen atom or a C.sub.1 alkyl group, in particular R.sup.1 and R.sup.2 represent a methyl group.

[0093] In a compound of formula (IA), a is defined according to the definition of a in formula (I).

[0094] In a compound of formula (IA), b is defined according to the definition of b in formula (I).

[0095] In a compound of formula (IA), m is defined according to the definition of m in formula (I).

[0096] In a compound of formula (IA), n is defined according to the definition of n in formula (I).

[0097] In an embodiment of the present invention, the one or more diepoxides are a salt of the compound of formula (IA). The salt of the compound of formula (IA) may be any salt, which is suitable for dental applications.

[0098] Additionally, the present invention provides a dental root canal filling composition, wherein the one or more diepoxides are selected from compounds of the following formula (IB) or a salt thereof:

##STR00011##

wherein R.sup.a, R.sup.b, and R.sup.c independently have the same meaning as R in formula (I), and R.sup.1, R.sup.2, a, b, and n are as defined in formula (IA).

[0099] In one embodiment of the present invention, the diepoxide is a compound of formula (IB) or a salt thereof, preferably the diepoxide is a compound of formula (IB).

[0100] In an embodiment of the present invention, the one or more diepoxides are a salt of the compound of formula (IB). The salt of the compound of formula (IB) may be any salt, which is suitable for dental applications.

[0101] In a particularly preferred embodiment, the one or more diepoxides are selected from compounds according to the following formula (IC) or a salt thereof:

##STR00012##

wherein R.sup.a, R.sup.b, and R.sup.c independently have the same meaning as R in formula (I), and n has the same meaning as n in formula (I).

[0102] In one embodiment of the present invention, the diepoxide is a compound of formula (IC) or a salt thereof, preferably the diepoxide is a compound of formula (IC).

[0103] Preferably, in a compound of formula (IC) R.sup.a, R.sup.b, and R.sup.c independently represent a hydroxyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkyl group a di-C.sub.1-6-alkylamino group, more preferable R.sup.a, R.sup.b, and R.sup.c independently represent a C.sub.1-6 alkyl group, a C.sub.1-6 alkoxy group, in particular R is a C.sub.1-6 alkoxy group.

[0104] In a particularly preferred embodiment, in a compound according to formula (IC) R.sup.a, R.sup.b, and R.sup.c independently represent a C.sub.1-3 alkoxy group, and even more preferred R.sup.a, R.sup.b, and R.sup.c are methoxy groups.

[0105] In an embodiment of the present invention, the one or more diepoxides are a salt of the compound of formula (IC). The salt of the compound of formula (IC) may be any salt, which is suitable for dental applications.

[0106] In another particularly preferred embodiment, the one or more diepoxides according to formula (I) is a compound according to the following formula:

##STR00013##

[0107] wherein n is defined as in formula (I).

[0108] Furthermore, the present invention provides a dental root canal filling composition, wherein the one or more diepoxides of component (a) have a dynamic viscosity at 23° C. of less than 10 Pa.Math.s. Preferably the one or more diepoxides of component (a) have a dynamic viscosity at 23° C. of less than 9 Pa.Math.s, more preferably the one or more diepoxides of component (a) have a dynamic viscosity at 23° C. of less than 8 Pa.Math.s.

[0109] Furthermore, the present invention provides a diepoxide according to formula (I) or a salt thereof. Preferably, the present invention provides a diepoxide according to formula (IA) or a salt thereof, more preferably the present invention provides a diepoxide according to formula (IB) or a salt thereof, even more preferably the present invention provides a diepoxide according to formula (IC) or a salt thereof, in particular the present invention provides a diepoxide according to the following formula

##STR00014##

[0110] wherein n is defined as in formula (I),

[0111] or a salt thereof.

[0112] In a preferred embodiment, the present invention provides a diepoxide according to formula (I), preferably a diepoxide according to formula (IA), even more preferably a diepoxide according to formula (IB), still more preferably a diepoxide according to formula (IC), in particular the present invention provides a diepoxide according to the following formula

##STR00015##

[0113] wherein n is defined as in formula (I),

[0114] Moreover, the present invention provides a diepoxide of formula (I) or a salt thereof, for use in the treatment of endodontic disease. Preferably, the present invention provides a diepoxide of formula (I), for use in the treatment of endodontic disease.

[0115] In a particularly preferred embodiment, the present invention provides a diepoxide compound according to the following formula or a salt thereof

##STR00016##

[0116] wherein n is defined as in formula (I);

[0117] for use in the treatment of endodontic disease.

