ANTICALCULUS/ANTIPLAQUE COMPOSITIONS USING AZACYCLOALKANE DIPHOSPHONATES

Abstract: Azacycloalkane diphosphonates are used in combination with antimicrobials, especially 5-chloro-2-(2,4-dichlorophenoxy)phenol, to provide anticalculus and antiplaque benefits on teeth. Oral care compositions such as dentifrices, mouthwashes and the like, are provided.

Description: ANTICALCULUS/ANTIPLAQUE COMPOSITIONS USING AZACYCLOALKANE DIPHOSPHONATES TECHNICAL FIELD The present invention relates to oral care compositions such as dentifrices, mouthwashes, lozenges, chewing gums, and the like, which are designed to prevent the accumulation of calculus, or "tartar", as it is sometimes called, and bacterial "plaque" on teeth. BACKGROUND OF THE INVENTION Dental calculus is a deposit which forms on the surfaces of the teeth at the gingival margin. Supragingival calculus appears principally in the areas near the orifices of the salivary ducts; e.g., on the lingual surfaces of the lower anterior teeth and on the buccal surfaces of the upper first and second molars, and on the distal surfaces of the posterior molars. Mature calculus consists of an inorganic material which is largely calcium phosphate arranged in a hydroxyapatite crystal lattice structure similar to bone, enamel and dentine. An organic portion is also present and consists of desquamated epithelial cells, leukocytes, salivary sediment, food debris and various types of microorganisms. As the mature calculus develops, it becomes visibly white or yellowish in color unless stained or discolored by some extraneous agent. In addition to being unsightly and undesirable from an aesthetic standpoint, the mature calculus deposits are constant sources of irritation of the gingiva. A wide variety of chemical and biological agents have been suggested in the art to retard calculus formation or to remove calculus after it is formed. Mechanical removal of this material periodically by the dentist is, of course, routine dental office procedure. The chemical approach to calculus inhibition generally involves crystal growth inhibition and/or chelation of calcium ion which prevents the calculus from forming and/or breaks down mature calculus by removing calcium. Dental plaque comprises an accumulation of bacteria and bacterial by-products on teeth. Plaque adheres tenaciously at points of irregularity or discontinuity, e.g., on rough calculus surfaces, at the gum line, and the like. The chemical approach to c plaque inhibition generally involves the use of antibacterials. o U.S. Patent 4,885,155, to Parran and Sakkab, granted December 5, 1989, relates to oral compositions containing pyrophosphate salts which provide an anticalculus benefit. As will be seen hereinafter from the discussion of the ιn literature, there has been a continuing search for anticalculus agents. Unfortunately, the chemical composition of calculus is sufficiently similar to that of the healthy tooth mineral (pri¬ marily, calcium hydroxyapatite) that many materials which can attack and remove calculus would also undesirably attack the 15 underlying tooth structure. This is particularly true with regard to many chelating agents which sequester calcium ions. There has also been a continuing search for effective antiplaque agents. Since both calculus and plaque affect oral health, it would be especially useful to provide compositions which provide both 0 anticalculus and antiplaque benefits. The present invention provides a new solution to the problem of dental calculus and dental plaque by means of the compositions disclosed hereinafter. BACKGROUND ART 5 U.S. Patent 3,941,772, March 2, 1976, relates to azacycloalkane diphosphonates and discloses their use to avoid the formation of tartar or plaque. U.S. Patent 3,678,154, July 18, 1972 to Widder, et al . discloses oral compositions containing certain phosphonates and fluoride. U.S. Patent 3,737,522, June 5, 0 1973 to Francis discloses oral compositions containing certain carbonyl diphosphonates. EPO Application 0,251,591, published January 7, 1988 and U.K. Application 2,200,551, published August 10, 1988, relate to the use of TRICL0SAN plus pyrophosphate in oral care compositions. 