WO1979000456A1 - Compositions and methods for inhibiting plaque formation - Google Patents

Compositions and methods for inhibiting plaque formation Download PDF

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Publication number
WO1979000456A1
WO1979000456A1 PCT/US1978/000257 US7800257W WO7900456A1 WO 1979000456 A1 WO1979000456 A1 WO 1979000456A1 US 7800257 W US7800257 W US 7800257W WO 7900456 A1 WO7900456 A1 WO 7900456A1
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Prior art keywords
membrane
dentifrice composition
composition according
forming material
carbon atoms
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PCT/US1978/000257
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French (fr)
Inventor
R Chang
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Minnesota Mining & Mfg
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Application filed by Minnesota Mining & Mfg filed Critical Minnesota Mining & Mfg
Priority to BR7808730A priority Critical patent/BR7808730A/en
Priority to JP50028078A priority patent/JPS54500061A/ja
Publication of WO1979000456A1 publication Critical patent/WO1979000456A1/en

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    • 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
    • A61K8/29—Titanium; Compounds 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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • 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
    • A61K8/55—Phosphorus 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
    • A61K8/30—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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/69—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
    • A61K8/70—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine containing perfluoro groups, e.g. perfluoroethers
    • 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
    • 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
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; 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
    • A61K8/81—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
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/58—Metal complex; Coordination compounds

Definitions

  • This invention relates to compositions for topical application to teeth. More particularly it relates to compositions and methods u s e f u l in inhibiting the growth of cariogenic bacteria and the formation of plaque on teeth in an oral environment.
  • Dental plaque results when cariogenic bacteria (e.g. Streptococcus Mutans) collect in colonies on the surface of teeth and form a tenacious deposit thereon.
  • cariogenic bacteria e.g. Streptococcus Mutans
  • fluoride solutions or gels have b e e n used.
  • Such treatments are typically performed in a dental office at periodic, but not frequent, intervals so as to render the tooth enamel more resistant to the acid action caused by plaque.
  • Such treatments do not, however, result in plaque control for an extended period.
  • a dentifrice composition which contains a water-dispersible, membrane-forming material which membrane-forming material, when applied to the surface of a tooth in an oral environment, attaches thereto and forms a substantially continuous hydrophobic barrier thereon.
  • Dentifrice Compositions Compositions for topical application to the teeth such as mouthwashes or rinses, toothpastes, toothpowders, gels, etc. Water Dispersible
  • a layer which does not adsorb or absorb water is not adsorb or absorb water.
  • compositions of the present invention contain at least about 0.005% and most preferably from about 0.01% to 5%, by weight of . the membrane-forming material.
  • a method for inhibiting plaque formation which comprises contacting teeth with an effective amount of the above-described composition .
  • compositions of the invention provide a simple and effective composition and process by which cariogenic bacteria and plaque formation may be controlled.
  • the barrier formed by compositions of the invention may itself provide the desired control (e.g. it may be toxic to cariogenic bacteria) or it may reduce the diffusion of therapeutic agents (e.g. caries-preventing agents such as fluoride treatments) therethrough thereby prolonging the effectiveness of such agents.
  • compositions of the invention may achieve the desired control by a combination of each of these methods. In either event it is only necessary to apply the compositions of the invention periodically (e.g. once daily). Best Mode For Carrying Out The Invention
  • compositions of the invention may be applied to the teeth by a variety of techniques such as painting or brushing, bathing, spraying, and rinsing. Other means of application are also possible and will be obvious to those skilled in the art as a result of this disclosure.
  • a variety of materials are useful as the membrane-forming material. They include polymeric and nonpolymeric ionic and nonionic materials. Ionic materials are attracted to either the positive or negative electrode during electrolysis. Thus, anionic materials are attracted to the positive electrode and cationic materials are attracted to the negative electrode. Nonionic materials are those materials which are not attracted to either of the electrodes during electrolysis.
  • Useful anionic membrane-forming materials are believed to attach to tooth surfaces and form a substantially continuous barrier thereon by complexing with calcium present in the teeth.
  • the strength of the complex structure formed may be represented by the formation constant of the complexing agent. This constant is expressed in terms of log 10 K and is based upon the complex formed between the membrane-forming material and an organic ligand. The formation constant is measured at about 25°C. and an ionic strength approaching 0 from the following:
  • [M] represents the concentration of the membrane-forming material
  • [L] represents the concentration of the organic ligand
  • [ML] represents the concentration of the complex at equilibriurn.
  • the formation constant of useful anionic membrane-forming materials is in the range of about 0.5 to 8. Preferably, it is in the range of about 0.6 to 6.
  • a formation. constant of more than 8 indicates a very strong calcium complexor. Such complexors tend to decalcify the tooth (i.e. withdraw the calcium from the tooth) thereby weakening its resistance to disease and wear.
  • polymeric anionic Membrane-Forming Materials include: polyacrylic acid having the repeating unit available in a wide range of mole cular weights (e.g. from about 2,000 to
  • mol ecu l ar weight of about 2,000,000 and available from Dow Chemical Company; sodium polysulfonate having the repeating unit a molecular weight in the range of
  • R f is a fluorinated, saturated aliphatic radical
  • Q is a divalent radical through which R f and Z are linked together
  • Z is an an i o n i c radical
  • d is 0 or 1
  • m is an integer of at least 1; provided that when d is 0, m is 1 or 2;
  • R 1 is a hydrocarbon radical, preferably an alkyl radical, containing from about 6 to 24 carbon atoms, A is hydrogen or a cation;
  • R 2 is a hydrocarbon group containing from about 10 to 20 carbon atoms.
  • the R f radicals usually are monovalent. Moreover, they are stable, inert, nonpolar moieties which can be both oleophobic and hydrophobic. They can be straight chain or branched chain radicals. Additionally, if the radicals are sufficiently large, they may be cyclic or combinations of cyclic and branched and straight chain, (e.g. al kylcycloal iphatic radicals).
