USE OF METALLOFLUOROCOMPLEXES FOR DENTAL COMPOSITIONS

Abstract: Dental compositions are provided with a fluoride releasing material that is a metal complex described by the formula M(G)g(F)n or M(G)g(ZFm)n, where M represents an element capable of forming a cationic species and having a valency of 2 or more; G is an organic chelating moiety capable of complexing with the element M; Z is hydrogen, boron, nitrogen, phosphorus, sulfur, antimony, arsenic; F is a fluoride atom; g, m and n are at least 1.

Description: USEOFMETALLOFLUOROCOMPLEXESFORDENTAL COMPOSITIONS Field of the Invention This invention relates to the use of metallofluorocomplexes in dental compositions Background The discovery ofthe effect of fluoride ion in the prevention and inhibition of caries was a major breakthrough in the preservation of dental health Subsequent research has demonstrated that the caries resistance was due to the incorporation of fluoride into dental enamel during matrix formation, calcification and pre-emptive maturation After the formation and eruption of the tooth crown the surface layers of enamel continue to acquire additional fluoride This discovery has lead to the development of many dentrifices and dental restorative materials that release fluoride into the surrounding oral environment Most of these compositions incorporate simple inorganic fluoride salts as the fluoride source The most common of these is sodium fluoride or sodium fluorophosphate, although compositions containing tin fluorides are becoming increasingly popular U S Pat No 4,629,746 calls for adding simple fluoride salts of rare earth elements (elements 57 -71 ofthe periodic table) into dental compositions, particularly dental restoratives U S Pat No 4,515,910 discloses a fluoride releasing interpolymer which is the reaction product of a monomer bearing an anion-exchange site carrying fluoride ions e g a quaternary ammonium fluoride Organic fluoride sources such as those from alkylonium tetrafluoborate sources have been described in U S Pat No 4,871,786 A very popular way of releasing fluoride in the oral environment has been the use of glass ionomer cements In these cases, an ion-leachable fluoride glass is utilized along with an aqueous acidic solution. The decomposition of the glass results in the slow release of fluoride ions See generally. Glass Ionomer Cement, A D Wilson and J W McLean, Quintessence Publishing Co , Inc 1988 Many modifications of these cements exist Summary of the Invention In the present invention, a curable dental composition is provided with a fluoride releasing material that is a metal complex described by formula M(G) g (F) n or M(G) g (ZF m ) n where M represents an element capable of forming a cationic species and having a valency of 2 or more, G is an organic chelating moiety capable of complexing with the element M Z is hydrogen, boron, nitrogen, phosphorus, sulfur, antimony, arsenic F is a fluoride atom g, m and n are at least 1 Detailed Description of the Invention This invention provides novel compositions which release fluoride into a surrounding aqueous environment Examples of preferred M elements are the metals of groups IIA, IIIA, IVA, and transition and inner transition metal elements ofthe periodic table Specific examples include Ca +2 , Mg +2 , Sr +2 , Zn +2 , Af \ Zr +4 , Sn' 2 ,Yb Y f \ Sn +4 Most preferably, M is Zn +2 The G group, as noted above, is an organic chelating moiety This chelating moiety may or may not contain a polymerizable group Although not absolutely essential, in some instances it may be advantageous for the chelating moiety to contain a polymerizable functionality that matches the reactivity of the polymerizable matrix into which it is incorporated A wide range of chelating moieties may be used in the present invention Chelates in which the metal ion is bound in a ring structure of 4-8 members are preferred, with the 5-7 membered ring chelates being particularly preferred The chelates useful in the present invention are multidentate, and are preferably bi-, tri- or quadra-dentate Chelates containing hydroxyl or carboxy groups or both are more particularly preferred Examples of such chelating agents are tartaric acid, citric acid, ethylenediamine tetraacetic acid, salicylic acid, hydroxybenzoic acids, hydroxytartaric acids, nitrilotriacetic acid, salicylic acid, melletic acids, and polyglycols Chelates containing one or more acid groups derived from phosphorus, boron or sulfur can also be used, with the proviso that the molecular weight of the chelating agent is less than about 1000 Examples of especially suitable metal chelates include complexes of β-diketones and β-ketoesters The polymerizable metal-fluoride chelates preferably contain one or more polymerizable groups that match the reactivity ofthe polymerizable matrix into which it is incorporated In addition to the chelating functionalities outlined above, these complexes can contain ethylenically unsaturated groups, epoxy groups, ethyleneimine groups and the like Preferred G groups include the polyphosphates, such as sodium tripolyphosphate and hexametaphosphoric acid, aminocarboxylic acids, such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, N-dihydroxyethylglycine and ethylenebis(hydroxyphenylglycine), 1 ,3-diketones, such as acetylacetone, trifluoroacetylacetone and thenoyltrifluoroacetone, hydroxycarboxylic acids, such as tartaric acid, citric acid, gluconic acid, and 5-sulfosalicylic acid, polyamines, such as malic acid, ethylenediamine, triethylenetetramine and triaminotπethylamine, aminoalcohols, such as triethanolamine and N-hydroxyethylethylenediamine, aromatic heterocyclic bases, such as dipyridyl and o-phenanthroline, phenols, such as salicyladehyde, disulfopyrocatechol and chromotropic acid; aminophenols, such as oxime, 8-hydroxyquinoline and oxinesulfonic acid, oximes, such as dimethylglyoxime and salicyladoxime hydroxamic acid and its derivatives, Schiff bases, such as disalicyladehyde 1 ,2-propylenedimine, tetrapyrroles, such as tetraphenylporphin and phthalocyanine, sulfur compounds, such as toluenedithiol(Dithiol), dimercaptopropanol, thioglycolic acid, potassium ethylxanthate, sodium diethyldithiocarbamate, dithizone, diethyl dithiophosphoric acid and thiourea, synthetic macrocyclic compounds, such as dibenzof 18]crown- 6(5), (CH 3 ) 6 [ 14]4, 1 l -dιeneN 4 (6) and (2 2 2-cryptate) (7), polymeπc compounds such as polyethylenimine, polymetharyloylacetone, and poly(p- vinylbenzyhminodiacetic acid), and phosphonic acids, such as nitrilotπmethylenephosphonic acid, ethyIenedιamιnetetra(methylenephosphonιc acid) and hydroxyethylidenediphosphonic acid Particularly preferred G groups are compounds o the following formulas Fluoride is associated with the complexed metal as either a counterion or as a ligand Thus, the designation (ZF) above indicates that the fluoride is associated with the Z group as a complex, which in turn is associated with the metal as a counterion or as a ligand The fluorocomplex materials ofthe invention can be incorporated into dental compositions that undergo setting reactions by virtue of a complexation reaction other than polymerization Thus they can form components of zinc phosphate cements, polycarboxylate cements, glass ionomer cements and dental amalgams in order to release or enhance the release of fluoride ions Additionally, these fluorocomplex materials can be incorporated into compositions that have both a complexation reaction as described above and a polymerization reaction Finally, the fluorocomplex materials of the invention can be incorporated into dental compositions that undergo only polymerization reactions as a cure mechanism Useful polymerizable monomers are described in US patent 4,871 ,786 Suitable initiators and fillers can be added to these compositions In general, the more hydrophilic the resin matrix is the greater the initial fluoride release rate provided all other factors are maintained equal In some instances, it may be advantageous to increase the water-absorbing property of the polymerizing matrix by incorporating hydrophilic monomers, oligomers, polymers or prepolymers with polymerizing groups The water absorbing capacity is thereby increased by the incorporation of suitable hydrophilic moieties Organic moieties suitable for this are pyrroiidone, alkylamides of lower alkyl groups, polyethers, polysulfones, derivatives of sulphonic and carboxylic acids and the like This type of polymerizable composition is described in more detail below The compositions of this invention have utility in dental applications where it is desirable to provide fluoride release into dentition The specific areas of application include, but are not limited to, sealants, adhesives, bases, temporary and permanent luting cements, orthodontic adhesives and cements, resin-based restoratives, glass ionomer based restoratives, core build-ups, and articles comprised thereof such as crowns, bridges, fillings, orthodontic appliances and removable prosthodontic devices. Particularly preferred compositions of the present invention comprise at least two sources of fluoride. The first source is the fluoride-containing metal complex as described above. The second source is a fluoride-releasing fluoroaluminosiiicate glass With the use of both materials, excellent fluoride release is provided both in the initial period and over the long term use of the composition. A particularly preferred dental composition that may contain the metallofluorocomplexes of the present invention is a dental composition comprising a) a polymerizable component, b) a fluoride-releasing material, c) a hydrophilic component, d) a polymerization initiator, and e) an acidic component. This dental composition is substantially free of added water, and has a Water Uptake Value of at least about 1 .5 g of water per 100 g composition in 2 weeks For purposes of the present invention, the term "substantially free of added water" means that the composition does not contain water that is intentionally added as a non-compiexed or coordinated