Oral care composition having enhanced calcium deposition

Abstract

A dentifrice composition comprising a calcium carbonate abrasive and a sodium olefin sulfonate surfactant for enhanced calcium deposition.

Description

ORAL CARE COMPOSITION HAVING ENHANCED CALCIUM DEPOSITIONField of the InventionThe present invention is concerned with oral care compositions having improved calcium availability.Background of the InventionThe present invention relates to toothpaste compositions having superior calcium availability and hence improved enamel remineralization.There are very many toothpaste compositions known in the art many of which comprise chalk as an abrasive. We have found such compositions, by the use of selected surfactants, can have an enhanced availability of free calcium available. The availability of free calcium leads to greater enamel remineralization which in turn leads to an anticavity benefit.Description of the InventionAccordingly, the present invention relates to a toothpaste composition comprising from 31 wt% to 60 wt% of the total composition of a calcium carbonate abrasive and from 1.5 to 10 wt% of the total composition of a sodium olefin sulfonate surfactant.A second aspect of the invention relates to the use of sodium olefin sulfonate surfactant in a calcium carbonate containing toothpaste composition to enhance calcium deposition.A third further aspect of the invention relates to a composition comprising sodium olefin sulfonate and calcium carbonate for use in a method to increase calcium deposition from a toothpaste composition.Detailed Description of the InventionExcept in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and / or use may optionally be understood as modified by the word “about”.All amounts are by weight of the composition, unless otherwise specified.It should be noted that in specifying any ranges of values, any upper value can be associated with any particular lower value.Where a feature is disclosed with respect to a particular aspect of the invention (for example a composition of the invention), such disclosure is also to be considered to apply to any other aspect of the invention (for example a method of the invention) mutatis mutandis.Any ingredients mentioned in this application that are natural or naturally derived have been sourced from Europe.Unless stated specifically otherwise "Particle size" for the purpose of the present invention means D50 particle size. The D50 particle size of a particulate material is the particle size diameter at which 50 wt% of the particles are larger in diameter and 50 wt% are smaller in diameter. For the purpose of the present invention, particle sizes and distribution are measured using a laser diffraction particle size analyser such as those made by Malvern.The composition of the invention is in the form of a toothpaste. Such a composition is not intentionally swallowed for purposes of systemic administration of therapeutic agents, but is applied to the oral cavity, used to treat the oral cavity and then expectorated. Typically, such a composition is used in conjunction with a cleaning implement such as a toothbrush, usually by applying it to the bristles of the toothbrush and then brushing the accessible surfaces of the oral cavity.The composition is a product which, during the normal course of usage, is not for the purpose of systemic administration or intentionally swallowed but is rather retained in the oral cavity for a time sufficient to contact substantially all of the dental surfaces and / or oral tissues for the purposes of oral activity.The toothpaste composition according to the invention comprises calcium carbonate. Natural calcium carbonate abrasive is typically a finely ground limestone which may optionally be refined or partially refined to remove impurities. The material preferably has an average particle size of less than 10 microns, e.g., 3-7 microns, e.g., about 5.5 microns. For example, a small particle silica may have an average particle size (D50) of 2.5 -4.5 microns. Because natural calcium carbonate may contain a high proportion of relatively large particles of not carefully controlled, which may unacceptably increase the abrasivity, preferably no more than 0.01 wt.%, preferably no more than 0.004 percent by weight of particles would not pass through a 325mesh. The material has strong crystal structure, and is thus much harder and more abrasive than precipitated calcium carbonate. The tapped density for the natural calcium carbonate is for example between 1 and 1.5 g / cc, e.g., about 1.2 for example about 1.19 g / cc. There are different polymorphs of natural calcium carbonate, e.g., calcite, aragonite and vaterite, calcite being preferred for purposes of this invention.Precipitated calcium carbonate has a different crystal structure from natural calcium carbonate. It is generally more friable and more porous, thus having lower abrasivity and higher water absorption. For use in the present invention, the particles are small, e.g., having an average particle size of 1-5 microns, and e.g., no more than 0.1 percent, preferably no more than 0.05 percent by weight of particles which would not pass through a 325 mesh. The particles may for example have a D50 of 3-6 microns, for example 3.8-4.9, e.g., about 4.3; a D50 of 1-4 microns, e.g., 2.2-2.6 microns, e.g., about 2.4 microns, and a D10 of 1-2 microns, e.g., 1.2- 1.4, e.g., about 1.3 microns. The particles have relatively high water absorption, e.g., at least 25 g / 100 g, e.g., 30-70 g / 100 g.In a preferred embodiment the calcium carbonate has an average particle size from 0.5 to 15 microns (D50), more preferably an average particle size (D50) from 2 to 10 microns.The level of calcium carbonate is preferably from 35 wt.% to 60 wt.% of the total composition, preferably from 40 to 50 wt.%.Compositions of the invention comprise a sodium olefin sulfonate surfactant, preferbaly the the sodium olefin sulfpnate is sodium C14-C16 olefin sulfonate.It is preferable if the level of sodium olefin sulfonate surfactant is from 1.5 to 10.0 wt.% of the total composition, more preferably from 2 to 7 wt.