[0118] In a particularly preferred embodiment, the present invention provides a diepoxide compound according to the following formula:

##STR00017##

[0119] wherein n is defined as in formula (I);

[0120] for use in the treatment of endodontic disease.

[0121] Additionally, the present invention provides a process for preparing a diepoxide according to formula (I) or a salt thereof, which comprises reacting one or more compounds of the following formula (II):

##STR00018##

[0122] wherein R and m are as defined as in formula (I), with an excess of one or more compounds of the following formula (III)

##STR00019##

[0123] wherein R.sup.1 and a are as defined as in formula (I).

[0124] If a salt of the compound of formula (I) is synthesized by the process, after reacting the compound of formula (II) and the compound of formula (III), subsequently an acid is added to form a salt of the compound of formula (I).

[0125] In a preferred embodiment, according to the present invention in the process for preparing a diepoxide according to formula (I), the compound of formula (II) is 3,4,5-trimethoxy aniline (CAS: 24313-88-0).

[0126] The One or More Primary Monoamines and/or Disecondary Diamines

[0127] The dental root canal filling composition according to the present invention comprises primary mono- and/or disecondary diamines. The primary mono- and/or disecondary diamines may be any primary mono- and/or disecondary diamines which are suitable in dental applications and/or known in the art.

[0128] In a preferred embodiment, the dental root canal filling composition according to the present invention comprises a primary monoamine selected from the group consisting of benzylamine, 1-aminoadamantane, α-phenylethylamine, dimethyl(aminomethyl) phosphine oxide and ethanolamine.

[0129] In a preferred embodiment, the dental root canal filling composition according to the present invention comprises a primary monoamine according to the following formula:

Q-NH.sub.2

wherein Q is a C.sub.2-20 hydrocarbyl group which may contain up to 10 heteroatoms selected from the group consisting of O, S, N, and Si. The C.sub.2-20 hydrocarbyl group may an C.sub.2-20 alkyl group, a C.sub.3-10 cycloalkyl group, or a C.sub.6-20 arylalkyl group. The C.sub.2-20 hydrocarbyl group may be substituted or unsubstituted. The C.sub.2-20 hydrocarbyl group may be substituted by hydroxyl groups, tertiary amine groups, halogen atoms, C.sub.1-6 alkyl groups, C.sub.3-10 cycloalkyl groups, C.sub.5-10 aryl groups, C.sub.6-11 arylalkyl groups, C.sub.1-6 alkoxy groups.

[0130] In a preferred embodiment, the dental root canal filling composition according to the present invention comprises a disecondary diamine selected from the group consisting of N,N′-dibenzylethylenediamine, N,N′-dibenzyl-3,6-dioxaoctandiamine-1,8, N,N′-dibenzyl-5-oxanonandiamine-1,9 (CAS: 113506-22-2), N,N′-dibenzyl-(2,2,4)trimethylhexamethylendiamine, N,N′-dibenzyl-(2,4,4)trimethylhexamethylendiamine.

[0131] In a preferred embodiment, the dental root canal filling composition according to the present invention comprises a disecondary diamine according to the following formula (IV):

##STR00020##

[0132] Wherein

[0133] A is a divalent substituted or unsubstituted C.sub.2-30 hydrocarbyl group, and

[0134] R.sup.3 and R.sup.4, which may be the same or different, independently represent a C.sub.1-10 alkyl group, a C.sub.3-10 cycloalkyl group, or a C.sub.5-11 arylalkyl group.

[0135] In a compound of formula (IV), A is a divalent substituted or unsubstituted C.sub.2-30 hydrocarbyl group, which may contain up to 10 heteroatoms selected from the group consisting of N, O, S, Si. Preferably, A is a divalent unsubstituted C.sub.2-30 hydrocarbyl group.

[0136] In one embodiment of the present invention in a compound of formula (IV), A is a divalent substituted C.sub.2-30 hydrocarbyl group, wherein the substituents are selected from the group consisting of a hydroxyl group, a tertiary amine group, a halogen atom, a C.sub.1-6 alkyl group, a C.sub.3-10 cycloalkyl group, a C.sub.1-6 alkoxy group, a C.sub.5-10 aryl group, a C.sub.5-11 arylalkyl group.

