WO2009140334A2 - Foamable compositions for dental coatings and methods - Google Patents

Abstract

A foamable dental composition that includes a film- forming component and a non-aqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof, wherein the film-forming component is dissolved in the carrier; wherein the film-forming component forms a retentive polymeric coating on a dental surface; and a method of forming a retentive polymeric coating on the dental surface are disclosed.

Description

FOAMABLE COMPOSITIONS FOR DENTAL COATINGS AND METHODS

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 61/053923, filed May 16, 2008, which is incorporated herein by reference in its entirety.

BACKGROUND Products and methods for providing dental agents (e.g., fluoride sources, whitening agents, anticaries agents, and remineralizing agents) to a dental surface by means of a coating on the dental surface have been described. For example, certain dental varnishes and foams containing such active ingredients have been applied to teeth and are commercially available. Although a number of dental agents are available to both dentists and consumers, not all of the products can be conveniently administered using simple and inexpensive equipment. Some of the products must be repeatedly applied over a sufficient period of time to provide a desired result.

Accordingly, there continues to be a need for new compositions and methods to provide dental agents and/or retentive coatings on dental surfaces.

SUMMARY

The present invention provides a film-forming foamable dental composition and methods. It has now been found that certain co-solvents for lower alcohols, which are less volatile than the lower alcohols, can be included as at least a portion of a non-aqueous carrier in the dental composition without loss of stability of retentive coatings formed on dental surfaces using the dental composition. The co-solvents have low odor and taste and have a boiling point of at least about 100 ⁰C. In some embodiments, the co-solvents are non- volatile, having a boiling point of at least about 200 ⁰C. Moreover, including the co- solvent in the dental composition allows a significant reduction in the level of any volatile solvent, such as a lower alcohol, for example, ethanol, which is known to be irritating and has a significant odor and taste. In some embodiments, preferably, the co-solvent is odorless, essentially tasteless, and non-irritating. In some embodiments, the co-solvent acts as a dispersant.

Accordingly, in one embodiment, there is provided a foamable dental composition comprising: a film-forming component; and a non-aqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof; wherein the film- forming component is dissolved in the carrier; and wherein the film-forming component forms a retentive polymeric coating on a dental surface, wherein the retentive polymeric coating remains on the dental surface for at least 8 hours under normal intraoral conditions.

In another embodiment, there is provided a method of forming a retentive polymeric coating on a dental surface. The method comprises: providing a foamable dental composition comprising a film-forming component; a non-aqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof; wherein the film-forming component is dissolved in the carrier; and applying the dental composition to a dental surface; wherein the film-forming component forms a retentive polymeric coating on the dental surface, and wherein the retentive polymeric coating remains on the dental surface for at least 8 hours under normal intraoral conditions.

For certain embodiments, the dental composition provided in the above method includes a propellant. For certain of these embodiments, the method further includes foaming the dental composition to provide a dental foam and applying the dental foam to a dental surface. Definitions

As used herein, the terms "normal intraoral conditions" and "normal conditions" means within the confines of a human oral cavity, normal salivating, and may further include external activities involving the oral cavity, such as eating, drinking, up to two episodes of recommended brushing (two minutes each), and rinsing with water.

As used herein, the term "dental surface" means soft or hard tissue of the oral environment including gums or a natural tooth surface (e.g., dentin or enamel) and also includes the surface of a cured dental restorative material (e.g., 3M FILTEK Supreme universal restorative, 3M ESPE, St. Paul, MN) or of a ceramic tooth.

As used herein, the term "foamable dental composition" means a composition compatible with use in the oral cavity, and capable of being dispensed from a container through, for example, an aerosol or mechanical device, into a dental foam. As used herein, the terms "dental foam" and "foam composition" are equivalent and refer to a dental foam compatible with the oral cavity and having gas voids for a period of at least about 15 seconds and up to about 10 minutes after the dental foam has been formed from a foamable dental composition dispensed from a container. Preferably, a dental foam formed on a surface will not run, drip, or fall from the surface of a substrate (e.g., a dental tray) when the surface is oriented upside down. Such a characteristic is typically referred to as a "self-supporting" dental foam.

As used herein, the term "dental agent" means a component that adds value, for example in terms of an aesthetic, cosmetic, preventative, diagnostic, and/or therapeutic benefit, that results from application to a dental surface. As used herein, the term "film- forming" means the action of a film- forming component such that, when the film-forming component (in certain embodiments comprising a substantive polymer) is applied to a dental surface, a coating is formed thereon.

As used herein, the term "substantive polymer" means a polymer compatible with the oral cavity and included in a film- forming component such that, when the film- forming component is applied to a dental surface, a retentive polymeric coating is formed on and adhered to the surface for an extended period of time (at least 8 hours) under normal conditions within the oral cavity.

As used herein, the terms "compatible with the oral cavity" and "orally compatible" refer to compositions, components, polymers, additives, and the like that are generally regarded non-irritating for use in the oral cavity. As used herein, a "reactive" group is a group that can react under selected conditions (e.g., in the presence of free radicals, under condensation reaction conditions, and/or in the presence of a multi-valent metal, such as from an ion-leachable powder) with another reactive group or another component (e.g., a crosslinker or a compound with condensation reaction sites). For example, in a polymer that includes a reactive group, the reactive group can react with another reactive group and/or another component to form crosslinks through dimerization, oligomerization, and/or polymerization reactions. In another example, in a polymer that includes a reactive group such as a carboxy group, the reactive group can react with another carboxy group in the presence of a multi-valent metal cation to form ionic crosslinks.

As used herein, "hardenable" refers to a material that can be "hardened." As used herein, "harden" is meant to encompass processes including, for example, crosslinking, dimerization, oligomerization, and/or polymerization reactions.

As used herein, "repeating unit" or "monomeric unit" refers to a unit in a polymer that is derived from an ethylenically unsaturated monomer. For example, polypropylene includes -CH₂CH(CH₃)- monomeric units that are derived from the ethylenically unsaturated monomer propylene, CH₂=CH(CHs).

As used herein, "dispersant" refers to material that acts as a wetting agent by aiding in spreading the composition over the dental surface, such as the surface of a tooth. As used herein, "lower alcohol" and "lower monohydric alcohol" refer to a mono- hydroxy alcohol of one to three carbon atoms, e.g., methanol, ethanol, n-propanol, and isopropanol. For certain embodiments, preferably the mono-hydroxy alcohol is ethanol, n- propanol, isopropanol, or a combination thereof. For certain embodiments, the mono- hydroxy alcohol is ethanol. As used herein, "retentive" refers to a coating that can withstand abrasion and other normal intraoral conditions described above.

As used herein, "(meth)acryl" is an abbreviation intended to refer collectively to "acryl" and/or "methacryl."

As used herein, "a," "at least one," and "one or more" are used interchangeably. The terms "comprises" and variations thereof do not have a limiting meaning where these terms appear in the description and claims.

The words "preferred" and "preferably" refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention provides film-forming foamable dental compositions suitable for coating oral surfaces and methods. Such compositions can be used to provide retentive polymeric coatings on dental surfaces and/or to apply a dental agent to a dental surface. In some embodiments, the foamable dental composition can form a retentive coating on an entire arch in one to three seconds. In some embodiments, the foamable dental composition can deliver a dental agent over an 8, 12, or 24 hour time period.

The foamable dental composition comprises a film- forming component; and a nonaqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof; wherein the film- forming component is dissolved in the carrier; and wherein the film-forming component forms a retentive polymeric coating on a dental surface, wherein the retentive polymeric coating remains on the dental surface for at least 8 hours under normal intraoral conditions. For certain embodiments, preferably the retentive polymeric coating remains on the dental surface for at least 12 hours, more preferably for at least 24 hours, under normal intraoral conditions. The present invention also provides a method of forming a retentive polymeric coating on a dental surface, the method comprising: providing a foamable dental composition comprising a film-forming component; and a non-aqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof; wherein the film-forming component is dissolved in the carrier; and applying the dental composition to a dental surface; wherein the film- forming component forms a retentive polymeric coating on the dental surface, and wherein the retentive polymeric coating remains on the dental surface for at least 8 hours under normal intraoral conditions. For certain embodiments, preferably the retentive polymeric coating remains on the dental surface for at least 12 hours, more preferably for at least 24 hours, under normal intraoral conditions. For certain embodiments, the provided dental composition further comprises a propellant. For certain of these embodiments, the method further comprises foaming the composition to produce a dental foam; and applying the dental foam to a dental surface.

As indicated above, certain co-solvents, which are less volatile than lower alcohols, can be included as at least a portion of the non-aqueous carrier in the foamable dental composition without loss of stability or durability of coatings formed from the compositions in the oral environment. This makes possible a reduction in the amount of a more volatile solvent, thereby reducing odor, taste, and irritation caused by the volatile solvent. The co-solvent may also provide improved dispersion of the composition over the dental surface.

For certain embodiments, preferably the foamable dental composition contains at least about 20 weight percent of the non-aqueous carrier. For certain embodiments, more preferably, the foamable dental composition contains at least about 25 weight percent, at least about 40 weight percent, at least about 50 weight percent, or at least about 60 weight percent of the non-aqueous carrier. For certain embodiments, preferably the foamable dental composition contains at most about 80 weight percent of the non-aqueous carrier. For certain embodiments, more preferably, the foamable dental composition contains at most about 75 weight percent, at most about 70 weight percent, or at most about 65 weight percent of the non-aqueous carrier. For certain embodiments, preferably the non-aqueous carrier is comprised of at least about 10 weight percent of the co-solvent. For certain embodiments, more preferably the non-aqueous carrier is comprised of at least about 25 weight percent, at least about 40 weight percent, or at least about 50 weight percent of the co-solvent. For certain embodiments, preferably the non-aqueous carrier is comprised of at most about 100 weight percent of the co-solvent. For certain embodiments, more preferably the nonaqueous carrier is comprised of at most about 90 weight percent, 85 weight percent, 75 weight percent, 70 weight percent, or 65 weight percent of the co-solvent.

For certain embodiments, including any one of the above compositions and methods where the carrier is comprised of less than 100 weight percent of the co-solvent, the carrier further comprises a lower monohydric alcohol. For certain embodiments, preferably the non-aqueous carrier is comprised of at least about 10 weight percent of the lower alcohol. For certain embodiments, the non-aqueous carrier is comprised of at least about 15 weight percent, at least about 20 weight percent, at least about 25 weight percent, or at least about 30 weight percent of the lower alcohol. For certain embodiments, preferably the non-aqueous carrier is comprised of at most about 80 weight percent of the lower alcohol. For certain embodiments, more preferably the non-aqueous carrier is comprised of at most about 75 weight percent, 50 weight percent, or 45 weight percent of the lower alcohol. For certain of these embodiments, the lower alcohol is ethanol. For certain embodiments, including any one of the above compositions and methods, the co-solvent is selected from the group consisting of diethylene glycol monoethyl ether (CH₃-O-CH₂CH₂-O-CH₂CH₂-OH), dipropylene glycol (HO-C₃H₆-O-C₃H₆-OH), polyethylene glycol 400 [H(-O-CH₂CH₂)_n-OH, average molecular weight of about 400], methoxypoly ethylene glycol 350 [H(-O-CH₂CH₂)_n-OCH₃, average molecular weight of about 350], hexamethyldisiloxane, and a combination thereof. For certain of these embodiments, the co-solvent is selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, polyethylene glycol 400, and methoxypolyethylene glycol 350, and a combination thereof. For certain of these embodiments, the co-solvent is diethylene glycol monoethyl ether. For certain embodiments, including any one of the above compositions and methods, the carrier comprises diethylene glycol monoethyl ether and ethanol. It has now been found that the diethylene glycol monoethyl ether acts as a dispersant alone or in addition to the ethanol acting as a dispersant.

