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WO2009140334A2 - Composition moussante pour revêtements dentaires et procédés associés - Google Patents

Composition moussante pour revêtements dentaires et procédés associés Download PDF

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Publication number
WO2009140334A2
WO2009140334A2 PCT/US2009/043712 US2009043712W WO2009140334A2 WO 2009140334 A2 WO2009140334 A2 WO 2009140334A2 US 2009043712 W US2009043712 W US 2009043712W WO 2009140334 A2 WO2009140334 A2 WO 2009140334A2
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WO
WIPO (PCT)
Prior art keywords
dental
agent
group
foamable
composition
Prior art date
Application number
PCT/US2009/043712
Other languages
English (en)
Other versions
WO2009140334A3 (fr
Inventor
Paul A. Burgio
Fong Vang
Mahfuza B. Ali
Robert A. Asmus
Original Assignee
3M Innovative Properties Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Company filed Critical 3M Innovative Properties Company
Publication of WO2009140334A2 publication Critical patent/WO2009140334A2/fr
Publication of WO2009140334A3 publication Critical patent/WO2009140334A3/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/046—Aerosols; Foams
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/20—Halogens; Compounds thereof
    • A61K8/21—Fluorides; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A61K8/345—Alcohols containing more than one hydroxy group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses

Definitions

  • BACKGROUND Products and methods for providing dental agents e.g., fluoride sources, whitening agents, anticaries agents, and remineralizing agents
  • dental agents e.g., fluoride sources, whitening agents, anticaries agents, and remineralizing agents
  • certain dental varnishes and foams containing such active ingredients have been applied to teeth and are commercially available.
  • 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.
  • 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 0 C. In some embodiments, the co-solvents are non- volatile, having a boiling point of at least about 200 0 C.
  • 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.
  • a volatile solvent such as a lower alcohol, for example, ethanol
  • the co-solvent is odorless, essentially tasteless, and non-irritating.
  • the co-solvent acts as a dispersant.
  • 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.
  • 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), hexamethyldisiloxan
  • a method of forming a retentive polymeric coating on a dental surface 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.
  • 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 monoethy
  • the dental composition provided in the above method includes a propellant.
  • the method further includes foaming the dental composition to provide a dental foam and applying the dental foam to a dental surface. Definitions
  • 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.
  • 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.
  • a cured dental restorative material e.g., 3M FILTEK Supreme universal restorative, 3M ESPE, St. Paul, MN
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • substantially 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.
  • 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).
  • the reactive group in a polymer that includes a reactive group, can react with another reactive group and/or another component to form crosslinks through dimerization, oligomerization, and/or polymerization reactions.
  • the reactive group in a polymer that includes a reactive group such as a carboxy group, can react with another carboxy group in the presence of a multi-valent metal cation to form ionic crosslinks.
  • 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.
  • repeating unit or “monomeric unit” refers to a unit in a polymer that is derived from an ethylenically unsaturated monomer.
  • 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.
  • the mono-hydroxy alcohol is ethanol, n- propanol, isopropanol, or a combination thereof.
  • the mono- hydroxy alcohol is ethanol.
  • “retentive” refers to a coating that can withstand abrasion and other normal intraoral conditions described above.
  • (meth)acryl is an abbreviation intended to refer collectively to “acryl” and/or “methacryl.”
  • 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.
  • the foamable dental composition can form a retentive coating on an entire arch in one to three seconds.
  • 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.
  • 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
  • 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 intra
  • 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 provided dental composition further comprises a propellant.
  • the method further comprises foaming the composition to produce a dental foam; and applying the dental foam to a dental surface.
  • 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.
  • the foamable dental composition contains at least about 20 weight percent of the non-aqueous carrier.
  • 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.
  • the foamable dental composition contains at most about 80 weight percent of the non-aqueous carrier.
  • 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.
  • the non-aqueous carrier is comprised of at least about 10 weight percent of the co-solvent.
  • 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.
  • the non-aqueous carrier is comprised of at most about 100 weight percent of the co-solvent.
  • 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.
  • the carrier further comprises a lower monohydric alcohol.
  • the non-aqueous carrier is comprised of at least about 10 weight percent of the lower alcohol.
  • 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.
  • the non-aqueous carrier is comprised of at most about 80 weight percent of the lower alcohol.
  • 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.
  • the lower alcohol is ethanol.