  • the skeletal chain of the R f radical can include catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms. Such hetero atoms provide stable linkages between fluorocarbon groups and do not interfere with the inert character of the radical.
  • R f has from about 4 to 16 carbon atoms.
  • R f generally contains about 40-80 weight percent, and preferably about 50-80 weight percent fluorine so that the fluorochemical material of formula I will contain from about 4 to 70 weight percent fluorine.
  • the most preferred anionic fluorochemical materials are those in which the R f group is fully or substantially fully fluorinated.
  • the preferred R f groups are perfluoroalkyl groups
  • the terminal portion of the R f group preferably contains a -CF 3 group, and most preferably has at least three fully fluorinated carbon atoms, (e.g. CF 3 CF 2 CF 2 -).
  • the Q radical may be monovalent or polyvalent (i.e. at least polyvalent). It must not interfere with the formation of the complex structure between the Z radicals and the tooth surfaces.
  • Useful Q radicals include hydrocarbon groups containing from about 1 to 30 carbon atoms, oxygen, sulfur and -SO 2 O-.
  • the hydrocarbon groups may be straight or branched chain radicals and may include unsaturation and aromatic groups.
  • the hydrocarbon groups may contain heteroatoms in the skeletal, chain. Typically the hetero atoms are selected from the group consisting of oxygen, nitrogen and sul fur.
  • Useful Z radicals are anionic in character and complex with calcium ions. Preferably they are l t d f
  • R 3 is selected from the group consisting of hydroxyl and mercapto;
  • R 4 is selected from the group consisting of sulfur and oxygen;
  • R 5 is an alkyl radical containing from about 10 to 20 carbon atoms;
  • R 6 is selected from the group consisting of hydrogen and hydroxyl;
  • R 7 is selected from the group consisting of hydrogen, and alkali metals (especially sodium and potassium); and
  • e is an integer of 1 or 2.
  • the carboxylic acids may be straight or branched chain and may contain unsaturation in the backbone. Preferably, however, the acids have fully saturated backbones.
  • the acid should be provided as a water-soluble salt thereof.
  • useful organic phosphates include (C 16 H 33 O) 2 POOH and (C 18 H 37 O) 2 POOH. d. Other Anionic And Non-Polymeric Materials
  • Examples of still other useful anionic nonpolymeric materials include sodium dioctyl sulfosuccinate (i.e. commercially available as
  • Useful cationic membrane-forming materials are believed to attach to tooth surfaces via a complexing interaction between the cationic portion of the material and the proteinaceous portion of the tooth.
  • polymeric Cationic Membrane-Forming Materials include polydimeryl polyamine, a polydimeryl polyamide which has (molecular weight of about 8000, amine number of about 120, available from General Mills Chemi cal Co.); polyethylene imine which has the repeating unit (CH 2 -CH 2 -NH) n (molecular weight of about 100,000, available from Dow Chemical Co.); 1,5-dimethyl hexamethrine bromide diazaundecamethylene polymethobromine hexademethrine bromide, a quaternary composition which has the repeating unit
  • Representative examples of useful nonpolymeric cationic membrane-forming materials may be represented by the formulae (R f ) m Q d D (V)
  • R f , Q, d and m are each as described above;
  • R 8 is an alkyl radical containing from about 4 to 20 carbon atoms and D is a cationic radical.
  • Useful D radicals are cationic in character and complex with the proteinaceous materials of the teeth, Representative examples of useful D groups include -NHC 2 H 4 NHC 2 H 4 NH 2 ; -NH 2 ; -NHC 2 H 4 NH 2 ;
  • Useful nonionic membrane-forming materials are believed to attach to tooth surfaces by interacting with either or both of (i) the hydroxyl groups of the hydroxyapetite (i.e. Ca 10 (PO 4 ) 6 (OH) 2 ) or (ii) the hydroxyl groups present on the tooth surfaces from water or saliva present in the mouth.
  • useful nonionic membrane-forming materials may be represented by the formulae
  • R 9 is selected from the group consisting of hydrocarbon and fluorocarbon radicals or combination.s of hydrocarbon and fluorocarbon radicals which may contain up to about 25 carbon atoms.
  • the R 9 radicals may be aliphatic, aromatic or aliphatic and aromatic. Moreover they may contain heteroatoms selected from nitrogen, sulfur, oxygen, and silicone. Preferably no .two of said hetero atoms are adjacent and the oxygen atoms present are in the form of ether linkages.
  • R 10 i an alkoxy radical containing from about 1 to 6, and preferably from about 1 to 3 carbon atoms.
  • R 11 is selected from the group consisting of alkoxy groups containing from about 1 to 10 carbon atoms and groups composed of hydrogen, carbon and oxygen wherein said groups contain from about 1 to 20 carbon atoms.
  • R 12 is selected from the group consisting of hydrocarbon radicals of about 1 to 20
  • R 13 is a heterocyclic group containing carbon oxygen and hydrogen.
  • the value of b and x is 0, 1 , 2 or 3,
  • nonionic membrane-forming materials useful in the present invention are set forth in Table IV. The portions of each material attributable to each section of the generic formula are given.
  • compositions of the present invention may be added to the dentifrice compositions of the present invention.
  • therapeutic agents such as caries prophylactic agents, polishing agents, surfactants, flavoring and sweetening agents, thickening agents and humectants may be included using techniques which are known to the art.
  • the other ingredients When such other ingredients are employed with (i) anionic membrane-forming materials or (ii) cationic membrane-forming materials which have a calcium complexing moiety Z, the other ingredients must be substantially free of polyvalent metal (e,g, calcium, magnesium, etc.). These metals interact with these particular types of membrane-forming materials and prevent them from forming the barrier. Thus while a minor amount of such polyvalent metal may be present, the total amount present must not prevent the membrane forming material from interacting with the teeth. Preferably these compositions are free of polyvalent metal.