%. most preferably from 2.1 to 5 wt%Preferably the weight ratio of the weight ratio of sodium olefin sulfonate to calcium carbonate abrasive is from 1 : 10 to 1 :40, more preferably from 1 : 15 to 1 :25.It is preferred if the sodium olefine surfactant comprises at least 50wt% of the total surfactant present in the composition, more preferably at least 75 wt.%, most preferably at least 99 wt.%.A composition according to the invention will generally contain further ingredients to enhance performance and / or consumer acceptability, in addition to the ingredients specified above.In some embodiments, additional calcium-containing abrasives, for example calcium phosphate abrasive, e.g., tricalcium phosphate, hydroxyapatite or dicalcium phosphate dihydrate or calcium pyrophosphate, and / or silica abrasives, sodium metaphosphate, potassium metaphosphate, aluminium silicate, calcined alumina, or other siliceous materials, or combinations thereof are used.The dentifrice composition according to the invention may comprise sodium bicarbonate at a level from 0.1 wt.% to 5 wt.%, preferably 0.1 wt.% to 1 wt.% of the total composition.Compositions according to the invention may comprise a pool such as propylene glycol, xylitol, and lactitol. Glycerol is a preferred polyol, sorbitol is particularly preferred.Composition of the invention may comprise 0.5 to 5 wt.% of the total composition of an antimicrobial quaternary ammonium material. Preferred antimicrobial quaternary ammonium material are cetylpyridinium chloride (CPC), CPC-claybenzalkonium chloride, tetradecylpyridinium chloride (TPC), N-tetradecyl-4-ethylpyridinium chloride (TDEPC). Particularly preferred is a cetylpyridium chloride clay complex.The composition may comprise a natural or synthetic thickener or gelling agent in proportions of about 0.10 to about 5% by weight depending on the material chosen. These proportions of thickeners in the dentifrice compositions of the present invention form an extrudable, shaperetaining product which can be squeezed from a tube onto a toothbrush and will not fall between the bristles of the brush but rather, will substantially maintain its shape thereon. Irish moss, iota-carrageenan, gum tragacanth, and polyvinylpyrrolidone. Sodium carboxymethylcellulose, hydroxyethyl cellulose (Natrosol®), xanthan gum, gum arabic etc. as well as synthetic polymers such as polyacrylates and carboxyvinyl polymers such as Carbopol®; Xanthan gum and Carrageenan are preferred, A dentifrice composition according to any preceding claim which further comprises a polymeric thickener selected from carboxy methyl cellulose, xanthan, carrageenan or mixtures thereof, particularly preferred is carboxy methyl cellulose.Compositions according to the invention may comprise a polymeric deposition aid. Preferably the composition comprises acid anhydride polymers, particularly preferred are co-polymers of maleic anhydride with methyl vinylether, in which the anhydride moiety may be in a partially or fully hydrolysed or alcoholised form. Preferred copolymers include Gantrez(R) polymers such as:Gantrez S-95: molecular weight 216,000; free acid;Gantrez S-96: molecular weight 700,000; free acid;Gantrez S-97: molecular weight 1,500,000; free acid; andGantrez MS-955: molecular weight 1,060,000; calcium / sodium salt.Particularly preferred co-polymers of maleic acid and methyl vinylether have a molecular weight of 1,000,000 or greater and an especially preferred material is Gantrez S-97.Compositions according to the invention may comprise a tooth whitening agent. The whitening agent preferably comprises a green and / or a blue pigment. In the context of the present invention a pigment is generally understood to be a shade / material which is insoluble in the relevant medium, at the relevant temperature. This is in contrast to dyes which are soluble. In the context of this invention, the "relevant medium" is human saliva, the liquid medium in which the composition is used, at the temperature of the oral cavity during brushing of the teeth, i.e. up to 37 Degrees C. As a reasonable approximation, the relevant medium may be considered to be water and the relevant temperature to be 25 Degrees C.Preferably the blue pigment is Pigment Blue 15, more preferably Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:5 or 15:6, most preferably 15:1. A preferred pigment is blue pigment is Phthalocyanine Blue Pigment, Cl No. 74160, blue covarine.The preferred Green pigment is Phthalocyanine Green, preferably Phthalocyanine Green CI-74260.Preferably the total level of pigment in the composition is from 0.01 wt.% to 3 wt., more preferably from 0.02 to 2 wt.%.If the composition is a toothpaste, it may be a dual phase paste, with the whitening pigments present in one phase.Compositions according to the invention may comprise water-soluble or sparingly water-soluble sources of metal salts Preferred are zinc ions such as zinc chloride, zinc acetate, zinc gluconate, zinc sulphate, zinc fluoride, zinc citrate, zinc lactate, zinc oxide, zinc monoglycerolate, zinc tartrate, zinc pyrophosphate and zinc maleate; also preferred are stannous ions such as stannous fluoride and stannous chloride.Compositions according to the invention may comprise oral care enzyme systems such as hydrogen peroxide producing enzyme systems (e.g. the oxidoreductase enzyme glucoseoxidase), amyloglucosidase, dextranase and / or mutanase, (optionally in the presence of zinc ion providing compounds and / or 8- hydroxyquinoline derivatives), lactoperoxidase, lactoferrin, lysozyme and mixtures thereof.Compositions of the invention may comprise fluoride sources such as sodium fluoride, stannous fluoride, sodium monofluorophosphate, zinc ammonium fluoride, tin ammonium fluoride, calcium fluoride, cobalt ammonium fluoride and mixtures thereof. Fluoride ion sources may be added to the compositions at a level of about 0.001 wt. percent to about 10 wt. percent, e.g., from about 0.003 wt. percent to about 5 wt. percent, 0.01 wt. percent to about 1 wt., or about 0.05 wt. percent. In some embodiment, the stannous fluoride is present in an amount of 0.1 wt. percent to 2 wt. percent (0.1 wt. percent -0.6 wt. percent) of the total composition weight. Fluoride ion sources may be added to the compositions at a level of about 0.001 wt. percent to about 10 wt. percent, e.g., from about 0.003 wt. percent to about 5 wt. percent, 0.01 wt. percent to about 1 wt., or about 0.05 wt. percent. 