For certain embodiments, including any one of the above compositions and methods, except where a lower alcohol is included in the carrier, the carrier comprises diethylene glycol monoethyl ether without a lower alcohol.

The above dental compositions can be applied to a dental surface by known methods. For example, the compositions can be applied by brushing, syringing, wiping, dip coating, applying from a substrate, or a combination thereof. When applied, the composition is dispersed over the dental surface, and a retentive polymeric coating forms on the dental surface. A portion of the non-aqueous carrier, such as ethanol, may be extracted by the aqueous oral environment.

Foaming the above dental compositions and then applying the resulting dental foam can reduce the amount of dental composition that needs to be dispensed in order to form a retentive polymeric coating on a dental surface. When the dental foam contacts the dental surface, such as a tooth, the bubbles in the foam break on the surface. The composition is dispersed over the dental surface, forming a retentive polymeric coating on the dental surface. Thus, in some embodiments, preferably the present compositions and methods can provide retentive polymeric coatings on the dental surface in a very short time, thereby saving time for the practioner and reducing discomfort as well as saving time for the patient. For certain embodiments, including any one of the above methods, applying the dental composition or dental foam to a dental surface is selected from the group consisting of painting, brushing, syringing, wiping, dip coating, applying from a substrate, or a combination thereof. For certain of these embodiments, applying (the dental composition or dental foam to a dental surface) comprises dip coating the dental surface (in the dental composition or dental foam) for not more than 10 seconds. For certain of these embodiments, applying comprises dip coating the dental surface for at least one second. For certain of these embodiments, applying comprises applying from a substrate. For certain of these embodiments, the substrate is a dental tray.

Dental trays are well known and have been used commercially for some time. Some examples of dental trays include those described in U.S. Patent Nos. 3,339,547;

3,416,527; 5,211,559; and 5,980,249. Foamable dental compositions described herein can be dispensed into the dental tray as a foam. The dental tray can then be placed over the dental surfaces to be treated, such as a subject's teeth, thereby, essentially dipping the dental surfaces in the foam contained in the dental tray. For certain embodiments, the dental tray preferably comprises a trough comprising a first wall, a second wall, and a floor, wherein at least one of the first wall, second wall, and floor comprises a contact surface, wherein at least a portion of the contact surface comprises a reticulated foam material. Such dental trays are described in U.S. Application Serial No. 61/024740, filed January 30, 2008. Here the dental tray is fitted over a subject's teeth and the contact surface typically contacts the surface of the subject's teeth. Because the contact surface of the dental tray includes reticulated foam material, in the event that there is an excess of dental foam in the dental tray, a substantial portion of excess dental foam is retained in the reticulated foam material rather than being expelled from the tray and left in the subject's mouth, where it might be swallowed and/or must be expectorated. With this dental tray, control over the degree of foaming of the dental foam is less critical, and the choice of propellant used to bring about the dental foam, therefore, may be less critical than with other known dental trays. For example, when the dental foam contacts the reticulated foam material of the dental tray, the bubbles forming the dental foam can burst, thereby wetting the reticulated foam material with the composition for contact with the surface of the subject's teeth. For certain of these embodiments, the propellant comprises a gas selected from the group consisting of air, oxygen, an inert gas, a fluorocarbon, a hydrocarbon, dimethyl ether, and a combination thereof. An inert gas includes nitrogen, carbon dioxide, helium, argon, nitrous oxide, and a combination thereof. A hydrocarbon includes propane, n-butane, isobutene, and a combination thereof.

For certain embodiments, including any one of the above compositions, the composition further comprises a propellant other than a hydrocarbon, and for certain embodiments, including any one of the above methods which includes a propellant, the propellant is other than a hydrocarbon. Hydrocarbon propellants, such as propane and butane, have now been found, in certain instances, to reduce adhesion of the retentive coating to the dental surface.

For certain embodiments, including any one of the above embodiments which includes a propellant, the propellant is dimethyl ether in combination with at least one inert gas. For certain of these embodiments, the inert gas is carbon dioxide, nitrogen, or a combination thereof. The dimethyl ether produces a stable foam that maintains its volume for a time sufficient to apply the dental foam to a dental surface. Moreover, dimethyl ether dissolves in the foamable dental compositions and further acts as a dispersant. The inert gas provides pressure, for example, about 70 psi (about 0.48 MPa), for dispensing the dental composition through an actuator. The inert gas has low solubility in the dental composition, but contributes to foam formation.

For certain embodiments, including any one of the above embodiments, the foamable dental composition further comprises a foam stabilizing agent. For certain of these embodiments, the foam stabilizing agent is selected from the group consisting of a surfactant, a foam stabilizer, a foam-wall thickener, surface-modified nanoparticles, and a combination thereof. Foam stabilizing agents are further described herein below. For certain of these embodiments, the foam stabilizing agent is a surfactant. For certain of these embodiments, not more than two surfactants are included in the foamable dental composition.

For certain embodiments, including any one of the above compositions and methods, the foamable dental composition further comprises a dental agent. For certain of these embodiments, the dental agent is selected from the group consisting of a fluoride source, a whitening agent, an anticaries agent, an anti-plaque agent, a remineralizing agent, an enzyme, a breath freshener, an anesthetic, a clotting agent, an acid neutralizer, a chemotherapeutic agent, an immune response modifier, a medicament, an indicator, an antimicrobial agent, an antifungal agent, an agent for treating xerostomia, a desensitizer, and a combination thereof. For certain of these embodiments, the dental agent includes an anticaries agent. For certain of these embodiments, the anticaries agent includes xylitol. For certain of these embodiments, the dental agent includes a fluoride source. For certain of these embodiments, alternatively to or in addition to the fluoride source, the dental agent includes a remineralizing agent. For certain of these embodiments, the remineralizing agent is selected from the group consisting of a phosphate compound, a calcium compound, a calcium phosphate compound, hydroxyapatite, a caseinate, a filler having a surface-treatment of a phosphorus compound, a phosphorous releasing glass, a calcium releasing glass, and combinations thereof. For certain of these embodiments, the remineralizing agent is a phosphate compound. For certain of these embodiments, the phosphate compound is selected from the group consisting of a monobasic phosphate compound, a dibasic phosphate compound, a tribasic phosphate compound, calcium glycerophosphate, and combinations thereof. For certain of these embodiments, the remineralizing agent is a calcium phosphate (dibasic) compound. Suitable dental agents are further described herein below.

The film- forming component of the dental compositions described herein forms a retentive polymeric coating on a dental surface, such as a tooth structure. For certain embodiments, the film-forming component comprises a substantive polymer. The substantivity of the polymer contributes to the retentive nature of the coating. Preferably, the substantive polymer is not significantly water soluble, although it may be water dispersible. When the dental composition comes in contact with water or saliva, the substantive polymer comes out of solution. For certain embodiments, including any one of the above compositions and methods, the substantive polymer comprises a repeating unit that includes a polar or polarizable group as described herein below. For certain of these embodiments, the substantive polymer also comprises a repeating unit that includes a fluoride releasing group, a repeating unit that includes a hydrophobic hydrocarbon group, a repeating unit that includes a graft polysiloxane chain, a repeating unit that includes a hydrophobic fluorine-containing group, a repeating unit that includes a modulating group, or a combination thereof, as described herein below.

In some embodiments, the polymer optionally includes a reactive group. Suitable reactive groups (e.g., ethylenically unsaturated groups, epoxy groups, silane moieties capable of undergoing a condensation reaction, ionically crosslinkable groups) are disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al), 5,662,887 (Rozzi et al), 5,866,630 (Mitra et al.), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.). Polymers, including those with reactive groups, can be adjusted or tailored for desired solubility in the non-aqueous carrier by selection of appropriate monomers and ratios of monomer used in making the polymers.

For certain embodiments, including any one of the above compositions and methods, the substantive polymer comprises a repeating unit including a polar or polarizable group and a repeating unit including a group selected from the group consisting of a hydrophobic hydrocarbon group, a graft polysiloxane chain, a hydrophobic fluorine-containing group, and a combination thereof. Preferably the hydrophobic hydrocarbon group or segment is derived from a hydrophobic monomer having a weight average molecular weight of at least 100. Preferably the graft polysiloxane chain has a molecular weight of at least 500. Preferably, the repeating unit including the polar or polarizable group is different than the repeating unit including the group selected from the group consisting of a hydrophobic hydrocarbon group, a graft polysiloxane chain, a hydrophobic fluorine-containing group, and a combination thereof. Optionally the polymer includes reactive groups.

For certain embodiments, including any one of the above compositions and methods where the substantive polymer may include a fluoride releasing group, the substantive polymer comprises a repeating unit including a polar or polarizable group; and a repeating unit including a fluoride releasing group (e.g., tetrafluoroborate anions). Preferably, the repeating unit including the polar or polarizable group is different than the repeating unit including the fluoride releasing group.

For certain embodiments, including any one of the above compositions and methods, except where excluded, the substantive polymer comprises: at least two repeating units comprising polar or polarizable groups; and a repeating unit comprising a group selected from the group consisting of a hydrophobic hydrocarbon group, a graft polysiloxane chain, a hydrophobic fluorine-containing group, and combinations thereof. For certain of these embodiments, the polar or polarizable groups include quaternary amine groups. For certain of these embodiments, as an alternative to or in addition to the quaternary amine groups the polar or polarizable groups include carboxylic acid groups. For certain of these embodiments, the substantive polymer comprises a repeating unit comprising a hydrophobic hydrocarbon group.

For certain embodiments, including any one of the above compositions and methods, except where a different substantive polymer is used, the film- forming component comprises a substantive polymer comprising a hydrophobic segment, a hydrophilic segment, and a quaternary amine segment. Alternatively, the substantive polymer comprises a hydrophobic segment, a hydrophilic segment, and a silicon- containing macromer segment. For certain embodiments, this alternative also comprises a quaternary amine segment. In certain embodiments, including any one of these embodiments, the substantive polymer further includes and an alkoxy silane crosslinkable segment.

In certain embodiments, the alkoxy silane crosslinkable segment is a (trialkoxysilyl)alkyl group. In certain embodiments, the silicon-containing macromer segment includes a polysiloxane chain having a molecular weight of at least 500.

In certain embodiments, the hydrophobic segment is a hydrocarbon group selected from the group consisting of dodecyl, isobutyl, octyl, octadecyl, and a combination thereof. In certain embodiments, the hydrophobic segment is derived from a hydrophobic monomer having a weight average molecular weight of at least 100. In certain embodiments, the hydrophobic monomer has a weight average molecular weight of at most 500,000. For certain of these embodiments, the hydrocarbon group is isobutyl. Alternatively, in certain embodiments, the hydrophobic segment is a fluorine-containing segment.