  • the co-solvent is selected from the group consisting of diethylene glycol monoethyl ether (CH 3 -O-CH 2 CH 2 -O-CH 2 CH 2 -OH), dipropylene glycol (HO-C 3 H 6 -O-C 3 H 6 -OH), polyethylene glycol 400 [H(-O-CH 2 CH 2 ) n -OH, average molecular weight of about 400], methoxypoly ethylene glycol 350 [H(-O-CH 2 CH 2 ) n -OCH 3 , average molecular weight of about 350], hexamethyldisiloxane, and a combination thereof.
  • 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.
  • the co-solvent is diethylene glycol monoethyl ether.
  • 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.
  • the carrier comprises diethylene glycol monoethyl ether without a lower alcohol.
  • compositions can be applied to a dental surface by known methods.
  • the compositions can be applied by brushing, syringing, wiping, dip coating, applying from a substrate, or a combination thereof.
  • 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.
  • 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.
  • 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.
  • 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.
  • applying comprises dip coating the dental surface (in the dental composition or dental foam) for not more than 10 seconds.
  • applying comprises dip coating the dental surface for at least one second.
  • applying comprises applying from a substrate.
  • 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;
  • 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.
  • 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.
  • 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.
  • 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.
  • the composition further comprises a propellant other than a hydrocarbon
  • a propellant other than a hydrocarbon
  • 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.
  • the propellant is dimethyl ether in combination with at least one inert gas.
  • 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.
  • 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.
  • the foamable dental composition further comprises a foam stabilizing agent.
  • 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.
  • the foam stabilizing agent is a surfactant.
  • not more than two surfactants are included in the foamable dental composition.
  • the foamable dental composition further comprises a dental agent.
  • 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.
  • the dental agent includes an anticaries agent.
  • the anticaries agent includes xylitol.
  • the dental agent includes a fluoride source.
  • the dental agent alternatively to or in addition to the fluoride source, the dental agent includes a remineralizing agent.
  • 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.
  • the remineralizing agent is a phosphate compound.
  • 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.
  • 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.
  • the film-forming component comprises a substantive polymer.
  • the substantivity of the polymer contributes to the retentive nature of the coating.
  • the substantive polymer is not significantly water soluble, although it may be water dispersible.
  • the dental composition comes in contact with water or saliva, the substantive polymer comes out of solution.
  • the substantive polymer comprises a repeating unit that includes a polar or polarizable group as described herein below.
  • 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.
  • 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
  • Suitable reactive 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.
  • 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.
  • a hydrophobic hydrocarbon group or segment is derived from a hydrophobic monomer having a weight average molecular weight of at least 100.
  • the graft polysiloxane chain has a molecular weight of at least 500.
  • 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.
  • the polymer includes reactive groups.
  • 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).
  • the repeating unit including the polar or polarizable group is different than the repeating unit including the fluoride releasing group.
  • 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.
  • the polar or polarizable groups include quaternary amine groups.
  • the polar or polarizable groups include carboxylic acid groups.
  • the substantive polymer comprises a repeating unit comprising a hydrophobic hydrocarbon group.
  • the film- forming component comprises a substantive polymer comprising a hydrophobic segment, a hydrophilic segment, and a quaternary amine segment.
  • the substantive polymer comprises a hydrophobic segment, a hydrophilic segment, and a silicon- containing macromer segment.
  • this alternative also comprises a quaternary amine segment.
  • the substantive polymer further includes and an alkoxy silane crosslinkable segment.
  • the alkoxy silane crosslinkable segment is a (trialkoxysilyl)alkyl group.
  • the silicon-containing macromer segment includes a polysiloxane chain having a molecular weight of at least 500.
  • the hydrophobic segment is a hydrocarbon group selected from the group consisting of dodecyl, isobutyl, octyl, octadecyl, and a combination thereof.
  • 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.
  • the hydrocarbon group is isobutyl.
  • the hydrophobic segment is a fluorine-containing 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.
  • the hydrophilic segments are carboxylic acids and trialkylammoniumalkyl esters with halide counterions.
  • the quaternary amine segment is selected from the group consisting of trialkylammoniumalkyl ester tetrafluoroborates, trialkylammoniumalkyl ester fluorophosphates, trialkylammoniumalkyl ester halides, and a combination thereof.
  • 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.
  • one or more tackif ⁇ ers or additional polymers may be included in the present foamable dental compositions.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the retentive polymeric coating is durable for at least 12 hours or at least 24 hours as measured by the Toothbrush Abrasion Test.
  • 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.
  • 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.
  • the retentive polymeric coating releases fluoride ions for a period of at least 12 hours.
