HUP9903532A2 - Dentifrice composition containing polyphosphate and fluoride as active ingredient in two detached compositions - Google Patents

Abstract

An oral formulation contained in a physically separated compartments of a dentrifice dispenser comprises: (a) a first composition (total water content of 5-20%) comprising: (i) linear polyphosphates having an average chain length of \- 4; (ii) buffering agent; and (iii) 50-99% of \- 1 aqueous carrier; and (b) a second composition comprising: (i) a soluble fluoride source capable of providing 50-3500 ppm of free fluoride ions; (ii) buffering agent; and (iii) 70-99% of aqueous carrier(s). Also claimed is an oral formulation contained in a physically separated compartments of a dentrifice dispenser comprising: (a) a first composition (water content of 7-14%) comprising: (i) 3-10% of linear polyphosphates having an average chain length of \- 6; (ii) 0.5-40% of an alkali metal bicarbonate salt; (iii) 0.1-30% of an alkali metal carbonate salt; (iv) 0.01-5% of calcium peroxide; (v) 10-70% of an abrasive polishing material, and (vi) 40-87% of \- 1 aqueous carrier; and (b) a second composition comprising: (i) NaF to provide 50-3500 ppm free fluoride ions; (ii) 1.5-10% of a pyrophosphate salt; (iii) 10-50 silica, and (iv) 40-89% of \- 1 aqueous carrier. The soluble fluoride source of the second composition is NaF. The polyphosphates of the first composition has a chain length of \- 6 and is in an amount of 0.5-20%. The buffering agent of the second composition is a pyrophosphate salt and the first and second compositions contain 0.1-30% of buffering agent. The first composition further comprises 0.01-10% of a peroxide source. The total water content of the first composition is 7-14%. The polyphosphates of the first composition is selected from linear glassy polyphosphates of formula XO(XPO3)nX (X = Na or K and n = 6-21). The first composition is a paste and the second is a gel.

Description

H-1062 Budawsi. Andrassy street 113.

Telephone: 34-24-950. Fax: 3^24-323

Polyphosphate and fluoride-containing dentifrices Q-sJr

HEAD

68.070/BE tartar is a deposit that forms on the surface of the tooth, at the edge of the gum.

Supragingival calculus appears in areas close to the salivary duct openings, i.e. on the lingual surfaces of the lower anterior teeth, and the buccal surfaces of the upper first and second molars, as well as on the distal surfaces of the posterior molars.

Mature tartar consists of an inorganic part, which is largely calcium arranged in a hydroxyapatite crystal lattice structure similar to bone, enamel and dentin.

-phosphate. An organic part is also present and consists of exfoliated epithelial cells, leukocytes, salivary sediment, food debris and various microorganisms.

When mature tartar develops, it will appear white or yellowish unless an external agent colors or discolors it. This is not aesthetically desirable.

Periodic mechanical removal of tartar by the dentist is a routine procedure in the dental office. Various chemical and biological agents have been proposed to delay the formation of tartar or to remove tartar once it has developed. Pyrophosphate salts are chemical agents known to delay the formation of tartar, as described, for example, in U.S. Patent No. 4,999,184, which is incorporated herein by reference in its entirety.

In addition to pyrophosphate salts, other polyphosphates are known to retard tartar formation. U.S. Patent No. 4,627,977 discloses the use of a linear, molecularly dehydrated polyphosphate salt in combination with two additional components that inhibit enzymatic hydrolysis of the polyphosphate. U.S. Patent No. 4,247,526 discloses the use of a pharmaceutically acceptable condensed phosphate salt in addition to dicalcium phosphate dihydrate and trimagnesium phosphate. Vitreous polyphosphates have also been known to react with ionic fluoride, but only at extreme temperatures (between 800°C and 900°C). Although oral care products containing polyphosphates are known, there is a continuing need to develop improved products.

The present inventors have found that certain polyphosphates, particularly linear polyphosphates with an average chain length greater than 4, react significantly with ionic fluoride in oral formulations at room temperature to form monofluorophosphate while also altering the pH of the formulation. This reaction represents the ability of the oral formulation to provide stable ionic fluoride and polyphosphate to oral surfaces.

Therefore, it is an object of the invention to provide stable oral formulations comprising two dentifrice compositions, the two dentifrice compositions being physically separated compartments, which provide maximum fluoride and polyphosphate delivery to the oral cavity. The first dentifrice composition comprises a polyphosphate and a buffering agent, while the second composition comprises a soluble fluoride ion source and a buffering agent. It is also an object of the invention to provide a polyphosphate

68.070/BE to provide a first dentifrice composition comprising phosphate, an alkali metal bicarbonate salt, an alkali metal carbonate salt, calcium peroxide and an abrasive, and a second composition comprising sodium fluoride, a mixture of pyrophosphate salts and silicon dioxide. It is also an object of the invention to provide dentifrice compositions having improved anti-tartar activity through the use of polyphosphates.