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. In some embodiment, the fluoride source is a fluoride salt present in an amount of 0.1 wt. percent to 2 wt. percent (0.1 wt. percent -0.6 wt. percent) of the total composition weight (e.g., sodium fluoride (e.g., about 0.32 wt. percent).Some embodiments of the invention are free from fluoride sources, that is the composition comprises less than 0.01 wt.% of a fluoride source.In one embodiment a preferred class of oral care active for inclusion in the compositions of the invention includes agents for the remineralisation of teeth. The term “remineralisation” in the context of the present invention means the in situ generation of hydroxyapatite on teeth.A specific example of a suitable agent for the remineralisation of teeth is a mixture of a calcium source and a phosphate source which, when delivered to the teeth results in the in situ generation of hydroxyapatite on teeth.Illustrative examples of the types of calcium source that may be used in this context (hereinafter termed “remineralising calcium sources”) include, for example, calcium phosphate, calcium gluconate, calcium oxide, calcium lactate, calcium glycerophosphate, calcium carbonate, calcium hydroxide, calcium sulphate, calcium carboxymethyl cellulose, calcium alginate,calcium salts of citric acid, calcium silicate and mixtures thereof. Preferably the remineralising calcium source is calcium silicate.The amount of remineralising calcium source(s) (e.g. calcium silicate) in the composition of the invention typically ranges from 1 to 30%, preferably from 5 to 20% by total weight remineralising calcium source based on the total weight of the oral care composition.Illustrative examples of the types of phosphate source that may be used in this context (hereinafter termed “remineralising phosphate sources”) include, for example, monosodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium dihydrogenphosphate, trisodium phosphate, tripotassium phosphate and mixtures thereof. Preferably the remineralising phosphate source is a mixture of trisodium phosphate and sodium dihydrogen phosphate.The amount of remineralising phosphate source(s) (e.g. trisodium phosphate and sodium dihydrogen phosphate) in the composition of this invention typically ranges from 2 to 15%, preferably from 4 to 10% by total weight remineralising phosphate source based on the total weight of the oral care composition.In some embodiments, the oral care compositions comprise an effective amount of one or more antibacterial agents, for example comprising an antibacterial agent selected from halogenated diphenyl ether (e.g. triclosan), triclosan monophosphate, herbal extracts and essential oils (e.g., rosemary extract, tea extract, magnolia extract, thymol, menthol, eucalyptol, geraniol, carvacrol, citral, hinokitol, magnolol, ursolic acid, ursic acid, catechol, methyl salicylate, epigallocatechin gallate, epigallocatechin, gallic acid, miswak extract, sea-buckthorn extract), bisguanide antiseptics (e.g., chlorhexidine, alexidine or octenidine), quaternary ammonium compounds (e.g., cetylpyridinium chloride (CPC), CPC-claybenzalkonium chloride, tetradecylpyridinium chloride (TPC), N-tetradecyl-4-ethylpyridinium chloride (TDEPC)), phenolic antiseptics, hexetidine furanones, bacteriocins, ethyllauroyl arginate, arginine bicarbonate, a Camellia extract, a flavonoid, a flavan, halogenated diphenyl ether, creatine, sanguinarine, povidone iodine, delmopinol, salifluor, metal ions (e.g., zinc salts, stannous salts, copper salts, iron salts), propolis and oxygenating agents (e.g., hydrogen peroxide, buffered sodium peroxyborate or peroxycarbonate), phthalic acid and its salts, monoperthalic acid and its salts and esters, ascorbyl stearate, oleoyl sarcosine, alkyl sulfate, dioctyl sulfosuccinate, salicylanilide, domiphen bromide, delmopinol, octapinol and other piperidino derivatives, nisin preparations, chloritesalts; parabens such as methylparaben or propylparaben and mixtures of any of the foregoing. One or more additional antibacterial or preservative agents may optionally be present in the composition in a total amount of from about 0.01 wt. percent to about 0.5 wt. percent, optionally about 0.05 wt. percent to about 0.1 wt. percent or about 0.3 percent, by total weight of the composition.In some embodiments, the oral care compositions 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 essential oils and various flavoring aldehydes, esters, alcohols, and similar materials, tea flavors, vanillin, sage, marjoram, parsley oil, spearmint oil, cinnamon oil, oil of Wintergreen, peppermint oil, clove oil, bay oil, anise oil, eucalyptus oil, citrus oils, fruit oils, sassafras 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, carvone, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone, a-irisone, , 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. percent to about 5 wt. percent, for example, from about 0.03 wt. percent to about 2.5 wt. percent, optionally about 0.05 wt. percent to about 1.5 wt. percent, further optionally about 0.1 wt. percent to about 0.3 wt. percent and in some embodiments in various embodiments from about 0.01 wt. percent to about 1 wt. percent, from about 0.05 to about 2 percent, from about 0.1 percent to about 2.5 percent, and from about 0.1 to about 0.5 percent by total weight of the composition.In some embodiments, the oral care compositions comprise at least one sweetener, useful for example to enhance taste of the composition. Sweetening agents among those useful herein include dextrose, polydextrose, sucrose, maltose, dextrin, dried invert sugar, mannose, xylose, ribose, fructose, levulose, galactose, corn syrup, partially hydrolyzed starch, hydrogenated starch hydrolysate, ethanol, sorbitol, mannitol, xylitol, maltitol, isomalt, aspartame, neotame, saccharin and salts thereof (e.g. sodium saccharin), sucralose, dipeptide-based intense sweeteners, cyclamates, dihydrochalcones.One or more sweeteners are optionally present in a total amount depending strongly on the particular sweetener(s) selected, but typically 0.005 wt. percent to 5 wt. percent, by total weight of the composition, optionally 0.005 wt. percent to 0.2 wt. percent, further optionally 0.05 wt. percent to 0.1 wt. percent by total weight of the composition.

