Oral care composition containing at least one biosurfactant and fluoride

This application is a 35 U.S.C. § 371 U.S. national phase entry of International Application No. PCT/EP2018/052335 having an international filing date of Jan. 31, 2018, which claims the benefit of European Application No. 17155558.4 filed Feb. 10, 2017, each of which is incorporated herein by reference in its entirety.

The present invention relates to oral care compositions comprising at least one biosurfactant and fluoride.

The fluoride ion has been widely used topically in the treatment of dental caries for its anticariogenic and antimicrobial properties.

The mechanisms suggested for the antimicrobial and remineralization roles of fluoride for oral health include:

reduction in demineralization by inhibition of microbial growth and metabolism promotion of remineralization and the formation of the fluorapatite mineral phase (Ca 10 (PO 4 ) 6 F 2 ) which is, compared to hydroxyapatite (Ca 10 (PO 4 ) 6 (OH) 2 ), more resistant to demineralization and acid dissolution following acid production by bacteria enzyme inhibition such as reduction of IgA protease synthesis reduction in extracellular polysaccharide production which helps in decreasing bacterial adherence to dental hard tissues.

Fluoride is added into toothpastes mostly as sodium fluoride (NaF), sodium monofluorophosphate (MFP), amine fluoride, and stannous fluoride. The other ingredients of toothpaste may also affect the availability of fluoride in the oral cavity. This is especially true in the case of calcium containing abrasives due to their potential to inactivate the fluoride.

Similarly, fluoride will react with silica to form fluorosilicates if a sufficient amount of detergent is not present.

Stannous fluoride gels (0.4% SnF 2 , equivalent to 970 ppm of fluoride) are effective in arresting root surface caries and have been incorporated into artificial saliva to reduce caries after radiation therapy in cancer patients. Stannous fluoride gel has a bad taste and may stain the teeth.

Thus, there is a need for improved oral care compositions such as toothpastes, mouth rinses, gels, varnishes etc. containing fluoride.

Surprisingly, it has been found that the oral care compositions described below containing biosurfactant and fluoride are able to solve the problem addressed by the invention.

An advantage of the present invention is that the compositions bear a reduced formation of insoluble complexes of fluoride with for example calcium.

A further advantage of the present invention is that the compositions induce a reduced staining of teeth.

A further advantage of the present invention is an improved taste of the compositions.

A further advantage of the invention is that the compositions have an improved deposition/retention of fluoride on surfaces.

A further advantage of the present invention is that the compositions reduce dental plaque.

A further advantage of the present invention is that the compositions reduce oral malodor.

The present invention relates to oral care compositions containing at least one biosurfactant and at least one fluoride ion source.

Within the context of the present invention, “biosurfactant” is understood to mean any glycolipid produced by fermentation.

Unless otherwise stated, all percentages (%) given are percentages by weight.

The oral care compositions can be present in various different forms, including a dentifrice, paste, gel, medicament, powder, mouthrinse, mouthwash, tooth hardener, oral film, slurry, injectable solution, chewing gum and lozenge, as well as any other form of oral care compositions known in the art.

In a preferred embodiment, the composition according to the invention is characterized in that the biosurfactant is selected from the group consisting of rhamnolipids, sophorolipids, glucose lipids, cellulose lipids and trehalose lipids, preferably rhamnolipids and sophorolipids with rhamnolipids being the most preferred.

The biosurfactants, in particular glycolipid surfactants, can be produced e.g. as in EP 0 499 434, U.S. Pat. No. 7,985,722, WO 03/006146, JP 60 183032, DE 19648439, DE 19600743, JP 01 304034, CN 1337439, JP 2006 274233, KR 2004033376, JP 2006 083238, JP 2006 070231, WO 03/002700, FR 2740779, DE 2939519, U.S. Pat. No. 7,556,654, FR 2855752, EP 1445302, JP 2008 062179 and JP 2007 181789 or the documents cited therein. Suitable biosurfactants can be acquired e.g. from Soliance, France and Evonik Industries AG, Germany.

The composition according to the invention preferably has, as biosurfactants, rhamnolipids, in particular mono-, di- or polyrhamnolipids, and/or sophorolipids.

The composition according to the invention particularly preferably has, as biosurfactants, one or more of the sophorolipids described in EP2501813 with the formulae (Ia) and (Ib).