These and other objects of the invention will become readily apparent from the following detailed description.

All percentages and ratios herein are by weight of the specialty dentifrice composition and not the entire oral formulation unless otherwise stated. All measurements are made at 25°C unless otherwise stated.

The present invention provides an oral formulation in physically separated compartments of a dentifrice dispenser device comprising a first dentifrice composition comprising an effective amount of one or more linear polyphosphates having an average chain length of about 4 or more, an effective amount of a buffering agent, from about 50% to about 99% of one or more aqueous carriers, wherein the total water content of the first dentifrice composition is from about 5% to about 20%, and a second dentifrice composition comprising a soluble fluoride source capable of providing from about 50 to about 3,500 parts per million (ppm) of free fluoride ion, an effective amount of a buffering agent, and from about 70% to about 99% of one or more aqueous carriers.

68.070/BE contains one or more aqueous carriers.

The oral formulation of the invention may be in the form of a toothpaste or a dentifrice. The term "dentifrice" as used herein means a paste, gel or liquid composition, unless otherwise indicated. The dentifrice composition may be in any desired form, such as deep striped, surface striped, multilayered, with the gel surrounding the paste, or any combination thereof. Each dentifrice composition is contained in a physically separate compartment of a dispenser and is administered in parallel with each other.

The term "dispenser", as used herein, means any pump, tube or container suitable for dispensing toothpaste.

The term "oral formulation" as used herein means any dentifrice intended to be applied to the surfaces of the mouth. An oral formulation is a combination of two or more dentifrice compositions. An oral formulation is a product that is not intentionally swallowed in ordinary use for the systemic administration of a particular therapeutic agent, but rather is retained in the oral cavity for a period of time sufficient to contact substantially all tooth surfaces and/or oral tissues to exert oral activity.

The term "aqueous carrier", as used herein, means any safe and effective material suitable for use in the compositions of the invention. Such materials include abrasives, peroxide sources, alkali metal hydrogen

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-carbonate salts, thickeners, wetting agents, water, surfactants, titanium dioxide, flavoring systems, sweeteners, xylitol, colorants and mixtures thereof.

The present compositions contain essential components as well as optional components. The essential and optional components of the compositions of the present invention are described below.

Polyphosphate source

The invention introduces a source of polyphosphate into the first dentifrice composition. A polyphosphate is generally understood to comprise two or more phosphate molecules arranged primarily in a linear configuration, although some cyclic derivatives may also be present. Although pyrophosphates are polyphosphates, the desired polyphosphates are those which comprise four or more phosphate molecules. The pyrophosphates are discussed separately. Desirable polyphosphate salts include, but are not limited to, tetrapolyphosphate and hexametaphosphate. Polyphosphates larger than tetrapolyphosphate are typically amorphous glassy materials. Preferred according to the invention are

Linear “glassy polyphosphates” with the general formula XO(XPO ₃ ) _n X, in which the formula

X represents a sodium or potassium atom;

The average value of n is between about 6 and about 125. Preferred are polyphosphates manufactured by EMC Corporation and are commercially known as Sodaphos (n ≤ 6), Hexaphos (n ≤ 13) and Glass H (n ≤ 21). These polyphosphates can be used

68.070/BE cases alone or in combination.

A more detailed description of polyphosphate sources is found in Kirk and Othmer's Encyclopedia of Chemical Technology, 4th Edition, Volume 18 (Wiley Interscience Publishers, 1996), which is hereby incorporated by reference in its entirety, together with the references used by Kirk and Othmer. The polyphosphate source comprises from about 0.5 to about 20%, preferably from about 4 to about 15%, more preferably from about 6 to about 10%, most preferably from about 7 to about 9%, by weight of the dentifrice composition.

Fluoride ion source

The second dentifrice composition of the invention comprises a soluble fluoride source capable of providing free fluoride ion. Preferred soluble fluoride ion sources include sodium fluoride, stannous fluoride, indium fluoride, and sodium monofluorophosphate. Sodium fluoride is the most preferred soluble fluoride ion source. Norris et al., U.S. Patent No. 2,946,725, Widder et al., U.S. Patent No. 3,678,154, and others disclose such fluoride ion sources. Both patents are incorporated herein by reference in their entirety.