  • the retentive polymeric coating releases fluoride ions for a period of at least 24 hours.
  • the method further comprises rinsing the dental surface immediately after applying the dental foam.
  • the dental surface is a tooth surface.
  • the dental surface comprises a cured dental restorative material.
  • 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.
  • the polymer typically a substantive polymer
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a catalyst e.g., stannous octoate
  • compositions of the present invention may include dental agents.
  • 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.
  • the dental agents are suitable for use in the oral environment.
  • the substantive polymer can act as a dental agent.
  • 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.
  • 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.
  • 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.
  • 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.
  • the dental agent is a phosphate compound.
  • the phosphate compound is a monobasic phosphate compound, a dibasic phosphate compound, a tribasic phosphate compound, calcium glycerophosphate, or combinations thereof.
  • the dental agent is a calcium phosphate (dibasic) compound.
  • the dental agent is a caseinate.
  • 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(NH 2 ) 2 » H 2 O 2 , also known as urea hydrogen peroxide, hydrogen peroxide carbamide, or perhydrol-urea), and combinations thereof.
  • hypochlorites e.g., sodium hypochlorite
  • peroxides e.g., hydroperoxides
  • hydrogen peroxide peracids
  • peroxyacids also known as peroxyacids
  • carbamide peroxide i.e., the urea complex of hydrogen peroxide, CO(NH 2 ) 2 » H 2 O 2 , also known as urea hydrogen
  • 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).
  • antibiotics e.g.
  • the concentration of a dental agent in the foamable dental composition can vary depending upon its activity.
  • a fluoride source may be used at a low concentration
  • 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.
  • 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.
  • 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.
  • Exemplary methods of preparing the substantive polymers 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.).
  • 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
  • Polar or Polarizable Groups 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 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.
  • 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.
  • 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.
  • 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:
  • CH 2 CR 2 G-(COOH) d
  • R 2 is H, methyl, ethyl, cyano, carboxy or carboxymethyl
  • d is an integer from 1 to 5
  • 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).
  • 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.
  • 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 .
  • Suitable monomers of this class are aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N- (dimethyl)aminoethyl (meth)acrylate, ⁇ f, ⁇ /-(diethyl)aminoethyl (meth)acrylate, N-[N, N- (dimethy l)aminopropy 1] (meth)acrylamide , N-[N-[N-[N-
  • 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:
  • R 2 , R 3 , R 4 , R 5 , L and d are as defined above, and where R 6 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-( ⁇ /, ⁇ /, ⁇ Mrimethylammonium)ethyl (meth)acrylate, 2-(N,N,N- triethylammonium)ethyl (meth)acrylate, 3 -( ⁇ /, ⁇ f, ⁇ /-trimethylammonium)propyl (meth)acrylate, 2-(N, ⁇ /-dimethyl- ⁇ /-hexadecylamino)ethyl methacrylate, N-[2-( ⁇ / I , ⁇ / I , ⁇ / I -trimethylarnmonium)ethyl](meth)acrylamide, N-[N, N -dimethyl-N- (hydroxyethyl)ammoniumpropyl](me
  • the monomer can also be ⁇ /,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 Kohlutkin 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.
  • 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- ( ⁇ /, ⁇ /-dimethyl- ⁇ /-hexadecylamino)ethyl methacrylate, itaconic acid, N- isopropylacrylamide, or combinations thereof.
  • Fluoride Releasing Groups include fluoride salts as disclosed, for example, in U.S. Pat. Nos.
  • 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.
  • 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.
  • the hydrocarbon moiety has a molecular weight of at least 160.
  • 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.
  • 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.
  • 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.).
  • Exemplary repeating units of hydrophobic fluorine-containing groups include acrylic or methacrylic acid esters of 1,1-dihydroperfluoroalkanols and homo logs: CF 3 (CF 2 ) X CH 2 OH and CF 3 (CF 2 ) x (CH 2 ) y OH, where x is 0 to 20 and y is at least 1 up to 10; ⁇ -hydrofluoroalkanols (HCF 2 (CF 2 ) x (CH 2 ) y OH), where x is 0 to 20 and y is at least 1 up to 10; fluoroalkylsulfonamido alcohols; cyclic fluoroalkyl alcohols; and CF 3 (CF 2 CF 2 ⁇ ) q (CF 2 O) x (CH 2 ) y OH, 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- ⁇ /-(nonafluorobutylsulfonyl)amino]ethyl acrylate, 2-[JV-methyl-JV-
  • 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,
  • 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.