Sophorolipids can be used according to the invention in their acid form or in their lactone form. The term “acid form” of sophorolipids refers to the general formula (Ia) of EP2501813; the term “lactone form” of sophorolipids refers to the general formula (Ib) of EP2501813.

For the determination of the content of sophorolipids in the acid or lactone form in a composition, reference is made to EP1411111B1, page 8, paragraph [0053].

Preferred compositions according to the invention comprise as biosurfactant a sophorolipid in which the weight ratio of lactone form to the acid form is in the range from 20-80 to 80-20, most preferably in the ranges from 30-70 to 40-60.

The term “rhamnolipid” in the context of the present invention is understood to mean particularly compounds of the general formula (I) or salts thereof,

where

m=2, 1 or 0, in particular 1,

n=1 or 0,

R 1 and R 2 =mutually independently, identical or different, organic radical having 2 to 24, preferably 5 to 13 carbon atoms, in particular optionally branched, optionally substituted, particularly hydroxy-substituted, optionally unsaturated, in particular optionally mono-, bi- or tri-unsaturated alkyl radical, preferably those selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl and (CH 2 ) o —CH 3 where o=1 to 23, preferably 4 to 12.

The term “di-rhamnolipid” in the context of the present invention is understood to mean compounds of the general formula (I) or salts thereof, where n=1.

The term “mono-rhamnolipid” in the context of the present invention is understood to mean compounds of the general formula (I) or salts thereof, where n=0.

Distinct rhamnolipids are abbreviated according to the following nomenclature: “diRL-CXCY” is understood to mean di-rhamnolipids of the general formula (I), in which one of the radicals R 1 and R 2 ═(CH 2 ) o —CH 3 where o=X-4 and the remaining radical R 1 or R 2 ═(CH 2 ) o —CH 3 where o=Y-4.

“monoRL-CXCY” is understood to mean mono-rhamnolipids of the general formula (I), in which one of the radicals R 1 and R 2 ═(CH 2 ) o —CH 3 where o=X-4 and the remaining radical R 1 or R 2 ═(CH 2 ) o —CH 3 where o=Y-4.

The nomenclature used therefore does not distinguish between “CXCY” and “CYCX”.

For rhamnolipids where m=0, monoRL-CX or diRL-CX is used accordingly.

If one of the abovementioned indices X and/or Y is provided with “:Z”, this signifies that the respective radical R 1 and/or R 2 is equal to an unbranched, unsubstituted hydrocarbon radical having X-3 or Y-3 carbon atoms having Z double bonds.

To determine the content of rhamnolipids in the context of the present invention, only the mass of the rhamnolipid anion is considered, i.e. “general formula (I) less one hydrogen”.

To determine the content of rhamnolipids in the context of the present invention, all rhamnolipids are converted by acidification into the protonated form (cf. general formula (I)) and quantified by HPLC.

A composition preferred according to the invention is characterized in that it comprises a mixture of rhamnolipids, where the weight ratio of di-rhamnolipids to mono-rhamnolipids in the mixture is greater than 51:49, preferably greater than 75:25, particularly preferably greater 90:10, particularly preferably greater 97:3 particularly preferably greater than 98:2.

A composition preferred according to the invention is characterized in that the rhamnolipid mixture comprises 51% by weight to 95% by weight, preferably 70% by weight to 90% by weight, particularly preferably 75% by weight to 85% by weight, of diRL-C10C10 and 0.5% by weight to 9% by weight, preferably 0.5% by weight to 3% by weight, particularly preferably 0.5% by weight to 2% by weight, of monoRL-C10C10, where the percentages by weight refer to the sum total of all rhamnolipids present.

A composition preferred according to the invention is characterized in that the rhamnolipid mixture, in addition to the diRL-C10C10 and monoRL-C10C10 contents mentioned above, comprises

0.5% by weight to 15% by weight, preferably 3% by weight to 12% by weight, particularly preferably 5% by weight to 10% by weight, of diRL-C10C12:1,

where the percentages by weight refer to the sum total of all rhamnolipids present.

A composition preferred according to the invention is characterized in that the rhamnolipid mixture, in addition to the diRL-C10C10 and monoRL-C10C10 contents mentioned above, comprises 0.1% by weight to 5% by weight, preferably 0.5% by weight to 3% by weight, particularly preferably 0.5% by weight to 2% by weight, of monoRL-C10C12 and/or, preferably and 0.1% by weight to 5% by weight, preferably 0.5% by weight to 3% by weight, particularly preferably 0.5% by weight to 2% by weight, of monoRL-C10C12:1, where the percentages by weight refer to the sum total of all rhamnolipids present.