[0041] In some embodiments, the oral care compositions further comprise an agent that interferes with or prevents bacterial attachment, e.g., ethyl lauroyl arginiate (ELA), solbrol or chitosan, as well as plaque dispersing agents such as enzymes (papain, glucoamylase, etc.).Mixtures of any of the above-described materials may also be used.The composition according to the invention will comprise further ingredients which are common in the art, such as: antimicrobial agents, e.g. chlorhexidine, sanguinarine extract, metronidazole, quaternary ammonium compounds, such as cetylpyridinium chloride; cetylpyridium chloride clay complex bis- guanides, such as chlorhexidine digluconate, hexetidine, octenidine, alexidine; and halogenated bisphenolic compounds, such as 2,2' methylenebis-(4-chloro-6-bromophenol). anti-inflammatory agents such as ibuprofen, flurbiprofen, aspirin, indomethacin etc.; anti-caries agents such as sodium- and stannous fluoride, aminefluorides, sodium monofluorophosphate, sodium trimeta phosphate and casein. plaque buffers such as urea, calcium lactate, calcium glycerophosphate and strontium polyacrylates; vitamins such as Vitamins A, C, D, B (preferably B3) and E; plant extracts; plant-derivable antioxidants such as flavonoid, catechin, polyphenol, and tannin compounds and mixtures thereof; desensitising agents, e.g. potassium citrate, potassium chloride, potassium tartrate, potassium bicarbonate, potassium oxalate, potassium nitrate and strontium salts; anti-calculus agents, e.g. alkali-metal pyrophosphates, hypophosphite-containing polymers, organic phosphonates and phosphocitrates etc.; biomolecules, e.g. bacteriocins, antibodies, enzymes, etc.; flavours, e.g. peppermint and spearmint oils; proteinaceous materials such as collagen; preservatives; opacifying agents;hyaluronic acid; amino acids such as arginine; colouring agents; pH-adjusting agents; sweetening agents; mouth feel agents pharmaceutically acceptable carriers, e.g. starch, sucrose, water or water / alcohol systems etc.; additional surfactants, such as anionic, nonionic, cationic and zwitterionic or amphoteric surfactants; polymeric compounds which can enhance the delivery of active ingredients such as antimicrobial agents can also be included; buffers and salts to buffer the pH and ionic strength of the oral care composition; and other optional ingredients that may be included are e.g. bleaching agents such as peroxy compounds e.g. potassium peroxydiphosphate, effervescing systems such as sodium bicarbonate / citric acid systems, colour change systems, and so on.In the following non-limiting Examples, Examples according to the invention are illustrated by a number while comparative Examples are illustrated by a letter.ExamplesToothpaste compositions were prepared as described in Table 1.Table 1The level of free calcium was measured by mixing the toothpaste and water at 1 to 3 ratio, followed by immediately centrifuging the resulting toothpaste slurry.The level of free calcium in the supernatant was measured using a Calcium Colorimetric Assay Kit (Sigma, MAK022) following the manufacturer instructions. The results are shown in Table 2.Table 2