[0137] In a compound of formula (IV), A represent a divalent substituted or unsubstituted C.sub.2-30 hydrocarbyl group, wherein the C.sub.2-30 hydrocarbyl group is a C.sub.2-30 alkylidene group, a C.sub.3-10 cycloalkylidene group, a C.sub.7-30 arylalkylidene group.

[0138] In a compound of formula (IV), R.sup.3 and R.sup.4, which may be the same or different, independently represent C.sub.1-10 alkyl group, a C.sub.3-10 cycloalkyl group, or a C.sub.6-11 arylalkyl group. The C.sub.1-10 alkyl group, the C.sub.3-10 cycloalkyl group, or the C.sub.6-11 arylalkyl group may be substituted or unsubstituted. Preferably, the C.sub.1-10 alkyl group, the C.sub.3-10 cycloalkyl group, or the C.sub.6-11 arylalkyl group is unsubstituted. If the C.sub.1-10 alkyl group, the C.sub.3-10 cycloalkyl group, or the C.sub.6-11 arylalkyl group is substituted, the substituents are selected from the group consisting of a hydroxyl group, a tertiary amine group, a halogen atom, a C.sub.1-6 alkyl group, a C.sub.3-10 cycloalkyl group, a C.sub.1-6 alkoxy group, a C.sub.5-10 aryl group, or a C.sub.6-11 arylalkyl group.

[0139] The Particulate Filler

[0140] The dental root canal filling composition according to the present invention, further comprises a particulate filler. The filler in the dental root canal filling composition according to the present invention may be any filler which is suitable for dental applications and/or known in the art.

[0141] In a specific embodiment, the filler according to the present invention is a radiopaque particulate filler. The radiopaque filler according to the present invention may be any radiopaque filler suitable for dental applications and/or known in the art.

[0142] The radiopaque particulate filler usually has an average particle size of from 0.005 to 100 μm, preferably of from 0.01 to 40 μm as measured using, for example, by electron microscopy or by using a conventional laser diffraction particle sizing method as embodied by a MALVERN Mastersizer S or MALVERN Mastersizer 2000 apparatus. The radiopaque particulate filler may be a multimodal radiopaque particulate filler representing a mixture of two or more radiopaque particulate fractions having different average particle sizes. The radiopaque particulate filler may also be a mixture of particles of different chemical composition.

[0143] The radiopaque filler may be selected from any of the zinc, ytterbium, yttrium, gadolinium, zirconium, strontium, tungsten, tantalum, thorium, niobium, barium, bismuth, molybdenum and lanthanum metals, alloys thereof, organometallic complexes thereof, oxides, sulfates, carbonates, halides, oxy-halides, subnitrates, tungstates and carbides thereof, iodine and inorganic iodides, either singly or in combination. In a preferred embodiment, the radiopaque filler is selected from any of bismuth trioxide, bismuth carbonate, bismuth oxy-chloride, bismuth subnitrate, zirconium oxide, barium sulfate, barium tungstate and calcium tungstate, either singly or in combination. In an even more preferred embodiment, the radiopaque filler is selected from barium tungstate and calcium tungstate, either singly or in combination. Preferably the radiopaque filler is CaWO.sub.4.

[0144] The dental root canal filling composition according to the present invention preferably comprises 1 to 85 percent by weight, more preferably 40 to 85 percent by weight, even more preferably 40 to 70 percent by weight, of the radiopaque particulate filler, based on the weight of the entire composition.

[0145] Further Components

[0146] Aliphatic Polyamines

[0147] The dental root canal filling composition according to the present invention, may further comprise an aliphatic polyamine. The aliphatic polyamine may be any aliphatic polyamine which is suitable in dental applications and/or known in the art.

[0148] In a specific embodiment, the aliphatic polyamine is selected among compounds of the following structures:

##STR00021##

[0149] wherein

[0150] R.sup.5 is hydrogen or a substituted or unsubstituted C.sub.1-18 alkyl group, a substituted or unsubstituted C.sub.3-18 cycloalkyl group, or a substituted or unsubstituted C.sub.7-18 arylalkyl group,

[0151] R.sup.6 is a difunctional substituted or unsubstituted C.sub.1 to C.sub.18 alkylene group, or a substituted or unsubstituted cycloalkylene group,

[0152] A′ is a moiety derived from a compound that is capable of an addition reaction with amines such as di- or polyepoxides, and

[0153] c is an integer.