In certain embodiments, including any one of the above embodiments which includes a substantive polymer with a hydrophobic segment and a hydrophilic segment, the hydrophilic segment is selected from the group consisting of carboxylic acids; lower alkyl (e.g., methyl, ethyl, and propyl) esters; hydroxyalkyl esters; alkoxyalkyl esters; aminoalkyl esters; alkylaminoalkyl esters; dialkylaminoalkyl esters; polyethylene glycol esters; polypropylene glycol esters; trialkylammoniumalkyl esters wherein the counterion can be halide, acetate, propionate, laurate, palmitate, stearate, or a combination thereof; and combinations thereof. For certain of these embodiments, the hydrophilic segments are carboxylic acids and trialkylammoniumalkyl esters with halide counterions. In certain embodiments, the quaternary amine segment is selected from the group consisting of trialkylammoniumalkyl ester tetrafluoroborates, trialkylammoniumalkyl ester fluorophosphates, trialkylammoniumalkyl ester halides, and a combination thereof. For certain of these embodiments, the quaternary amine segments are trialkylammoniumalkyl ester halides. Halides include fluorides, chlorides, and bromides, and in certain embodiments, the halide is a chloride or a bromide.

Substantive polymers are described further herein below.

Along with the substantive polymer, one or more tackifϊers or additional polymers may be included in the present foamable dental compositions. For example, a natural rosin, acidified rosin, esterified rosin, polymerized rosin, and combinations thereof may be used. Such materials may be used to modify release of a dental agent, surface quality of the retentive polymeric coating, feel of the coating, and other characteristics. For certain embodiments, including any one of the above compositions and methods, the composition further comprises a polymerizable component. Suitable polymerizable components include compounds with reactive groups such as ethylenically unsaturated groups, epoxy groups, silane groups which can undergo a condensation reaction, and the like.

For certain embodiments, including any one of the above compositions and methods, the foamable dental composition further comprising an additive selected from the group consisting of an acidifying agent, a buffering agent, an emulsifier, an emulsion oil, an emulsion stabilizer, a viscosity modifier, a thixotrope, a filler, a polyol, a flavoring agent, and a combination thereof. Some examples include, fumed silica, glycerol, and propylene glycol. These and other optional additives are further described herein below.

For certain embodiments, including any one of the above compositions and methods, the retentive polymeric coating is durable for at least 12 hours or at least 24 hours as measured by the Toothbrush Abrasion Test. For certain embodiments, the wear rate is approximately linear over time, with about 1 mil (25.4 micrometers) of wear occurring after each about 80 brush strokes. Marketed foam fluoride treatment products have no retentive coating and are removed even when rinsed with water. Marketed fluoride treatment varnishes are removed in less than several strokes of a toothbrush.

The foamable dental compositions and methods described herein which include a source of fluoride ions in the composition may also provide a sustained release of fluoride ions over many hours. Moreover, in some embodiment, the present foamable dental compositions and methods were found to provide retentive polymeric coatings which released more fluoride ion than certain commercially available fluoride treatments even though the present dental compositions contained less fluoride than the commercial treatments.

For certain embodiment, including any one of the above embodiments which includes a source of fluoride ions in the foamable dental composition, the retentive polymeric coating releases fluoride ions for a period of at least 12 hours. Preferably, the retentive polymeric coating releases fluoride ions for a period of at least 24 hours. For certain embodiments, including any one of the above methods, the method further comprises rinsing the dental surface immediately after applying the dental foam. For certain embodiments, including any one of the above compositions and methods, the dental surface is a tooth surface.

For certain embodiments, including any one of the above compositions and methods, the dental surface comprises a cured dental restorative material. For certain embodiments, including any one of the above compositions and methods, the dental surface comprises a ceramic tooth.

Foamable dental compositions of the present invention may be prepared as a single-part liquid by combining the appropriate components. For example, the polymer (typically a substantive polymer) may be mixed at the desired temperature (e.g., room temperature) with the non-aqueous carrier using simple mixing, for example, with a mixer at about 100-500 revolutions per minute (rpm). A dental agent can be added to the resulting polymer solution with simple mixing. Alternatively, a dental agent, such as calcium phosphate and/or a fluoride source can be combined with the carrier using high shear mixing to provide smooth, homogeneous formulations with uniform release of a dental agent, such as fluoride ion. The resulting mixture can then be combined with the polymer solution with simple mixing. When combining the polymer with other components of the composition, low shear mixing is desirable to avoid degradation of the polymer. Some components may be mixed with the carrier at an elevated temperature to facilitate dissolving or suspending the component. Alternatively, compositions of the present invention may be prepared as multiple- part systems comprising liquids, foams, pastes, gels, or combinations thereof, that are mixed prior to delivery to the dental surface. Such multiple-part systems may provide increased shelf stability over single-part compositions. In one example, a composition which includes a multi-valent metal ion-releasing powder, and in another example, a composition which includes an additive that is incompatible with other materials in the composition may be prepared as multiple-part systems.

If the composition includes a polymer with a crosslinkable segment, the composition may be provided to the user with a catalyst (e.g., stannous octoate). After application of the dental composition to the dental surface, the catalyst may be applied to crosslink the polymer on the dental surface. DENTAL AGENTS

In some embodiments, compositions of the present invention may include dental agents. Exemplary dental agents include, for example, fluoride sources, whitening agents, anticaries agents (e.g., xylitol), an anti-plaque agents, remineralizing agents, enzymes, breath fresheners, anesthetics, clotting agents, acid neutralizers, chemotherapeutic agents, immune response modifiers, medicaments, indicators (e.g., dyes, pigments), antimicrobial agents, antifungal agents, agents for treating xerostomia, desensitizers, and combinations thereof. Preferably the dental agents are suitable for use in the oral environment.

In some embodiments, the substantive polymer can act as a dental agent. For example, when the polymer includes an antimicrobial quaternary amine segment, a remineralizing phosphorous containing segment, a remineralizing calcium containing segment, a fluoride releasing segment, or combinations thereof, the polymer itself provides a dental agent.

Useful fluoride sources used in the present invention may be any material that has the effect of releasing fluoride ion into the oral cavity or onto a dental surface. Typically, useful fluoride sources have the effect of desensitizing teeth by occluding dentinal tubules and remineralizing enamel. Useful fluoride sources include, for example, sodium fluoride, stannous fluoride, sodium monofluorophosphate, fluoroalkyl phosphate salts such as monoammonium 1,1,7-trihydroperfluoroheptyl phosphate, quaternary ammonium fluorides such as dodecyltrimethylammonium fluoride, quaternary ammonium tetrafluoroborates such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, and tetrabutylammonium tetrafluoroborates, and combinations thereof. Other fluoride sources are disclosed, for example, in U.S. Pat. Nos. 4,871,786 (Assen et al.) and 5,071,637 (Pellicano). In certain embodiments, the substantive polymers disclosed herein also include a repeating unit that includes a fluoride releasing group. A preferred fluoride releasing group includes tetrafluoroborate anions as disclosed, for example, in U.S. Pat. No. 4,871,786. Preferred repeating units for the fluoride releasing groups include, for example, those resulting from the polymerization of trimethylammoniumethyl methacrylate.

Further, suitable precursors for fluoride ion include, for example, ammonium fluoride, sodium fluoride, stannous fluoride, tetrabutylammonium fluoride, tetrabutylammonium hexafluorophosphate, sodium fluorophosphates, ammonium hydrogen difluoride, hexafluorosilicic acid and salts thereof, monofluorophosphoric acid and salts thereof, hexafluorophosphoric acid and salts thereof, and combinations thereof.

Useful remineralizing agents used in the present invention may be any material that is capable of remineralizing enamel. Useful remineralizing agents include, for example, phosphate compounds, calcium compounds, calcium phosphate compounds, hydroxyapatite, casemates, fillers having a surface-treatment of a phosphorus compound, phosphorous releasing glasses, calcium releasing glasses, and combinations thereof. In certain embodiments, the dental agent is a phosphate compound. In certain embodiments, the phosphate compound is a monobasic phosphate compound, a dibasic phosphate compound, a tribasic phosphate compound, calcium glycerophosphate, or combinations thereof. In certain embodiments, the dental agent is a calcium phosphate (dibasic) compound. In certain embodiments, the dental agent is a caseinate. In certain embodiments, the caseinate is a salt of calcium, phosphate, fluoride, or combinations thereof. Various remineralizing agents are described in U.S. Pat. No. 6,497,858 (Takatsuka et al.) and in U.S. Pat. App. Serial Nos. 10/989,780; 11/719,466; and 61/013,464.

Useful whitening agents used in the present invention may be any material that has the effect of whitening teeth. Useful whitening agents include, for example, hypochlorites (e.g., sodium hypochlorite), peroxides, hydroperoxides, hydrogen peroxide, peracids (also known as peroxyacids), carbamide peroxide (i.e., the urea complex of hydrogen peroxide, CO(NH₂)₂ ^»H₂O₂, also known as urea hydrogen peroxide, hydrogen peroxide carbamide, or perhydrol-urea), and combinations thereof.

Useful breath fresheners include, for example, zinc chloride. Useful antimicrobial agents include agents for controlling bacteria growth associated with caries, periodontitis, and halitosis. Such agents include, for example, chlorohexidine and salts thereof such as chlorhexidine digluconate, parachlorometaxylenol, triclosan, polyhexamethylenebiguanidine and salts thereof such as polyhexamethylenebiguanidine hydrochloride, iodine, iodophores, poly-N- vinylpyrrolidone-iodophores, silver oxide, silver and salts thereof, peroxides such as hydrogen peroxide, glycerol esters of fatty acids optionally in combination with acidic components, propylene glycol esters of fatty acids optionally in combination with acidic components, quaternary ammonium compounds, and antibiotics (e.g., neomycin, bacitracin, and polymixinB).

The concentration of a dental agent in the foamable dental composition can vary depending upon its activity. For example, a fluoride source may be used at a low concentration, while a calcium source or xylitol may be used at a relatively high concentration. Compositions of the present invention may be adjusted as desired to include the amount of dental agent as desired for the specific application. For certain embodiments, including any one of the above embodiments which includes a dental agent, preferably, the dental composition includes at least 0.1% by weight of the dental agent. In certain embodiments, at least 0.5% by weight, or at least 1% by weight of the dental agent is included, based on the total weight of the composition. Preferably, the foamable dental composition includes at most 40% by weight of the dental agent. In certain embodiments, at most 25% by weight or at most 10% by weight of the dental agent is included, based on the total weight of the composition.

SUBSTANTIVE POLYMERS

Exemplary methods of preparing the substantive polymers are known in the art and include, for example, free radical polymerization conditions as disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al), 5,662,887 (Rozzi et al), 5,866,630 (Mitra et al), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.).

For certain embodiments, including any one of the above embodiments, the foamable dental compositions preferably include at least 10 % by weight polymer, more preferably at least 15 % by weight polymer, at least 20 % by weight polymer, or at least 25 % by weight polymer, based on the total weight of the composition. The foamable dental compositions preferably include at most 60 % by weight polymer, more preferably at most

50 % by weight polymer, at most 40 % by weight polymer, or at most 35 % by weight polymer, based on the total weight of the composition. Polar or Polarizable Groups:

Repeating units including a polar or polarizable group are typically hydrophilic groups and are derived from vinylic monomers such as acrylates, methacrylates, crotonates, itaconates, and the like. The polar groups can be acidic, basic, or a salt. These groups can also be ionic or neutral. Examples of polar or polarizable (e.g., hydrophilic ) 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), ionic groups (such as quarternary ammonium, carboxylate salts, sulfonic acid salts and the like), and the precursors and protected forms of these groups. Additionally, a polar or polarizable group could be a macromonomer. More specific examples of such groups follow.