These compositions contain a fluoride ion source capable of providing between about 50 and about 3,500 parts per million (ppm), preferably between about 500 and about 3,000 ppm, of free fluoride ion.

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Buffering agent

Each of the compositions of the invention comprises a buffering agent. Buffering agents, as used herein, are agents which can be used to adjust the pH of the compositions to between about 6.5 and about 10. Such agents include alkali metal hydroxides, carbonates, sesquicarbonates, borates, silicates, phosphates, imidazole and mixtures thereof. Specific buffering agents include sodium dihydrogen phosphate, sodium phosphate, sodium hydroxide, potassium hydroxide, alkali metal carbonate salts, sodium carbonate, imidazole, pyrophosphate salts, citric acid and sodium citrate. Buffering agents are used in an amount of from about 0.1 to about 30%, preferably from about 1 to about 10%, more preferably from about 1.5 to about 3%, by weight of the composition.

Pyrophosphate salts

Pyrophosphate salts are preferred buffering agents for the second dentifrice composition. Pyrophosphate salts useful in the present compositions include dialkali metal pyrophosphate salts, tetraalkali metal pyrophosphate salts, and mixtures thereof. Disodium dihydrogen pyrophosphate (Na ₂ H ₂ P ₂ O ₇ ), tetrasodium pyrophosphate (Na ₄ P ₂ O ₇ ), and tetrapotassium pyrophosphate (K ₄ P ₂ O ₇ ), in their anhydrous and hydrated forms, are preferred. In the compositions of the present invention, the pyrophosphate salts may be present in one of three ways: predominantly dissolved, predominantly undissolved, or a mixture of dissolved and undissolved pyrophosphate.

68.070/BE in .

Compositions comprising predominantly pyrophosphate are compositions in which at least one source of pyrophosphate ion is present in an amount sufficient to provide at least about 1% free pyrophosphate ion. The amount of free pyrophosphate ion may be from about 1 to about 15% by weight of the composition, preferably from about 1.5 to about 10%, most preferably from about 2 to about 6%. The free pyrophosphate ion may be present in various protonation states depending on the pH of the composition.

Compositions containing predominantly insoluble pyrophosphate refer to compositions which contain no more than 20% of the total pyrophosphate salt in the composition dissolved, preferably no more than 10% of the total pyrophosphate salt dissolved. In these compositions, the tetrasodium pyrophosphate may be in the form of the anhydrous salt or the decahydrate, or any other form which is stable in the solid form in dentifrice compositions. The salt is present in the form of solid particles, which may be in its crystalline and/or amorphous state, wherein the particle size of the salt is preferably small enough to be aesthetically acceptable and readily soluble during use. The amount of pyrophosphate salt useful in the preparation of such compositions is an effective amount of any tartar-dissolving agent, and is generally present in an amount of from about 1.5 to about 15%, preferably from about 2 to about 10%, most preferably from about 2.5 to about 8% by weight of the composition. Some or all of the tetrasodium pyrophosphate may be undissolved in the product and may be present in the form of tetrasodium pyrophosphate particles. The pyrophosphate ions may be present in various protonated states (e.g., HPp ₇ ³ ') depending on the pH of the composition and if some of the tetrasodium pyrophosphate is dissolved.

The compositions may also contain a mixture of dissolved and undissolved pyrophosphate salts. Any of the above-mentioned pyrophosphate salts may be used.

A more detailed description of pyrophosphate salts can be found in Kirk and Othmer's Encyclopedia of Chemical Technology, 3rd edition, volume 17 (Wiley Interscience Publishers, 1982), which is hereby incorporated by reference in its entirety, together with the references used by Kirk and Othmer.

Agents that may be used in place of or in combination with pyrophosphate salts include those known to be effective in reducing calcium phosphate mineral deposition associated with dental calculus formation. Such agents include synthetic anionic polymers [including polyacrylates and maleic anhydride or copolymers of maleic acid and methyl vinyl ether (e.g., gantrez), such as those disclosed in U.S. Patent No. 4,627,977, the disclosure of which is incorporated herein by reference in its entirety; as well as polyaminopropanesulfonic acid (AMPS)], zinc citrate trihydrate, diphosphonates (e.g., EHDP; AHP), polypeptides (e.g., polyaspartic acid and polyglutaric acid), and mixtures thereof.

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Aqueous media

In preparing these compositions, it is desirable to add one or more aqueous carriers to the compositions. Such materials are well known in the art and can be readily selected by one skilled in the art based on the desired physical and aesthetic properties of the compositions to be prepared. The aqueous carriers typically comprise from about 40 to about 99%, preferably from about 70 to about 98%, more preferably from about 90 to about 95%, by weight of the dentifrice composition.