  • polyvalent metal e,g, calcium, magnesium, etc.
  • suitable therapeutic agents such as caries prophylactic agents, include soidum fluoride, stannous fluoride, potassium fluoride, hexylamine hydrofluoride, myristylamine hydrof1 uoride, betaine fluoride, glycine potassium fluoride, etc.
  • a particularly preferred fluoride is sodium fluoride.
  • the therapeutic agents may be applied previously to or simultaneously with the compositions of the invention. When applied simultaneously with said compositions, they are typically present in sufficient concentration so as to provide an available fluoride ion concentration of up to about 2% by weight, and preferably in the range of about 0.5-2% by weight, of the dentifrice composition. Additionally, it is preferred that the weight ratio of prophylactic ingredient to membraneforming material be in the range of about 1:0.5 to 1:5 and most preferably in the range of about 1:0.5 to 1:1.
  • Suitable polishing agents include abrasive materials such as nonionic polymers.
  • abrasive materials such as nonionic polymers.
  • such materials are water impervious crosslinked thermosetting resins (e.g. the condensation product of melamine and urea with formaldehyde), powdered polymethylmethacrylate, and powdered polyethylene.
  • the polishing agent is not so abrasive so as to scratch or unduly abrade the tooth surface or the dentin, Rather it only cleans the tooth surface.
  • the polishing agents may comprise up to 95% by weight of the dentifrice composition.
  • Surfactants useful in the present invention include, for example, nonionic surfactants which are known to the art. These materials typically comprise up to about 5% by weight of the dentifrice composition.
  • Flavoring and sweetening agents include, for example , the oils of wintergreen, peppermint, spearmint, sassafras and anise. Additionally small amounts of sweetening agents such as saccharin, dextrose, levulose, etc., may also be added to such compositions. These flavoring and sweetening agents may comprise up to about 5% by weight of the dentifrice composition.
  • Gelling or thickening agents include, for example, water-soluble salts of cellulose ethers such as sodium carboxy methyl cellulose and sodium carboxy methyl hydroxy ethyl cellulose, natural gums such as gum karaya, gum arabic, and gum tragacanth; and colloidal magnesium-aluminum silicate or finely divided silica.
  • Such thickening agents may comprise up to about 5% by weight of the dentifrice composition.
  • dentifrices of the present invention typically comprise a solution of the membrane-forming material in water or a mixture of water and an alcohol.
  • the alcohol is a lower alkanol (e.g. ethanol, propanol, etc.). These compositions are particularly useful as mouthwashes or rinses.
  • Example 1 This example demonstrates that compositions of the invention form substantially continuous barriers on teeth which reduce the ellution of a previously applied fluoride treatment from said teeth.
  • Separate bovine central incisors were used in the tests. A flat surface was provided on each of the teeth by first polishing them with 240 grit silicon carbide abrasive paper; and then with 400 grit silicon carbide abrasive paper. The teeth were then given a 5 minute soak with a 2% by weight solution of sodium fluoride (NaF) in de i on i zed water. One-half of the number of the teeth were then given a 5 minute soak with a 1% by weight solu tion of membrane forming material (C 16 H 33 O) 2 POOH, in deionized water. The other half of the number of the teeth was given no treatment with the membraneforming composition. All of the teeth were then tested for initial water contact angle, initial fluoride level, water contact angle after a 26 hour water soak and fluoride content after a 26 hour water soak
  • Comparision of treatments A and B shows the dramatic increase in water contact angle caused by the addition of the membrane-forming material, (C 16 H 33 O) 2 POOH.
  • Comparison of treatments C and D shows that, even after soaking the teeth for 26 hours in water, the membrane remains on the surface and that it substantially reduces ellution of the initial fluoride treatment.
  • Bovine teeth were prepared and treated with NaF as described in Example 1. Certain of the teeth were then soaked for 5 minutes with compositions containing various membrane-forming materials. Each of the teeth were then soaked in separate 100 ml deionized water baths for 24 hours. The teeth were removed from the baths and each bath was then analyzed for fluoride ion content using a fluoride ion electrode. The results of these tests are set forth in Table VI.
  • Comparison of treatments A and B (which were run simultaneously) graphically illustrates the decrease in ellution of the NaF as a result of the membraneforming material. Comparison of treatments D and E with treatment C (which were run simultaneously but at a different time than tests A and B) further graphically illustrate the decrease in ellution of the NaF as a result of membrane-forming material.
  • Example 3 This example demonstrates the durability of the membrane. Bovine central incisors were prepared and the initial water contact angle measured as described in Example 1. The teeth were then soaked for 5 minutes with 0.1% by weight solutions of various membrane-forming materials in deionized water. The water contact angle was then measured after the teeth had been soaked in deionized water for 10 and 60 minutes and 24 hours. The results are given in Table VII.
  • Example 3 The procedures of Example 3 were repeated except that the teeth were given a fluoride treatment before being soaked for 5 minutes with a 0.1% by weight solution of membrane-forming material in deionized water.
  • the fluoride treatment consisted of a 5 minute soak with an acidulated phosphate fluoride which comprised 40 grams (g) of NaF, 11.8ml of HF, 126 ml of H 3 PO 4 and 1400 ml of deio ⁇ nized water.
  • the results of the water contact angle measurements are given in Table VIII.

Abstract

The object of the invention is to provide a dentifrice composition for inhibiting plaque formation on teeth. Said composition contains a waterdispersible membrane-forming material which, when applied to the surface of a tooth in an oral environment, attaches thereto and forms a substantially continuous, hydrophobic barrier thereon.