[0154] In an aliphatic polyamine according to the structures above, preferably R.sup.5 is hydrogen, a substituted or unsubstituted C.sub.3-18 cycloalkyl group, or a C.sub.7-18 arylalkyl group. More preferably, R.sup.5 is a substituted or unsubstituted C.sub.3-18 cycloalkyl group, or a substituted or unsubstituted C.sub.7-18 arylalkyl group. Even more preferably, R.sup.5 is a substituted or unsubstituted C.sub.7-18 arylalkyl group. In a particularly preferred embodiment, R.sup.5 is an unsubstituted C.sub.7-18 arylalkyl group.

[0155] In an aliphatic polyamine according to the structures above, preferably R.sup.6 is difunctional substituted or unsubstituted C.sub.1 to C.sub.18 alkylene group, more preferably R.sup.6 is a difunctional unsubstituted C.sub.1 to C.sub.18 alkylene group.

[0156] In an aliphatic polyamine according to the structure above, A′ is a moiety derived from a compound that is capable of an addition reaction with amines such as di- or polyepoxides. The di- or polyepoxides may be any di- or polyepoxides suitable for dental applications and/or known in the art. Preferably, A′ is a moiety derived from an addition reaction of a diepoxide and amines.

[0157] In a preferred embodiment, A′ is a moiety derived from an addition reaction of a diepoxide and amines, wherein A′ is a moiety which contains one of the following moieties:

##STR00022##

[0158] In an aliphatic polyamine according to the structure above, c is an integer. Preferably, c is an integer of from 1 to 10, more preferably c is an integer of from 2 to 8, even more preferably c is an integer of from 4 to 6.

[0159] Aliphatic Diamines

[0160] In a particularly preferred embodiment, the dental root canal filling composition according to the present invention comprises one or more primary aliphatic diamines. Preferably, the dental root canal composition comprises one primary aliphatic diamine.

[0161] Preferably, the primary aliphatic diamines are compounds according to the following formula (V):

##STR00023##

[0162] wherein

[0163] Q′ represents a substituted or unsubstituted C.sub.3-20 alkylene group or a substituted or unsubstituted C.sub.3-20 cycloalkylene group, wherein the substituted C.sub.3-20 alkylene group and the substituted C.sub.3-20 cycloalkylene group may be substituted by one or more fluorine atoms, hydroxy groups, C.sub.1-6 alkyl groups, C.sub.3-12 cycloalkyl groups, a C.sub.1-6 alkoxy groups, a C.sub.1-6 alkylthio groups, a C.sub.6-10 aryl groups, a C.sub.6-10 aryloxy groups, a C.sub.7-14 arylalkyl groups, or a C.sub.7-14 arylalkoxy groups.

[0164] In a compound of formula (V), preferably Q′ represents a substituted or unsubstituted C.sub.3-20 cycloalkylene group, more preferably Q′ represents a substituted cycloalkylene group, and even more preferably Q′ represents a substituted cycloalkylene group, wherein the substituents may be one or more C.sub.1-6 alkyl groups, C.sub.3-12 cycloalkyl groups.

[0165] In a particularly preferred embodiment, the dental composition according to the present invention comprises a primary aliphatic diamine, which is selected from the group consisting of octahydro-4,7-methano-1H-indenedimethylamine (CAS: 68889-71-4) and isophorone diamine (CAS: 2855-13-2).

[0166] One or More Di- or Polyepoxides

[0167] The dental root canal filling composition according to the present invention may comprise one or more di- or polyepoxides. The one or more di- or polyepoxides may be any di- or polyepoxides suitable in dental applications and/or known in the art.

[0168] In a specific embodiment, the one or more di- or polyepoxides are compound of the following formula (VI):

##STR00024##

[0169] wherein

[0170] Q″ is an (m+1)-valent organic group,

[0171] R.sup.7, R.sup.8 and R.sup.9 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C.sub.1-6 alkyl group,

[0172] the R.sup.10, R.sup.11 and R.sup.12 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C.sub.1-6 alkyl group.

[0173] d is an integer of from 1 to 3.

[0174] In a compound of formula (VI), Q″ represents an (m+1)-valent organic group. Preferably, Q″ represents a 2-valent organic group, or a 3-valent organic group, and more preferably, Q″ represents a 2-valent organic group.