Abrasive materials

An abrasive material may also be included in the dentifrice compositions. The abrasive material contemplated for use in the compositions of the present invention may be any material that does not excessively abrade the dentin. Typical abrasive materials include silicas, including gels and precipitates; aluminas; phosphates, including orthophosphates, polymetaphosphates, and pyrophosphates; and mixtures thereof. Specific examples include dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate, insoluble sodium polymetaphosphate, hydrated aluminas, beta-calcium pyrophosphate, calcium carbonate, and resinous abrasives such as particulate condensation products of urea and formaldehyde, among others; as disclosed in U.S. Patent No. 3,070,510 to Cooley et al., which is incorporated herein by reference.

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Mixtures of coatings can also be used.

Various types of silica dental abrasives are advantageous due to their unique benefits of exceptionally good cleaning and grinding performance on the tooth without excessive abrasion of the enamel and dentin. The silica abrasives and other abrasives used herein generally have an average particle size of between about 0.1 and 30 pm, preferably between about 5 and about 15 pm. The abrasive can be precipitated silica or silica gel, such as the silica xerogels described in U.S. Patent No. 3,538,230 to Pader et al. and U.S. Patent No. 3,862,307 to DiGiulio, which are incorporated herein by reference. Preferred are silica xerogels sold under the trade name "Syloid" by W.R. Grace and Company, Davison Chemical Division. Precipitated silica materials such as those sold under the trade name "Zeodent" by J.M. Huber Corporation, especially those under the trade name "Zeodent 119", are also preferred. A more detailed description of the types of silica abrasive silicas useful in the toothpastes of the invention is found in U.S. Patent No. 4,340,583, which is incorporated herein by reference. The silica abrasive materials described in U.S. Patent Applications Nos. 08/434,147 and 08/434,149 are also incorporated herein by reference. The abrasive in the toothpaste compositions described herein will generally be present at a concentration of from about 6% to about 70% by weight of the composition. is present.

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Toothpastes preferably contain an abrasive material in an amount of from about 10 to about 50% by weight of the dentifrice composition.

Peroxide source

The invention may comprise a peroxide source in the first dentifrice composition. The peroxide source is selected from the group consisting of hydrogen peroxide, calcium peroxide, carbamide peroxide and mixtures thereof. The preferred peroxide source is calcium peroxide. The amounts given below are the amount of peroxide raw material, although the peroxide source may comprise other ingredients in addition to the peroxide raw material. The composition may comprise an amount of peroxide source of from about 0.01 to about 10%, preferably from about 0.1 to about 5%, more preferably from about 0.2 to about 3%, most preferably from about 0.3 to about 0.8%, by weight of the dentifrice composition.

Alkali metal bicarbonate salt

A. The compositions of the invention may also contain an alkali metal bicarbonate salt. If present, this bicarbonate salt is generally present in the first dentifrice composition. Alkali metal bicarbonate salts are water soluble and, unless stabilized, tend to release carbon dioxide in an aqueous system. The preferred alkali metal bicarbonate salt is sodium bicarbonate, also known as baking powder. The alkali metal bicarbonate salt also serves as a buffering agent. The present composition may contain from about 0.5 to about 50%, preferably from about 0.5 to about

68.070/BE%, more preferably from about 2 to about 20%, most preferably from about 5 to about 18%, of an alkali metal bicarbonate salt, based on the weight of the dentifrice composition.

Other aqueous media

The toothpaste compositions of the invention typically contain thickeners or binders to provide the desired consistency. Preferred thickeners include carboxyvinyl polymers, carrageenan, (hydroxyethyl) cellulose, and water-soluble salts of cellulose ethers, such as (carboxymethyl) cellulose sodium and (hydroxyethyl) cellulose sodium. Natural gums, such as karaya gum, xanthan gum, gum arabic, and gum tragacanth, may also be used. Colloidal magnesium aluminum silicate or finely divided silica may be used as part of the thickening agent to further improve the texture. The thickening agents may be used in an amount of from about 0.1 to about 15% by weight of the dentifrice compositions.

Another desirable component of the compositions herein is a humectant. The humectant serves to protect the toothpaste compositions from hardening upon exposure to air, and some humectants may also impart a desirable sweet taste to the toothpaste compositions. Suitable humectants for use in the present invention include glycerin, sorbitol, polyethylene glycol, propylene glycol, and other edible polyhydroxy alcohols. The humectant generally comprises from about 0 to 70% by weight of the composition, preferably from about 15 to 55%.