  • modulating groups include the lower to intermediate methacrylic acid esters of 1 to 12 carbon straight, branched or cyclic alcohols.
  • modulating groups include styrene, vinyl esters, vinyl chloride, vinylidene chloride, acryloyl monomers and the like.
  • Dental compositions described herein may optionally include an initiator system or catalyst that enables the composition to be hardened (e.g., polymerized or crosslinked).
  • an initiator system or catalyst that enables the composition to be hardened (e.g., polymerized or crosslinked).
  • visible and/or near-infrared photoinitiator systems may be used to initiate photopolymerization in compositions including free-radically polymerizable components.
  • 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.).
  • 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.)).
  • a sensitizer e.g., camphor quinone
  • 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.)
  • acylphosphine oxides useful in the invention are those in which the R and R 1 groups are phenyl or lower alkyl- or lower alkoxy-substituted phenyl.
  • R and R 1 groups are phenyl or lower alkyl- or lower alkoxy-substituted phenyl.
  • lower alkyl and lower alkoxy is meant such groups having from 1 to 4 carbon atoms.
  • 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).
  • redox catalysts including oxidants and reductants for inducing free radical polymerization in multi-component systems are 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.
  • 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).
  • 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).
  • 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 sulf ⁇ nate, or sulfite anions.
  • amines e.g., aromatic amines
  • metal complexed ascorbic acid metal complexed ascorbic acid
  • cobalt (II) chloride ferrous chloride
  • ferrous sulfate ferrous sulfate
  • hydrazine hydroxylamine
  • oxalic acid thiourea
  • salts of dithionite, thiosulfate, benzene sulf ⁇ nate, or sulfite anions e.g.
  • 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.
  • 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.
  • 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.
  • a propellant other than a hydrocarbon propellant is preferred.
  • the propellant is dimethyl ether in combination with at least one inert gas.
  • 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.
  • a foam stabilizing agent which is a surfactant may also be a foam stabilizer, a foam- wall thickener, or a combination of these.
  • 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.
  • 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 Ci 4 _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
  • 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.
  • 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
  • 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.
  • 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.
  • 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).
  • compositions of the present invention can also include additives (other than the additives described above for preparing foamable compositions).
  • additives include, for example, buffering agents, acidifying agents, viscosity modifiers, thixotropes, fillers, flavoring agents, sweetening agents, polysaccharides, and combinations thereof.
  • the foamable dental composition further comprises a water soluble acidifying agent.
  • 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.
  • 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.
  • 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).
  • 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.
  • foamable dental compositions described herein may be delivered to the desired site by known methods.
  • 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.
  • suitable containers or dispensers include, for example, bottles, vials, syringes, and tubes.
  • the composition can be delivered by using a brush, sponge, applicator, or swab to paint or coat the composition onto the tissue.
  • 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.
  • 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).
  • 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.
  • 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.
  • a substrate e.g., a dental tray
  • dip coating e.g., a dental tray
  • 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.
  • the composition is applied by dip coating the dental surface in the dental composition for at least one second.
  • 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.
  • the composition includes a polymer with a crosslinkable segment, typically, the composition is provided to the user with a catalyst (e.g., stannous octoate).
  • 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.
  • the catalyst is applied to crosslink the polymer on the dental surface.
  • the polymer is “nonpolymerizable” and is hardened and adhered to the tooth simply by coating, dipping, etc.
  • 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.
  • 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.
  • the composition may include two or more parts, with one part including an oxidizing agent, and another part including a reducing agent.
  • 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.
  • 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 0 C 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 0 C 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.
  • 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 ⁇ L 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.
  • TISAB buffer total ionic strength adjustment buffer
  • TISAB buffer 75 ⁇ L 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
  • 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.
  • Adhesion to enamel scale (Thumb is rubbed over the surface of the tooth with 1500 to 2000 grams of force.)
  • Cohesion scale (Coating must not delaminate from enamel or indicate adhesive failure.)
  • IBMA 60 parts
  • AA 20 parts
  • DMAEMA-Ci 6 Br 20 parts
  • VAZO-67 0.5 parts
  • ethanol 267 parts
  • 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-Ci 6 Br.
  • 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-Ci 6 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.
  • 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.
  • 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.
  • 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-Ci 6 Br, 18.75 weight percent ethanol, and 43.75 weight percent DGME.
  • DGME 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.
  • Example 5 To a portion of C4 propellant was added as in Example 1 , and a dental foam was dispensed from the can.