[0175] The (m+1)-valent organic group, may be a group having a total of 1 to 40 carbon atoms, preferably 2 to 20 carbon atoms. The organic group may include an aliphatic, alicyclic, or aromatic moiety or a combination of two or more of such moieties. The organic group may further include one or more functional groups such as amide groups, ester groups, urethane groups, urea groups, keto groups, ether groups, thioether groups, carbonate groups, or tertiary amino groups, which link two or more aliphatic, alicyclic, or aromatic moieties. Furthermore, the organic group may be substituted by one or more substituents selected from hydroxyl groups, halogen atoms, a C.sub.1-6 alkyl group, a C.sub.1-6 alkoxy group, a C.sub.1-6 alkylthio group, a C.sub.6-10 aryl group, a C.sub.6-10 aryloxy group, a C.sub.7-14 arylalkyl group, or a C.sub.7-14 arylalkoxy group.

[0176] Preferably, the (m+1)-valent organic group may include alicyclic or aromatic moiety, and more preferably the (m+1)-valent organic group includes an aromatic moiety.

[0177] In one embodiment, Q″ represents the following group:

##STR00025##

[0178] In a compound of formula (VI), m is an integer of from 1 to 3. Preferably, m is an integer of from 1 to 2, and more preferably m is 1.

[0179] In a compound of formula (VI), R.sup.7, R.sup.8 and R.sup.9 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C.sub.1-6 alkyl group. Preferably, R.sup.7, R.sup.8 and R.sup.9 represent a hydrogen atom. In a particularly preferred embodiment, all three of R.sup.7, R.sup.8 and R.sup.9 represent a hydrogen atom.

[0180] In a compound of formula (VI), the R.sup.10, R.sup.11 and R.sup.12 which may be the same or different and which are independent from each other, represent a hydrogen atom, or a C.sub.1-6 alkyl group. Furthermore, in a compound of formula (VI), if more than one R.sup.10 is present, the more than one R.sup.10 may be different. In a compound of formula (VI), if more than one R.sup.11 is present, the more than one R.sup.11 may be different. In a compound of formula (VI), if more than one R.sup.12 is present, the more than one R.sup.12 may be different. Preferably, R.sup.10, R.sup.11 and R.sup.12 represent a hydrogen atom. In a particularly preferred embodiment, all of the R.sup.10, R.sup.11 and R.sup.12 moieties which are present are hydrogen atoms.

[0181] In particularly preferred embodiment, the compound according to formula (VI) is Bis-[4-(-2,3-epoxypropoxy)phenyl]-methane (CAS: 9003-36-5).

[0182] Further Optional Components

[0183] The dental root canal filling composition according to the present invention may, besides of the above described components, comprise additional optional components. The dental root canal filling composition according to the present invention may optionally contain any additive suitable for dental applications and/or known in the art.

[0184] For example, the dental root canal filling composition according to the present invention may comprise water, or any solvent known in the art. The dental root canal filling composition of the present invention may preferably comprise 5 to 20 percent by weight based on the total weight of the composition of water or any solvent known in the art.

[0185] Optionally, the dental root canal filling composition may further comprise stabilizer(s), and/or pigments.

[0186] The dental root canal filling composition according to the present invention has a gel time of at most 20 hours. Preferably, the dental root canal filling composition according to the present invention has a gel time of at most 18 hours, more preferably the dental root canal filling composition according to the present invention has a gel time of at most 15 hours.

[0187] Finally, the present invention provides storage-stable two-pack dental root canal filling composition comprising a first past and a second paste, which pastes each having a dynamic viscosity at 23° C. which differ by less than 20 Pa.Math.s, wherein the dental root canal filling composition is a composition as defined according to the present invention.

[0188] The invention will now be further illustrated by the following Examples.

EXAMPLES

[0189] In the following section, the preparation of epoxide prepolymers with aromatic amines and characterization of respective paste formulations are presented fulfilling the claimed properties with setting times at body temperature below 16 h, flow behavior comparable to AH Plus® (19-25 mm), elevated resin viscosities of the amine resin and slightly reduced resin of epoxide resin.

[0190] Dynamic viscosities may be measured at 23° C. by using a Bohlin CS50 rheometer.