5 Various references in addition to U.S. Patent 4,885,155, cited above, relate to anticalculus agents of various types. The prior art discloses a number of chelating agents for this purpose. British Patent No. 490,384, February 15, 1937, discloses oral compositions containing ethylenediaminetetraacetic acid, nitrilo- triacetic acid and related compounds as anticalculus agents. In addition to the above references, the prior art discloses dentifrices and mouthwashes containing soluble pyrophosphate salts which have been indicated for a variety of purposes. Included among such references are U.S. Patent 2,941,926, June 21, 1960 to Salzmann, et al . which discloses dental powders containing chloro¬ phyll and pyrophosphate salts. U.S. Patent 3,137,632, June 16, 1964 to Schiraldi discloses toothpastes containing pyrophosphate salts. U.S. Patents 3,927,201 and 3,927,202, December 16, 1975 to Baines, et al . and Harvey, et al., respectively, disclose tooth¬ pastes which utilize soluble pyrophosphates as abrasives. U.S. Patent 4,244,931, January 13, 1981 and 4,247,5226, January 27, 1981 to Jarvis, et al . disclose pyrophosphate salts in dicalcium phosphate systems. Japanese Patent Application Disclosure No. 4945-1974 discloses soluble pyrophosphates in a variety of dentifrice systems. U.S. Patent 4,333,551, April 6, 1982 to Parran discloses tetraalkali metal salts in mouthwash composi¬ tions. Draus, Lesniewski and Miklos, Pyrophosphate and Hexametaphosphate Effects In Vitro Calculus Formation, Arch. Oral Biol., Vol. 15, pp. 893-896 (1970), disclose the in vitro effec¬ tiveness of soluble pyrophosphate salts against calculus. How¬ ever, they indicate that pyrophosphate efficacy would be inhibited by phosphatases in vivo . The references suggesting that pyrophosphates could reduce calculus, but either suggesting problems associated with their use or not recognizing problems, are Rapp, G. W. et al, "Pyrophos¬ phate: a factor in Tooth Erosion", J. D. Res. March-April 1960, Vol. 39, No. 2 pp. 372-376; the Draus article cited above; Briner et al, "In Vitro and In Vivo Evaluation of Anticalculus Agents", Ca7c. Tiss. 11 , pp. 10-22 (1973); U.S. Patent 3,934,002, Jan. 20, 1976 to Haefele; and British Patent No. 490,384, Feb. 15, 1937. U.S. Patent 4,847,070, July 11, 1989 to Pyrz et al . relates to oral compositions which are effective against calculus contain¬ ing a chelating agent which is an acrylic acid polymer or copolymer or EDTA, together with a strontium source, a fluoride ion source and a pyrophosphate ion source. U.S. Patent 4,661,341, April 28, 1987 to Benedict et al . relates to oral compositions containing an anticalculus agent which is an acrylic acid polymer or copolymer. U.S. Patent 4,022,880, May 10, 1977 to Vinson et al . relates to compositions for inhibiting dental plaque and calculus forma¬ tion comprising zinc ions and a nontoxic, organoleptically accept¬ able antibacterial agent. U.K. Patent Application GB 2,200,551, Gaffar, Nabi and Jannone, filed January 27, 1988, published August 10, 1988, relates to antibacterial, antiplaque and anticalculus oral compo¬ sitions containing a linear molecularly dehydrated polyphosphate salt and a noncationic antibacterial agent. U.S. Patent 4,656,031, April 7, 1987 to Lane et al . relates to a dentifrice which includes a surfactant and an antiplaque agent comprising a substantially water-insoluble noncationic antimicrobial agent or a zinc salt or a mixture thereof. European Patent Application 0,251,591, Jackson et al., filed June 19, 1987 relates to oral hygiene compositions comprising specified pyrophosphates and antibacterials. As noted above, U.S. Patent 4,885,155, December 5, 1989 to Parran, Jr. et al. relates to oral compositions containing partic¬ ular pyrophosphate salts which provide an anticalculus benefit. SUMMARY OF THE INVENTION The present invention encompasses oral care compositions, comprising: (a) an effective amount (generally, at least about 0.05%) of a source of an azacycloalkane-2,2-diphosphonate anion as an anticalculus agent; (b) an effective amount (generally, at least about 0.05%) of an antimicrobial agent; and (c) a toxicologically acceptable oral carrier. Preferably, the oral care compositions herein additionally comprise a course of an effective amount of fluoride ions. Other oral care adjunct materials such as pyrophosphate, various metal cations, and the like, can optionally be used