entity. It is understood that many materials, such as metals or glasses, contain water that is taken up from the atmosphere or is present as a coordination complex in its normal state Water taken up by hygroscopic materials or present as a hydrate is permissibly present in the compositions described herein. Any water that is present in the composition, regardless of source, should not be present in amounts such that the water will have a deleterious effect ofthe long term properties ofthe composition. For example, water should not be present in an amount that would facilitate reaction ofthe fluoride-releasing material with the acidic component so that lurnpiness or graininess ofthe material develops during commercially required storage time. The polymerizable component of the preferred compositions are compounds, which may be monomers, oligomers, or polymers, containing a polymerizable group. These polymerizable groups may be selected from free radically polymerizable groups, cationically polymerizable groups, or mixtures thereof. Preferably, the polymerizable compound has a molecular weight of between about 100 to 5000, and more preferably, has a molecular weight between about 200 and 1000. Mixtures of both higher and lower molecular weight polymerizable materials are also contemplated as providing special benefits in handling properties and ultimate cure material physical properties. In a preferred aspect ofthe present invention, at least some of the polymerizable material is relatively lower in viscosity than other ingredients of the composition so that it serves a viscosity lowering function in the overall uncured material. Preferably, at least some ofthe polymerizable material has a viscosity of less than 2000 cp, more preferably less than 500 cp, and most preferably less than 300 cp Preferred materials that provide the polymerizable component are the esters of acrylic or methacrylic acid. Examples of these compounds are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, 2-hydroxyethyl acrylate, 2- hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, glycidyl acrylate, glycidyi methacrylate, the diglycidyi methacrylate of bis-phenol A ("bis- GMA"), glycerol mono- and di- acrylate, glycerol mono- and di- methacrylate, ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, polyethyleneglycol diacrylate (where the number of repeating ethylene oxide units vary from 2 to 30), polyethyleneglycol dimethacrylate (where the number of repeating ethylene oxide units vary from 2 to 30 especially triethylene glycol dimethacrylate ("TEGDMA"), neopentyl glycol diacrylate, neopentylglycol dimethacrylate, trimethylolpropane triacrylate, trimethylol propane trimethacrylate, mono-, dt-, tri-, and tetra- acrylates and methacrylates of pentaerythritol and dipentaerythritol, 1 ,3-butanedioI diacrylate, 1,3-butanediol dimethacrylate, 1 ,4-butanedioldiacrylate, 1 , 4-butanediol dimethacrylate, 1 ,6-hexane diol diacrylate, 1 ,6-hexanediol dimethacrylate di-2- methacryloyloxethyl hexamethylene dicarbamate, di-2-methacryloyloxyethy! trimethylhexanethylene dicarbamate, di-2-methacryloyl oxyethyl dimethylbenzene dicarbamate, methylene-bis-2-methacryloxyethyl-4-cyclohexyl carbamate, di-2-methacryloxyethyl-dimethylcyclohexane dicarbamate, methylene-bis-2- rnethacryloxyethyl-4-cyclohexyl carbamate, di- 1 -methyl-2-methacryloxyethyl- trimethyl-hexamethylene dicarbamate, di- l -methyl-2-methacryloxyethyl- dimethylbenzene dicarbamate, di-l -methyl-2-methacryloxyethyl- dimethylcyclohexane dicarbamate, methylene-bis- 1 -methyl-2-methacryloxyethyl-4- cyclohexyl carbamate, di- 1 -chloromethyl-2-methacryloxyethyl-hexamethylene dicarbamate, di- 1 -chloromethyl-2-methacryloxyethyl-trimethylhexamethylene dicarbamate, di-l -chioromethyl-2-methacryloxyethyl-dimethylbenzene dicarbamate, di- 1 -chloromethyl-2-methacryloxyethyl-dimethylcyclohexane dicarbamate, methylene-bis-2-methacryloxyethyl-4-cyclohexyl carbamate, di- 1 -methyl-2- methacryloxyethyl-hexa ethylene dicarbamate, di- 1 -methyl-2-methacryloxyethyl- trimethylhexamethylene dicarbamate, di- 1 -methyl-2-methacryloxyethyl- dimethylbenzene dicarbamate, di-l-methyl-2-metha-cryloxyethyl- dimethylcyclohexane dicarbamate, methylene-bis-l-methyl-2-methacryloxyethyl-4- cyclohexyl carbamate, di-b l -chloromethyl-2-methacryloxyethyl-hexamethylene dicarbamate, di- 1 -chloromethy!-2-methacryloxyethyl-trimethylhexamethylene dicarbamate, di- 1 -chloromethyl-2-methacryloxyethyl-dimethylbenzene dicarbamate, di-l -chloromethyl-2-methacryloxyethyl-dimethylcyclohexane dicarbamate, methylene-bis-l-chloromethyl-2-methacryloxyethyl-4-cyclohexyl carbamate, 2,2'- bis(4-methacryloxyphenyl)propane, 2,2'bis(4-acryloxyphenyl)propane, 2,2'-bis[4(2- hydroxy-3-methacryloxy-phenyl)]propane, 2,2'-bis[4(2-hydroxy-3-acryloxy- phenyl)propane, 2,2'-bis(4-methacryloxyethoxyphenyl)propane, 2,2'-bis(4- acryloxyethoxyphenyl)propane, 2,2'-bis(4-methacryloxypropoxyphenyl)propane, 2,2'-bis(4-acryloxypropoxyphenyl)propane, 2,2'-bis(4- methacryloxydiethoxyphenyl)propane, 2,2'-bis(4-acryloxydiethoxyphenyl)propane, 2,2'-bis[3(4-phenoxy)-2-hydroxypropane-l-methacrylate]propane, 2,2'-bis[3(4- phenoxy)-2-hydroxypropane-l -acryalte]propane, and the like Other preferred polymerizable components can be substituted acryl amides and methacrylamides Examples are acrylamides, methylene bis-acrylamides, methylene bis-methacrylamide, diacetone/acrylamide diacetone methacylamide, N- alkyl acrylamide and N-alkyl methacrylamide where alkyl is a lower hydrocarbyl unit of 1 -6 carbon atoms. Other suitable examples of polymerizable components are isopropenyl oxazoline, vinyl azalactone, vinyl pyrroiidone, styrene, divinylbenzene, urethane acrylates or methacrylates, epoxy acrylates or methacrylates and polyol acrylates or methacrylates. Alternatively, the polymerizable component may be a cationically cured material, such as epoxy materials, oxetanes, oxolanes, cyclic acetals, lactams, lactones, and vinyl ethers or spirocyclic compounds containing oxygen atoms in the ring. The cationically polymerizable epoxy resins useful in the compositions of the invention comprise organic compounds having an oxirane ring, i e , polymerizable by ring opening Such materials, broadly called epoxides, include monomeric epoxy compounds and epoxides ofthe polymeric type and can be aliphatic, cycloaliphatic, aromatic or heterocyclic These materials generally have, on the aveiage, al least 1 μυlyniei izable epυxy grυup per moiecuie, and preferarjiy at least about 1 5 polymerizable epoxy groups per molecule The polymeric epoxides include linear polymers having terminal epoxy groups (e g , a diglycidyl ether ofa polyoxyalkylene glycol), polymers having skeletal oxirane units (e g , polybutadiene polyepoxide), and polymers having pendent epoxy groups (e g , a glycidyl methacrylate polymer or copolymer) The epoxides may be pure compounds or may be mixtures containing one, two, or more epoxy groups per molecule The "average" number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in epoxy-containing material by the total number of epoxy molecules present These epoxy-containing materials may vary from low molecular weight monomeric materials to high molecular weight polymers and may vary greatly in the nature of their backbone and substituent groups For example, the backbone may be of any type and substituent groups thereon can be any group that does not substantially interfere with cationic cure at room temperature Illustrative of permissible substituent groups include halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups, phosphate groups, and the like The molecular weight ofthe epoxy-containing materials may vary from about 58 to about 100,000 or more Useful epoxy-containing materials include those which contain cyclohexene oxide groups such as the epoxycyclohexanecarboxylates, typified by 3,4- epoxycyclohexylmethyI-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2- methyIcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane carboxylate, and bis(3,4- epoxy-6-methylcyclohexylmethyl) adipate For a more detailed list of useful epoxides of this nature, reference is made to the U S Patent No 3, 1 17,099, incorporated herein by reference Further epoxy-containing materials which are particularly useful in the practice of this invention include glycidyl ether monomers of the formula R'(OCH — CH— CH 2 )„ \ / O where R 1 is alkyl or aryl and n is an integer of 1 to 6 Examples are glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of chlorohydrin such as epichlorohydrin (e g , the diglycidyl ether of 2,2-bis-(2,3- epoxypropoxyphenol)-propane) Further examples of epoxides of this type which can be used in the practice of this invention are described in U S Patent No 3,018,262, incorporated herein by reference, and in "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co , New York ( 1967) There are a host of commercially available epoxy resins which can be used in this invention In particular, epoxides which are readily available include octadecylene oxide, epichlorohydrin, styrene oxide, vinyl cyclohexene oxide, glycidol, glycidylmethacrylate, diglycidyl ether of Bisphenol A (e.g , those available under the trade designations "Epon 828", "Epon 825", "Epon 1004" and "Epon 1010" from Shell Chemical Co , "DER-331 ", "DER-332", and "DER-334", from Dow Chemical Co ), vinylcyclohexene dioxide (e g , "ERL-4206" from Union Carbide Corp ), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carboxylate (e g , "ERL-4221 " or "UVR 61 10" or "UVR 6105" from Union Carbide Corp ), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexene carboxylate (e g , "ERL-4201 " from Union Carbide Corp ), bis(3,4-epoxy-6- methylcyciohexylmethyl) adipate (e g , "ERL-4289" from Union Carbide Corp ), bis(2,3-epoxycyclopentyl) ether (e g , "ERL-0400" from Union Carbide Corp.), aliphatic epoxy modified with polypropylene glycol (e g , "ERL-4050" and "ERL- 4052" from Union Carbide Corp ), dipentene dioxide (e g , "ERL-4269" from Union Carbide Corp ), epoxidized polybutadiene (e g , "Oxiron 2001 " from FMC Corp ), silicone resin containing epoxy functionality, flame retardant epoxy resins (e g , "DER-580", a brominated bisphenol type epoxy resin available from Dow Chemical Co ), 1 ,4-butanediol diglycidyl ether of phenolformaldehyde novolak (e.g., "DEN-431 " and "DEN-438" from Dow Chemical Co ), and resorcinol diglycidyl ether (e g , "Kopoxite" from Koppers Company, Inc ) bis(3,4- epoxycyclohexyl)adipate (e g , "ERL-4299" or "UVR-6128", from Union Carbide Corp ), 2-(3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-meta-dioxane (e g., "ERL-4234" from Union Carbide Corp ), vinylcyclohexene monoxide (from Union Carbide Corp ), 1 ,2-epoxyhexadecane (e g , "UVR-6216" from Union Carbide Corp ), alkyl glycidyl ethers such as alkyl C 3 -Cιo glycidyl ether (e g , "HELOXY Modifier 7" from Shell Chemical Co ), alkyl C 12 -C )4 glycidyl ether (e g , "JHELOXY Modifier 8" from Shell Chemical Co ), butyl glycidyl ether (e g , "HELOXY Modifier 61 " from Shell Chemical Co ), cresyl glycidyl ether (e.g , "HELOXY Modifier 62" from Shell Chemical Co ), p-tert butylphenyl glycidyl ether (e.g , "HELOXY Modifier 65" from Shell Chemical Co ), polyfunctional glycidyl ethers such as diglycidyl ether of 1 ,4-butanediol (e g , "HELOXY Modifier 67" from Shell Chemical Co ), diglycidyl ether of neopentyl glycol (e g , "HELOXY Modifier 68" from Shell Chemical Co ), diglycidyl ether of cyclohexanedimethanol (e g , "HELOXY Modifier 107" from Shell Chemical Co ), trimethylol ethane triglycidy! ether (e g , "HELOXY Modifier 44" from Shell Chemical Co ), trimethylol propane triglycidyl ether (e g , "HELOXY Modifier 48" from Shell Chemical Co ), polyglycidyl ether of an aliphatic polyol (e g , "HELOXY Modifier 84" from Shell Chemical Co ), polyglycol diepoxide (e.g , "HELOXY Modifier 32" from Shell Chemical Co ), bisphenol F epoxides (e.g , "EPN-1 138" or "GY-281 " from Ciba-Geigy Corp.), 9,9-bis[4-(2,3-epoxypropoxy)-phenyI]fluorenone (e.g , "Epon 1079" from Shell Chemical Co.) Still other epoxy resins contain copolymers of acrylic acid esters or glycidol such as glycidylacrylate and glycidylmethacrylate with one or more copolymerizable vinyl compounds Examples of such copolymers are 1 1 styrene- glycidylmethacrylate, 1 1 methylmethacrylate-glycidylacrylate and a 62.5 24 13 5 methylmethacryiate-ethyl acrylate-glycidylmethacrylate Other useful epoxy resins are well known and contain such epoxides as epichlorohydrins, e.g , epichlorohydrin, alkylene oxides, e g , propylene oxide, styrene oxide, alkenyl oxides, e g , butadiene oxide, glycidyl esters, e g , ethyl glycidate The polymers of the epoxy resin may optionally contain other functionalities that do not substantially interfere with cationic cure at room temperature Blends of various epoxy-containing materials are particularly contemplated in this invention Examples of such blends include two or more molecular weight distributions of epoxy-containing compounds, such as low molecular weight (below 200), intermediate molecular weight (about 200 to 10,000) and higher molecular weight ( above about 10,000) Alternatively or additionally, the epoxy resin may contain a blend of epoxy-containing materials having different chemical nature, such as aliphatic and aromatic, or functionality, such as polar and non-polar Other cationically polymerizable polymers may additionally be incorporated Particularly preferred epoxy containing composition also contain materials having hydroxyl functionality Mixtures of polymerizable materials, including hybrid systems containing both free-radically polymerized components and cationically polymerized components, are also contemplated The fluoride-releasing material of the preferred composition may include, in addition to the metallofluoro complexes described above, a naturally occuring or synthetic fluoride minerals, fluoride glass such as fluoroaluminosilicate glass, simple and complex inorganic fluoride salts, simple and complex organic fluoride salts or combinations thereof Optionally these fluoride sources can be treated with surface treatment agents. Examples of the fluoride-releasing material are fluoroaluminosilicate glasses described in U S Pat No 4,3814,717, which may be optionally treated as described in U.S Pat No 5,332,429, the disclosures of which are both incorporated by reference herein The hydrophilic component can be provided as a monomer, oligomer or polymer Preferably, it is provided as either a linear homopolymer or copolymer, either of which may optionally be lightly crosslinked The hydrophilic component is preferably miscible in water at concentrations of about 3% by weight or can absorb at least 2g of water per hundred g of polymer Optionally, the hydrophilic component can be a hydrophilic monomer which undergoes polymerization in situ leading to a hydrophilic, water-absorbing polymer In many cases, compounds containing acidic functionality are hydrophilic in nature Such compounds may be useful in the present invention is they satisfy the above hydrophilicity characteristics It has been found, however, that preferred hydrophilic components for use in the piesent invention have at least a portion of their hydrophilic properties provided by non-acidic functionalities Thus, preferred hydrophilic compounds for use in the present invention contain acidic functionality and non-acidic hydrophilic functionality, and most preferred hydrophilic compounds for use in the present invention contain no acidic functionalities Examples of hydrophilic components include monomers or polymers such as pyrroiidone, a moiety containing a sulfonate group (SO ), a moiety containing a sulfonic group (SO ), N-oxysuccinimide, N-vinylacetamide and acrylamide More specific examples of preferred hydrophilic components are non-ionic polymers or copolymers, e g polyalkylene oxides (polyoxymethylene, polyethyleneoxide, polypropylene oxide) polyethers (polyvinylmethyl ether), polyethyleneimine copolymers, polyacrylamides and poiymethacrylamides, polyvinylalcohol, saponified polyvinylacetate, polyvinylpyrrolidone, polyvinyloxazolidone, polymers containing N-oxysuccinimdo groups, ionic or lonizable polymers and copolymers containing polyacrylic acid, polymethacrylic acid in unionized, partially neutralized or fully neutralized form, polyethyleneimine and its salts, polyethylene sulfonic acid and polyaryl sulfonic acids in unionized, partially neutralized or fully neutralized form, polyphoshoπc and phosphonic acids in unionized, partially neutralized or fully neutralized form Generally, any compound having a polar group may provide a hydrophilic aspect to a composition Preferred hydrophilic compounds may be prepared by reaction of vinylic monomers such as acrylates, methacrylates, crotonates, itaconates and the like that contain polar groups that are acidic, basic or provided as a salt These groups can also be ionic or neutral Examples of polar or polarizable groups include neutral groups such as hydroxy, thio, substituted and unsubstituted amido, cyclic ethers (such as oxanes, oxetanes, furans and pyrans), basic groups (such as phosphines and amines, including primary, secondary, tertiary amines), acidic groups (such as oxy acids, and thiooxyacids of C, S, P, B) and ionic groups (such as quarternary ammonium, carboxylate salt, sulfonic acid salt and the like) and the precursors and protected forms of these groups More specific examples of such groups follow The hydrophilic component may be derived from mono- or multifunctional carboxyl group containing molecules represented by the general formula CH 2 -CR 2 G-(COOH) d where R 2 =H, methyl, ethyl, cyano, carboxy or carboxymethyl, d=l -5 and G is a bond or a hydrocarbyl radical linking group containing from 1 -12 carbon atoms of valence d+ 1 and optionally substituted with and/or interrupted with a substituted or unsubstituted heteroatom (such as O, S, N and P) Optionally, this unit may be provided in its salt form The preferred monomers in this class are acrylic acid, methacrylic acid, itaconic acid and N-acryloyl glycine The hydrophilic component may, for example, be derived from mono- or multifunctional hydroxy group containing molecules represented by the general formula CH 2 =CR -CO-L-R : -(OH) d where R 2 =H, methyl, ethyl, cyano, carboxy or carboxyalkyl, L=0, NH, d= l -5 and R is a hydrocarbyl radical of valence d+1 containing from 1 - 12 carbon atoms The preferred monomers in this class are hydroxyethyl (meth)acrγlate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, tris(hydroxymethyl)ethane monoacrylate, pentaerythritol mono(meth)acrylate, N- hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide and hydroxypropyl (meth)acrylamide The hydrophilic component may alternatively be derived from mono- or multifunctional amino group containing molecules of the general formula CH 2 =CR 2 -CO-L-R ? -(NRV) d where R 2 , L, R\ and d are as defined above and R 4 and R 3 are H or alkyl groups of 1-12 carbon atoms or together they constitute a carbocyclic or heterocyclic group Preferred monomers of this class are aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N- isopropyla inopropyl (meth)acrylamide and 4-methyl-l -acryloyl-piperazine The hydrophilic component may also be derived from alkoxy substituted (meth)acrylates or (meth)acrylamides such as methoxyethyl (meth)acrylate, 2(2- ethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol mono(meth)acryiate or polypropylene glycol mono(meth)acrylate Hydrophilic components may be derived from substituted or unsubstituted ammonium monomers ofthe general formula ® CH 2 =CR 2 -CO-L-R'-(NR 't R 5 R 6 ) d Q- where R 2 , R\ R 4 , R\ L and d are as defined above, and where R f ' is H or alkyl of 1 - 12 carbon atoms and Q- is an organic or inorganic anion Preferred examples of such monomers are 2-N,N,N-trimethylammonium ethyl (meth)acrylate, 2-N,N,N- triethylammonium ethyl (meth)acrylate, 3-N,N,N-trimethylarnmonium propyl (meth)acrylate, N(2-N',N',N'-trimethylammonium) ethyl (meth)acrylamide, N- (dimethyl hydroxyethyl ammonium) propyl (meth)acrylamide etc where the counterion