It can be advantageous and is therefore preferred if the rhamnolipid mixture present in the composition according to the invention, in addition to the diRL-C10C10 and monoRL-C10C10 contents mentioned above, comprises 0.1% by weight to 25% by weight, preferably 2% by weight to 10% by weight, particularly preferably 4% by weight to 8% by weight, of diRL-C8C10, where the percentages by weight refer to the sum total of all rhamnolipids present.

The composition according to the invention preferably has, the fluoride ion source selected from the group consisting of stannous fluoride, sodium fluoride, potassium fluoride, potassium monofluorophosphate, sodium monofluorophosphate, ammonium monofluorophosphate, sodium fluorosilicate, ammonium fluorosilicate, amine fluorides such as olaflur (N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride) and ammonium fluoride.

The fluoride ion source is preferably contained in the composition according to the invention in an amount sufficient to supply 50 to 25000 ppm fluoride ion, e.g., from 100 to 1000, from 200 to 500, or 250 ppm fluoride ion %, based on the total weight of the composition. Fluoride ion sources may be added to the compositions of the invention at a level of 0.001 wt. % to 10 wt. %, e.g., from 0.003 wt. % to 5 wt. %, 0.01 wt. % to 1 wt., or 0.05 wt. %, based on the total weight of the composition. However, it is to be understood that the weights of fluoride salts to provide the appropriate level of fluoride ion will obviously vary based on the weight of the counter ion in the salt, and one of skill in the art may readily determine such amounts. A preferred fluoride salt may be sodium fluoride.

The composition according to the invention preferably is characterized in that the biosurfactant is contained in an amount from 0.005 wt. % to 20 wt. %, preferably 0.1 wt. % to 10 wt. %, more preferably 0.5 wt % to 5 wt % and particular preferably from 0.1 wt. % to 2 wt. % based on the total weight of the composition.

The fluoride ion source should provide from about 50 ppm to about 25000 ppm, preferably from about 50 ppm to 2500 ppm fluoride, particular preferably from about 50 ppm to 250 ppm for mouthrinses and from about 250 ppm to about 1500 ppm for toothpastes and gels. Particularly preferred compositions according to the invention are characterized in that the biosurfactant is selected from the group consisting of rhamnolipids in an amount from 0.1 wt. % to 2 wt. %, and the fluoride ion source is contained in an amount sufficient to supply from 50 ppm to 1500 ppm fluoride ion.

Particularly preferred compositions according to the invention are characterized in that they are selected from toothpastes and gels, and that the biosurfactant is selected from the group consisting of rhamnolipids in an amount from 0.1 wt. % to 2 wt. %, and the fluoride ion source is contained in an amount sufficient to supply from 500 ppm to 1500 ppm ppm fluoride ion. Particularly preferred compositions according to the invention are characterized in that they are selected from mouthrinses, and that the biosurfactant is selected from the group consisting of rhamnolipids in an amount from 0.1 wt. % to 2 wt. %, and the fluoride ion source is contained in an amount sufficient to supply from 50 ppm to 250 ppm fluoride ion.

The oral care compositions may be provided in an orally acceptable carrier or vehicle. The carrier can be a liquid, semi-solid, or solid phase, in the form of a mouth rinse, dentifrice (including toothpastes, toothpowders, and prophylaxis pastes), confectionaries (including lozenges, and gum), medicament, film, or any other form known to one of skill in the art. Selection of specific carrier components is dependent on the desired product form.

In embodiments where the oral care composition is in the form of a mouthrinse, an exemplary carrier is substantially liquid. The term “mouthrinse” includes mouthwashes, sprays and the like. In such a composition the orally acceptable carrier typically has an aqueous phase comprising either water, or a water and alcohol, preferably ethanol, mixture.

The oral care compositions of the present invention may further comprise additional ingredients. These additional ingredients may include, but are not limited to, diluents, bicarbonate salts, surfactants, foam modulators, sweeteners, flavorants, pigments, colorants, antibacterial agents, anticaries agents, anticalculus, tooth whitening agents, coolants or tartar control agents, and mixtures thereof.