Description

Description
Compositions And Methods For Inhibiting Plaque Formation
Technical Field
This invention relates to compositions for topical application to teeth. More particularly it relates to compositions and methods u s e f u l in inhibiting the growth of cariogenic bacteria and the formation of plaque on teeth in an oral environment.
Background Art
The prevention of the formation of dental plaque on teeth is a highly desired result. Dental plaque results when cariogenic bacteria (e.g. Streptococcus Mutans) collect in colonies on the surface of teeth and form a tenacious deposit thereon.
The presence of the bacteria and the deposits is extremely detrimental to the health of the teeth because if left unchecked they may cause infected gingival tissue, the formation of dental caries and periodontal disease. In extreme cases t h ey may result in the loss of teeth:
Many attempts have been made to control each. For example, fluoride solutions or gels have b e e n used. Such treatments are typically performed in a dental office at periodic, but not frequent, intervals so as to render the tooth enamel more resistant to the acid action caused by plaque. Such treatments do not, however, result in plaque control for an extended period.
Even when the frequency of application of such solutions and gels is increased only pirtial control has been shown. For example, studies wherein a fluoride-containing solution ( 1 % fluoride concentration) was applied four to five times in the course of a year demonstrated only limited success. Moreover, the daily application of a fluoride gel by means of a customfitted polyvinyl mouthpiece for a period of twentyone months also showed no substantial change in plaque formation among treated and untreated patients. See "Clinical Anticaries Effect Of A Repeated Sodium Fluoride Application By Mouthpiece", Journal of the American Dental Association, V. 75, No. 3, September, 1967, pages 638-644.
As a result, there has been no truly effective prop hy l a c t i c treatment for teeth made available to the public. However, the present invention provides such a treatment.
Disclosure of Invention
In accordance with the present invention there is provided a dentifrice composition which contains a water-dispersible, membrane-forming material which membrane-forming material, when applied to the surface of a tooth in an oral environment, attaches thereto and forms a substantially continuous hydrophobic barrier thereon. As used throughout this specification the following terms have the following meanings: Dentifrice Compositions Compositions for topical application to the teeth such as mouthwashes or rinses, toothpastes, toothpowders, gels, etc. Water Dispersible
Materials which may be either dispersed or dissolved in aqueous media at a level of at least about 10 parts of such material per one million parts of media (i.e. 0.001%) , and preferably at a Tevel of at least about
100 parts of such material per one million parts of media (i.e. 0,01%).
Hydrophobic Barrier
A layer which does not adsorb or absorb water.
Preferably the compositions of the present invention contain at least about 0.005% and most preferably from about 0.01% to 5%, by weight of. the membrane-forming material.
In another embodiment of the present invention there is provided a method for inhibiting plaque formation which comprises contacting teeth with an effective amount of the above-described composition .
The present invention provides a simple and effective composition and process by which cariogenic bacteria and plaque formation may be controlled. The barrier formed by compositions of the invention may itself provide the desired control (e.g. it may be toxic to cariogenic bacteria) or it may reduce the diffusion of therapeutic agents (e.g. caries-preventing agents such as fluoride treatments) therethrough thereby prolonging the effectiveness of such agents. Moreover compositions of the invention may achieve the desired control by a combination of each of these methods. In either event it is only necessary to apply the compositions of the invention periodically (e.g. once daily). Best Mode For Carrying Out The Invention
The compositions of the invention may be applied to the teeth by a variety of techniques such as painting or brushing, bathing, spraying, and rinsing. Other means of application are also possible and will be obvious to those skilled in the art as a result of this disclosure.
A variety of materials are useful as the membrane-forming material. They include polymeric and nonpolymeric ionic and nonionic materials. Ionic materials are attracted to either the positive or negative electrode during electrolysis. Thus, anionic materials are attracted to the positive electrode and cationic materials are attracted to the negative electrode. Nonionic materials are those materials which are not attracted to either of the electrodes during electrolysis.
A. Anionic Membrane-Forming Materials
Useful anionic membrane-forming materials are believed to attach to tooth surfaces and form a substantially continuous barrier thereon by complexing with calcium present in the teeth. The strength of the complex structure formed may be represented by the formation constant of the complexing agent. This constant is expressed in terms of log10 K and is based upon the complex formed between the membrane-forming material and an organic ligand. The formation constant is measured at about 25°C. and an ionic strength approaching 0 from the following:
Figure imgf000006_0001
In these formulae [M] represents the concentration of the membrane-forming material, [L] represents the concentration of the organic ligand and [ML] represents the concentration of the complex at equilibriurn.
The formation constant of useful anionic membrane-forming materials is in the range of about 0.5 to 8. Preferably, it is in the range of about 0.6 to 6. A formation. constant of more than 8 indicates a very strong calcium complexor. Such complexors tend to decalcify the tooth (i.e. withdraw the calcium from the tooth) thereby weakening its resistance to disease and wear.