  • Example 5 To a portion of C4 propellant was added as in Example 1 , and a dental foam was dispensed from the can.
  • DGME DGME
  • jet milled sodium fluoride 4.00 g
  • jet milled calcium phosphate 2.00 g
  • 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.
  • Example 6 To a portion of C5 propellant was added as in Example 1 , and a dental foam was dispensed from the can.
  • Example 6 To a portion of C5 propellant was added as in Example 1 , and a dental foam was dispensed from the can.
  • 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.
  • Example 7 To a portion of C6 propellant was added as in Example 1 , and a dental foam was dispensed from the can.
  • Example 7 To a portion of C6 propellant was added as in Example 1 , and a dental foam was dispensed from the can.
  • 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.
  • DGME 24.10 g
  • jet milled sodium fluoride (4.00 g)
  • 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.
  • 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.
  • 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.
  • 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.
  • IBMA/AA/DMAEMA-Ci 6 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-Ci ⁇ Br and 60.9 weight percent DGME.
  • DGME 32.25 g
  • jet milled sodium fluoride 3.00 g
  • jet milled calcium phosphate (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.
  • 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.
  • DGME 13.05 g
  • jet milled sodium fluoride 3.00 g
  • jet milled calcium phosphate (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-Ci 6 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.
  • 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.
  • 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 0 C 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).
  • Sm smoothness
  • Adh adhesion
  • Hard hardness
  • Coh cohesion
  • 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 0 C 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.
  • 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 1 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.
  • Example 1 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 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)

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dental Preparations (AREA)
  • Cosmetics (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention porte sur une composition dentaire moussante comprenant un composant filmogène et un véhicule non aqueux renfermant un cosolvant choisi dans le groupe composé du diéthylène glycol monoéthyl éther, du dipropylène glycol, du poly(éthylène glycol) à poids moléculaire de 200 à 45 000, de méthoxydes de poly(éthylène glycol) à poids moléculaire de 200 à 45 000, de l'hexaméthyldisiloxane, et d'une combinaison desdits éléments, le composant filmogène étant dissous dans le véhicule et formant un revêtement polymérique de rétention sur une surface dentaire. L'invention se rapporte également à un procédé de formation d'un revêtement polymérique de rétention sur une surface dentaire.
PCT/US2009/043712 2008-05-16 2009-05-13 Composition moussante pour revêtements dentaires et procédés associés WO2009140334A2 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013070184A1 (fr) * 2011-11-07 2013-05-16 Colgate-Palmolive Company Formulations de film dentaire
WO2018183647A1 (fr) * 2017-03-29 2018-10-04 Dentsply Sirona Inc. Système d'hydrogel à base de polyphénols/peg pour vernis dentaire

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4474750A (en) * 1976-12-27 1984-10-02 Colgate-Palmolive Company Anticalculus oral composition
WO2007070650A2 (fr) * 2005-12-14 2007-06-21 3M Innovative Properties Company Films antimicrobiens adhesifs
WO2007079069A1 (fr) * 2005-12-29 2007-07-12 3M Innovative Properties Company Compositions dentaires moussantes et procedes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4474750A (en) * 1976-12-27 1984-10-02 Colgate-Palmolive Company Anticalculus oral composition
WO2007070650A2 (fr) * 2005-12-14 2007-06-21 3M Innovative Properties Company Films antimicrobiens adhesifs
WO2007079069A1 (fr) * 2005-12-29 2007-07-12 3M Innovative Properties Company Compositions dentaires moussantes et procedes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013070184A1 (fr) * 2011-11-07 2013-05-16 Colgate-Palmolive Company Formulations de film dentaire
CN104023703A (zh) * 2011-11-07 2014-09-03 高露洁-棕榄公司 牙齿膜制剂
US8883212B2 (en) 2011-11-07 2014-11-11 Colgate-Palmolive Company Tooth film formulations
WO2018183647A1 (fr) * 2017-03-29 2018-10-04 Dentsply Sirona Inc. Système d'hydrogel à base de polyphénols/peg pour vernis dentaire
CN110505864A (zh) * 2017-03-29 2019-11-26 登士柏希罗纳有限公司 用于牙科漆的多酚/peg基水凝胶体系
JP2020515550A (ja) * 2017-03-29 2020-05-28 デンツプライ シロナ インコーポレイテッド 歯科用バーニッシュのためのポリフェノール／ｐｅｇベースヒドロゲル系

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