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The water used in the preparation of commercially suitable oral compositions is preferably low in ionic content and free from organic impurities. In the second dentifrice composition, the water generally comprises from about 5 to about 70%, preferably from about 10 to about 50%, by weight of the composition. The first dentifrice composition contains less water, generally comprising from about 5 to about 20%, preferably from about 7 to about 14%, more preferably from about 7 to about 12%, by weight of the dentifrice composition. The amount of water includes added free water and that which is incorporated with other materials such as sorbitol, silica, surfactant solutions and/or colorant solutions.

These compositions may also contain surfactants, commonly referred to as foaming agents. Suitable surfactants are those which are acceptably stable and foam over a wide pH range. The surfactant may be anionic, nonionic, amphoteric, zwitterionic, cationic or mixtures thereof. Anionic surfactants useful herein include water-soluble salts of alkyl sulfates having from 8 to 20 carbon atoms in the alkyl group (such as sodium alkyl sulfates) and water-soluble salts of sulfonated monoglycerides of fatty acids having from 8 to 20 carbon atoms. Sodium lauryl sulfate and sodium coco monoglyceride sulfonates are examples of this type of anionic surfactant. Other suitable anionic surfactants are sarcosinates, such as sodium lauroyl sarcosinate;

68.070/BE taurinates, sodium lauryl sulfoacetate, sodium lauroyl isethionate, sodium laureth carboxylate and sodium dodecylbenzenesulfonate. Mixtures of anionic surfactants may also be used. Agricola et al., U.S. Patent No. 3,959,458, discloses many suitable anionic surfactants, which are incorporated herein by reference in their entirety. The nonionic surfactants useful in the compositions of the present invention may be broadly defined as those formed by the condensation of alkylene oxide groups of hydrophilic nature with organic hydrophobic compounds, which may be aliphatic or alkyl-aromatic in nature. Suitable nonionic surfactants include poloxamers (sold under the trade name Pluronic), poly(oxyethylene), poly(oxyethylene) sorbitan esters (sold under the trade name Tweens), fatty alcohol ethoxylates, poly(ethylene oxide) condensates of alkyl phenols, products derived from the condensation of ethylene oxide with the reaction product of propylene oxide and ethylenediamine, condensates of ethylene oxide with aliphatic alcohols, long chain tertiary amine oxides, long chain tertiary phosphine oxides, long chain dialkyl sulfoxides, and mixtures of such materials. Amphoteric surfactants useful in the present invention can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic group may be straight or branched chain, and in which one of the aliphatic substituents contains from about 8 to about 18 carbon atoms, and one of the substituents contains an anionic water-solubilizing group, a carboxy, sulfonate, sulfate, phos

68.070/BE fatty or phosphonate group. Other suitable amphoteric surfactants are betaines, especially cocamidopropyl betaine. Mixtures of surfactants may also be used. Many of these suitable nonionic and amphoteric surfactants are described in U.S. Patent No. 4,051,234 to Gieske et al., which is incorporated herein by reference in its entirety. The composition of the invention typically comprises one or more surfactants, each present in an amount of from about 0.25 to about 12%, preferably from about 0.5 to about 8%, most preferably from about 1 to about 6%, by weight of the composition.

Titanium dioxide may also be added to the composition. Titanium dioxide is a white powder that provides opacity to the composition. Titanium dioxide is generally present in an amount of from about 0.25 to about 5% by weight of the composition.

Dyes may also be added to the composition of the invention. The dye may be in the form of an aqueous solution, preferably a 1% dye in aqueous solution. Dye solutions generally comprise from about 0.01 to about 5% by weight of the composition.

A flavoring system may also be added to the compositions. Suitable flavoring components include wintergreen oil, peppermint oil, spearmint oil, clove bud oil, menthol, anethole, methyl salicylate, eucalyptol, cassia, 1-menthyl acetate, sage oil, eugenol, parsley oil, oxanone, alpha-irizone, marjoram oil, lemon oil, orange oil, propenyl guaethol, oil of celandine, vanillin,

68.070/BE ethyl vanillin, heliotropine, 4-cis-heptenal, diacetyl, methyl para-(tert-butyl)phenylacetate and mixtures thereof. Cooling agents may also be part of the flavoring system. Preferred cooling agents for the compositions are paramenthane carboxamide agents, such as N-ethyl-p-menthane-3-carboxamide, commercially known as "WS-3", and mixtures thereof. The flavoring system is generally used in the composition in an amount of from about 0.001 to about 5% by weight of the composition.