Polar or polarizable groups may be derived from mono- or multi-functional carboxyl group containing molecules represented by the general formula:

CH₂=CR²G-(COOH)_d where R² is H, methyl, ethyl, cyano, carboxy or carboxymethyl, d is an integer from 1 to 5 and G is a bond or a hydrocarbyl radical linking group containing from 1 to 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 iV-acryloylglycine.

Polar or polarizable groups may, for example, be derived from mono- or multifunctional hydroxy group containing molecules represented by the general formula: CH₂=CR²-CO-L-R³-(OH)_d where R² is H, methyl, ethyl, cyano, carboxy or carboxyalkyl, L is O or NH, d is an integer from 1 to 5, and R is a hydrocarbyl radical of valence d + 1 containing from 1 to 12 carbon atoms. Suitable monomers in this class are hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, tris(hydroxymethyl)ethane monoacrylate, pentaerythritol mono(meth)acrylate, N- hydroxymethyl(meth)acrylamide, JV-hydroxyethyl(meth)acrylamide, and N- hydroxypropyl(meth)acrylamide .

Polar or polarizable groups may alternatively be derived from mono- or multifunctional amino group containing molecules of the general formula: CH₂=CR²-CO-L-R³-(NR⁴R⁵)_d where R², L, R³, and d are as defined above, and R⁴ and R⁵ are H or alkyl groups of 1 to 12 carbon atoms or together they constitute a carbocyclic or heterocyclic group. Suitable monomers of this class are aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N- (dimethyl)aminoethyl (meth)acrylate, Λf,Λ/-(diethyl)aminoethyl (meth)acrylate, N-[N, N- (dimethy l)aminopropy 1] (meth)acrylamide , N-[N-

(isopropyl)aminopropyl](meth)acrylamide, and 4-methyl- 1 -acryloyl-piperazine. Polar or polarizable groups 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)acrylate or polypropylene glycol mono(meth)acrylate.

Polar or polarizable groups units may be derived from substituted or unsubstituted ammonium monomers of the general formula:

^P

CH₂=CR²-CO-L-R³-(NR⁴R⁵R⁶)_dQ^~

where R², R³, R⁴, R⁵, L and d are as defined above, and where R⁶ is H or alkyl of 1 to 18 carbon atoms, and Q^" is an organic or inorganic anion. Suitable examples of such monomers include 2-(Λ/,Λ/,ΛMrimethylammonium)ethyl (meth)acrylate, 2-(N,N,N- triethylammonium)ethyl (meth)acrylate, 3 -(Λ/,Λf,Λ/-trimethylammonium)propyl (meth)acrylate, 2-(N,Λ/-dimethyl-Λ/-hexadecylamino)ethyl methacrylate, N-[2-(Λ/^I,Λ/^I,Λ/^I-trimethylarnmonium)ethyl](meth)acrylamide, N-[N, N -dimethyl-N- (hydroxyethyl)ammoniumpropyl](meth)acrylamide, or combinations thereof, where the counterion may include fluoride, chloride, bromide, acetate, propionate, laurate, palmitate, stearate, or combinations thereof. The monomer can also be Λ/,jV-dimethyl-JV,iV- diallylammonium salt of an organic or inorganic anion. Anions suitable for the forgoing ammonium monomers include, for example, tetrafluoroborate, monosodium fluorophosphate, chloride, bromide, and the like.

Ammonium group containing polymers can also be prepared by using as the polar or polarizable group any of 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. Polar or polarizable groups can also be derived from sulfonic acid group containing monomers, such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2- methylpropane sulfonic acid, allyloxybenzene sulfonic acid, and the like. Alternatively, polar or polarizable groups 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.

Exemplary polar or polarizable groups are disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al), 5,662,887 (Rozzi et al), 5,866,630 (Mitra et al), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.).

Preferred repeating units of a polar or polarizable group include acrylic acid, 2- (Λ/,Λ/-dimethyl-Λ/-hexadecylamino)ethyl methacrylate, itaconic acid, N- isopropylacrylamide, or combinations thereof. Fluoride Releasing Groups: Suitable fluoride releasing groups include fluoride salts as disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al.), 5,662,887 (Rozzi et al.), 5,866,630 (Mitra et al.), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.). A preferred fluoride releasing group includes tetrafluoroborate anions as disclosed, for example, in U.S. Pat. No. 4,871,786 (Aasen et al.). A preferred repeating unit of a fluoride releasing group includes trimethylammoniumethyl methacrylate. Hydrophobic Hydrocarbon Groups:

An exemplary hydrophobic hydrocarbon group is derived from an ethylenically unsaturated preformed hydrocarbon moiety (i.e., a hydrophobic monomer) having a weight average molecular weight greater than 100. Preferably the hydrocarbon moiety has a molecular weight of at least 160. Preferably the hydrocarbon moiety has a molecular weight of at most 500,000, more preferably at most 100,000, and even more preferably at most 50,000. The hydrocarbon moiety may be aromatic or non-aromatic in nature, and optionally may contain partially or fully saturated rings. Preferred hydrophobic hydrocarbon moieties are dodecyl, isobutyl, octyl and octadecyl acrylates and methacrylates. Other preferred hydrophobic hydrocarbon moieties include macromonomers of the desired molecular weights prepared from polymerizable hydrocarbons, such as ethylene, styrene, alpha-methyl styrene, vinyltoluene, and methyl methacrylate.

Exemplary hydrophobic hydrocarbon groups are disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al), 5,662,887 (Rozzi et al), 5,866,630 (Mitra et al), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.).

Hydrophobic Fluorine-Containing Groups:

Exemplary repeating units of hydrophobic fluorine-containing groups include acrylic or methacrylic acid esters of 1,1-dihydroperfluoroalkanols and homo logs: CF₃(CF₂)_XCH₂OH and CF₃(CF₂)_x(CH₂)_yOH, where x is 0 to 20 and y is at least 1 up to 10; ω-hydrofluoroalkanols (HCF₂(CF₂)_x(CH₂)_yOH), where x is 0 to 20 and y is at least 1 up to 10; fluoroalkylsulfonamido alcohols; cyclic fluoroalkyl alcohols; and CF₃(CF₂CF₂θ)_q(CF₂O)_x(CH₂)_yOH, where q is 2 to 20 and greater than x, x is 0 to 20, and y is at least 1 up to 10.

Preferred repeating units of a hydrophobic fluorine-containing group include 2-[N- methyl-Λ/-(nonafluorobutylsulfonyl)amino]ethyl acrylate, 2-[JV-methyl-JV-

(nonafluorobutylsulfonyl)amino]ethyl methacrylate, or a combination thereof.

Exemplary hydrophobic fluorine containing groups are disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al.), 5,662,887 (Rozzi et al.), 5,866,630 (Mitra et al.), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.). Graft Polysiloxane Chains:

The graft polysiloxane chain is derived from an ethylenically unsaturated preformed organosiloxane chain. The molecular weight of this unit is generally at least 500. Preferred repeating units of a graft polysiloxane chain include a silicone macromer.

Monomers used to provide the graft polysiloxane chain are terminally functional polymers having a single functional group (vinyl, ethylenically unsaturated, acryloyl, or methacryloyl group) and are sometimes termed macromonomers or "macromers." Such monomers are known and may be prepared by methods as disclosed, for example, in U.S. Pat. Nos. 3,786,116 (Milkovich et al.) and 3,842,059 (Milkovich et al.). The preparation of polydimethylsiloxane macromonomer and subsequent copolymerization with vinyl monomer have been described in several papers by Y. Yamashita et al., [Polymer J. 14,

913 (1982); ACS Polymer Preprints 25 (1), 245 (1984); Makromol. Chem. 185, 9 (1984)]. Exemplary polysiloxane chains are disclosed, for example, in U.S. Pat. Nos. 5,468,477 (Kumar et al), 5,607,663 (Rozzi et al), 5,662,887 (Rozzi et al), 5,725,882 (Kumar et al.), 5,866,630 (Mitra et al.), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al). Modulating Groups:

Exemplary modulating groups are derived from acrylate or methacrylate or other vinyl polymerizable starting monomers and optionally contain functionalities that modulate properties such as glass transition temperature, solubility in the carrier medium, hydrophilic-hydrophobic balance and the like. Examples of modulating groups include the lower to intermediate methacrylic acid esters of 1 to 12 carbon straight, branched or cyclic alcohols. Other examples of modulating groups include styrene, vinyl esters, vinyl chloride, vinylidene chloride, acryloyl monomers and the like.

Additional exemplary modulating groups are disclosed, for example, in U.S. Pat. Nos. 5,607,663 (Rozzi et al.), 5,662,887 (Rozzi et al.), 5,866,630 (Mitra et al.), 5,876,208 (Mitra et al.), 5,888,491 (Mitra et al.), and 6,312,668 (Mitra et al.). Initiator System:

Dental compositions described herein may optionally include an initiator system or catalyst that enables the composition to be hardened (e.g., polymerized or crosslinked). For example, visible and/or near-infrared photoinitiator systems may be used to initiate photopolymerization in compositions including free-radically polymerizable components. For example, a monomer can be combined with a three component or ternary photoinitiator system including a sensitizer, an electron donor, and an iodonium salt as disclosed, for example, in U.S. Pat. No. 5,545,676 (Palazzotto et al.). Alternatively, the composition may include a binary initiator system including a sensitizer (e.g., camphor quinone) and an electron donor (e.g., a secondary or a tertiary alkyl amine compound as disclosed, for example, in U.S. Pat. No. 4,071,424 (Dart et al.)).

Another class of useful photoinitiators includes acylphosphine oxides, as disclosed in European Pat. Publ. No. 173,567 (Ying). Such acylphosphine oxides are of the general formula (R)₂ P(=O)C(=O) — R¹, wherein each R individually can be a hydrocarbyl group (e.g., alkyl, cycloalkyl, aryl, and aralkyl), which may be substituted with a halo-, alkyl- or alkoxy-group, or the two R groups may be joined to form a ring along with the phosphorous atom, and wherein R¹ is a hydrocarbyl group, an S-, O-, or N-containing five- or six-membered heterocyclic group, or a -Z-C(=O)-P(=O)- (R)₂ group, wherein Z represents a divalent hydrocarbyl group (e.g., alkylene or phenylene) having from 2 to 6 carbon atoms. Preferred acylphosphine oxides useful in the invention are those in which the R and R¹ groups are phenyl or lower alkyl- or lower alkoxy-substituted phenyl. By "lower alkyl" and "lower alkoxy" is meant such groups having from 1 to 4 carbon atoms. Most preferably, the acylphosphine oxide is bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide available under the trade designation IRGACURE 819 from Ciba Specialty Chemicals (Tarrytown, NY).

The use of redox catalysts including oxidants and reductants for inducing free radical polymerization in multi-component systems is also useful for generating hardened compositions. A preferred mode of initiating the polymerization reaction uses oxidizing and reducing agents as a redox catalyst system. Various redox systems optionally including microencapsulated reducing and/or oxidizing agents are disclosed in U.S. Pat.

No. 5,154,762 (Mitra et al).