Claims

CLAIMS1. A toothpaste composition comprising from 31.0 wt% to 60.0 wt% of the total composition of a calcium carbonate abrasive and from 1.5 wt% to 10.0wt% of the total composition of a sodium olefin sulfonate surfactant.

2. A toothpaste composition according to claim 1 in which the sodium olefin sulfonate is sodium C14-C16 olefin sulfonate.

3. A toothpaste composition according to claim 1 or claim 2 in which the weight ratio of the weight ratio of sodium olefin sulfonate to calcium carbonate abrasive is from 1:10 to 1:40.

4. A toothpaste composition according to any preceding claim in which the level of sodium olefin sulfonate surfactant is from 2.1 wt% to 5.0 wt.% of the total composition.

5. A toothpaste composition according to any preceding claim in which the calcium carbonate has an average particle size from 0.5 to 15 microns (D50).

6. A toothpaste composition according to any preceding claim in which the calcium carbonate abrasive has a n particle size (D50) from 2 to 10 microns.

7. toothpaste composition according to any preceding claim which further comprises a polymeric thickener selected from carboxy methyl cellulose., xanthan, carrageenan or mixtures thereof.

8. A toothpaste composition according to claim 7 in which the polymeric thickener is carboxy methyl cellulose.

9. The use of sodium olefin sulfonate surfactant in a calcium carbonate containing toothpaste composition to enhance calcium deposition.

10. A composition comprising sodium olefin sulfonate and calcium carbonate for use in a method to increasecalcium deposition from a toothpaste composition.

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