The invention may also include xylitol. Xylitol is a sugar alcohol used as a sweetener and humectant. Xylitol may also have therapeutic effects, such as antibacterial and anti-caries effects. The compositions typically contain xylitol in an amount of from about 0.01 to about 25%, preferably from about 3 to about 15%, more preferably from about 5 to about 12%, most preferably from about 9 to about 11%, by weight of the total composition. Alternatively, when xylitol is used as a sweetener, it may be present at lower levels, such as from about 0.005 to about 5% by weight of the dentifrice composition.

Sweetening agents may also be added to the compositions. These include saccharin, D-glucose, sucrose, lactose, maltose, levulose, L-aspartyl-L-phenylalanine methyl ester (aspartame), sodium cyclamate, D-tryptophan, dihydrochalcones, acesulfame, and mixtures thereof. Various colorants may also be included in the compositions of the invention. Sweetening and coloring agents are generally used in toothpastes in amounts ranging from about 0.005 to about 5%.

68.070/BE is used in proportion to the weight of the composition.

Other agents may also be used in the invention, such as antimicrobial agents. Such agents include water-insoluble non-cationic antimicrobial agents, such as halogenated diphenyl ethers, phenolic compounds, including phenol and its homologues, mono- and polyalkyl and aromatic halogenated phenols, resorcinol and its derivatives, biphenolic compounds, and halogenated salicylanilides, benzoic acid esters, and halogenated carbanilides. Water-soluble antimicrobial agents include, but are not limited to, quaternary ammonium salts and bisguanidine salts. Triclosan monophosphate is another water-soluble antimicrobial agent. Quaternary ammonium agents include those in which one or two of the substituents on the quaternary nitrogen have a carbon chain (typically an alkyl group) of about 8 to 20, typically 10 to 18, carbon atoms, while the other substituents (typically an alkyl or benzyl group) have a smaller number of carbon atoms, typically methyl or ethyl. Dodecyltrimethylammonium bromide, tetradecylpyridinium chloride, domiphen bromide, N-tetradecyl-4-ethylpyridinium chloride, [dodecyldimethyl-(2-phenoxyethyl)]-ammonium bromide, (benzyldimethylstearyl)-ammonium chloride, hexadecylpyridinium chloride, quaternized 5-amino-1,3-bis(2-ethylhexyl)-5-methylhexahydropyrimidine, benzalkonium chloride, benzethonium chloride and methylbenzethonium chloride are typical examples of quaternary ammonium antimicrobial agents. Other such compounds are bis[4-(R-amino)-1-pyridinium]-alkanes, such as those disclosed in U.S. Patent No. 4,206,215, which is incorporated herein by reference.

68.070/BE. Stannous salts such as stannous pyrophosphate and stannous gluconate and other antimicrobial agents such as copper diglycinate, copper glycinate, zinc citrate and zinc lactate may also be included in the composition. Enzymes such as endoglucosidase, papain, dextranase, mutanase and mixtures thereof may also be used. Such agents are described in U.S. Patents 2,946,725 and 4,051,234, which are incorporated herein by reference. Specific antimicrobial agents include chlorhexidine, triclosan, triclosan monophosphate, and flavoring oils such as thymol. Triclosan and other agents of this type are described in U.S. Patent Nos. 5,015,466 and 4,894,220, which are incorporated herein by reference. The water-insoluble antimicrobial agents, water-soluble agents, and enzymes may be present in either the first or second dentifrice composition. Quaternary ammonium agents, stannous salts, and substituted guanidines are preferably present in the second dentifrice composition. These agents are present in an amount of from about 0.01 to about 1.5% by weight of the dentifrice composition.

The first and second dentifrice compositions are physically separated from each other in a dentifrice dispenser. The dentifrice compositions may be pastes, gels, or any configuration or combination thereof. It is preferred that the first dentifrice composition be a paste and the second dentifrice composition be a gel. The dispenser may be a tube, a pump, or any other container suitable for dispensing the toothpaste. Suitable dual-compartment packaging methods for this purpose are described in US Pat. Nos. 4,528,180;

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U.S. Patent Nos. 4,687,663 and 4,849,213, which are incorporated herein by reference in their entirety. The dispensing device dispenses approximately equal amounts of the dentifrice composition through an orifice. The compositions may be mixed together after dispensing. Alternatively, the oral formulation may be provided in a kit comprising two separate dispensing devices, each of which is used to deliver two dentifrice compositions to be used together.

Method of treatment

In addition to the compositions of the invention, the invention also provides a method for reducing the formation of tartar on tooth enamel. The method comprises contacting tooth enamel surfaces in the mouth with the oral compositions of the invention.