1. Polymeric Anionic Membrane-Forming Materials Representative examples of useful polymeric anionic membrane-forming materials include: polyacrylic acid having the repeating unit available in a wide range of mole
Figure imgf000007_0001
cular weights (e.g. from about 2,000 to
4,000,000) from Aldrich Chemical Company,
Inc. ;
"Separan A. P. 30" having the repeating unit
Figure imgf000007_0002
mol ecu l ar weight, of about 2,000,000 and available from Dow Chemical Company; sodium polysulfonate having the repeating unit a molecular weight in the range of
Figure imgf000007_0003
about 5,000 to 6,000,000 and available from
Dow Chemical Company; copolymers of acrylates which contain acid functionalities such as "Carboset" 514, 515 and 525", having molecular weights of about
30,000; 7,000 and 260,000 respectively and available from B. F. Goodrich Chemical
Company;
"Gantrez" AN having the repeating unit
Figure imgf000008_0001
and available from GAF Corporation;
"EMA" 11, 21 and 31 having the repeating unit
Figure imgf000008_0002
and available from Monsanto Chemical Company; and polyvinylphosphate having the repeating unit
Figure imgf000008_0003
and available from Polysciences, Inc
2. Non-Polymeric Membrane-Forming Materials
Representative examples of useful nonpolymeric anionic membrane-forming materials include
Fluorochemical materials of the formula
Carboxy
Figure imgf000008_0004
lic acids of the formula
Figure imgf000008_0005
Organic phosphate materials of the formulae
Figure imgf000009_0001
In the above four formulae Rf is a fluorinated, saturated aliphatic radical; Q is a divalent radical through which Rf and Z are linked together; Z is an an i o n i c radical; d is 0 or 1; and m is an integer of at least 1; provided that when d is 0, m is 1 or 2;
R1 is a hydrocarbon radical, preferably an alkyl radical, containing from about 6 to 24 carbon atoms, A is hydrogen or a cation; and
R2 is a hydrocarbon group containing from about 10 to 20 carbon atoms.
a. Fluorochemical Materials (Formula I)
The Rf radicals usually are monovalent. Moreover, they are stable, inert, nonpolar moieties which can be both oleophobic and hydrophobic. They can be straight chain or branched chain radicals. Additionally, if the radicals are sufficiently large, they may be cyclic or combinations of cyclic and branched and straight chain, (e.g. al kylcycloal iphatic radicals). The skeletal chain of the Rf radical can include catenary oxygen and/or trivalent nitrogen hetero atoms bonded only to carbon atoms. Such hetero atoms provide stable linkages between fluorocarbon groups and do not interfere with the inert character of the radical. Rf has from about 4 to 16 carbon atoms. Preferably it has from about 6 to 12 carbon atoms. Moreover Rf generally contains about 40-80 weight percent, and preferably about 50-80 weight percent fluorine so that the fluorochemical material of formula I will contain from about 4 to 70 weight percent fluorine.
The most preferred anionic fluorochemical materials are those in which the Rf group is fully or substantially fully fluorinated. Thus the preferred Rf groups are perfluoroalkyl groups
(e.g. CnF2n+1-). Additionally the terminal portion of the Rf group preferably contains a -CF3 group, and most preferably has at least three fully fluorinated carbon atoms, (e.g. CF3CF2CF2-).
The Q radical may be monovalent or polyvalent (i.e. at least polyvalent). It must not interfere with the formation of the complex structure between the Z radicals and the tooth surfaces. Useful Q radicals include hydrocarbon groups containing from about 1 to 30 carbon atoms, oxygen, sulfur and -SO2O-. The hydrocarbon groups may be straight or branched chain radicals and may include unsaturation and aromatic groups. Moreover the hydrocarbon groups may contain heteroatoms in the skeletal, chain. Typically the hetero atoms are selected from the group consisting of oxygen, nitrogen and sul fur.
Useful Z radicals are anionic in character and complex with calcium ions. Preferably they are l t d f
Figure imgf000010_0001
-SO2R7; wherein R3 is selected from the group consisting of hydroxyl and mercapto; R 4 is selected from the group consisting of sulfur and oxygen;
R5 is an alkyl radical containing from about 10 to 20 carbon atoms; R6 is selected from the group consisting of hydrogen and hydroxyl; R7 is selected from the group consisting of hydrogen, and alkali metals (especially sodium and potassium); and e is an integer of 1 or 2.
Representative examples of useful Z radicals include -COOH, =POOH, -OPO(OH)2; -PO(OH)2, =PSSH,
-PS(SH)2; -SO3H and -OSO3H.
Specific examples of useful anionic fluorochemical materials of formula I type are set forth in Table I. The portions of each material attributable to each section of the generic formula are given.
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
b. Carboxylic Acids (Formula II)
The carboxylic acids may be straight or branched chain and may contain unsaturation in the backbone. Preferably, however, the acids have fully saturated backbones. When the compositions employing carboxylic acid membrane-forming materials are formulated in water, the acid should be provided as a water-soluble salt thereof.
Specific examples of useful carboxylic acids of formula II are set forth in Table II. The portions of each material attributable to each section of the generic formula are given.
TABLE II R'COOA R_' CH3(CH2)10COOH CH3(CH2)10-
(Lauric acid )
CH3(CH2)12COOH CH3(CH2)12-
(Myristic acid)
CH3 ( CH2 ) 14COOH CH3 ( CH 2 ) 1 4- (Palmitic acid)
CH3(CH2)16COOH CH3(CH2)16-
(Stearic acid)
CH3(CH2)7CH=CH(CH2)7COOH CH3(CH2)7,CH=CH(CH2)7-
(Oleic acid)
c. Phosphates (Formula III and IV)
Specific examples of useful organic phosphates include (C16H33O)2POOH and (C18H37O)2POOH. d. Other Anionic And Non-Polymeric Materials
Examples of still other useful anionic nonpolymeric materials include sodium dioctyl sulfosuccinate (i.e. commercially available as
Figure imgf000017_0001
"Aerosol OT" from American Cyanimide Company; fatty hydroxamic acids of the formula wherein R is described above;
Figure imgf000017_0002
C12H25SO3Na;
Figure imgf000017_0003
C18H37SH; and
C18H37SSC18H37
B. Cationic Membrane-Forming Materials
Useful cationic membrane-forming materials are believed to attach to tooth surfaces via a complexing interaction between the cationic portion of the material and the proteinaceous portion of the tooth.