may be fluoride, chloride, bromide, acetate, propionate, laurate, palmitate, stearate etc The monomer can also be N, N-dimethyl diallyl ammonium salt of an organic or inorganic counterion Ammonium group containing polymers can also be prepared by using as the hydrophilic component any o the amino group containing monomer described above, and acidifying the resultant polymers with organic or inorganic acid to a pH where the pendant amino groups are substantially protonated Totally substituted ammonium group containing polymers may be prepared by alkylating the above described amino polymers with alkylating groups, the method being commonly known in the art as the Menschutkin reaction The hydrophilic component of the invention can also be derived from sulfonic acid group containing monomers, such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, allyloxybenzene sulfonic acid, and the like Alternatively, the hydrophilic component may be derived from phosphorous acid or boron acid group-containing monomers These monomers may be used in the protonated acid form as monomers and the corresponding polymers obtained may be neutralized with an organic or inorganic base to give the salt form of the polymers Compositions of the preferred compositions of the present invention contain one or more suitable polymerization initiators, so that the composition may be polymerized in use The initiator is selected such that it is capable of initiating the polymerization ofthe polymerizable material That is, if the polymerizable material is a free radical polymerizable material, the initiator is a free-radical polymerization initiator Likewise, if the polymerizable material is a cationically polymerizable material, the initiator is a cationic polymerization initiator Compositions of the invention that are free-radically polymerized preferably contain one or more suitable photopolymerization initiators that act as a source of free radicals when activated Such initiators can be used alone or in combination with one or more accelerators and/or sensitizers The photoinitator should be capable of promoting free radical crosslinking of the ethylenically unsaturated moiety on exposure to light of a suitable wavelength and intensity It also preferably is sufficiently shelf stable and free of undesirable coloration to permit its storage and use under typical dental conditions Visible light photoinitiators are preferred The photoinitiator frequently can be used alone, but typically it is used in combination with a suitable donor compound or a suitable accelerator (for example, amines, peroxides, phosphorus compounds, ketones and alpha-diketone compounds) Preferred visible light-induced initiators include camphorquinone (which typically is combined with a suitable hydrogen donor such as an amine) diaryliodonium simple or metal complex salts chromophore-substituted halomethyl- s-tπazines and halomethyl oxadiazoles Particularly preferred visible light-induced photoinitiators include combinations of an alpha-diketone, e g , camphorquinone, and a diaryliodonium salt, e g , diphenyliodonium chloride, bromide, iodide or hexafluorophosphate, with or without additional hydrogen donors (such as sodium benzene sulfinate, amines and amine alcohols) Preferred ultraviolet light-induced polymerization initiators include ketones such as benzyl and benzoin, and acyloins and acyloin ethers Preferred commercially available ultraviolet light-induced polymerization initiators include 2,2-dιmethoxy-2-phenylacetophenone ("IRGACURE 651 ") and benzoin methyl ether (2-methoxy-2-phenylacetophenone), both from Ciba-Geigy Corp The photoinitiator should be present in an amount sufficient to provide the desired rate of photopolymerization This amount will be dependent in part on the light source, the thickness of the layer to be exposed to radiant energy, and the extinction coefficient of the photoinitiator Typically, the photoinitiator components will be present at a total weight of about 0 01 to about 5%, more preferably from about 0 1 to about 5%, based on the total weight of the composition The compositions ofthe present invention may alternatively incorporate a mode of initiation of the polymerization reaction to initiate a crosslinking reaction without the need to expose the system to visible light A preferred alternative mode for initiation of the polymerization reaction is the incorporation of an oxidizing agent and a reducing agent as a redox catalyst system to enable the dental composition to cure via a redox reaction Various redox systems is described in U S Patent No 5,154,762, the disclosure of which is expressly incorporated herein by reference The oxidizing agent should react with or otherwise cooperate with the reducing agent to produce free radicals capable of initiating polymerization ofthe ethylenically unsaturated moiety. The oxidizing agent and the reducing agent preferably are sufficiently shelf stable and free of undesirable coloration to permit their storage and use under typical dental conditions The oxidizing agent and the reducing agent should also preferably be sufficiently soluble and present in an amount sufficient to permit an adequate free radical reaction rate. This can be evaluated by combining the ethylenically unsaturated moiety, the oxidizing agent and the reducing agent and observing whether or not a hardened mass is obtained Suitable oxidizing agents include persulfates such as sodium, potassium, ammonium and alkyl ammonium persulfates, benzoyl peroxide, hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide and 2,5-dihydroperoxy-2,5-dimethylhexane, salts of cobalt (III) and iron (III), hydroxylamine, perboric acid and its salts, salts of a permanganate anion, and combinations thereof. Hydrogen peroxide can also be used, although it may, in some instances, interfere with the photoinitiator, if one is present. The oxidizing agent may optionally be provided in an encapsulated form as described in U.S Patent No. 5, 154,762 Preferred reducing agents include amines (and preferably aromatic amines), ascorbic acid, metal complexed ascorbic acid, cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine, oxalic acid, thiourea and salts of a dithionite, thiosulfate, benzene sulfinate, or sulfite anion. The use of redox initiator systems is generally less preferred to photoinitiator systems, because care must be taken to keep the reducing agent from reacting with the oxidizing agent before polymerization is desired. Generally, the use ofa redox system necessitates providing the material in a two-part format. One-part dental compositions utilizing a photoinitiator system are preferred. For compositions that are polymerized by a cationic mechanism, suitable initiators include salts that are capable of generating cations such as the diaryliodonium, triarylsulfonium and aryldiazonium salts The acidic component of the preferred compositions of the present invention is provided by compounds that are monomers, oligomers or polymers of molecular weight less than 10,000 and containing at least one acidic group The acidic group is preferably selected from oxyacids or thio-oxy acids of B, C, N, S, P More preferably, the acidic component is a compound that is an acid of C or P If desired, a precursor to the acid such as an acid anhydride, e g 4-Methacryloxyethyl Tnmel tate Anhydnde (4-META), or ester can be used in place ofthe acid itself e g , to generate the desired acid in situ Suitable acids include, carboxylic acids, sulfonic acids, and phenols, with carboxylic acids, alkylsulfonic acids, arylsulfonic acids, and phosphonic acids being preferred Suitable organic acids include acetic acid, -ch!oropropιonιc acid, 2- acrylamιdo-2-methylpropane sulfonic acid, acrylic acid, benzenesulfonic acid benzoic acid, bromoacetic acid, 10-camphorquιnone-sulfonιc acid 10-camphorsulfonic acid, chloroacetic acid, citraconic acid, citric acid, dibromoacetic acid, dichloroacetic acid, di- He a ester of 1 ,2,4,5 benzenetetracarboxylic acid, 2,4-dιnιtrophenoI, formic acid, fumanc acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonιc acid, maleic acid, methacrylic acid, 2-naphthalene sulfonic acid, nitric acid, oxalic acid, p-nitrophenol, phenol, phosphonc acid, phosphorous acid esters (such as 2,2'-bιs(a-methacryIoxy-b- hydroxypropoxyphenyl) propane diphosphonate (Bis-GMA diphosphonate) dibutyl phosphite, dι-2-ethyl-hexyl phosphate, dι-2-ethyl-hexyl phosphite, hydroxyethyl methacrylate monophosphate, glyceryl dimethacrylate phosphate, glyceryl-2-phosphate, glycerylphosphonc acid, methacryloxyethyl phosphate, pentaerythritol tnacrylate monophosphate, pentaerythntol tπmethacrylate monophosphate, dipentaerythπtol pentaacrylate monophosphate, and dipentaerythntol pentamethacrylate monophosphate), pivaiic acid, propionic acid, sulfuπc acid, toluene sulfonic acid, tπbromoacetic acid, tπchloroacetic acid, tπfluoroacetic acid tnfluoromethanesulfonic acid, and tπhydroxybenzoic acid Mixtures of such acids can be used if desired Preferred acids are capable of complexmg with a reactive glass The mixtures can if necessary also contain other compounds that although they contain acid groups, their salts, or their reactive derivative groups, do not contain polymenzable groups Preferred in this case are multibasic acids such as tartaric, citric, mellitic, polycarboxylic, polyphosphoric, polyphosphonic, or polysulfonic acids along with chelating agents such as ethylenediamine-tetraacetic acid, and especially their salts Particularly preferred compositions of the present invention are those wherein at least a portion of the polymenzable component and at least a portion of the acidic component of the composition are provided by the same chemical compound Examples of such compounds are monomers, oligomers or polymers of molecular weight less than 10,000 and containing at least one acidic groups and at least one polymenzable group Preferably, these compounds hav a molecular weight of between about 100-5000, and more preferably between about 200-1000 The acidic group can be oxyacids or