Examples and methods of preparation

The following examples further describe and illustrate embodiments within the scope of the invention. These examples are presented for illustrative purposes only and are not to be construed as limiting the scope of the invention, as many variations thereof are possible without departing from the spirit and scope of the invention.

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Example 1:

First toothpaste

Components % by weight (Carboxymethyl)cellulose 0.60 Water 7.00 flavoring agent 1.00 Glycerin 43.2 Poloxamer 407 5.00 Propylene glycol 5.00 Sodium alkH sulfate' 4.00 Silicon dioxide 20.0 Sodium carbonate 2.00 Saccharin sodium 0.50 Titanium dioxide 0.50 Xanthan gum 0.20 Glass H Polyphosphate 7.00 Poly(ethylene glycol) 3.00 Calcium peroxide 1.00 ^Ia) 27.9% solution Second dentifrice Components % by weight Color 0.30 Water 33.00 Flavoring agent 0.40 Glycerin 44,514 Poloxamer 407 21.00

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Sodium fluoride0.486

Saccharin sodium0.30

Example 2:

First dentifrice Ingredients % by weight (Carboxymethyl) cellulose 0.60

Water7.00

Flavoring1.00

Glycerin26.8

Poloxamer 4075.00

Propylene glycol5.00

Sodium alkyl sulfate ^(at '4.00

Silicon dioxide22.0

Sodium bicarbonate15.00

Sodium carbonate2.00

Saccharin sodium0.50

Titanium dioxide0.50

Xanthan gum0.20

Glass H Polyphosphate7.00

Poly(ethylene glycol)3.00

Calcium peroxide0.40 ^<a) 27.9% solution

Second dentifrice composition Ingredients % by weight

Carbomer0.200

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23 ·· ···· · · · · · Color 0.400 Water 25.1 Flavoring agent 0.90 Glycerin 9.00 Poly(ethylene glycol) 3.00 Sodium alkyl sulfate 4.00 Silicon dioxide 22.5 Saccharin sodium 0.50 Serbit 29,594 Sodium diphosphate acid 0.50 Tetrasodium diphosphate 3.22 Xanthan gum 0.60 Sodium fluoride 0.486

Example 3:

First toothpaste

Components % by weight (Carboxymethyl)cellulose 0.60 Water 7.00 Flavoring agent 1.00 Glycerin 24.2 Poloxamer 407 5.00 Propylene glycol 5.00 Sodium alkyl sulfate ^<a) 4.00 Silicon dioxide 22.0 Sodium bicarbonate 15, 0 Sodium carbonate 2.00

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Saccharin sodium0.50

Titanium dioxide0.50

Xanthan gum0.20

Sodaphos Polyphosphate7.00

Poly(ethylene glycol)3.00

Calcium peroxide3.00

Second dentifrice composition Ingredients % by weight

Carbomer0.200

Dye0.400

Water25.1 flavoring0.90

Glycerin9.00

Poly(ethylene glycol)3.00

Sodium alkyl sulfate ^la) 4.00

Silicon dioxide22.5

Saccharin sodium0.50

Sorbitol 29,644

Acid sodium diphosphate0.75

Tetrasodium diphosphate2.92

Xanthan gum0.60

Sodium fluoride0.486 ^<al 27.9% solution

Example 4:

First toothpaste

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Ingredients (Carboxymethyl)cellulose

Water

Flavoring agent

Glycerol

Poloxamer 407

Propylene glycol

Sodium alkyl sulfate ^1.11

Silicon dioxide

Sodium bicarbonate

Sodium carbonate

Saccharin sodium

Titanium dioxide

Xanthan gum

Glass H Polyphosphate

Poly(ethylene glycol)

Second tooth cleaning product

Components

Carbomer

Dye

Water flavoring

Glycerol

Poly(ethylene glycol)

Sodium alkyl sulfate ^(a>

Silicon dioxide

Saccharin sodium weight %

0.60

7.00

1.00

27.2

5.00

5.00

4.00

22.0

15.0

2.00

0.50

0.50

0.20

7.00

3.00% by weight

0.200

0.400

22,834

0.90

9.00

3.00

4.00

22.5

0.50

68.070/BE

Sorbitol 24 _y 00

Acid sodium diphosphate2.05

Xanthan gum0.60

Sodium fluoride0.486

Triclosan0.60

Tetrapotassium diphosphate ^<b| 6.830

27.9% solution 60% solution

Example 5: First dentifrice composition Ingredients % by weight (Carboxymethyl)cellulose 0.60