in the compositions and methods herein. An oral care composition in the form of dentifrices, mouthwashes, lozenges, chewing gums, and the like, are provided by this invention. Typical oral care compositions according to this invention comprise: (a) from about 0.1% to about 5% by weight of a source of l-azacycloheptylidene-2,2-diphosphonate anions; (b) from about 0.1% to about 2% by weight of 5-chloro-2- (2,4-dichlorophenoxy)phenol ; and (c) an oral carrier. Preferred oral carriers assist in the e ulsification or solubilization of the 5-chloro-2-(2,4-dichlorophenoxy)phenol . This can be achieved, for example, by inclusion of surfactants in the oral carrier. Preferred compositions herein additionally comprise a source which will provide from about 100 ppm to about 1500 ppm of fluoride ions. This invention also encompasses a method for preventing the accumulation of calculus and plaque on dental enamel comprising contacting said dental enamel with a composition as disclosed above. Said method is assisted by brushing said dental enamel with a toothpaste which contains an abrasive. Highly preferred oral care compositions according to this invention additionally comprise a source of an effective amount of fluoride ions. Such sources can include, for example, sodium fluoride, stannous fluoride, sodium monofluorophosphate, and the like. Said source of fluoride ions preferably comprises from about 0.01% to about 1% by weight of the compositions herein. Dentifrice and outhwash compositions containing the tartrate monosuccinate, tartrate disuccinate or mixtures thereof with fluoride sources are exemplified hereinafter. Moreover, the oral care compositions according to this invention can also additionally comprise an effective amount of a source of pyrophosphate ions to provide additional calculus- controlling benefits. In addition, oral care compositions herein can additionally comprise an effective amount of zinc citrate as an adjunct calcu- lus-controlling agent. Still other oral care compositions according to this inven¬ tion can additionally comprise an effective amount of a source of a cation selected from the group consisting of zinc, indium, strontium and stannous cations, and mixtures thereof. Such compositions, or compositions which additionally comprise an effective amount of a member selected from the group consisting of sodium nitrate and potassium nitrate, are useful when treating c sensitive teeth, e.g., in older patients. Of course, since the compositions herein are intended for oral use, toxicologically-acceptable materials are used in the various compositions and methods disclosed hereinafter. All percentages, weights, ratios and proportions herein are Q by weight, unless otherwise specified. DETAILED DESCRIPTION OF THE INVENTION The azacycloalkane diphosphonates used in the practice of this invention are known in the literature and their synthesis forms no part of this invention. Reference can be made to U.S. 5 Patent 3,941,772, to Ploger et al, March 2, 1976, for syntheses of these materials. In general , azacycl oal kane-2,2-diphosphonates have the formula 0 0 (CH 2 ) η - N-R wherein R can be hydrogen or lower alkyl, e.g., methyl, ethyl, 5 propyl, and the like, and n is an integer from 3 to 5. Such materials are prepared by reaction of the corresponding cyclic lacta with, for example, H 3 P0 3 . In this manner are prepared, for example, azacyclopentane-2,2-diphosphonic acid ("ACP"), N-methyl- azacyclopentane-2,2-diphosphonic acid ("NMAP") and azacyclohep- Q tane-2,2-diphosphonic acid, which is more properly named as 1-azacycloheptylidene-2,2-diphosphonic acid. Use of such materials as their acids or water-soluble salts, e.g., Na + , K+, NHJ, salts, is contemplated by this invention. The sodium salts of l,azacycloheptylidene-2,2-diphosphonic acid are referred to 5 herein, collectively, as "AHP". (It will be appreciated that, as long as the salt is water soluble, the particular salt form used herein, i.e., mono-, di-, tri- or tetra-salt, is of no particular consequence in the practice of this invention, since it is the anion that provides the anticalculus benefit.) By "effective amount" of such diphosphonates herein is meant an amount sufficient to provide an anticalculus benefit. The antimicrobials used herein can be any of the known c materials which control oral bacterial species. Such materials include cetyl pyridiniu chloride ("CPC"), N-tetradecyl-4-ethyl- pyridinium chloride ("TDEPC"), peroxides such as sodium peroxide, H 2 0 2 and magnesium onoperphthalate ("PAM"; U.S. Patent 4,670,252). However, a highly preferred antimicrobial herein is 10 TRICLOSAN (especially at levels of 0.3-0.6%) which is the trade name of 5-chloro-2-(2,4-dichlorophenoxy)phenol, also known as 2,4,4'-trichloro-2'-hydroxydiphenyl ether; see U.S. Patent 3,506,720. By "effective amount" of such antimicrobials herein is meant an amount sufficient to provide an antiplaque benefit. 