thio-oxy acids of B, C, N, S, P Preferably it is an These preferred compounds are defined by the structure (P) p — (Q)n--(R) r where P = backbone with acidic functionality Q= backbone with a curable group, e g acrylate methacrylate, epoxy etc R= backbone of a non-reactive modifying unit p l 1 , 1 > 1 , an d r = 0 or more Especially preferable acid groups are carboxylic acids, sulfonic acids, phoshoπc acids, phosphonic acids, and bone acids the salts of the foregoing acids or precursors of the foregoing acids that are easily converted to these acids in conditions encountered during a dental restorative procedure Examples of such compounds are acryloyl or methacryloyl substituted polycarboxylic acids, phosphoric acid esters of hydroxyethyl methacrylate, hydroxy propyl methacrylate, acrylates and methacrylates of pentaerythritol dimethacrylate and glyceroldimethacrylate Examples of such preferred compounds include the aliphatic carboxy compounds, such as acrylic acid methacrylic acid, maleic acid fumaric acid, itaconic acid, crotonic acid, aconitic acid, glutaconic acid, mesaconic acid, tiglicinic acid, 2-chloroacryIιc acid, 3-chloroacrylιc acid, 2-bromoacrylιc acid, 1 -methacryloyl malonic acid, 1-acryloyl malic acid, N-methacryloyl and N-acryloyl derivatives of amino acids, and acids such as tartaric acid, citric acid, malic acid that have been further functionalized with an ethylenic functionality For example, citric acid may be ethylenically functionalized by substituting with an acryloyl or methacryloyl functionality Other preferred compounds are the aromatic carboxy compounds, such as benzoic acid, and acryloyl or methacryloyl derivatives of salicyc c acid, tπmellitic acid, phthalic acιd,and the like Reactive fillers suitable for use in the systems of this invention include those that are commonly used with lonomers to form ionomer cements Examples of suitable reactive fillers include metal oxides such as zinc oxide and magnesium oxide, and lon-leachable glasses, e g , as described in U S Pat Nos 3,655,605, 3,814,717, 4, 143,018, 4,209,434, 4,360,605 and 4,376,835 The reactive filler is preferably a finely divided reactive filler The filler should be sufficiently finely-divided so that it can be conveniently mixed with the other ingredients and used in the mouth Preferred average particle diameters for the filler are about 0 2 to about 15 micrometers, more preferably about 1 to 10 micrometers, as measured using, for example, a sedimentation analyzer Preferred reactive fillers are acid-reactive Suitable acid-reactive fillers include metal oxides, metal salts and glasses Preferred metal oxides include barium oxide, calcium oxide, magnesium oxide and zinc oxide Pieferred metal salts include salts of multivalent cations, for example aluminum acetate aluminum chloride, calcium chloride, magnesium chloride, zinc chloride, aluminum nitrate, barium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate and calcium fluoroborate Preferred glasses include borate glasses, phosphate glasses and fluoroaluminosilicate glasses Fillers that are reactive as described above provide excellent handling properties and final composition properties because, when reacted, they impart a gel or partial gel structure to the material Most preferred o the reactive fillers are those that release fluoride Fluoride releasing glasses, in addition to providing good handling and final composition properties as discussed above, provide the benefit of long-term release of fluoride in use, for example in the oral cavity Fluoroaluminosilicate glasses are particularly preferred Suitable reactive fillers are also available from a variety of commercial sources familiar to those skilled in the art For example, suitable fillers can be obtained from a number of commercially available glass ionomer cements, such as "GC Fuji LC" and "Kerr XR" ionomer cement Mixtures of fillers can be used if desired If desired, the reactive filler can be subjected to a surface treatment Suitable surface treatments include acid washing, treatment with phosphates, treatment with chelating agents such as tartaric acid, treatment with a silane or silanol coupling agent Particularly preferred reactive fillers are silanol treated fluoroaluminosilicate glass fillers, as described in U S Patent Number 5,332,429 the disclosure of which is expressly incorporated by reference herein Non-reactive fillers may be selected from one or more of any material suitable for incorporation in compositions used for medical applications, such as fillers currently used in dental restorative compositions and the like The filler is finely divided and preferably has a maximum particle diameter less than about 50 micrometers and an average particle diameter less than about 10 micrometers The filler can have a unimodal or polymodal (e g , bimodal) particle size distribution The filler can be an inorganic material It can also be a crosslinked organic material that is insoluble in the polymerizable resin, and is optionally filled with inorganic filler The filler should in any event be non-toxic and suitable for use in the mouth The filler can be radiopaque, radiolucent or non-radiopaque Examples of suitable non-reactive inorganic fillers are naturally-occurring or synthetic materials such as quartz, nitrides (e g , silicon nitride), glasses derived from, for example Ce, Sb, Sn, Zr, Sr, Ba and Al, colloidal silica, feldspar, borosilicate glass, kaolin, talc, titania, and zinc glass, low Mohs hardness fillers such as those described in U S Patent No 4,695,251 , and submicron silica particles (e.g , pyrogenic silicas such as the "Aerosil" Series "OX 50", " 130", " 150" and "200" silicas sold by Degussa and "Cab-O-Sil M5" silica sold by Cabot Corp ) Examples of suitable non-reactive organic filler particles include filled or unfilled pulverized polycarbonates, polyepoxides, and the like Preferred non-reactive filler particles are quartz, submicron silica, and non-vitreous microparticles of the type described in U S Patent No 4,503, 169 Mixtures of these non-reactive fillers are also contemplated, as well as combination fillers made from organic and inorganic materials Preferably the surface of the filler particles is treated with a coupling agent in order to enhance the bond between the filler and the polymenzable resin The use of suitable coupling agents include gamma-methacryloxypropyltπmethoxysilane, gamma-mercaptopropyltπethoxysilane, gamma-aminopropyltπmethoxysilane and If desired, the compositions ofthe invention can contain adjuvants such as cosolvents, pigments, inhibitors, accelerators, viscosity modifiers, surfactants, rheology modifieers, colorants, medicaments and other ingredients that will be apparent to those skilled in the art Optionally, the compositions may contain stabilizers The incorporation of stabilizers serves to further improve the color stability of paste paste compositions Suitable stabilizers include oxalic acid, sodium metabisulfite, metaphosphonc acid, sodium bisulfite, sodium thiosulfate, and combinations thereof Oxalic acid and sodium metabisulfite are preferred stabilizers Cosolvents useful in the present invention include, but are not limited to, low molecular weight organic solvents The word "cosolvent" as used herein refers to a material that aids in the dissolution of materials in the composition, in order to form a homogeneous composition Examples of suitable cosolvents include ethanol, propanol, and glycerol The compositions of this invention can be used in a variety of applications in the dental or medical fields in which a material is desired that will adhere well to the surrounding tooth or bone structure For instance these compositions can be used as dental restoratives, liners, bases, cements, sealants and as dental or orthodontic adhesives The present compositions are preferably provided initially as a one-part paste composition For purposes of the present invention, a paste is defined as a material wherein the inelastic modules is less than the elastic modulus of the material Preferably, the paste has a viscosity between about 1 X IO 2 and 1 X IO 11 Cps More preferably, the paste has a viscosity between about 1 X I O 7 and 1 X I O 9 Cps Viscosity is measured using a rheometer at a shear rate between 0 01 and 0 1 sec " 1 at about 25°C A preferred test protocol is to utilize a Bohlin CS50 controlled stress rheometer (Metric Group, Inc , Bohlin Instruments Division, Cranbury, NJ) with 20 mm parallel plates and a gap of 2mm The stress is ramped from 1 Pascal up to a stress sufficient to reach a shear rate of approximately 0 1 sec "1 Water Uptake Test Water uptake was measured by forming each composition into disks 20 mm in diameter and 1 mm thick Both sides of each disk were covered with polyethylene terephthalate ("PET") film and light cured for 30 seconds on each side using two oppositely-disposed 3M™ Visilux™ 2 Visible Light Curing Units with about a 1 cm distance between the output end of the light guide and the sample The film was then removed and the exposed samples allowed to cure for 1 hour at 37°C/95% relative humidity ("RH") Each disk was weighed and placed in a glass jar to which was added 25 L of deionized water The sample was maintained at 37°C for a specified time period At the specified time, the sample was removed from the jar, the superficial water was removed using a facial tissue or cotton and the sample was immediately weighed The weight was recorded and the sample was returned to the water in the sample jar At periodic designated intervals, the above procedure was repeated and the sample weight recorded At each specified time interval, water uptake for 3 samples of each composition was measured and the average reported in grams per 100 grams of cured composition The present invention will be further understood in view of the following examples which are merely illustrative and not meant to limit the scope ofthe invention Unless otherwise indicated, all parts and percentages are by weight and all molecular weights are weight average molecular weights