An abrasive polishing material may also be included in the oral care compositions according to the present invention. The abrasive polishing material contemplated for use in the compositions of the present invention can be any material which does not excessively abrade dentin. The abrasive polishing material should be formulated in the oral composition so that it does not compromise the stability of any ingredients, such as stannous fluoride. Typical abrasive polishing materials include silica 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 alumina, beta calcium pyrophosphate, calcium carbonate, and resinous abrasive materials such as particulate condensation products of urea and formaldehyde, and others such as disclosed in U.S. Pat. No. 3,070,510. Mixtures of abrasives may also be used.

Silica dental abrasives of various types are preferred because of their unique benefits of exceptional dental cleaning and polishing performance without unduly abrading tooth enamel or dentine. The silica abrasive polishing materials herein, as well as other abrasives, generally have an average particle size ranging between about 0.1 to about 30 microns, and preferably from about 5 to about 15 microns. The abrasive can be precipitated silica or silica gels such as the silica xerogels described in U.S. Pat. Nos. 3,538,230 and 3,862,307. Preferred are the silica xerogels marketed under the trade name “Syloid” by the W.R. Grace & Company, Davison Chemical Division. Also preferred are the precipitated silica materials such as those marketed by the J. M. Huber Corporation under the trade name, “Zeodent”, particularly the silica carrying the designation “Zeodent 119”. The types of silica dental abrasives useful in the toothpastes of the present invention are described in more detail in U.S. Pat. No. 4,340,583. Silica abrasives are also described in U.S. Pat. Nos. 5,589,160, 5,603,920, 5,651,958, 5,658,553 and 5,716,601. The abrasive in the toothpaste compositions described herein is generally present at a level of from about 6% to about 70% by weight of the composition. Preferably, toothpastes contain from about 10% to about 50% of abrasive, by weight of the dentifrice composition.

In some embodiments, the compositions of the present invention also comprise an antibacterial or preservative agent, such as benzyl alcohol, chlorohexidine digluconate, triclosan, benzalkonium chloride, cetyl pyridinium chloride or parabens such as methylparaben or propylparaben. In some embodiments, the preservative is benzyl alcohol. The antibacterial or preservative agent may be present in the composition in an amount of from 0.1 to 1 weight %; 0.2 to 0.5 weight %; or about 0.3 weight % by total weight of the composition.

In some embodiments, the oral care compositions further comprise a humectant. In certain embodiments, the humectant is selected from sorbitol, glycerin, xylitol, polyethylene glycol, propylene glycol, and combinations thereof. In some embodiments, the humectant is glycerin. In some embodiments, the humectant is sorbitol, In certain embodiments, the humectant is present in the composition in an amount of from 5 to 20 weight %; from 7 to 17 weight %; or from 8 to 13 weight %; or from 9 to 10 weight %, based on the total weight of the composition. When the humectant is supplied as a solution in water, for example sorbitol as a 70 weight % solution in water, the amount of humectant is calculated as the active weight of the humectant, e.g. for a composition comprising 25 weight % sorbitol (as 70 weight % aqueous solution), the concentration of humectant is 17.5 weight %.

In some embodiments, the composition has a pH of from 3.5 to 10.5, preferably from 8.5 to 10.5; or from 9.2 to 10.2. The “pH” in connection with the present invention is defined as the value which is measured for the relevant substance at 25° C. after stirring for 5 minutes using a pH electrode calibrated in accordance with ISO 4319 (1977).

In certain embodiments, the composition comprises a buffer system, which may be: (a) a combination of sodium silicate and tetrasodium pyrophosphate; (b) a combination of sodium hydroxide, sodium bicarbonate and tetrasodium pyrophosphate; or (c) a combination of sodium bicarbonate and sodium carbonate.

In some embodiments, the buffer system is 0.04 to 0.5 weight % sodium hydroxide, 0.25 to 0.75 weight % sodium bicarbonate and 0.25 to 1.5 weight % tetrasodium pyrophosphate; or about 0.12 weight % sodium hydroxide, about 0.25 weight % sodium bicarbonate and about 1.25 weight % tetrasodium pyrophosphate; or about 0.06 weight % sodium hydroxide, about 0.5 weight % sodium bicarbonate and about 0.5 weight % tetrasodium pyrophosphate based on the total weight of the composition. In some embodiments, the buffer system is 0.05 to 0.5 weight % sodium bicarbonate and 0.2 to 0.6 weight % sodium carbonate; or about 0.1 weight % sodium bicarbonate and 0.4 weight % sodium carbonate, based on the total weight of the composition.