15 The combination or conjoint use of AHP and TRICLOSAN consti¬ tutes a preferred embodiment of the present invention. It is to be understood that the compositions and processes herein are designed to deliver an effective amount of the func¬ tional ingredients to the oral cavity safely and conveniently so 20 that the desired anticalculus benefits are achieved. For most purposes, contacting the teeth which are prone to calculus and plaque accumulation with the AHP and TRICLDSAN for a period of from about 10 seconds to about 3 minutes once, or preferably three times, daily in an otherwise conventional oral care regimen of 25 tooth brushing and/or use of mouthwash, will provide the desired benefits. Lesser or greater degrees of anticalculus benefits can be achieved by modifying the regimen. For example, use of a lozenge or chewing gum provides prolonged contact of the teeth with the functional ingredients. 30 The formulation of oral care compositions in the manner of this invention employs otherwise conventional ingredients such as well-known dentifrice abrasives, flavorants, thickening agents, fluid carriers (especially water-ethanol), sweetening agents, especially noncariogenic sweeteners such as the aspartic acid¬ i c derived sweeteners, saccharin and/or cyclamate, standard dental grade sources of fluoride ions such as sodium fluoride, stannous fluoride, and sodium onofluorophosphate (which are noted herein by way of exemplification, and not by way of limitation) and like materials which have come into broad usage in the dental arts. Various formularies are available and can be referred to for details of such materials. In particular, the oral care compositions of this invention can comprise an effective amount of fluoride ions. By "effective amount" is meant sufficient fluoride ions to provide a dental enamel-strengthening or anticaries effect. Typically, composi¬ tions comprising from about 0.0025% to about 2%, preferably from about 0.01% to about 1% by weight of said fluoride ion source will provide sufficient fluoride ions for these desired benefits. Highly preferred compositions herein comprise effective amounts of AHP plus TRICLOSAN plus fluoride. Various other oral care adjunct materials can also be used herein. Such materials are, for example, pyrophosphate, zinc citrate, metal cations, and the like. By an "effective amount" of a source of pyrophosphate ions herein is meant an amount which will provide adjunct anticalculus benefits. Typically, compositions can comprise from about 0.1% to about 10% by weight of pyrophosphate ions, which can be sourced from pyrophosphate salt such as tetrasodium, tetrapotassium, and disodium dihydrogen pyrophosphates. By an "effective amount" of zinc citrate herein is meant an amount sufficient to provide adjunct anticalculus benefits. Typically, an amount of zinc citrate of from about 0.1% to about 5% by weight of the compositions herein is sufficient. By an "effective amount" of a source of cation, especially cations selected from zinc, indium, strontium and stannous cations, and mixtures thereof, herein is meant a sufficient amount of said cations to provide the benefits which are normally associ- ated with the use of these particular materials in oral composi¬ tions. For example, the stannous cation has been associated with an anticaries benefit, as has the indium cation. Zinc and stron¬ tium cations have been noted for use in, for example, dentifrice compositions which are used in situations where the tee+h have been made "sensitive" to pain, particularly in older teeth which have undergone serious erosion of the dental enamel. Typical usage levels to provide