PREPARATORY EXAMPLE 1 Treated Fluoroaluminosilicate Glass The ingredients set out below in TABLE 1 were mixed, melted in an arc furnace at about 1350-1450°C, poured from the furnace in a thin stream and quenched using chi'led rollers to provide an amorphous single-phase fluoroaluminosilicate glass TABLE 1 Ingredient Parts SιO 2 37 A1F, 23 SrCO, 20 Al 2 O, 10 Na,AlFc 6 P 2 O 5 4 The glass was ball-milled to provide a pulverized frit with a surface area of 2 5-3 2 m 2 /g measured using the Brunauer, Emmet and T ellei (BET) method A silanol solution was prepared by mixing together 2 4 parts gamma- methacryloxypropyl trimethoxysilane ("A- 174", Union Carbide Corp ), 12 6 parts methanol, 36 5 parts water and 0 33 parts acetic acid The mixture was stirred magnetically for 60 minutes at ambient temperature, added to 60 8 parts of the glass powder and slurned for 30 minutes at ambient temperature The slurry was poured into a plastic-lined tray and dried for 10 hours at 80°C The silanol treated dried powder was sieved through a 60 micrometer mesh screen PREPARATORY EXAMPLE 2 Treated OX-50 A- 174 (3 7g) was added with stirring to 50g of deionized water acidified to pH 3-3 3 by dropwise addition of trifluoroacetic acid The resultant mixture was stirred at about 25°C for 1 hour at which time 95g of OX-50 were added to the mixture with continued stirring for 4 hours The slurry was poured into a plastic- lined tray and dried at 35°C for 36 hours The silanol treated dried powder was sieved through a 74 micrometer mesh screen PREPARATORY EXAMPLE 3 Treated ZirconiarSilica Filler 25 5 Parts silica sol ("LUDOX" LS, E 1 duPont de Nemours & Co ) were acidified by the rapid addition of 0 255 parts concentrated nitric acid In a separate vessel, 12 9 parts ion-exchanged zirconyl acetate (Magnesium Elecktron Inc ) were diluted with 20 parts deionized water and the resultant solution acidified with 0 255 parts concentrated nitric acid The silica sol was pumped into the stirred zirconyl acetate solution and mixed for one hour while filtering the stirred mixture through "CUNO" 5 micrometer and 1 micrometer filters (Commercial Intertech Corp ) The stirred, filtered mixture was further filtered though a 1 micrometer "HYTREX" filter (Osmonics, Inc ) followed by a 0 22 micrometer "BALSTRON" filter (Balston Inc ) The filtrate was poured into trays to a depth of about 25 mm and dried at 65°C in a forced air oven for about 24 hours The resultant dried material was removed from the oven and tumbled through a rotary tube furnace (Harper Furnace Corporation) preheated to 600°C to provide 21 parts of calcined microparticles The calcined microparticles were comminuted in a tumbling ball mill until all of the microparticles were less than 10 micrometers in particle diameter 0 3 Part portions ofthe milled microparticles were placed in ceramic saggers and fired in an electric kiln (Harper Furnace Corporation) in air at 825°C for 1 hour The fired microparticles were allowed to cool in air The cooled microparticles were slurried in hydrolyzed A- 174 silane at a ratio of 1 1 1 parts silane to 100 parts microparticles, dried in a forced air oven and screened through a 74 micrometer mesh screen EXAMPLE 1 Preparation of Polymerizable Component "Al" Citric acid (400g) was dissolved in 2 L of tetrahydrofuran ("THF") in a reaction vessel fitted with a mechanical stirrer, condenser, addition funnel and air inlet tube To the resultant homogenous solution was added 0 52g butylated hydroxytoluene ("BHT"), 0 5g of tπphenylantimony ("TPS") and 0 98g dibutyltin dilaurate ("DBTDL") Dry air was inti oduced into the reaction mixture through the inlet tube 2-Isocyanatoethyl methacrylate ("IEM", 161 5g, 1 04 moles) was added dropwise through the addition funnel so as to maintain the reaction temperature at about 40°C The reaction was followed by infraied spectroscopy ("IR") After all the IEM had been added and the IR spectrum no longer showed the presence of isocyanate group, the solvent was removed under vacuum from the reaction mixture and the resultant viscous liquid was dried Nuclear magnetic resonance spectroscopy ("NMR") confirmed the presence of added methacrylate functionalities and the retention of carboxy groups EXAMPLE 2 Preparation of Polymerizable Component "A2' Polyacrylic acid (8 64g, molecular weight 2,000) and 75 mL THF were added to a reaction flask equipped with a stirrer, condenser, addition funnel and air inlet tube After stirring at a bath temperature of 50-70°C for 2-3 hours, a cloudy solution was obtained The temperature of the bath was maintained at 40-50°C and a solution containing 0 093g BHT, 0 093g TPS and 0 64g DBTDL in 5 mL of dry THF was added to the reaction mixture IEM (9 3g) was added dropwise through the addition funnel over a period of 1 hour The mixture was allowed to stir until the IR spectrum showed complete disappearance o the isocyanate band at which time the reaction mixture was poured into petroleum ether A white, solid polymer precipitated and was isolated by filtration, washed and dried under vacuum EXAMPLE 3 Preparation of Metal Fluorocomplexes Metal fluorocomplexes DI-DXI were independently prepared by dissolving the quantity ofthe carboxylic acid complexing agent set out in TABLE 2 in water For Complex nos DI-DIX, zinc fluoride powder was slurried with each aqueous solution for about one-half hour, after which time the slurry was poured into a shallow tray and dried at 55°C overnight Each complex was then sieved through a 100 micrometer mesh screen to provide a free-flowing powder Complex nos. DX and DXI were prepared as detailed for the zinc complexes except that 20g aluminum trifluoride and 20g zirconium tetrafluoride respectively were substituted for the zinc fluoride and the resultant complexes were sieved through a 74 micrometer mesh screen Complex no DXI I was prepared by mixing the zinc fluoride with a mixture of acetoacetoxyethylmethacrylate ("AAEM", Eastman Chemicals, TN), 10g ethanol and 5g deionized water The resultant mixture was allowed to stir for 12 hours at ambient temperature The solid was then collected by filtration and dried under vacuum at 45°C for 12 hours The dried solid was crushed with a mortar and pestle to yield a fine powder of Complex no DXII TABLE 2 Complex No Complexing Agent Water ZnF Type Amount (g) (g) <g) DI Tartaric acid 20 20 20 DI1 Tartaric acid 20 20 80 Dili Tartaric acid 30 20 20 DIV Tartaric acid 20 20 30 DV N-methacryloyl glutamic acid 20 20 20 DVI Itaconic acid 20 300 80 DVII Itaconic acid 20 300 40 DVIII Itaconic acid 25 350 25 D1X Itaconic acid 30 380 20 DX Tartaric acid 20 20 — DXI Tartaric acid 20 20 — DXII AAEM 20 — 10 EXAMPLE 4 Preparation of Hydrophilic Component "CI" A glass reaction flask equipped with magnetic stirrer, two addition funnels connected to peristaltic pumps, thermometer, gas inlet tube and reflux condenser was charged with 300 mL of dry THF. One addition funnel was charged with a solution of ethylmethacrylate ( 18.24g, 0 16 moles), acrylic acid (28 8g, 0 4 moles), N-vinylpyrrolidone ("NVP", 26 98g, 0 24 moles) and THF to a volume of 200 mL The second addition funnel was charged with a solution of 0 82g azobisisobutyronitrile ("AIBN") in 60 mL THF Both solutions were purged with dry nitrogen for 15 minutes The reaction vessel was heated to 60°C and the charges from both addition funnels were added via the peristaltic pumps over a course of 6 hours After addition was complete, the reaction was stirred at 60°C overnight Then 300 mL of dry dimethylformamide ("DMF") was added to the reaction vessel and the temperature lowered to 40°C BHT (0 094g), TPS (0 094g) and DBTDL (0 644g) were added to the reaction mixture and the nitrogen in the inlet tube was switched to dry air A solution of IEM ( 18 6g, 0 12 mole) in 45 mL THF was added dropwise to the reaction mixture over 2 hours The reaction mixture was then allowed to stir at 40°C for an additional hour The solvents were partially removed under vacuum to reduce the volume to about one-half of the original and the resultant solution poured into ethyl acetate The precipitated polymer was collected by filtration, washed and dried under vacuum EXAMPLE 5 Preparation of Hydrophilic Component "C2" A glass reaction flask equipped with magnetic stirrer, two addition funnels connected to peristaltic pumps, thermometer, gas inlet tube and reflux condenser was charged with 500 mL of dry THF One addition funnel was charged with a solution of ethylmethacrylate (34 25 g, 0 3 moles), acrylic acid (50 4g, 0 7 moles) and THF to a volume of 200 mL. The second addition funnel was charged with a solution of 0 82g AIBN in 60 mL THF. The solutions were purged with dry nitrogen for 15 minutes The reaction vessel was heated to 60°C and the charges from both addition funnels were added via the peristaltic pumps over a course of 6 hours After addition was complete, the reaction was stirred at 60°C overnight Then the reaction temperature was lowered to 35°C BHT (0.165g), TPS (0 165g) and DBTDL ( 1.13g) were added to the reaction mixture and the nitrogen in the inlet tube was switched to dry air A solution of IEM (32 55g, 0 21 moles) in 200 mL THF was added dropwise to the reaction mixture over 2 hours The reaction mixture was then allowed to stir at 35-40°C for an additional hour The solvents were partially removed under vacuum to reduce the volume to about one-third of the original and the resultant solution poured into ethyl acetate The precipitated polymer was collected by filtration, washed and dried in under vacuum EXAMPLE 6 Preparation of Hydrophilic Component "C3" A glass reaction flask equipped with magnetic stirrer, two addition funnels connected to peristaltic pumps, thermometer, gas inlet tube and reflux condenser was charged with 500 mL of dry THF One addition funnel was charged with a solution of ethylmethacrylate (17.12g, 0 15 moles), acrylic acid (50 4g, 0 7 moles), methacrylic acid ( 12 9g, 0 1 5 moles) and THF to a volume of 200 mL The second addition funnel was charged with a solution of 0 82g of AIBN in 60 mL THF Both solutions were