In some embodiments, the oral care compositions of the present invention comprise at least one bicarbonate salt useful for example to impart a “clean feel” to teeth and gums due to effervescence and release of carbon dioxide. Any orally acceptable bicarbonate can be used, including without limitation, alkali metal bicarbonates such as sodium and potassium bicarbonates, ammonium bicarbonate and the like. The one or more additional bicarbonate salts are optionally present in a total amount of about 0.1 wt. % to about 50 wt. %, for example about 1 wt. % to 20 wt. %, by total weight of the composition.

The oral care compositions of the invention may also comprise at least one polymeric viscosity modifier. Suitable polymeric viscosity modifiers include cellulose derivatives (“cellulose gums”) such as carboxymethyl cellulose (CMC), methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and mixtures thereof; polyvinyl pyrrolidone; xanthan; carrageenans such as iota-carrageenan, kappa-carrageenan, kappa2-carrageenan, lambda-carrageenan, and mixtures thereof; guar gum; gum karaya; gum arabic; gum tragacanth; and mixtures thereof. Other suitable polymeric viscosity modifiers include Carbomer 910, Carbomer 934, Carbomer 940, and Carbomer 980 and similar polymers of acrylic acid which are cross-linked with polyalcohol allyl ethers.

The oral care compositions of the invention may also comprise at least one further (non-bio-) surfactant. Any orally acceptable surfactant, most of which are anionic, nonionic or amphoteric, can be used. Suitable anionic surfactants include without limitation, water-soluble salts of C8-20 alkyl sulfates, sulfonated monoglycerides of C8-20 fatty acids, sarcosinates, taurates and the like. Illustrative examples of these and other classes include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl isethionate, sodium laureth carboxylate and sodium dodecyl benzenesulfonate. Suitable nonionic surfactants include without limitation, poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, dialkyl sulfoxides and the like. Suitable amphoteric surfactants include without limitation, derivatives of C8-20 aliphatic secondary and tertiary amines having an anionic group such as carboxylate, sulfate, sulfonate, phosphate or phosphonate. Betaines may also be used, a suitable example of which is cocoamidopropyl betaine. One or more surfactants are optionally present in a total amount of about 0.01 wt. % to about 10 wt. %, for example, from about 0.05 wt. % to about 5 wt. %, or from about 0.1 wt. % to about 2 wt. % by total weight of the composition.

The oral care compositions of the invention may comprise at least one foam modulator, useful for example to increase amount, thickness or stability of foam generated by the composition upon agitation. Any orally acceptable foam modulator can be used, including without limitation, polyethylene glycols (PEGs), also known as polyoxyethylenes. High molecular weight PEGs are suitable, including those having an average molecular weight of 200,000 to 7,000 000, for example 500,000 to 5,000,000, or 1,000,000 to 2,500,000. One or more PEGs are optionally present in a total amount of about 0.1 wt. % to about 10 wt. %, for example from about 0.2 wt. % to about 5 wt. %, or from about 0.25 wt. % to about 2 wt. %, by total weight of the composition.

The oral care compositions of the present invention may comprise at least one sweetener (such as, for example, sodium saccharin), useful for example to enhance taste of the composition. One or more sweeteners are optionally present in a total amount depending strongly on the particular sweetener(s) selected, but typically 0.005 wt. % to 5 wt. %, by total weight of the composition, optionally 0.005 wt. % to 0.2 wt. %, further optionally 0.05 wt. % to 0.1 wt. % by total weight of the composition.

The compositions of the present invention may also comprise at least one flavorant, useful for example to enhance taste of the composition. Any orally acceptable natural or synthetic flavorant can be used, including without limitation tea flavors, vanillin, sage, marjoram, parsley oil, spearmint oil, cinnamon oil, oil of wintergreen (methylsalicylate), peppermint oil, clove oil, bay oil, anise oil, eucalyptus oil, citrus oils, fruit oils and essences including those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, pineapple, etc., bean- and nut-derived flavors such as coffee, cocoa, cola, peanut, almond, etc., adsorbed and encapsulated flavorants and the like. Also encompassed within flavorants herein are ingredients that provide fragrance and/or other sensory effect in the mouth, including cooling or warming effects. Such ingredients illustratively include menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia , oxanone, α-irisone, propenyl guaiethol, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthan-3-carboxamine, N,2,3-trimethyl-2-isopropylbutanamide, 3-(1-menthoxy)-propane-1,2-diol, cinnamaldehyde glycerol acetal (CGA), menthone glycerol acetal (MGA) and the like. One or more flavorants are optionally present in a total amount of from about 0.01 wt. % to about 5 wt. %, for example, from about 0.03 wt. % to about 2.5 wt. %, optionally about 0.05 wt. % to about 1.5 wt. %, further optionally about 0.1 wt. % to about 0.3 wt. % by total weight of the composition.