Water7.00

Flavoring1.00

Glycerin31.2

Poloxamer 4075.00

Propylene glycol5.00

Sodium alkyl sulfate ^<al 4.00

Silicon dioxide27.0

Sodium bicarbonate5.0

Sodium carbonate2.00

Saccharin sodium0.50

Titanium dioxide0.50

Xanthan gum0.20

Glass H Polyphosphate7.00

68.070/BE

Poly(ethylene glycol)3.00

Calcium peroxide1.00

Second dentifrice composition Ingredients % by weight

Carbomer0.200

Dye0.400

Water25.1

Flavoring0.90

Glycerin9.00

Poly(ethylene glycol)3.00

Sodium alkyl sulfate ^(a> 4.00

Silicon dioxide22.5

Saccharin sodium0.50

Sorbitol 33,314

Xanthan gum0.60

Sodium fluoride0.486 ^(al 27, 9% solution

The first dentifrice compositions are prepared as follows: Water and saccharin are placed in a mixing vessel. Thickening agents, such as (carboxymethyl) cellulose and xanthan gum, are dispersed in glycerin. This glycerin mixture of dispersed thickening agents is placed in the mixing vessel, mixed well and heated to at least 40°C. The flavoring agent is mixed into the poloxamer and added to the former mixture. Then the polyethylene glycol, propylene glycol and sodium carbonate are added. Mix well. Then the titanium dioxide is added.

68.0WBE and the silica. After mixing, add the sodium bicarbonate (if used) and the sodium alkyl sulfate. Finally, add the polyphosphate and calcium peroxide (if used). Continue mixing the mixture until it becomes homogeneous.

The second dentifrice compositions are prepared using standard methods used in the preparation of dentifrice compositions.

68.070/BE

Claims (10)

PATENT CLAIMS 1. An oral formulation in physically separated compartments of a dentifrice dispensing device, comprising: a) a first dentifrice composition comprising the following components: i) an effective amount of one or more linear polyphosphates having an average chain length of at least 4; ii) an effective amount of a buffering agent; iii) from 50% to 99% of one or more aqueous carriers; wherein the total water content of this first dentifrice composition is from 5% to 20%; and b) a second dentifrice composition comprising the following components: i) a soluble fluoride source capable of providing free fluoride ion in an amount ranging from 50 parts per million (ppm) to 3,500 parts per million; ii) an effective amount of a buffering agent; and iii) from 70% to 99% of one or more aqueous carriers. 2. The oral formulation of claim 1, wherein the soluble fluoride source of the second dentifrice composition is sodium fluoride. 3. An oral formulation according to claim 1 or 2, wherein the one or more polyphosphates of the first dentifrice composition have a chain length of at least 6 and are present in an amount of from 0.5% to 20%. 4. An oral formulation according to any one of the preceding claims, wherein the second dentifrice composition buffering agent is not a pyrophosphate salt. An oral formulation according to any one of the preceding claims, wherein the buffering agent of the first and second dentifrice compositions is present in an amount of from 0.1% to 30%. An oral formulation according to any one of the preceding claims, wherein the first dentifrice composition further comprises a peroxide source in an amount of from 0.01% to 10%. An oral formulation according to any one of the preceding claims, wherein the total water content of the first dentifrice composition is from 7% to 14%. 8. An oral formulation in physically separated compartments of a dentifrice dispensing device, comprising: a) a first dentifrice composition comprising the following components: (i) one or more linear polyphosphates with an average chain length of at least 6 in an amount ranging from 3 % to 10 %; ii) from 0.5% to 40% of an alkali metal bicarbonate salt; iii) an alkali metal carbonate salt in an amount ranging from 0.1% to 30%; (iv) calcium peroxide in an amount ranging from 0.01% to 5%; v) from 10% to 70% of an abrasive material; and vi) from 40% to 87% of one or more aqueous carriers; wherein the total water content of the first dentifrice composition ranges from 7% to 14%; and 68.070/BE b) a second dentifrice composition comprising the following components: i) a sodium fluoride source capable of providing from 50 parts per million (ppm) to 3,500 parts per million of free fluoride ion; (ii) from 1.5% to 10% of a pyrophosphate salt; (iii) from 10% to 50% silica; and (iv) from 40% to 89% one or more aqueous carriers. 9. An oral formulation according to any one of the preceding claims, wherein each of the one or more polyphosphates in the first dentifrice composition is XO(XPO ₃ ) _n X has the general formula — in the formula X is a sodium atom or a potassium atom; and n has an average value of from about 6 to about 21—selected from the group consisting of linear "glassy" polyphosphates. An oral formulation according to any one of the preceding claims, wherein the first dentifrice composition is a paste and the second dentifrice composition is a gel. 68.070/BE