1. Polymeric Cationic Membrane-Forming Materials Representative examples of useful polymeric cationic membrane-forming materials include polydimeryl polyamine, a polydimeryl polyamide which has (molecular weight of about 8000, amine number of about 120, available from General Mills Chemi cal Co.); polyethylene imine which has the repeating unit (CH2-CH2-NH)n (molecular weight of about 100,000, available from Dow Chemical Co.); 1,5-dimethyl hexamethrine bromide diazaundecamethylene polymethobromine hexademethrine bromide, a quaternary composition which has the repeating unit
Figure imgf000018_0001
(available from Aldrich Chemical Company as Polybrene); poly(N,N-dimethyl-3,5-dimethyenepiperidinium chloride) which has the repeating unit
Figure imgf000018_0002
(available from Aldrich Chemical Company); and "Protamine" a grouping of simple proteins wh i ch yield only amino acids, especially diamino acids, upon cleavage by enzymes or acids and is commercially available from Pfaltz and Bauer, Inc.
2. NonPolymeric Membrane-Forming Materials
Representative examples of useful nonpolymeric cationic membrane-forming materials may be represented by the formulae (Rf)mQdD (V)
(R8)mQdD (VI)
wherein Rf, Q, d and m are each as described above;
R8 is an alkyl radical containing from about 4 to 20 carbon atoms and D is a cationic radical.
Useful D radicals are cationic in character and complex with the proteinaceous materials of the teeth, Representative examples of useful D groups include -NHC2H4NHC2H4NH2 ; -NH2; -NHC2H4NH2;
and quaternary nitrogen
Figure imgf000019_0001
radicals such as
Cl Θ.
Figure imgf000019_0002
Specific examples of useful cationic materials of the formula V and VI type are set forth in Table III. The portions of each material attributable to each section of the generic formula are given.
Figure imgf000020_0001
Figure imgf000021_0001
C. Nonionic Membrane-Forming Materials
Useful nonionic membrane-forming materials are believed to attach to tooth surfaces by interacting with either or both of (i) the hydroxyl groups of the hydroxyapetite (i.e. Ca10(PO4)6(OH)2) or (ii) the hydroxyl groups present on the tooth surfaces from water or saliva present in the mouth. In any event, useful nonionic membrane-forming materials may be represented by the formulae
Organosiloxanes
[R9]b-Si[R10]4-b (vII)
Organotitanates [R11]x-R.-[OR12]4-x (VIII)
[R13]xTi[R12]4-x
In these formulae R9 is selected from the group consisting of hydrocarbon and fluorocarbon radicals or combination.s of hydrocarbon and fluorocarbon radicals which may contain up to about 25 carbon atoms. The R9 radicals may be aliphatic, aromatic or aliphatic and aromatic. Moreover they may contain heteroatoms selected from nitrogen, sulfur, oxygen, and silicone. Preferably no .two of said hetero atoms are adjacent and the oxygen atoms present are in the form of ether linkages. R10 i s an alkoxy radical containing from about 1 to 6, and preferably from about 1 to 3 carbon atoms. R11 is selected from the group consisting of alkoxy groups containing from about 1 to 10 carbon atoms and groups composed of hydrogen, carbon and oxygen wherein said groups contain from about 1 to 20 carbon atoms. R12 is selected from the group consisting of hydrocarbon radicals of about 1 to 20
, _ i , — v;1,-,. ■ carbon atoms which may be aliphatic, aromatic or aliphatic and aromatic and hydrocarbon radicals which contain nitrogen, phosphorous, oxygen and sulfur substitution. R13 is a heterocyclic group containing carbon oxygen and hydrogen. The value of b and x is 0, 1 , 2 or 3,
Specific examples of nonionic membrane-forming materials useful in the present invention are set forth in Table IV. The portions of each material attributable to each section of the generic formula are given.
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Other ingredients may be added to the dentifrice compositions of the present invention. Thus, for example, therapeutic agents, such as caries prophylactic agents, polishing agents, surfactants, flavoring and sweetening agents, thickening agents and humectants may be included using techniques which are known to the art.
When such other ingredients are employed with (i) anionic membrane-forming materials or (ii) cationic membrane-forming materials which have a calcium complexing moiety Z, the other ingredients must be substantially free of polyvalent metal (e,g, calcium, magnesium, etc.). These metals interact with these particular types of membrane-forming materials and prevent them from forming the barrier. Thus while a minor amount of such polyvalent metal may be present, the total amount present must not prevent the membrane forming material from interacting with the teeth. Preferably these compositions are free of polyvalent metal.
When such other ingredients are employed with (i) nonionic membrane-forming materials or (ii) with cationic membrane-forming materials which are free from calcium complexing moieties then such ingredients need not be substantially free from polyvalent metal,
With these factors in mind, then, suitable therapeutic agents, such as caries prophylactic agents, include soidum fluoride, stannous fluoride, potassium fluoride, hexylamine hydrofluoride, myristylamine hydrof1 uoride, betaine fluoride, glycine potassium fluoride, etc. A particularly preferred fluoride is sodium fluoride. The therapeutic agents may be applied previously to or simultaneously with the compositions of the invention. When applied simultaneously with said compositions, they are typically present in sufficient concentration so as to provide an available fluoride ion concentration of up to about 2% by weight, and preferably in the range of about 0.5-2% by weight, of the dentifrice composition. Additionally, it is preferred that the weight ratio of prophylactic ingredient to membraneforming material be in the range of about 1:0.5 to 1:5 and most preferably in the range of about 1:0.5 to 1:1.
Suitable polishing agents include abrasive materials such as nonionic polymers. Representative of such materials are water impervious crosslinked thermosetting resins (e.g. the condensation product of melamine and urea with formaldehyde), powdered polymethylmethacrylate, and powdered polyethylene. Preferably the polishing agent is not so abrasive so as to scratch or unduly abrade the tooth surface or the dentin, Rather it only cleans the tooth surface. The polishing agents may comprise up to 95% by weight of the dentifrice composition.
Surfactants useful in the present invention include, for example, nonionic surfactants which are known to the art. These materials typically comprise up to about 5% by weight of the dentifrice composition.