purged with dry nitrogen for 1 5 minutes The reaction vessel was heated to 60°C and the charges from the addition funnels were added via the peristaltic pumps over a course of 6 hours After the addition was complete, the reaction was stirred at 60°C overnight. Then the reaction temperature was lowered to 35°C. BHT (0 165g), TPS (0 165g) and DBTDL (1 13g) were added to the reaction mixture The nitrogen in the inlet tube was switched to dry air A solution of IEM (32 55g, 0.21 mole) in 200mL THF was added dropwise to the reaction mixture over 2 hours The mixture was then allowed to stir at 35-40°C for an additional hour. The solvents were partially removed under vacuum to reduce the volume to about one-third of he original and the resultant solution poured into ethyl acetate The precipitated polymer was collected by filtration, washed and dried under vacuum EXAMPLE 7 Preparation of Hydrophilic Component "C4" A glass reaction flask equipped with magnetic stirrer, two addition funnels connected to peristaltic pumps, thermometer, gas inlet tube and reflux condenser was charged with 210 mL of dry THF One addition funnel was charged with a solution of acrylic acid (50 4g, 0 7 moles), NVP (33 3g, 0 3 moles) and THF to a volume of 250 mL The second addition funnel was charged with a solution of 0 82g AIBN in 60 mL THF Both solutions were purged with dry nitrogen for 15 minutes The reaction vessel was heated to 60°C and the charges from both addition funnels were added via the peristaltic pumps over a course of 4 hours After addition was complete, 22 mL of dry DMF was added and the reaction was stirred at 60°C overnight The reaction temperature was then lowered to 35°C BHT (0 15g), TPS (0 15g) and DBTDL ( 1 03g) were added to the reaction mixture and the nitrogen in the inlet tube was switched to dry air A solution of IEM (32.55g, 0 21 mole) in 200 mL THF was added dropwise to the reaction mixture over 2 hours The reaction mixture was then allowed to stir at 35-40°C for an additional 24 hours The solvents were partially removed under vacuum to reduce the volume to about one-third of the original and the resultant solution poured into ethyl acetate The precipitated polymer was collected by filtration, washed and dried under vacuum EXAMPLE 8 Pastes were prepared by mixing the ingredients shown in TABLE 3 The specified quantities of polymerizable component Al of EXAMPLE 1 , glycerol dimethacrylate ("GDMA", Rohm Tech, Inc , Maiden, MA) and 1 lg or no poly(N- vinyl pyrroiidone) ("PVP", International Specialty Products, Wayne, NJ) were thoroughly mixed with 0 095g camphorquinone ("CPQ") and 0 37g ethyl(4- dimethylamino)benzoate ("EDMAB") A portion of the resultant mixture was combined with the specified amounts ofthe glass of PREPARATORY EXAMPLE 1 ("PE1 ") + 2% OX-50 of PREPARATORY EXAMPLE 2 ("PE2") and 4g or no Complex Dl from TABLE 2 The pastes were either hand-mixed or mechanically mixed using a double planetary mixer TABLE 3 Water uptake of each composition in TABLE 3 as well as that of Dyract™ Light Cured Compomer ("Dyract", Dentsply International Inc ) was measured on day 7 and day 14 using the procedure described in the Water Uptake Test The results are set out in TABLE 4 Incremental fluoride release of each composition was measured after 3 days and compared with that of Dyract Disks of each composition were prepared and cured as described for the Water Uptake Test Each disk was placed in ajar containing 25 mL of deionized water at 37°C A fluoride-selective electrode, Orion Model 96-09-00 (from Orion Research Inc , Cambridge, MA) was used to quantify the amount of fluoride ion released from the sample in the water The electrode was calibrated using Fluoride Activity Standards #940907 and #040908, a 100 parts per million ("ppm") and a 10 ppm respectively, fluoride standard fluid (both from Orion Research Inc ) For the measurement of fluoride ions released into the water, 10 mL of the sample solution was transferred on the day specified to a 60 mL beaker and 10 L of TISAB solution (total ionic strength adjustment buffer, Orion Research Inc , Cambridge, MA) was added to the beaker The contents were mixed for 10 seconds. The calibrated fluoride-selective electrode was placed in the solution and the ppm F " were recorded and converted to micrograms of F " per cm 2 of the cured disk The residual liquid was then removed from the sample jar and replaced with a fresh 25 mL quantity of deionized water The sample jar was transferred to a 37°C oven for the specified interval in days, at which time, the sample jar was removed from the oven and the ppm F " released during that interval were measured as described above Micrograms of F ' per cm 2 ofthe cured disk were again calculated and these values were reported as a function of time of storage in the water Fluoride release values for 3 samples of each composition were measured and the average recorded The results are set out in TABLE 4 TABLE 4 Run No Water Uptake in g/I OOg of Cured μg/cm 2 F " Released Composition Measured on Day After 3 Days 7 14 1 1 7 1 9 43 38 2 1 9 2 1 26 03 3 1 5 1 8 34 70 4 1 6 1 9 19 52 Dyract 1 1 1 2 2 2 The incremental fluoride release data in TABLE 4 show that although Run nos 1 -4 with a fluoroaluminosilicate glass in a hydrophilic resin matrix showed good fluoride release compared to a commercial one-paste fluoride releasing material, Dyract, the addition of a metallo-fluorocomplex to the compositions of Run nos 1 and 3 substantially increased the fluoride release EXAMPLE 9 Pastes were prepared by mixing the ingredients shown in TABLE 5 The specified quantities of polymerizable component Al of EXAMPLE 1 , GDMA and component C were thoroughly mixed with CPQ at a concentration of 0 42 parts per hundred and EDMAB at a concentration of 1 65 parts per hundred A portion of the resultant mixture was combined with the specified amounts of the glass of PE1 + 2% OX-50 of PE2 and the Complex of EXAMPLE 3 as outlined in TABLE 5 The pastes were either hand-mixed or mechanically mixed using a double planetary mixer For determination of compressive strength ("CS") and diametral tensile strength ("DTS"), the composition of each run no was packed into a 4 mm inside diameter glass tube, capped with silicone rubber plugs and axially compressed at about 0 28 MPa for 15 minutes, then light cured for 80 seconds by exposure to two oppositely-disposed Visilux units Each sample was then irradiated for 30 seconds using a Dentacolor XS unit (Kulzer) Cured samples were cut on a diamond saw to form cylindrical plugs 8 mm long for measurement of CS and 2 mm long for measurement of DTS The plugs were stored in distilled water at 37°C for 24 hours CS and DTS values for each composition were measured according to ADA ("American Dental Association") specification No 9 and ADA specification No 27 respectively TABLE 5 * Pc )ly(N-viny pyrroli done), Internat ιonal Specialt y Products, Wa\ /ne, NJ The CS and DTS of the paste compositions of Run nos 1-14 were superior to the mechanical properties of two commercial fluoride releasing materials, 3M™ Vitremer™ Glass Ionomer Core Build-up Restorative ("Vitremer", 3M) with a CS of 214 MPa and Dyract with a CS of 262 MPa Water uptake of the compositions of Run nos 3, 5 and 7 in TABLE 5 as well as that of Dyract was measured on days 5, 12 and 28 using the procedure described in the Water Uptake Test The results are set out in TABLE 6 Incremental fluoride release of the compositions of Run nos 1, 3, 7, 10 and 1 1 as well as that of Dyract and Vitremer was measured on days 4, 8, 14, 21 and 27 using the procedure described in EXAMPLE 8 The results are set out in TABLE 6 TABLE 6 Water Uptake in g/100g of Cured Incremental F Release in μ « /cm 2 Measured on Composition Measured on ϋa D;ι Run No. Da> 5 12 28 4 8 14 21 27 1 — — — 28 3 17 6 36 4 25 3 20 8 3 1 6 2 03 2 47 17 1 14 2 20 5 20 8 19 3 5 1 69 2 09 2 56 ... ... ... — — 7 1 6 2 1 7 2 54 19 1 16 5 23 4 18 7 19 5 10 ... — — 18 2 15 3 21 2 22 8 20 4 1 1 — — — 52 1 3 1 8 48 1 49 1 35 6 Dvract 0 65 1 05 I 26 8 1 10 7 1 3 4 13 1 16 9 Vitremer — ... ... 33 3 17 6 36 4 27 5 22 1 The data in TABLE 6 show that compositions containing the fluorocomplex salts exhibited fluoride release that was much higher than that of a commercial fluoride-releasing one-paste material, Dyract, and was comparable to that ofa water-based powder Iiquid glass ionomer material, Vitremer EXAMPLE 10 Three resin mixtures were prepared by mixing together 7 Og polymenzable component Al of EXAMPLE 1 , 13 9g GDMA, 1 lg PVP, 0 095g CPQ and 0 37g EDMAB to provide a homogeneous mixture Pastes were then compounded by adding to each mixture 74g of a blend of the glass of PE 1 , 2% OX-50 of PE2 and 4 Og ofthe designated Complex from TABLE 2 All three resultant pastes were stable at room temperature whereas control pastes prepared using untreated zinc fluoride showed substantial thickening on standing and became crumbly after 24 hours Using the procedure described in EXAMPLE 8, incremental fluoride release ofthe compositions of Run nos 1-3 was measured and compared with that of Dyract and Vitremer The results are set out in TABLE 7 TABLE 7 Run No Complex Incremental F Released in μg cur Measured on Day lrom Table 2 1 2 3 4 5 6 7 14 21 1 DU 79 53 28 20 32 53 18 08 17 35 14 46 8 68 35 43 20 24 2 DI 79 53 20 24 21 69 13 01 9 40 10 12 7 23 27 83 1721 3 DVTI 79 53 36 15 26 75 20 24 16 63 15 91 10 85 44 54 22 27 Dvract — 7 95 1 95 2 02 1 37 2 46 1 5 1 45 4 55 3 54 Vitremer — 65 07 16 63 13 01 10 12 8 68 6 51 5 06 27 83 16 70 The incremental fluoride release results in TABLE 7 show that paste compositions ofthe invention containing fluorocomplex salts showed much higher fluoride release compared to a commercial one-paste fluoride-releasing material, Dyract The amount of fluoride released was comparable to a water-based powder liquid glass ionomer, Vitremer EXAMPLE 11 Two resin mixtures were prepared by mixing 1 1 Og Bis-GMA, 1 1 Og TEGDMA, 0 06g CPQ and 0 12g EDMAB to provide a homogeneous mixture Pastes were then compounded by adding to each mixture the