Preferably, the oxidizing agent reacts with or otherwise cooperates with the reducing agent to produce free radicals. The free radicals are capable of initiating polymerization of the ethylenically unsaturated moiety. The oxidizing and reducing agents preferably are sufficiently soluble and are present in an amount sufficient to permit an adequate free radical reaction rate as disclosed in U.S. Pat. No. 6,136,885 (Rusin et al.). A preferred class of oxidizing agents includes persulfates (e.g., sodium, potassium, ammonium, and alkyl ammonium persulfates). Another preferred class of oxidizing agents includes peroxides or peroxide salts (e.g., hydrogen peroxide, benzoyl peroxide, and hydroperoxides including, for example cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, and 2,5-dihydroperoxy-2,5-dimethylhexane). Other preferred oxidizing agents include salts of cobalt (III) and iron (III), perboric acid and its salts, and salts of a permanganate anion. Combinations of any of the above mentioned oxidizing agents can also be used. Preferred reducing agents include, for example, amines (e.g., aromatic amines), ascorbic acid, metal complexed ascorbic acid, cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine, oxalic acid, thiourea, and salts of dithionite, thiosulfate, benzene sulfϊnate, or sulfite anions.

If initiators are included in compositions described herein, the compositions preferably include at least 0.01% by weight of the initiator and more preferably at least 0.1% by weight of the initiator, based on the total weight of the composition. If initiators are included in compositions described herein, the compositions preferably include at most 10% by weight of the initiator and more preferably at most 5% by weight of the initiator, based on the total weight of the composition.

FOAMABLE DENTAL COMPOSITIONS AND FOAMS

The foamable dental compositions of the present invention can include, for example, one or more foam stabilizing agents and/or one or more propellants.

Suitable propellants include, for example, a gas. Suitable gases include, for example, air, oxygen, an inert gas, a fluorocarbon, a hydrocarbon, dimethyl ether, and a combination thereof. An inert gas includes nitrogen, carbon dioxide, helium, argon, nitrous oxide, and a combination thereof. A fluorocarbon includes 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,3,3,3-heptafluoropropane, (available as 152A, 134A, and 227EA from E. I. du Pond de Nemours and Co., Wilmington, Delaware), and a combination thereof. A hydrocarbon includes propane, n-butane, isobutene, and a combination thereof. As indicated above, for certain embodiments, a propellant other than a hydrocarbon propellant is preferred. For certain embodiments, the propellant is dimethyl ether in combination with at least one inert gas. For certain embodiments, the inert gas is preferably carbon dioxide, nitrogen, or a combination thereof.

The amount of propellant in the foamable dental compositions of the present invention is preferably at least 5 weight percent (wt-%), more preferably at least 7 wt-%, and most preferably at least 10 wt-%, based on the total weight of the composition. The amount of foaming agent in a composition of the present invention is preferably no greater than 20 wt-%, more preferably no greater than 15 wt-%, based on the total weight of the composition. Suitable foam stabilizing agents include, for example, surfactants, surface- modified nanoparticles, foam stabilizers, foam-wall thickeners, and combinations thereof. Each of these types of stabilizing agents may be categorized in one or more of these exemplary groups. For example, a foam stabilizing agent which is a surfactant may also be a foam stabilizer, a foam- wall thickener, or a combination of these. In general, the number and amounts of foam stabilizing agents may be reduced in the present foamable dental compositions, since dental foams formed from these compositions need not stay up very long, as the time required for application is quite short. The present foamable dental compositions may be prepared with fewer ingredients, thereby reducing manufacturing cost. Moreover, it has now been found that by removing certain foam stabilizing agents, an increase in abrasion resistance can be obtained.

Suitable surfactants include, for example, ionic, nonionic, cationic, amphoteric, or combinations thereof. Examples of suitable surfactants are disclosed, for example, in U.S. Pat. Nos. 6,361,761 (Joziak et al), 5,071,637 (Pellicano), and 5,824,289 (Stoltz). Suitable surfactants include TOMADOL 45-13 (ethoxylated Ci₄_is alcohol, available from Tomah Reserve Inc., Reserve, LA), UNITHOX 420 and UNITHOX 720 (ethoxylated long chain alcohols, molecular weights of about 575 and 875, respectively, available from Baker Petrolite Corp., Tulsa, OK), Dow Corning 193 Fluid, a silicone-ethylene oxide copolymer

(available from Dow Corning, Midland, MI), sucrose stearate (available as CRODESTA F- 160 from Croda, Yorkshire, England), sucrose distearate (available as CRODESTA F- 10), a mixture of sucrose stearate and sucrose distearate (available as CRODESTA F-110), sodium cocoyl isethionate (available as PUREACT 1-78 (formerly TAURANOL 1-78) from Innospec Inc., Spencer, NC), and a combination thereof.

In some embodiments, the substantive polymer can act as the surfactant, for example, when the polymer includes amphoteric segments, such as a quaternary amine segment, or includes the combination of hydrophobic and hydrophilic segments.

The amount of surfactant in a foamable composition of the present invention is preferably at least 0.25 wt-%, more preferably at least 2 wt-% or at least 3 wt-%, based on the total weight of the composition. The amount of surfactant in a foamable composition of the present invention is preferably no greater than 20 wt-%, more preferably no greater than 15 wt-% or no greater than 10 wt-%, based on the total weight of the composition. Suitable surface-modified nanoparticles have an average particle diameter of not more than 100 nanometers. Examples of such surface-modified nanoparticles are disclosed, for example, in U.S. Pat. No. 6,586,483 (KoIb). Suitable foam stabilizers and foam-wall thickeners include, for example, cetyl alcohol, sodium monostearate, cocoamide diethanolamine, lauramide diethanolamine, propylene glycol 14-butyl ether, glycerol, sorbitol, hydrogenated starch hydro lysate, 2- octadecanol (stearyl alcohol), HYSTAR TPF (a hydrogenated starch hydrolysate available from Lonza, Inc., Fair Lawn, NJ), TOMADOL 45-13 (Tomah Reserve Inc.), and

UNITHOX 720 (Baker Petrolite Corp.), or mixtures thereof. The amount of foam stabilizer and foam- wall thickener in a foamable composition of the present invention is preferably at least 0.5 wt-%, at least 2 wt-%, or at least 3 wt-%, based on the total weight of the composition. The amount of foam stabilizer and foam- wall thickener in a foamable composition of the present invention is preferably no greater than 10 wt-% or no greater than 5 wt-%, based on the total weight of the composition.

In some embodiments, the substantive polymer can act as the foam stabilizer, for example when the polymer includes an acidic and/or basic segment that aids in adjusting the pH of the foamable dental composition to an optimum level. Various other components of foamable compositions and methods of making foamable compositions and foams, including further information about propellants, foaming agents, aerosol and non-aerosol containers, nozzles, etc., are described, for example, in U.S. Pat. No. 6,142,338 (Pellicano), 5,071,637 (Pellicano), and 5,824,289 (Stoltz).

OTHER OPTIONAL ADDITIVES

Compositions of the present invention can also include additives (other than the additives described above for preparing foamable compositions). Such additives include, for example, buffering agents, acidifying agents, viscosity modifiers, thixotropes, fillers, flavoring agents, sweetening agents, polysaccharides, and combinations thereof.

For certain embodiments, including any one of the above compositions and methods, the foamable dental composition further comprises a water soluble acidifying agent. Such acidifying agents may promote adhesion between the composition or a coating derived from the composition and a tooth structure (e.g., enamel and dentin). Suitable acidifying agents include hydrochloric acid, hydrofluoric acid, phosphoric acid, and the like. For certain of these embodiments, acids, such as hydrochloric acid, which provide a high number of protons per unit mass, are preferred. The acidifying agents are included at a concentration of at most about 500 mmol per gram and preferably at a concentration of about 100-200 mmol per gram.

The selection and amount of such additives for desired effects is well-known to one of skill in the art.

METHODS

Methods of the present invention provide for the treatment of dental surfaces that include soft and hard tissues, including human and animal tissues. Hard tissues include, for example, bone, teeth, and the component parts of teeth (e.g., enamel, dentin, and cementum). Soft tissues include, for example, mucosa (e.g., tongue, gingiva, and throat).

In some embodiments, dental surfaces include a hardened restorative surface, such as a cured restorative material, or a ceramic surface, such as a ceramic tooth, in the oral cavity.

As indicated above, foamable dental compositions described herein may be delivered to the desired site by known methods. For example, the composition may be delivered directly onto a dental surface from a container or dispenser, such as a foam dispensing can or an aerosol can. Other suitable containers or dispensers include, for example, bottles, vials, syringes, and tubes. Alternatively, the composition can be delivered by using a brush, sponge, applicator, or swab to paint or coat the composition onto the tissue.

Alternatively, the composition can be applied to a substrate, and the substrate having the composition thereon (or therein as in the case of a dental tray) can be applied to the desired surface. Suitable substrates include, for example, polymeric films, paper, woven and non- woven sheets, and foams. For certain embodiments, a preferred substrate is a tray type dispenser, for example, a dental tray. Methods of using dental trays are known and described, for example, in U.S. Pat. Nos. 6,361,761 (Joziak et al), 5,071,637 (Pellicano), and 5,824,289 (Stoltz). For certain embodiment, a preferred dental tray is comprised of a reticulated foam material as described supra. The composition can also be applied to a brush, spatula, medical/dental instrument, or an applicator prior to application to the desired surface.

In certain preferred embodiments, the compositions described herein are applied to a dental surface by methods including, for example, painting, brushing, syringing, wiping, applying the dental composition from a substrate (e.g., a dental tray), dip coating, or combinations thereof. For certain embodiments, the composition is applied by dip coating, preferably dip coating the dental surface in the dental composition for not more than 10 seconds, and more preferably for not more than 5 seconds. For certain embodiments, the composition is applied by dip coating the dental surface in the dental composition for at least one second.

When the dental compositions described herein include two or more parts, the two or more parts are preferably mixed just prior to or during the application process. Suitable mixing devices include, for example, static mixing devices. If the composition includes a polymer with a crosslinkable segment, typically, the composition is provided to the user with a catalyst (e.g., stannous octoate). Such two-part systems may be applied to a dental surface, such as a tooth structure, by using a dispenser that allows a first part to be mixed with a second part as the components exit the dispenser, for example, through a nozzle. Alternatively, after applying the dental composition to the dental surface, the catalyst is applied to crosslink the polymer on the dental surface.

Typically, in certain embodiments, the polymer is "nonpolymerizable" and is hardened and adhered to the tooth simply by coating, dipping, etc. However, for some embodiments of the present invention, dental compositions may be hardened (e.g., polymerized or crosslinked), for example, by inducing a reactive polymer to react. If the dental composition includes an optional polymerizable component different than the reactive polymer, hardening of the composition may also include polymerization of the polymerizable component. For example, when the reactive polymer or the polymerizable component includes an ethylenically unsaturated group, polymerization may be induced by the application of actinic radiation. Preferably the composition is irradiated with radiation having a wavelength of 400 to 1200 nanometers, and more preferably with visible radiation. Visible light sources include, for example, the sun, lasers, metal vapor (e.g., sodium and mercury) lamps, incandescent lamps, halogen lamps, mercury arc lamps, fluorescent room light, flashlights, light emitting diodes, tungsten halogen lamps, and xenon flash lamps. Alternatively, for embodiments of the present invention in which the reactive polymer or the polymerizable component includes an ethylenically unsaturated group, the composition may include two or more parts, with one part including an oxidizing agent, and another part including a reducing agent.

Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. Unless otherwise indicated, all parts and percentages are on a weight basis, all water is deionized water, and all molecular weights are weight average molecular weight.

EXAMPLES In the following preparations, mixes, and Examples, all parts and percents are by weight.