the aforesaid effective amount of such cations generally ranges from about 0.01% to about 3% by weight of the compositions. Materials such as indium chloride, stannous fluoride, strontium chloride, zinc chloride, and the like can be used for such purposes. By an "effective amount" of sodium nitrate and potassium c nitrate (preferred) herein is meant sufficient amounts of such materials to provide desensitization of otherwise sensitive teeth (as noted above). Typically, such amounts can comprise from about 0.01% to about 5% of the compositions herein. Formulation of dentifrices typically involves the use of 20 abrasives that are safe for use on teeth. Representative examples of abrasives useful herein include calcium carbonate, hydrated alumina, urea-formaldehyde resins (see U.S. Patent 3,070,510) and, as noted, the silica abrasives (see U.S. Patents 3,538,230 and 3,862,307). "Syloid" silica xerogels, available from W. R. Grace 5 and Company and precipitated silicas, e.g., "Zeodent 119" from J. M. Humber Corporation are a preferred class of abrasives used herein. Abrasives are typically in the 0.1 to 30 micron size, and are typically used in toothpastes at the 6% to about 80% level and in toothpowders at levels up to 99%. Silica abrasives are pre- 0 ferred herein. Another embodiment of the present invention is a mouthwash composition. Conventional mouthwash compositions components can comprise the carrier for the actives of the present invention. Mouthwashes generally comprise from about 20:1 to about 2:1 of a water/ethyl alcohol solution and preferably other ingredients such as flavoring agents, sweeteners, humectants and sudsing agents such as those described above. The humectants, such as glycerin and sorbitol, give a moist feel to the mouth. Generally, on a weight basis the mouthwashes of the invention comprise from about 0 5% to about 60%, preferably from about 10% to about 25%, of ethyl alcohol; from 0% to about 20%, preferably from about 5% to about 20%, of a humectant, from 0% to about 2%, preferably from about 0.01% to about 0.15%, of an emulsifying agent; from 0% to about 0.5% of a sweetening agent; from about 0.03% to about 0.3% of a 5 flavoring agent; and the above-specified levels of AHP, TRICLOSAN, fluoride, and the like. Likewise, the formulation of chewing gums and lozenges presents no particular difficulties so long as toxicologically- acceptable carriers are used, as would naturally be the case in any product used in the oral cavity where ingestion of various ingredients by the user might occur. Suitable lozenge and chewing gum components are disclosed in U.S. Patent 4,083,955, issued April 11, 1978 to Grabenstetter et al. Suitable topical dental gels generally comprise a base of a humectant such as glycerin thickened with a suitable agent. Such gels generally do not contain an abrasive. Flavoring agents can also be added to the compositions of the present invention. Suitable flavoring agents include oil of wintergreen, oil of peppermint, oil of spearmint, oil of sassafras and oil of clove. Sweetening agents are also useful and include aspartame, acesulfame, saccharin, dextrose, levulose and sodium cyclamate. Flavoring and sweetening agents are generally used in the compositions herein at levels of from about 0.005% to about 2% by weight. The compositions of this invention may also contain emulsify- ing agents. Suitable emulsifying agents are those which are reasonably stable and foam throughout a wide pH range, and include non-soap anionic, nonionic, cationic, zwitterionic and amphoteric organic synthetic detergents. Many of these suitable surfactants are disclosed by Gieske et al . in U.S. Patent 4,051,234, issued September 27, 1977, which is incorporated herein by reference. It is preferred that the dentifrice compositions herein contain at least about 0.2%, preferably about 0.5% to about 6%, by weight of a surfactant, especially sodium C 12 -C 18 alkyl sulfate, to help emulsify or partly dissolve TRICLOSAN. Water may also be present in the compositions of this inven¬ tion. Water employed in the preparation of commercially suitable compositions should preferably be deionized and free of organic impurities. Water generally comprises from about 10% to about 50% by weight, preferably from about 20% to about 40% by