The compositions of the present invention may comprise at least one colorant. Colorants herein include pigments, dyes, lakes and agents imparting a particular luster or reflectivity such as pearling agents. Any orally acceptable colorant can be used, including without limitation titanium dioxide, zinc oxide, red, yellow, brown and black iron oxides, ferric ammonium ferrocyanide, manganese violet, ultramarine, titaniated mica, bismuth oxychloride, and the like. One or more colorants are optionally present in a total amount of from about 0.001 wt. % to about 20 wt. %, for example, from about 0.01 wt. % to about 10 wt. %, or from about 0.1 wt. % to about 5 wt. %, by total weight of the composition.

The compositions of the present invention may comprise a saliva stimulating agent useful, for example, in amelioration of dry mouth. Any orally acceptable saliva stimulating agent can be used, including without limitation food acids such as citric, lactic, malic, succinic, ascorbic, adipic, fumaric and tartaric acids, and mixtures thereof. One or more saliva stimulating agents are optionally present in saliva stimulating effective total amount.

The compositions of the present invention may include antisensitivity agents, e.g., potassium salts such as potassium nitrate, potassium bicarbonate, potassium chloride, potassium citrate, and potassium oxalate; capsaicin; eugenol; strontium salts; chloride salts and combinations thereof. Such agents may be added in effective amounts, e.g., from about 1 wt. % to about 20 wt. % by weight based on the total weight of the composition, depending on the agent chosen.

The composition of the present invention may further comprise an antioxidant. Any orally acceptable antioxidant can be used, including butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), vitamin A, carotenoids, vitamin E, flavonoids, polyphenols, ascorbic acid, herbal antioxidants, chlorophyll, melatonin, and mixtures thereof.

The compositions of the present invention may additionally optionally comprise a tartar control (anticalculus) agent as provided below. Tartar control agents among those useful herein include salts of the specified agents, including alkali metal and ammonium salts. The agents include: phosphates and polyphosphates, polyaminopropanesulfonic acid (AMPS), polyolefin sulfonates, polyolefin phosphates, diphosphonates such as azacycloalkane-2,2-diphosphonates (e.g., azacycloheptane-2,2-diphosphonic acid), N-methyl azacyclopentane-2,3-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid (EHDP) and ethane-1-amino-1,1-diphosphonate, phosphonoalkane carboxylic acids and. Useful inorganic phosphate and polyphosphate salts include monobasic, dibasic and tribasic sodium phosphates, sodium tripolyphosphate, tetrapolyphosphate, sodium trimetaphosphate, sodium hexametaphosphate and mixtures thereof. Other useful tartar control agents include polycarboxylate polymers and polyvinyl methyl ether/maleic anhydride (PVM/MA) copolymers, such as GANTREZ®.

The composition of the invention may further comprise enzymes, including endoglycosidase, papain, dextranase, mutanase, amyloglucosidase, glucose oxidase, lysozyme, lactoperoxidase, and mixtures thereof.

The present invention further relates to the use of biosurfactants selected from the group consisting of rhamnolipids, sophorolipids, glucose lipids, cellulose lipids and trehalose lipids, preferably rhamnolipids and/or sophorolipids, particularly preferred rhamnolipids, for a reduced formation of insoluble complexes of fluoride, preferably with calcium.

The present invention further relates to the use of biosurfactants selected from the group consisting of rhamnolipids, sophorolipids, glucose lipids, cellulose lipids and trehalose lipids, preferably rhamnolipids and/or sophorolipids, particularly preferred rhamnolipids, for a reduced staining of teeth.

The present invention further relates to the use of biosurfactants selected from the group consisting of rhamnolipids, sophorolipids, glucose lipids, cellulose lipids and trehalose lipids, preferably rhamnolipids and/or sophorolipids, particularly preferred rhamnolipids, for an improved deposition/retention of fluoride on surfaces, especially teeth.