amount of a blend of the glass of PEl, 2% OX-50 of PE2 and 4 Og or no Complex DI from TABLE 2 as set out in TABLE 8 Incremental fluoride release of each composition was measured after 3 days using the procedure described in EXAMPLE 8 The results are set out below in TABLE 8 TABLE 8 The data in TABLE 8 show that although the use of the Bis-GMA/TEGDMA resin system of TABLE 8 decreases the overall fluoride release compared to the more hydrophilic matrix used for EXAMPLE 8, the amount of fluoride ion released was still higher for Run no 1 than that of Run no 2 which did not contain the zincfluorocomplex and was comparable to a commercial fluoride-releasing one-paste material, Dyract EXAMPLE 12 Four resin mixtures were prepared by mixing 7 35g polymerizable component A l of EXAMPLE 1 , 14 65g GDMA, 0 095g CPQ and 0 37g EDMAB to provide a homogeneous mixture Pastes were then compounded by adding to each mixture the filler type and amount and 2 Og or none of Complex D l from TABLE 2 as set out in TABLE 9 Cumulative fluoride release was measured on disks ofthe compositions prepared and cured as described for the Water Uptake Test Each disk was placed in ajar of phosphate buffer prepared by mixing 0 7g KH 2 PO 4 and 0 71g Na 2 HPO 4 in 1 liter of deionized water to provide a 0 01 M solution having a pH of 6 8-7 0 at 37°C A calibrated fluoride-selective electrode as described for incremental fluoride release in EXAMPLE 8 was placed in the buffer solution containing the disk on the days designated in TABLE 9 and ppm F " recorded Micrograms of F ' per cm 2 of the cured disk were then calculated and these values were reported as a function of time of storage in the buffer Fluoride release values for 3 samples of each composition were measured and the average reported in TABLE 9 The composition of Run no 4 showed no measurable fluoride release TABLE 9 Run Complex Cumulative F Release in No. DI Ev μg/cιvr Measured on Day Type Filler Amount(g) 3(g) 0 7 24 1 Glass of PE 1 + 2% OX-50 of PE2 78 0 1 30 45 2 Glass of PE 1 + 2% OX-50 of PE2 76 2 2 45 95 3 PREPARATORY EXAMPLE 3 76 2 1 20 35 4 PREPARATORY EXAMPLE 3 78 0 ... — — The data in TABLE 9 show that the incorporation of a fluorocomplex increased the fluoride release of the compositions of Run nos 2 and 3 This effect was exhibited even when no other acid-reaαive fiilei as incυψυidted into the sysiem Thus both Run nos 3 and 4 contained a non-acid reactive filler, but only Run no 3, which contained a fluorocomplex salt, showed appreciable fluoride release EXAMPLE 13 A stock liquid was made up by blending 219g polymerizable component Al of EXAMPLE 1 , 400g GDMA, 30g PVP, 1 1 g EDMAB and 2 8g CPQ Six pastes were then formulated using 12 6g ofthe stock liquid, 43.8g of the glass of PEl , 1 2 g of OX-50 of PE2 and 2 4 g of the Complex of EXAMPLE 3 identified in TABLE 10 The CS and DTS of the compositions were measured according to the procedure detailed in EXAMPLE 9 TABLE 10 Run. No Complex of Ex 3 CS (MPa) DTS (MPa) 1 DI 324 53.8 2 Dili 324 5 1 7 - J DIV 33 1 5 1 0 4 DVI1 3 10 53 1 5 DVII1 303 48 3 6 DIX 3 1 7 55 2 The data in TABLE 10 show that one-paste compositions containing a hydrophilic resin matrix and zincfluorocomplexes provided cured specimens exhibiting excellent mechanical properties EXAMPLE 1 Two pastes were formulated using 12 4g ofthe stock liquid ofEXAMPLE 13, 43.8g ofthe glass of PEl , 1.2g of OX-50 of PE2 and 2 4g of the aluminumfluorocomplex or the zirconiumfluorocomplex o EXAMPLE 3 A third paste was formulated as described for the first two pastes, except that 12 6g of the stock liquid ofEXAMPLE 13 was used and the fluorocomplex was DXII CS and DTS was measured according to the procedure described in EXAMPLE 9 and incremental fluoride release was measured according to the procedure detailed in EXAMPLE 8 TABLE 11 The data in TABLE 1 1 show additional examples of pastes containing metallo-fluorocomplexes of various metals and ligands These pastes exhibited excellent mechanical properites as well as very high fluoride release EXAMPLE 15 A stock solution was prepared by dissolving 40g GDMA, 3g PVP, 1 lg benzoyl peroxide and 0 088g BHT. Then 8.4g of the stock solution was combined with 4.2g of the polymerizable component A 1 of EXAMPLE 1 The resulting homogeneous liquid was combined with 43 8g ofthe glass of PE l , 1.2g OX-50 of PE2 and 2 4g of Complex Dl ofEXAMPLE 3 to provide a Paste "A" Three Paste "B" formulations were prepared by combining 43 8g of the glass of PEl, 1.2g OX-50 of PE2 and 2 4g of Complex DI ofEXAMPLE 3 with 12.6g of the ingredients set out below in TABLE 12 TABLE 12 Paste B Liquid Paste B l Paste B2 Paste B3 Ingredients (g) (g) (g) CD-541 1 47 5 — — PEG 6 uoDMA 2 ... 23 7 ... UDMA ... 23 7 35 PVP 2 5 2 5 2 5 HEMA 4 10 10 12 5 DMAPE 5 1 5 1 5 1 5 Sartomer, Exton, PA 2 Polyethyleneglycol-600 dimethacrylate (Sartomer) ' Urethane dimethacrylate (Rohm Tech, Inc , Maiden, MA) 4 2-Hydroxyethyl methacrylate 4-(Dimethylamιno)phenethanol Compositions were prepared by combining four parts of Paste A with one part of Paste B l, B2 and B3 respectively Set time was measured according to ISO specification 9917 and CS and DTS were measured according to the procedure described in EXAMPLE 9 TABLE 13 Run Paste B Sel Time CS (MPa) DTS (MPa) No (mm sec ) 1 B l 4 00 310 44 8 2 B2 3 30 303 37 9 3 B 2 30 255 27 6 The data in TABLE 13 illustrate two-paste compositions containing a hydrophilic resin matrix and a fluorocomplex that cured upon mixing to yield materials exhibiting good physical properties and set times that were clinically acceptable

Claims: What is Claimed: 1 A curable dental composition comprising a metal complex described by formula M(G) g (F) n or M(G)„(ZF m ) n where M represents an element capable of forming a cationic species and having a valency of 2 or more. G is an organic chelating moiety capable of complexing with the element M Z is hydrogen, boron, nitrogen, phosphorus, sulfur, antimony, arsenic F is a fluoride atom g, m and n are at least 1 2 A dental composition according to claim 1 , wherein M is selected from the group consisting of Ca +2 , Mg +2 , Sr" 2 , Zn" 2 , Al +' \ Zr +4 , Sn +2 , Yb" ' Y"\ and Sn +4 3 A dental composition according to claim 1 , wherein M is Zn + " 4 A dental composition according to claim 1 , wherein the chelating moiety G comprises a polymerizable group 5 A dental composition according to claim 1 , wherein the chelating moiety G is bound in a ring structure, together with the metal ion, of 4-8 members 6 A dental composition according to claim 1 , wherein the chelating moiety G is bound in a ring structure, together with the metal ion, of 5-7 members 7 A dental composition according to claim 1, wherein the chelating moiety G is selected from the group consisting of bi-, tri- or quadra-dentate chelates 8 A dental composition according to claim 1 , wherein the chelating moiety G is selected from the group consisting of malic acid, tartaric acid, citric acid, ethylenediamine tetraacetic acid, salicylic acid, hydroxybenzoic acids, hydroxytartaric acids, nitrilotriacetic acid, salicylic acid, melletic acids, polyglycols, β-diketones and β-ketoesters 9 A dental composition according to claim 1 , wherein the chelating moiety G is selected from the group consisting of polyphosphates, aminocarboxylic acids, 1 ,3-diketones, hydroxycarboxylic acids,, polyamines, aminoalcohols, aromatic heterocyclic bases, phenols, aminophenols, oximes, Schiff bases, tetrapyrroles, sulfur compounds, synthetic macrocyclic compounds, phosphonic acids, and hydroxyethylidenediphosphonic acid I O A dental composition according to claim 1 , wherein the chelating moiety G is selected from the group consisting of sodium tripolyphosphate, hexametaphosphoric acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, N- dihydroxyethylglycine and ethylenebis(hydroxyphenylglycine), acetylacetone, trifluoroacetylacetone, thenoyltrifluoroacetone, tartaric acid, citric acid, gluconic acid, 5-sulfosslicylic acid, ethylenediamine, triethylenetetramine, triaminotriethylarnine, triethanolamine, N-hydroxyethylethylenediamine, dipyridyl, o-phenanthroline, salicyladehyde, disulfopyrocatechol, chromotropic acid, oxine, 8- hydroxyquinoline, oxinesulfonic acid, dimethylglyoxime, salicyladoxime, disalicyladehyde, 1,2-propylenedimine, tetraphenylporphin, phthalocyanine, toluenedithiol(Dithiol), dimercaptopropanol, thioglycolic acid, potassium ethylxanthate, sodium diethyldithiocarbamate, dithizone, diethyl dithiophosphoric acid, thiourea, dibenzof 18]crown-6(5), (CH 3 )r,[ 14]4, l l -dieneN (6) and (2 2 2- cryptate) (7), polyethylenimine, polymetharyloylacetone, poly(p- vinylbenzyliminodiacetic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetra(methylenephosphonic acid) and hydroxyethylidenediphosphonic acid, and crown ethers 1 1 A dental composition according to claim 1 , wherein the chelating moiety G is selected from the group consisting of compounds of the following formulas. HO— CH— CO 2 H CO H H 2 C= C HO— CH— CO 2 H CH 2 CO 2 H 12 A dental composition according to claim 1 , wherein said dental composition additionally comprises a fluoride-releasing fluoroaluminosilicate glass 13 A dental composition according to claim 1 , wherein said composition is cured through a polymerization reaction 14 A dental composition according to claim 1 , wherein said composition is cured through a setting reaction by virtue of a complexation reaction other than polymerization 15 A dental composition according to claim 12, wherein said composition is selected from the group consisting zinc phosphate cements, polycarboxylate cements, glass ionomer cements and dental amalgams 16 A dental composition according to claim 1, wherein said composition is cured through both a polymerization reaction and through a setting reaction by virtue of a complexation reaction other than polymerization

Inventors: MITRA SUMITA B, WANG BING, MITRA, SUMITA, B., WANG, BING
Applicants: MINNESOTA MINING & MFG, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1996
Main classification: A61K6
IPC codes: A61K6