weight, of the toothpaste compositions herein. These amounts of water include the free water which is added plus that which is intro¬ duced with other materials, such as with sorbitol. In preparing toothpastes, it is common to add some thickening material to provide a desirable consistency. Preferred thickening agents are carboxyvinyl polymers, carrageenan, hydroxyethyl cellulose and water soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hydroxy¬ ethyl cellulose. Natural gums such as gum karaya, gum arabic and gum tragacanth, and polysaccharide gums such as xanthan gum can also be used. Colloidal magnesium aluminum silicate can be used as part of the thickening agent to further improve texture. Thickening agents in an amount from about 0.5% to about 5.0% by weight of the total composition may be used. It is also desirable to include a hu ectant in a toothpaste to keep it from hardening. Suitable humectants include glycerin, sorbitol and other edible polyhydric alcohols at a level of from about 10% to about 70% by weight. The pH of the present compositions and/or their pH in the mouth can be any pH which is safe for the mouth's hard and soft tissues. Such pH's are generally from about 3 to about 10, preferably from about 7 to about 9. The following Examples further illustrate the practice of this invention, and describe typical formulations employing safe and effective amounts of the active ingredients, as well as various optional adjunct oral care ingredients encompassed by this invention and their uses, but are not intended to be limiting thereof. EXAMPLE I A toothpaste composition is as follows. Ingredient Percent fwt.) Sorbitol 24.0 AHP (disodiu salt) 1.0 TRICLOSAN 0.3 NaF 0.24 NaSaccharin 0.45 Polyethylene glycol 3.0 10 Mol/L NaOH to pH 7 Ti0 2 0.5 FD&C Blue #1 0.05 Silica 21.7 Glycerin 8.9 Xanthan gum 0.6 Carbopol 0.2 Flavor 1.0 Sodium alkyl sulfate (27.9% aqueous solution) 6.5 Water (deionized) Balance EXAMPLE II A mouthwash composition is- as follows. Ingredient Percent (wt.) EtOH (190) by wt. 8.5 Sorbitol (70% aqueous solution) 18.0 AHP (trisodium salt) 1.5 TRICLOSAN 0.6 Polysorbate 80 0.6 Dye (2% aqueous solution) 0.07 Pluronic F127 0.2 Flavor 0.075 NaSaccharin 0.04 Sodium fluoride 0.05 50% NaOH to pH 7 Water Balance EXAMPLE III A toothpowder composition is prepared by dry-blending ingre¬ dients, as follows: Ingredient Percent (wt.) AHP (monosodium salt) 2.5 Cetyl pyridinium chloride 0.25 Flavorant 1.0 Sodium alkyl sulfate 6.0 Silica xerogel (9 micron) Balance EXAMPLE IV A toothpaste composition is prepared according to Example I, but with the addition of 0.5% by weight of TDEPC in place of an equivalent weight of TRICLOSAN. The resulting for 'ilation provides anticalculus, antiplaque and anticaries benefits. EXAMPLE V A lozenge comprising 80% maltose, 2% azacyclopentane-2,2- diphosphonic acid (triethanolammonium salt form), 1% sodium monofluorophosphate, 1.5% gum arabic, 0.1% strontium chloride, 0.1% flavorant, 0.05% magnesium stearate (tableting aid), the balance comprising corn starch, is prepared in a standard tablet press. In use, the lozenge is allowed to dissolve slowly in the mouth to bathe the teeth in the combination of active ingredients. EXAMPLE VI A chewing gum comprises 99.0% standard chewing gum base (chicle), 0.5% flavorant and 0.1% AHP, 0.1% NaF and 0.3% CPC. EXAMPLE VII A dentifrice powder comprises the following mixture of o ingredients. Ingredient Percent (wt.) AHP 1.5 TRICLOSAN 1.5 Silica xerogel (as "Syloid") 90.0 5 Tetrasodium pyrophosphate 4.0 Sodium fluoride 1.0 Sodium alkyl sulfate (C 1 ) 2.0 The composition of Example VII can be modified by replacing the tetrasodium pyrophosphate with an equivalent amount of 0 tetrapotassium pyrophosphate. EXAMPLE VIII A mild toothpowder for sensitive teeth comprises 90% silica abrasive, 0.2% stannous fluoride, 0.1% potassium nitrate, 0.15% zinc sulfate, 1% sodium alkyl sulfate, 1% AHP (K salt), 1% TRICLOSAN, 0.25% CPC, the balance, corn starch, (per Reaction B, herein), the balance comprising flavorant. EXAMPLE IX An oral gel dentifrice comprises 3% AHP with 1.5% TRICLOSAN and 1.5% sodium lauryl sulfate, 1.5% Veegum, 1.5% carboxymethyl cellulose, 1.0% NaF, the balance comprising water. EXAMPLE X Base toothpaste compositions comprising standard amounts and types