Preferred use according to the invention uses the preferred oral care compositions mentioned above.

The examples adduced below illustrate the present invention by way of example, without any intention of restricting the invention, the scope of application of which is apparent from the entirety of the description and the claims, to the embodiments specified in the examples.

In all examples, a mixture of rhamnolipids as listed below was used:

The following examples are for the purpose of illustration and are not to be construed as limitations of the present invention since many variations thereof are possible without departing from its scope.

The compositions are made using conventional methods. The pH value, if necessary, was adjusted by addition of either aqueous sodium hydroxide or citric acid.

Example Formulation 1 a,b: Toothpaste

Example Formulation 2 a,b: Toothpaste

Example Formulation 3 a,b: Toothpaste

Example Formulation 4: Toothpaste

Example Formulation 5: Toothpaste

Example Formulation 6: Toothpaste

Example Formulation 7: Toothpaste

Example Formulation 8: Toothpaste

Example Formulation 9: Toothpaste

Example Formulation 10: Toothpaste

Example Formulation 11: Toothpaste

Example Formulation 12: Toothpaste

Example Formulation 13: Toothpaste

Example Formulation 14: Toothpaste

Example Formulation 15: Toothpaste

Example Formulation 16: Toothpaste

Example Formulation 17: Toothpaste

Example Formulation 18: Toothpaste

Example Formulation 19: Toothpaste

Example Formulation 20: Toothpaste

Example Formulation 21: Toothpaste

Example Formulation 22: Toothpaste

Example Formulation 23: Toothpaste

Example Formulation 24: Toothpaste

Example Formulation 25: Toothpaste

Example Formulation 26: Toothpaste

Example Formulation 27: Toothpaste

Example Formulation 28: Toothpaste

Example Formulation 29: Toothpaste

Example Formulation 30: Toothpaste

Example Formulation 31 a,b: Toothpaste for Kids

Example Formulation 32: Toothpaste for Children

Example Formulation 33: Baby Toothpaste

Example Formulation 34: Toothpaste for Children

Example Formulation 35: Kids Toothpaste

Example Formulation 36 a,b: 2 in 1 Toothpaste+Mouthwash

Example Formulation 37 a,b: 2 in 1 Toothpaste+Mouthwash

Example Formulation 38 a,b: Mouthrinse without Alcohol

Example Formulation 39: Mouthrinse without Alcohol

Example Formulation 40: Mouthrinse without Alcohol

Example Formulation 41 a,b: Mouthrinse without Alcohol

Example Formulation 42: Mouthrinse

Example Formulation 43 a,b: Mouthrinse without Alcohol

Example Formulation 44 a,b: Mouthrinse without Alcohol

Example Formulation 45: Mouthrinse without Alcohol

Example Formulation 46: Mouthrinse without Alcohol

Example Formulation 47: Mouthrinse without Alcohol

Example Formulation 48: Mouthrinse without Alcohol

Example Formulation 49: Mouthrinse without Alcohol

Example Formulation 50 Mouthrinse without Alcohol

Example Formulation 51 a,b: Mouthrinse

Example Formulation 52 a,b: Mouthrinse

Example Formulation 53 a,b: Mouthrinse

Example Formulation 54 a,b: Mouthrinse

Example Formulation 55 a,b: Mouthrinse

Example Formulation 56 a,b: Mouthrinse

Example Formulation 57 a,b: Mouthrinse

Example Formulation 58: Mouthrinse

Example Formulation 59: Mouthrinse

Example Formulation 60: Mouthrinse

Example Formulation 61: Mouthrinse

Example Formulation 62: Mouthrinse

Example Formulation 63: Mouthrinse

Example Formulation 64 a,b: Mouthrinse

Example Formulation 65 a,b: Mouthrinse

Example Formulation 66 a,b: Mouthrinse Concentrate

Example Formulation 67 a,b: Mouthrinse Concentrate

Example Formulation 68 a,b: Mouthrinse Concentrate

Example Formulation 69 a,b: Peroxide Mouthrinse

Example Formulation 70 a,b: Fluoride Gel

Example Formulation 71 a,b: Fluoride Gel

Example Formulation 72 a,b: Dental Floss

Example Formulation 73 a,b: Teeth Wipe

Example Formulation 74 a,b: Chewing Gum