[0191] Materials

[0192] Polypropylene glycol diglycidyl ether (PPO-DGE, Mn˜640 g/mol) and 3,4,5-trimethoxy anillin (TMA) was purchased from Sigma Aldrich. 4,4′-Isopropylidendicyclohexanol diglycidyl ether

[0193] (DENACOL EX-252, CAS 30583-72-3, η=2.2 Pa*s) was provided by Nagase Chemistry. Priamine 1071 and Priamine 1075 (η=0.2 Pa*s) were provided from Crode and used as received. Bisphenol A diglycidyl ether (Araldite GY 250, CAS 25068-38-6) and bisphenol F diglycidyl ether (Araldite GY 285, CAS 9003-36-5). N,N′-Dibenzyl-5-oxanonandiamin-1,9 (OPC-91) was obtained from A.M.B. LIFE & SCIENCE ApS. CaWO.sub.4 (1 □m and 6 □m Grade B) particles were purchased from Starck H. C. GmbH and ZrO.sub.2 particles (CAS 1314-23-4) were purchased from S. Goldmann GmbH & Co. KG. Aerosil.sub.200 was provided by CSC Jäkle Chemie. SICOVIT® (Yellow 10 E 172) was purchased from Simon und Werner GmbH. All other chemicals were purchased from common chemical suppliers.

[0194] Prepolymer Synthesis

[0195] Synthesis of Pre-TMA-PPO(1:2,5) (ASO4-50-02)

[0196] 3,4,5-trimethoxy anillin (TMA) (2,634 g, 14.375 mmol) and polypropylene glycol diglycidyl ether (PPO-DGE. M.sub.n=640 g/mol) (23.013 g, 35.938 mmol) were stirred in a round-bottom flask (100 mL) at 100° C. The final product was obtained in quantitative yield after 187 h exhibiting a viscosity of η=1.47 Pa*s.

TABLE-US-00001 TABLE 1 Results of four different epoxide-prepolymer batches Pre-TMA-PPO (1:2.5) showing values of viscosity η and epoxide content n.sub.f of the recovered prepolymers. Epoxide content n.sub.f Reaction Polymer Batch Final viscosity qNMR time t Composition Number η [Pa * s] [mmol/g] [h] Pre-TMA-PPO(1:2.5) ASO4-49-01 1.41 1.647 187 Pre-TMA-PPO(1:2.5) ASO4-50-02 1.47 1.670 187 Pre-TMA-PPO(1:2.5) ASO4-58-01 1.54 1.600 161 Pre-TMA-PPO(1:2.5) ASO4-105-01 1.45 1.721 161

[0197] Synthesis of Pre-PPO-OPC91 (ASO449-02)

[0198] N,N′-Dibenzyl-5-oxanonandiamin-1,9 (OPC-91) (10.642 g, 31.250 mmol) and polypropylene glycol diglycidyl ether (PPO-DGE, Mn=640 g/mol) (9.993 g, 15.625 mmol) were stirred in a round-bottom flask (100 mL) at 40° C. The final product was obtained in quantitative yield after 71 h exhibiting a viscosity of η=3.8 Pa*s.

[0199] Paste Formulations

[0200] Paste A.1.

[0201] Preparation of Epoxide Paste A1 (ASO4-92-01)

[0202] Pre-TMA-PPO(1:2,5) (1.6016 g) and 4,4′-Isopropylidendicyclohexanol diglycidyl ether (1.6031 g) were transferred into a speed mixer container and mixed for 1 min with 2150 rpm under reduced pressure (p=1000 mbar). CaWO.sub.4 1 μm (8.1395 g), Aerosil®.sub.200 (0.1156 g) and SICOVIT® (Yellow 10 E172) (0.0120 g) were added and speed mixing was applied (1 min, 2150 rpm, 100 mbar). The paste was manually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm, 100 mbar) to afford a homogenous, light yellow paste. Flow (ISO6876): 20.83 mm.

[0203] Preparation of Amine Paste A1 (ASO3-90-02)

[0204] Pre-PPO-OPC91(1:2) (2.151 g), Priamine1075 (0.922 g), CaWO.sub.4 1 μm (7.340 g) and Aerosil®200 (0.114 g) were transferred into a speed mixer container and mixed for 1 min with 2150 rpm under reduced pressure (p=1000 mbar). The pastes were manually mixed with a spatula followed by another speed mixer run (1 min, 2150 rpm, 1000 mbar) to afford a homogenous, white paste. Flow (ISO6876): 26.8 mm.

[0205] Mixtures of Paste A1 (SAR2-147-01+SAR2-155-01)

[0206] Amine Paste A1 and epoxide Paste A1 were mixed in a ratio m.sub.Epoxide/m.sub.Amine=1.09795. The mixed pastes exhibit a setting time of <16 h, flow of 19.8 mm, film thickness of 9 μm (all according to ISO 6876).