Test Methods

Fluoride Release from Coating Test Bovine incisor teeth, free from obvious defects such as decay or visible cracks, which had a relatively flat buccal surface, and which had been freshly obtained and stored refrigerated in de-ionized water, were used for this test. The root portion of each tooth was removed with a saw, avoiding heating the tooth, and tissue from the pulp chamber was removed. The teeth were allowed to surface dry, and after potting in QUICKMOUNT resin (Fulton Metallurgical Products Corp., Valencia, PA), the potted teeth were each sanded (successively with 120, 320 and 600 grit WETORDRY TRI-M-ITE sandpaper, available from 3M Company, St. Paul, MN) and polished (with a METADI polishing cloth impregnated with METADI fluid and charged with either 3 or 9 micron METADI diamond paste, available from Buehler, Lake Bluff, IL) to expose and flatten a 3 mm diameter surface of enamel. The resulting potted enamel samples were stored refrigerated in de-ionized water for not more than one month until used.

Potted enamel samples were allowed to come to room temperature and dried. Double-sided foam mounting tape (3M Company, St. Paul, MN) cut to approximately 2.5 cm by 2.5 cm with a 3 mm diameter hole in the center was applied to each potted enamel sample, such that the enamel is exposed only through the hole in the foam tape. The exposed enamel of each potted enamel sample was demineralized with 35 mL of demineralization solution (0.1M lactic acid, 0.2% CARBOPOL 907, 50% saturated hydroxyapatite, pH 5.0) at 37 ⁰C for 72 hours. The demineralized potted enamel samples were then rinsed with de-ionized water, blotted with paper tissue, and 50 - 200 mg of the composition to be evaluated was applied to the exposed enamel within the hole in the foam tape. The coated samples were each placed in 35 mL of de-ionized water for 1, 4, 7, and 24 hours at 37 ⁰C without agitation in the dark. Following the incubation, the aqueous extract was analyzed for fluorine ion concentration using a Cole Partner fluoride ion specific electrode (Cole-Parmer Instrument Company, Vernon Hills, IL) according to manufacturer's directions and standard methodology. Final results were reported as micrograms of fluoride per gram of coated test sample. Each reported value was based upon tests on six to ten samples.

Fluoride Uptake by Demineralized Bovine Enamel Test

Following the incubation described above, the coated samples were rinsed with de- ionized water, the foam tape was removed, and the coating was scraped off without impacting the underlying enamel.

A 5 mm diameter disk of WHATMAN No. 41 filter paper (Whatman Inc., Florham Park, NJ) was placed over the exposed enamel area of the sample, and 25 μL of 0.5 M hydrochloric acid was pipetted onto the filter paper, and allow to sit for sixty seconds. Any acid that could be removed with the pipette was then pipetted off and placed in a test tube containing 1.4 mL of TISAB buffer (total ionic strength adjustment buffer, contains sodium chloride, sodium acetate, and sodium citrate, available from TPS Pty. Ltd., Brisbane, Australia). The filter paper disk was transferred from the enamel and placed in the test tube. The remaining acid was blotted with a second filter paper disk, which was added to the tube. Next, 75 μL of TISAB buffer was added in a pool to the area of enamel extracted with the acid. After mixing this pool of liquid several times with the pipette tip used to pipette off the acid above; this pipette tip was used to transfer the pool of TISAB buffer to the test tube, and the enamel was blotted dry with a third filter paper disk, which was also transferred to the test tube. The test tube was covered and the contents were mixed to insure that all the filter paper disks were immersed in the buffer and the sides of the test tube were rinsed with the buffer in the test tube. The fluorine ion concentration of this mixture was measured and reported as above. Toothbrush Abrasion Test

Frosted microscope slides (fully frosted slides from Electron Microscopy Sciences, Hatfield, PA) were primer coated with a 25% solids primer (photopolymerizable methacrylate resin formulation described in U.S. Patent No. 6,030,606) in ethyl acetate, covered with a polyester release liner, and the coating was cured by exposure to a Hanau

Xenon lamp (60Hz./1500 watt) for 2 minutes. The liner was removed, and the coating was soaked in methanol for 5 minutes. The primed slides were removed from the methanol, dried by wiping with a paper towel, measured for thickness with a micrometer, and coated with the composition to be tested by evenly coating to a coating weight of 0.150 to 0.250 g as determined by weighing the slides before and after coating. The coated slides were immediately placed in a 37.5 ⁰C water bath for 1 hour. The unabraded coating thickness was measured using a micrometer, and then the coatings were abraded with a 50/50 mixture of CREST toothpaste and de-ionized water using an ACCLEAN (Henry Schien #102-8013 full head size, Adult 47 Tuft, 0.007" Filament) toothbrush head. The thickness of the coatings on the coated slides were measured after various numbers of strokes with the toothbrush head. The results were reported as a) coating thickness (micrometers) associated with the cumulative number of strokes or b) wear factor. Wear factor is calculated by plotting the number of strokes on the X axis and accumulated thickness loss in microns on the Y axis using the average of six slides, and then calculating the slope of the least squares fit straight line from the origin through the points for the first 400 strokes of the wear test. The wear factor (WF) is reported as microns per 1000 strokes.

Four Evaluation Parameters Smoothness of coating scale:

5 = smooth with no observable stress lines or lumps.

4 = smooth with no stress lines and lumps smaller than 0.1 mm and at least one lump per 5 mm² of tooth surface.

3 = rough with no stress lines but has lumps smaller than 0.1 mm and at least 5 lumps per mm² of tooth surface.

2 = rough with no stress lines but has lumps smaller than 0.5 mm but greater than 0.1 mm, and there is at least 1 lump per 5 mm² of tooth surface. 1 = rough with stress lines or lumps 0.5 mm or larger, and there is at least 2 lumps per 5 mm² of tooth surface.

Hardness of coating scale: (Thumb is rubbed over the surface of the tooth with 1500 to 2000 grams of force.) 5 = coating is hard and feels like an egg shell.

4 = coating is hard and has significant friction during the rubbbing cycle.

3 = coating is not soft and does not feel slimy so the thumb has significant friction during the rubbing cycle.

2 = coating is soft. 1 = coating is soft and feels slimy, so that the thumb easily glides over the coating.

Adhesion to enamel scale: (Thumb is rubbed over the surface of the tooth with 1500 to 2000 grams of force.)

5 = coating does not delaminate from the tooth after 20 rubbing cycles.

4 = coating delaminates from the tooth after 16 to 20 rubbing cycles. 3 = coating delaminates from the tooth after 11-15 rubbing cycles.

2 = coating delaminates from the tooth after 6-10 rubbing cycles.

1 = coating delaminates from the tooth after 1-5 rubbing cycles.

Cohesion scale: (Coating must not delaminate from enamel or indicate adhesive failure.)

5 = coating does not wear after more than 20 rubbing cycles. 4 = coating wears out aft 15-20 rubbing cycles.

3 = coating wears out after 10-15 rubbing cycles.

2 = coating wears out after 6-10 rubbing cycles. 1 = coating wears out after 1-5 rubbing cycles.

Abbreviations/Definitions

Preparation of Starting Materials Starting Material 1 (SM-I):

Synthesis of 2-(N,Λ/-Dimethyl-Λ/-hexadecylammonium)ethyl Methacrylate Bromide (DMAEMA-Ci₆Br)

A 500-ml round-bottom flask was charged with 42.2 parts of DMAEMA, 154.7 parts of acetone, 93.2 parts of 1-bromohexadecane (Sigma-Aldrich), and 0.34 parts of BHT. The mixture was stirred for 16 hours at 35° C and then allowed to cool to room temperature. The resulting white solid precipitate was isolated by filtration, washed with cold ethyl acetate, and dried under vacuum at 40° C. An NMR analysis of the solid product revealed the structure to be pure 2-(N,Λ/-dimethyl-Λ/-hexadecylammonium)ethyl methacrylate bromide. Substantive Polymer:

The substantive polymer IBMA/AA/DMAEMA-Cie Br that contained 60/20/20 parts by weight of the respective monomeric units, was prepared in an ethyl alcohol solution according to the following procedure.

IBMA (60 parts), AA (20 parts), DMAEMA-Ci₆ Br (SM 1) (20 parts), VAZO-67 (0.5 parts) and ethanol (267 parts) were combined in a reaction vessel and the resulting mixture purged with nitrogen for 2 minutes. The vessel was sealed and maintained at 65° C in a constant temperature -rotating device for 18 hours during which time a clear viscous polymer solution was formed. The reaction vessel was removed from the bath and cooled to room temperature. Percent solids analysis (37.4 % solids in ethanol) revealed a quantitative conversion to the polymer designated as IBMA/ AA/D MAEMA-Ci₆ Br.

Foam Stabilizer Premix A, FS(I):

In a glass jar, UNITHOX 420 (10 parts) and then 1-octadecanol (10 parts) were mixed in ethanol (80 parts) with high shear cowl mixing at 70 ⁰C to provide a stable suspension.

Example 1

Foamable Dental Composition

A composition containing the ingredients and amounts thereof shown in Table 1 was prepared.

Table 1

The composition was formulated by mixing DGME (52 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute.

Premix A (8.00 g) and then Dow Corning 193 fluid (3.00 g) were added to the above mixture with propeller mixing to provide Premix B.

IBMA/AA/DMAEMA-Ci₆ Br (37.4 % solids in ethanol) (106.95 g) was placed in a 473 mL (16 ounce) glass jar and mixed a low speed (-500 rpm). Ethanol (2.25 g), IN HCl (0.90 g), and the above Premix B were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (20.00 g), sodium cocoyl isethionate (0.70 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting mixture (Premix C) was mixed for an additional 15 minutes.

The propellants and amounts thereof shown in Table 2 were added to Premix C. Table 2

Premix C (115 g) was weighted into an aerosol can with 240 - 260 mL capacity. A valve was placed on top and sealed to the can with a valve crimper. The sealed aerosol can was charged with 1.50-1.80 grams of carbon dioxide with a propellant charging apparatus. The can was shaken for five minutes. Carbon dioxide was again charged into the can and the can shaken until a total of 2.10 grams carbon dioxide was in the can. After shaking the can for fifteen minutes, the can was charged with dimethyl ether (11.5 g). After shaking the can for fifteen more minutes, an actuator was placed on the can.

A dental foam was dispensed from the can. Example 2

Foamable Dental Composition With Fewer Foam Stabilizing Agents A composition containing the ingredients and amounts thereof shown in Table 3 was prepared.

Table 3

The composition was formulated using the above amounts as in Example 1 , except that no Premix A and no Dow Corning 193 fluid were added. To a portion of this composition (C2), propellant was added as in Example 1, and a dental foam was dispensed from the can.

Example 3

Lower Alcohol Polymer Solution

IBMA/AA/DMAEMA-Cie Br (37.4 % solids in ethanol) (100.27 parts by weight) was combined with DGME (43.75 parts by weight), and the resulting mixture was rotary evaporated to remove 43.85 parts by weight of ethanol to provide a polymer solution containing 37.5 weight percent IBMA/AA/DMAEMA-Ci₆ Br, 18.75 weight percent ethanol, and 43.75 weight percent DGME. Example 4

Foamable Dental Composition With Lower Ethanol Content A composition containing the ingredients and amounts thereof shown in Table 4 was prepared. Table 4

DGME (15.26 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B4.