of abrasives, thickeners, humectants, surfactants and flavorants and prepared and blended with the following combina- tions of ingredients to provide dentifrice compositions A through E as follows. Ingredient (wt. ratio) Percent (wt.) in Dentifrice A. Zinc citrate/AHP/TRICLOSAN (1:1:1) 10 B. KF/PAM/TDEPC/ACP (1:0.1:0.1:5) 15 C. Sodium peroxide/AHP 5 D. Indium trichloride/CPC/NMAP (0.2:1:1) 5 E. TRICLOSAN/tetrasodiu pyrophosphate/AHP (0.5:1:1) 10 While the foregoing illustrates not only the use of the basic compositions of this invention and several embodiments thereof, but also various combinations of the herein-disclosed active ingredients with various adjunct agents for oral care, it is to be understood that such adjunct agents are given by way of exemplifi¬ cation and not by way of limitation. Other adjunct oral care agents can be used in such compositions, including materials such as: the ethylenediamine tetraacetates (EDTA) generally at effec¬ tive levels of 0.1%, or less; peroxides, especially 1% aqueous hydrogen peroxide; sodium tripolyphosphate (STPP), typically at 0.5%-10% levels, and the like. The following examples provide further guidance to the formulator. EXAMPLE XI Base mouthwash compositions comprising water, 15% ethanol, standard flavorants and dyes are prepared and blended with the following combinations of ingredients to provide mouthwash compositions A, B and C, as follows. Ingredient (wt. ratio) Percent (wt.) in Mouthwash A. H 2 0 2 /AHP (1:1) 2.0 B. EDTA/AHP/CPC (0.1:1:0.5) 2.0 C. STPP/AHP/CPC (10:1:0.5) 5.0 As can be seen from the foregoing, a wide variety of composi¬ tions useful for treating teeth in patients who are susceptible to dental calculus formation and in need of such treatment are provided by the practice of this invention. It will also be appreciated that "multiple" compositions can be used in conjunc¬ tion with each other, e.g., a toothpaste comprising AHP plus a separate toothpaste, mouthwash or spray comprising TRICLOSAN, can be separately applied to the teeth to afford multiple benefits. Such separate usage would not depart from the spirit and scope of this invention.

Claims: CLAIMS 1. An oral care composition, comprising: (a) an effective amount of a source of an azacycloalkane- 2,2-diphosphonate anion as an anticalculus agent; (b) an effective amount of an antimicrobial agent; and (c) a toxicologically acceptable oral carrier. 2. A composition according to Claim 1 wherein said anticalculus agent (a) is a salt of l-azacycloheptylidene-2,2-diphosphonate. 3. A composition according to Claim 1 wherein said antimicrobial agent (b) is 5-chloro-2-(2,4-dichlorophenoxy)phenol . 4. An oral care composition according to Claim 1 which additionally comprises a source of an effective amount of fluoride ions. 5. An oral care composition according to Claim 1 in the form of a dentifrice or a mouthwash. 6. An oral care composition according to Claim 1 which comprises: (a) from 0.1% to 5% by weight of a source of 1-azacyclohep- tylidene-2,2-diphosphonate anions; (b) from 0.1% to 2% by weight of 5-chloro-2-(2,4-dichloro- phenoxy)phenol ; (c) an oral carrier; and, preferably, (d) from 100 ppm to 1500 ppm of fluoride ions. 7. A composition according to Claim 6 wherein said oral carrier assists in the e ulsification or solubilization of the 5-chloro-2- (2,4-dichlorophenoxy)phenol . 8. An oral care composition according to Claim 1 which additionally comprises a member selected from the group consisting of a source of pyrophosphate ions, a metal cation selected from the group consisting of zinc, indium, strontium and stannous cations, sodium nitrate, potassium nitrate, or mixtures thereof. 9. A method for preventing the accumulation of calculus and plaque on dental enamel comprising contacting said dental enamel with a composition according to Claim 1. 10. A method for preventing the accumulation of calculus and plaque on dental enamel comprising brushing said dental enamel with a toothpaste composition according to Claim 6, said composi¬ tion additionally comprising an abrasive.

Inventors: NELSON DENNIS GEORGE ANTHONY, SMITHERMAN HERBERT CHARLES, NELSON, DENNIS, GEORGE, ANTHONY, SMITHERMAN, HERBERT, CHARLES
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1991
Main classification: A61K7
IPC codes: A61K8, A61Q11