Flavoring and sweetening agents include, for example , the oils of wintergreen, peppermint, spearmint, sassafras and anise. Additionally small amounts of sweetening agents such as saccharin, dextrose, levulose, etc., may also be added to such compositions. These flavoring and sweetening agents may comprise up to about 5% by weight of the dentifrice composition.
Gelling or thickening agents include, for example, water-soluble salts of cellulose ethers such as sodium carboxy methyl cellulose and sodium carboxy methyl hydroxy ethyl cellulose, natural gums such as gum karaya, gum arabic, and gum tragacanth; and colloidal magnesium-aluminum silicate or finely divided silica. Such thickening agents may comprise up to about 5% by weight of the dentifrice composition.
When provided in solution, dentifrices of the present invention typically comprise a solution of the membrane-forming material in water or a mixture of water and an alcohol. Typically the alcohol is a lower alkanol (e.g. ethanol, propanol, etc.). These compositions are particularly useful as mouthwashes or rinses.
The present invention is further illustrated in the following examples.
Example 1 This example demonstrates that compositions of the invention form substantially continuous barriers on teeth which reduce the ellution of a previously applied fluoride treatment from said teeth. Separate bovine central incisors were used in the tests. A flat surface was provided on each of the teeth by first polishing them with 240 grit silicon carbide abrasive paper; and then with 400 grit silicon carbide abrasive paper. The teeth were then given a 5 minute soak with a 2% by weight solution of sodium fluoride (NaF) in de i on i zed water. One-half of the number of the teeth were then given a 5 minute soak with a 1% by weight solu tion of membrane forming material (C16H33O)2POOH, in deionized water. The other half of the number of the teeth was given no treatment with the membraneforming composition. All of the teeth were then tested for initial water contact angle, initial fluoride level, water contact angle after a 26 hour water soak and fluoride content after a 26 hour water soak.
The water contact angle was measured by placing a drop of water on the flat polished surface of the tooth using a Model #710 "Hamilton" microliter syringe. The drop was then photographed using a Polaroid ® camera which had a telescopic lens. The maximum perpendicular height (H) of the drop from the surface of the tooth to the top of the drop and the maximum length (L) of the drop in contact with the surface of the tooth were measured. These values were used to calculate the contact angle ⊝ by inserting them in the formula (tan ⊝ )/2 = 2H/L.
As the water contact angle increases, the water repellancy of the surfaces increases, High water contact angles (e.g. at least about 70°) are characteristic of the anionic membrane-forming materials. The fluoride content was measured with an electron microprobe Model 400 available from Materials Analysis Co, This test is a destructive test so that duplicate sets of teeth had to be tested in order to determine the initial fluoride content and the fluoride content after water soak. The results obtained are given in Table V.
Figure imgf000031_0001
Comparision of treatments A and B shows the dramatic increase in water contact angle caused by the addition of the membrane-forming material, (C16H33O)2POOH. Comparison of treatments C and D shows that, even after soaking the teeth for 26 hours in water, the membrane remains on the surface and that it substantially reduces ellution of the initial fluoride treatment.
Example 2
Bovine teeth were prepared and treated with NaF as described in Example 1. Certain of the teeth were then soaked for 5 minutes with compositions containing various membrane-forming materials. Each of the teeth were then soaked in separate 100 ml deionized water baths for 24 hours. The teeth were removed from the baths and each bath was then analyzed for fluoride ion content using a fluoride ion electrode. The results of these tests are set forth in Table VI.
Figure imgf000032_0001
Comparison of treatments A and B (which were run simultaneously) graphically illustrates the decrease in ellution of the NaF as a result of the membraneforming material. Comparison of treatments D and E with treatment C (which were run simultaneously but at a different time than tests A and B) further graphically illustrate the decrease in ellution of the NaF as a result of membrane-forming material.
Example 3 This example demonstrates the durability of the membrane. Bovine central incisors were prepared and the initial water contact angle measured as described in Example 1. The teeth were then soaked for 5 minutes with 0.1% by weight solutions of various membrane-forming materials in deionized water. The water contact angle was then measured after the teeth had been soaked in deionized water for 10 and 60 minutes and 24 hours. The results are given in Table VII.
Figure imgf000033_0001
The high water contact angles, even after 24 hours of water soaking, demonstrate that the membranes retain their integrity for extended periods of time. EXAMPLE 4
The procedures of Example 3 were repeated except that the teeth were given a fluoride treatment before being soaked for 5 minutes with a 0.1% by weight solution of membrane-forming material in deionized water. The fluoride treatment consisted of a 5 minute soak with an acidulated phosphate fluoride which comprised 40 grams (g) of NaF, 11.8ml of HF, 126 ml of H3PO4 and 1400 ml of deio¬nized water. The results of the water contact angle measurements are given in Table VIII.
Figure imgf000034_0001
This data demonstrates the durability of membranes formed from membrane-forming materials according to the invention.

Claims

Claims 1. A dentifrice composition which contains a waterdispersible membrane-forming material, which membrane-forming material, when applied to the surface of a tooth in an oral environment, attaches to said tooth and forms a substantially continuous hydrophobic barrier thereon.
2. A dentifrice composition according to claim 1 comprising at least about 0.005% by weight of said membrane-forming material.