The polymer solution (168.06 g) from Example 3 containing 37.5 % IBMA/AA/DMAEMA-Cie Br polymer, 18.75 % ethanol, and 43.75 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). Ethanol (7.58 g), 1 N HCl (0.90 g), and Premix B4 were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C4) was mixed for an additional 15 minutes.

To a portion of C4 propellant was added as in Example 1 , and a dental foam was dispensed from the can. Example 5

Foamable Dental Composition With Lower Ethanol Content A composition containing the ingredients and amounts thereof shown in Table 5 was prepared.

Table 5

DGME (5.26 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B5.

The polymer solution (168.06 g) from Example 3 containing 37.5 % IBMA/AA/DMAEMA-Cie Br polymer, 18.75 % ethanol, and 43.75 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). Ethanol (7.58 g), 1 N HCl (0.90 g), and Premix B5 were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (10.00 g), sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C5) was mixed for an additional 15 minutes.

To a portion of C5 propellant was added as in Example 1 , and a dental foam was dispensed from the can. Example 6

Foamable Dental Composition With Lower Ethanol Content A composition containing the ingredients and amounts thereof shown in Table 6 was prepared. Table 6

The polymer solution (168.06 g) from Example 3 containing 37.5 % IBMA/AA/DMAEMA-Cie Br polymer, 18.75 % ethanol, and 43.75 % DGME, jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 473 mL (16 oz.) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute. Ethanol (2.84 g) and 1 N HCl (0.90 g), were sequentially and slowly added into the resulting mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (20.00 g), sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C6) was mixed for an additional 15 minutes.

To a portion of C6 propellant was added as in Example 1 , and a dental foam was dispensed from the can. Example 7

Lower Alcohol Polymer Solution

IBMA/AA/DMAEMA-C16 Br (37.4 % solids in ethanol) (104.65 parts by weight) was combined with DGME (42.60 parts by weight), and the resulting mixture was rotary evaporated to remove 47.25 parts by weight of ethanol to provide a polymer solution containing 39.14 weight percent IBMA/AA/DMAEMA-C16 Br, 18.26 weight percent ethanol, and 42.6 weight percent DGME.

Example 8

Foamable Dental Composition With Lower Ethanol Content A composition containing the ingredients and amounts thereof shown in Table 7 was prepared. Table 7

DGME (24.10 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B8.

The polymer solution (127.75 g) from Example 7 containing 39.14 % IBMA/AA/DMAEMA-C16 Br polymer, 18.26 % ethanol, and 42.60 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). Ethanol (19.05 g), 1 N HCl (0.90 g), and Premix B8 were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (20.00 g), sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C8) was mixed for an additional 15 minutes.

Example 9 Foamable Dental Composition With Lower Ethanol and Higher Polymer Content

A composition containing the ingredients and amounts thereof shown in Table 8 was prepared. Table 8

DGME (19.34 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B9.

The polymer solution (137.97 g) from Example 7 containing 39.14 % IBMA/AA/DMAEMA-Cie Br polymer, 18.26 % ethanol, and 42.60 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). Ethanol (13.59 g), 1 N HCl (0.90 g), and Premix B9 were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (20.00 g), sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C9) was mixed for an additional 15 minutes.

Example 10 Foamable Dental Composition With Lower Ethanol and Higher Polymer Content

A composition containing the ingredients and amounts thereof shown in Table 9 was prepared. Table 9

DGME (12.82 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix BlO.

The polymer solution (153.30 g) from Example 7 containing 39.14 % IBMA/AA/DMAEMA-Cie Br polymer, 18.26 % ethanol, and 42.60 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). Ethanol (4.78 g), 1 N HCl (0.90 g), and Premix BlO were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (20.00 g), sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (ClO) was mixed for an additional 15 minutes.

Example 11 Foamable Dental Composition With Lower Ethanol and Higher Polymer Content

A composition containing the ingredients and amounts thereof shown in Table 10 was prepared. Table 10

DGME (9.95 g), jet milled sodium fluoride (4.00 g), and jet milled calcium phosphate (dibasic) (2.00 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix BI l.

The polymer solution (160.96 g) from Example 7 containing 39.14 % IBMA/AA/DMAEMA-Cie Br polymer, 18.26 % ethanol, and 42.60 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). 1 N HCl (0.90 g) and Premix BI l were sequentially and slowly added into the mixing solution. Mixing was continued for 5-10 minutes. Sucrose stearate (20.00 g), sodium cocoyl isethionate (2.00 g), and xylitol (0.20 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (Cl 1) was mixed for an additional 15 minutes. Example 12

100 Percent DGME Co-Solvent Polymer Solution

IBMA/AA/DMAEMA-Ci₆ Br (37.4 % solids in ethanol) (104.61 parts by weight) was combined with DGME (60.90 parts by weight), and the resulting mixture was rotary evaporated to remove 65.51 parts by weight of ethanol to provide a polymer solution containing 39.1 weight percent IBMA/AA/DMAEMA-Ciβ Br and 60.9 weight percent DGME.

Example 13

Foamable Dental Composition With 100 Percent DGME Co-Solvent A composition containing the ingredients and amounts thereof shown in Table 11 was prepared. Table 11

DGME (32.25 g), jet milled sodium fluoride (3.00 g), and jet milled calcium phosphate (dibasic) (1.50 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B13.

The polymer solution (95.93 g) from Example 12 containing 39.1 % IBMA/AA/DMAEMA-Cie Br polymer and 60.9 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). 1 N HCl (0.68 g) and Premix B13 were sequentially and slowly added into the mixing solution. Mixing was continued for 5- 10 minutes. Sucrose stearate (15.00 g), sodium cocoyl isethionate (1.50 g), and xylitol (0.15 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C 13) was mixed for an additional 15 minutes.

Example 14

Foamable Dental Composition With 100 Percent DGME Co-Solvent A composition containing the ingredients and amounts thereof shown in Table 12 was prepared. Table 12

DGME (22.65 g), jet milled sodium fluoride (3.00 g), and jet milled calcium phosphate (dibasic) (1.50 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B14.

The polymer solution (105.53 g) from Example 12 containing 39.1 % IBMA/AA/DMAEMA-Cie Br polymer and 60.9 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). 1 N HCl (0.68 g) and Premix B14 were sequentially and slowly added into the mixing solution. Mixing was continued for 5- 10 minutes. Sucrose stearate (15.00 g), sodium cocoyl isethionate (1.50 g), and xylitol (0.15 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C 14) was mixed for an additional 15 minutes.

Example 15

Foamable Dental Composition With 100 Percent DGME Co-Solvent A composition containing the ingredients and amounts thereof shown in Table 13 was prepared. Table 13

DGME (13.05 g), jet milled sodium fluoride (3.00 g), and jet milled calcium phosphate (dibasic) (1.50 g) were mixed together in a 118 mL (4 ounce) glass jar. Mixing was carried out first with a propeller mixer for 5 minutes and then a high shear mixer (4000-5000 rpm) for about 1 minute to provide Premix B15.

The polymer solution (115.12 g) from Example 12 containing 39.1 % IBMA/AA/DMAEMA-Ci₆ Br polymer and 60.9 % DGME was placed in a 473 mL (16 oz.) glass jar and mixed at a slow speed (-500 rpm). 1 N HCl (0.68 g) and Premix B15 were sequentially and slowly added into the mixing solution. Mixing was continued for 5- 10 minutes. Sucrose stearate (15.00 g), sodium cocoyl isethionate (1.50 g), and xylitol (0.15 g) were slowly and sequentially added to the mixture with 5-10 minutes of mixing between additions. The resulting composition (C 15) was mixed for an additional 15 minutes. Example 16 Uniform Coating

The dental foam of Example 1 was evaluated for its ability to produce a uniform coating and to flow interproximally . A calf arch was dipped in the dental foam, and a panel of 5 people rated the resulting coating using a set criteria where 5 was excellent and 1 was poor. The buccal, lingual, and interproximal surfaces of the tooth were rated with a range of sores from 4.0 - 4.8 with an average of 4.5. The coating had good uniformity on the buccal and lingual surfaces and flowed interproximally. A coating thickness of 6 mils (152 micrometers) was found as measured with a micrometer.

Example 17

Compositions Applied to Bovine Enamel with Brush

The compositions C2 and C4-C6 of Examples 2 and 4-6 above were applied to bovine enamel (prophied with Preppies pumice and immersed in 37 ⁰C water for 30 minutes) using a 100 bristle brush (100BB) and a larger and softer bristle brush (SBB). The resulting coatings were rated using the Four Evaluation Parameters described above, with 5 being most desirable, for several characteristics, including smoothness (Sm), adhesion (Adh), hardness (Hard), and cohesion (Coh). The results are shown in Table 14 below for IOOBB and in Table 15 below for SBB.

Table 14. Composition applied with IOOBB.

Table 15. Composition applied with SBB.

Example 18

Foamed Compositions Applied to Bovine Enamel with Brush The foamed compositions of Examples 2 and 4-6 above were applied to bovine enamel (prophied with PREPPIES pumice (Whip Mix Corp., Louisville, KY)and immersed in 37 ⁰C water for 30 minutes) using a 100 bristle brush (100BB). The resulting coatings were rated using the Four Evaluation Parameters described above, with 5 being most desirable, for several characteristics, including smoothness (Sm), adhesion (Adh), hardness (Hard), and cohesion (Coh). The results are shown in Table 16 below.

Table 16. Foamed Composition applied with 100BB.

Example 19 Toothbrush Abrasion

A retentive coating made from the dental foam of Example 1 was evaluated for resistance to abrasion as measured by the Toothbrush Abrasion Test described above. The wear rate was found to be approximately linear over time and is shown in Table 17 below. These results showed that the retentive coating could resist wear for a period of at least 24 hours. Table 17. Toothbrush Abrasion of Retentive Coating From Example 1 Dental Foam

Example 20

Toothbrush Abrasion of Coated Compositions

The compositions of Examples 2 (C2) and Examples 8-11 (C8-C11) were coated and tested for resistance to abrasion according to the Toothbrush Abrasion Test described above. The results are shown in Table 18 below.

Table 18. Toothbrush Abrasion, Reported as Wear Factor, of Coated Compositions of Examples 2, and 8-11.

Example 21 Toothbrush Abrasion of Coated Compositions with 100 Percent DGME Co-Solvent

The compositions of Examples 2 (C2) and Examples 13-15 (C 13-Cl 5) were coated and tested for resistance to abrasion according to the Toothbrush Abrasion Test described above. The results are shown in Table 19 below. Table 19. Toothbrush Abrasion, Reported as Wear Factor, of Coated Compositions of Examples 2, and 13-15.

Example 22

Fluoride Release From Coating and Uptake Into Enamel

The dental foam of Example 1 was applied to demineralized bovine enamel, and the amount of fluoride released by the resulting coating as well as the amount of fluoride taken up by the demineralized enamel were measured according the to Fluoride Release and Fluoride Uptake tests described above. The release and uptake over 24 hours are shown in Tables 20 and 21 below, respectively.

Comparative Examples

Marketed fluoride treatments (DURAPHAT Fluoride Varnish, contains 5 % sodium fluoride, available from Colgate-Palmolive Company, Canton, MA; and Prevident, contains 1.1 % sodium fluoride, available from Colgate-Palmolive Company) were applied to demineralized bovine enamel, and the amount of fluoride released by the resulting coating as well as the amount of fluoride taken up by the demineralized enamel were measured according the to Fluoride Release and Fluoride Uptake tests described above. The release and uptake over 24 hours are shown in Tables 20 and 21 below, respectively. Table 20. Fluoride Released Over 24 Hours from Example 1 Dental Foam and DURAPHAT Fluoride Varnish and Prevident Treatments

Table 21. Fluoride Uptake Over 24 Hours by Enamel from Example 1 Dental Foam and DURAPHAT Fluoride Varnish and Prevident Treatments

Even though the dental foam of Example 1 contained less fluoride than DURAPHAT Fluoride Varnish, Example 1 dental foam released more fluoride than DURAPHAT Fluoride Varnish.

Example 23 Fluoride Release From Coatings

The compositions of Examples 2 (C2) and Examples 13-15 (C 13-Cl 5) were applied to demineralized bovine enamel, and the amount of fluoride released by the resulting coatings were measured according the to Fluoride Release test described above. The release results over 24 hours are shown in Table 21. Table 22. Fluoride Released from Examples 2 (C2) and Examples 13-15 (C 13-Cl 5)

The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not intended to be unduly limited by the illustrative embodiments and examples set forth herein and that such examples and embodiments are presented by way of example only with the scope of the invention intended to be limited only by the claims set forth herein as follows.

Claims

WHAT IS CLAIMED IS:

1. A foamable dental composition comprising: a film-forming component; and a non-aqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof; wherein the film- forming component is dissolved in the carrier; and wherein the film-forming component forms a retentive polymeric coating on a dental surface, wherein the retentive polymeric coating remains on the dental surface for at least 8 hours under normal intraoral conditions.

2. The foamable dental composition of claim 1 , wherein the carrier further comprises a lower monohydric alcohol.

3. The foamable dental composition of claim 1 or claim 2, wherein the co-solvent is selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, polyethylene glycol 400, methoxypolyethylene glycol 350, hexamethyldisiloxane, and a combination thereof

4. The foamable dental composition of any one of claims 1, 2, and 3, wherein the carrier comprises diethylene glycol monoethyl ether and ethanol.

5. The foamable dental composition of any one of claims 1 through 4, further comprising a propellant other than a hydrocarbon propellant.

6. The foamable dental composition of claim 5, wherein the propellant is dimethyl ether in combination with at least one inert gas.

7. The foamable dental composition of claim 6, wherein the inert gas is carbon dioxide, nitrogen, or a combination thereof.

8. The foamable dental composition of any one of claims 1 through 7, further comprising a foam stabilizing agent.

9. The foamable dental composition of claim 8, wherein the foam stabilizing agent is a surfactant.

10. The foamable dental composition of any one of claims 1 through 9, further comprising a dental agent.

11. The foamable dental composition of claim 10, wherein the dental agent is selected from the group consisting of a fluoride source, a whitening agent, an anticaries agent, an anti-plaque agent, a remineralizing agent, an enzyme, a breath freshener, an anesthetic, a clotting agent, an acid neutralizer, a chemotherapeutic agent, an immune response modifier, a medicament, an indicator, an antimicrobial agent, an antifungal agent, an agent for treating xerostomia, a desensitizer, and a combination thereof.

12. The foamable dental composition of claim 11 , wherein the dental agent includes an anticaries agent.

13. The foamable dental composition of claim 12, wherein the anticaries agent includes xylitol.

14. The foamable dental composition of any one of claims 11, 12, and 13, wherein the dental agent includes a fluoride source.

15. The foamable dental composition of any one of claims 11 through 14, wherein the dental agent includes a remineralizing agent.

16. The foamable dental composition of claim 15, wherein the remineralizing agent is selected from the group consisting of a phosphate compound, a calcium compound, a calcium phosphate compound, hydroxyapatite, a caseinate, a filler having a surface- treatment of a phosphorus compound, a phosphorous releasing glass, a calcium releasing glass, and combinations thereof.

17. The foamable dental composition of claim 16, wherein the remineralizing agent is a phosphate compound.

18. The foamable dental composition of claim 17, wherein the phosphate compound is selected from the group consisting of a monobasic phosphate compound, a dibasic phosphate compound, a tribasic phosphate compound, calcium glycerophosphate, and combinations thereof.

19. The foamable dental composition of any one of claims 1 through 18, wherein the film-forming component comprises a substantive polymer.

20. The foamable dental composition of claim 19, wherein the substantive polymer comprises: at least two repeating units comprising polar or polarizable groups; and a repeating unit comprising a group selected from the group consisting of a hydrophobic hydrocarbon group, a graft polysiloxane chain, a hydrophobic fluorine- containing group, and combinations thereof.

21. The foamable dental composition of claim 20, wherein the polar or polarizable groups include quaternary amine groups and carboxylic acid groups, and wherein the substantive polymer comprises a repeating unit comprising a hydrophobic hydrocarbon group.

22. The foamable dental composition of any one of claims 1 through 19, wherein the film-forming component comprises a substantive polymer comprising a hydrophobic segment, a hydrophilic segment, and a quaternary amine segment.

23. The foamable dental composition of any one of claims 1 through 22, further comprising a polymerizable component.

24. The foamable dental composition of any one of claims 1 through 23, further comprising an additive selected from the group consisting of an acidifying agent, a buffering agent, an emulsifϊer, an emulsion oil, an emulsion stabilizer, a viscosity modifier, a thixotrope, a filler, a polyol, a flavoring agent, and a combination thereof.

25. The foamable dental composition of any one of claims 1 through 24, wherein the retentive polymeric coating remains on a tooth surface for at least 12 hours according to the Toothbrush Abrasion Test.

26. A method of forming a retentive polymeric coating on a dental surface, the method comprising: providing a foamable dental composition comprising a film-forming component; a non-aqueous carrier comprising a co-solvent selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, 200 to 45,000 molecular weight poly(ethylene glycol), methoxides of 200 to 45,000 molecular weight poly(ethylene glycol), hexamethyldisiloxane, and a combination thereof; wherein the film-forming component is dissolved in the carrier; and applying the dental composition to a dental surface; wherein the film-forming component forms a retentive polymeric coating on the dental surface, and wherein the retentive polymeric coating remains on the dental surface for at least 8 hours under normal intraoral conditions.

27. The method of claim 26, wherein the dental composition further includes a propellant, and wherein the method further includes foaming the dental composition to provide a dental foam and applying the dental foam to a dental surface.

28. The method of claim 26 or claim 27, wherein the carrier further comprises a lower monohydric alcohol.

29. The method of any one of claims 26, 27, and 28, wherein the co-solvent is selected from the group consisting of diethylene glycol monoethyl ether, dipropylene glycol, methoxypolyethylene glycol 350, polyethylene glycol 400, hexamethyldisiloxane, and a combination thereof.

30. The method of claim 28 or claim 29, wherein the carrier comprises diethylene glycol monoethyl ether and ethanol.

31. The method of any one of claims 26 through 30, wherein applying is selected from the group consisting of painting, brushing, syringing, wiping, dip coating, applying from a substrate, or a combination thereof.

32. The method of claim 31 , wherein applying comprises dip coating the dental surface for not more than 10 seconds.

33. The method of claim 31 or claim 32, wherein applying comprises dip coating the dental surface for at least one second.

34. The method of any one of claims 31 , 32, and 33, wherein applying comprises applying from a substrate.

35. The method of claim 34, wherein the substrate is a dental tray.

36. The method of claim 35, wherein the dental tray comprises a trough comprising a first wall, a second wall, and a floor, wherein at least one of the first wall, second wall, and floor comprises a contact surface, wherein at least a portion of the contact surface comprises a reticulated foam material.

37. The method of claim 36 except as dependent on claim 26, wherein the propellant comprises a gas selected from the group consisting of air, oxygen, an inert gas, a fluorocarbon, a hydrocarbon, dimethyl ether, and a combination thereof.

38. The method of any one of claims 27, 28 through 36 except as dependent on claim 26, and 37, wherein the propellant is other than a hydrocarbon.

39. The method of claim 38, wherein the propellant is dimethyl ether in combination with at least one inert gas.

40. The method of claim 39, wherein the inert gas is carbon dioxide, nitrogen, or a combination thereof.

41. The method of any one of claims 26 through 40, wherein the foamable dental composition further comprises a foam stabilizing agent.

42. The method of claim 41, wherein the foam stabilizing agent is a surfactant.

43. The method of any one of claims 26 through 42, wherein the foamable dental composition further comprises a dental agent.

44. The method of claim 43, wherein the dental agent is selected from the group consisting of a fluoride source, a whitening agent, an anticaries agent, an anti-plaque agent, a remineralizing agent, an enzyme, a breath freshener, an anesthetic, a clotting agent, an acid neutralizer, a chemotherapeutic agent, an immune response modifier, a medicament, an indicator, an antimicrobial agent, an antifungal agent, an agent for treating xerostomia, a desensitizer, and a combination thereof.

45. The method of claim 44, wherein the dental agent includes an anticaries agent.

46. The method of claim 45, wherein the anticaries agent includes xylitol.

47. The method of any one of claims 44, 45, and 46, wherein the dental agent includes a fluoride source.

48. The method of any one of claims 44 through 47, wherein the dental agent includes a remineralizing agent.

49. The method of claim 48, wherein the remineralizing agent is selected from the group consisting of a phosphate compound, a calcium compound, a calcium phosphate compound, hydroxyapatite, a caseinate, a filler having a surface-treatment of a phosphorus compound, a phosphorous releasing glass, a calcium releasing glass, and combinations thereof.

50. The method of claim 49, wherein the remineralizing agent is a phosphate compound.

51. The method of claim 50, wherein the phosphate compound is selected from the group consisting of a monobasic phosphate compound, a dibasic phosphate compound, a tribasic phosphate compound, calcium glycerophosphate, and combinations thereof.

52. The method of any one of claims 26 through 51 , wherein the film- forming component comprises a substantive polymer.

53. The method of claim 52 wherein the substantive polymer comprises: at least two repeating units comprising polar or polarizable groups; and a repeating unit comprising a group selected from the group consisting of a hydrophobic hydrocarbon group, a graft polysiloxane chain, a hydrophobic fluorine- containing group, and combinations thereof.

54. The method of claim 53, wherein the polar or polarizable groups include include quaternary amine groups and carboxylic acid groups, and wherein the substantive polymer comprises a repeating unit comprising a hydrophobic hydrocarbon group.

55. The method of any one of claims 26 through 52, wherein the film- forming component comprises a substantive polymer comprising a hydrophobic segment, a hydrophilic segment, and a quaternary amine segment.

56. The method of any one of claims 26 through 55, wherein the composition further comprises a polymerizable component.

57. The method of any one of claims 26 through 56, further comprising an additive selected from the group consisting of an acidifying agent, a buffering agent, an emulsifier, an emulsion oil, an emulsion stabilizer, a viscosity modifier, a thixotrope, a filler, a polyol, a flavoring agent, and a combination thereof.

58. The method of any one of claims 26 through 57, wherein the retentive polymeric coating remains on a tooth surface for at least 12 hours according to the Toothbrush Abrasion Test.

59. The method of any one of claims 26 through 58, further comprising rinsing the dental surface immediately after applying the dental foam.

60. The method of any one of claims 26 through 59, wherein the dental surface comprises gums, a tooth surface, or both.

61. The method of any one of claims 26 through 60, wherein the dental surface comprises a cured dental restorative material.

62. The method of any one of claims 26 through 61 , wherein the dental surface comprises a ceramic tooth.