3. A dentifrice composition according to claim 2 wherein said membrane-forming material is an ionic material.
4. A dentifrice composition according to claim 3 wherein said ionic material is anionic and has a formation constant in the range of about 0.5 to 8. 5. A dentifrice composition according to claim 4 wherein said membrane-forming material has the formula (Rf)mQdZ wherein Rf is a fluorinated, saturated aliphatic radical; Q is a linking radical through which Rf and Z are joined together; Z i.s an anionic radical; d is 0 or 1; and m is an integer of at least 1 provided that when d is 0, m is 1 or 2,
6. A dentifrice composition according to claim 5 wherein said membrane forming material is selected from the group consisting of
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000036_0003
Figure imgf000036_0004
Figure imgf000036_0005
Figure imgf000036_0006
Figure imgf000036_0007
Figure imgf000036_0008
Figure imgf000036_0009
C8F17COOH
C11F23COOH
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0003
Figure imgf000037_0004
Figure imgf000037_0005
C8F17SO3K
Figure imgf000037_0006
7. A dentifrice composition according to claim 4 wherein said membrane-forming material has the formula R1COOA wherein R1 is a hydrocarbon radical containing from about 6 to 24 carbon atoms, and wherein A is hydrogen or a cation. A dentifrice composition according to claim 7 wherein said membrane-forming material is selected from the group consisting of setaric, lauric, palmitic, myristic, oleic acids and water-soluble salts thereof.
A dentifrice composition according to claim 4 wherein said membrane-forming material has the formula (R2O)2POOH wherein R2 is an alkyl radical containing from about 10 to 20 carbon atoms
10 A dentifrice composition according to claim 4 wherein said membrane-forming material has the formula (R2O)PO(OH)2, wherein R2 is a hydro carb on group containing from about 10 to 20 carbon atoms.
11 A dentifrice composition according to claim 4 wherein said membrane-forming material is selected from the group consisting of:
Figure imgf000038_0001
C18H37SH; and C18H37SSC18H37.
12. A dentifrice composition according to claim 4 wherein said membrane-forming material has the formula wherein R2 is a hydrocarbon group
Figure imgf000038_0002
containing from about 10 to 20 carbon atoms. f3. A dentifrice composition according to claim 4 wherein said membrane-forming material is selected from the group consisting of polyacrylic acid; polymers having the repeating unit polymers having the repeating
opolymers of (i) acrylates
Figure imgf000039_0001
which contain pendant acid functionalities and (ii) polyvinylphosphate.
14. A dentifrice composition according to claim 3 wherein said ionic material is cationic.
15. A dentifrice composition according to claim 17 wherein said membrane-forming material is selected from formula (Rf)mQdD and (R8)mQdD wherein Rf is a fluorinated, saturated al i p hati c radical; Q is a linking radical through which Rf and D are joined together; D is a cationic radical; R8 is an alkyl radical containing from about 4 to 20 carbon atoms; d is 0 or 1; and m is an integer of at least
1 provided that when d is 0, m is 1 or 2.
16. A dentifrice composition according to claim 2 wherein said membrane-forming material is an organosi loxane having the formula [R9]b-Si[R10] 4- b wherein R 9 is selected from hydrocarbon and fluorocarbon radicals con ta i n i ng up to about 25 carbon atoms; R10 is an alkoxy radical containing from about 1 to 6 carbon atoms; and b is 0, 1 , 2 or 3.
17. A dentifrice composition according to claim 22, wherein said organosiloxane is selected from
C8F17CH2CHClSi(OCH3)3 C8F17CH2CHClSi(OCH2CH3)3
Figure imgf000040_0001
18. A dentifrice composition according to claim
2 wherein said membrane-forming material is an organotitanate having the formula [R11]xTi
[OR12]4-x wherein R11 is selected from alkoxy
groups containing from about 1 to 10 carbon atoms and groups composed of hydrogen, carbon and oxygen wherein said groups contain from about 1 to 20 carbon atoms; R12 is selected from hydrocarbon groups containing from about
10 to 20 carbon atoms and hydrocarbon groups having nitrogen, phosphorous, oxygen and sulfur substitution; and x is o, 1, 2 or 3.
19. A dentifrice composition according to calim 25 wherein said organotitanate is selected from
Figure imgf000041_0001
Figure imgf000041_0002
20. A dentifrice composition according to claim 2 wherein said membrane-forming material is an organotitanate having the formula [ R13]xTi[ R12] 4-x wherein R12 is selected from hydrocarbon groups containing from about 10 to 20 carbon atoms and hydrocarbon groups having nitrogen, phosphorous, oxygen and sulfur backbone sub stitution; R1 3 is a heterocyclic group containing carbon, oxygen and hydrogen; and x is 0, 1, 2 or 3.
21. A dentifrice composition according to claim 20 wherein said organotitanate is selected from
Figure imgf000042_0001
Figure imgf000042_0002
22. The method of inhibiting plaque formation by contacting teeth with an effective amount of a dentifrice composition which contains a waterdispersible membrane-forming material, which membrane-forming material, when applied to the surface of a tooth in an oral environment, attaches to said tooth and forms a substantially continuous hydrophobic barrier thereon.
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GB2126081A (en) * 1982-08-24 1984-03-21 Nat Res Dev Fluoride-containing compositions containing permselective polymers
EP0105982A1 (en) * 1980-07-25 1984-04-25 Johnson & Johnson Products Inc. Sulfonated vinylaromatic homopolymers and copolymers as dental plaque barriers
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EP0105984A1 (en) * 1980-07-25 1984-04-25 Johnson & Johnson Products Inc. Aromatic formaldehyde condensation polymers as dental plaque barriers
EP0267994A1 (en) * 1986-11-18 1988-05-25 National Research Laboratories The use of a metal complex for the manufacture of a composition for treating dental structures
EP0310753A2 (en) * 1987-10-08 1989-04-12 Colgate-Palmolive Company Antiplaque oral composition
EP0319884A1 (en) * 1987-12-08 1989-06-14 Colgate-Palmolive Company Dentifrice having decreased abrasivity
US4992260A (en) * 1989-07-26 1991-02-12 Forsyth Dental Infirmary For Children Method of inhibiting the formation of plaque

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US5370865A (en) 1992-05-15 1994-12-06 Kao Corporation Composition for use in oral cavity

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IT7852477A0 (en) 1978-12-28
EP0007913A4 (en) 1981-09-21

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