Color-changing oral care compositions

Abstract

Disclosed herein are color-changing oral care compositions comprising (i) a water-soluble film comprising at least one cellulose polymer, at least one dye, and at least one coating, such as calcium carbonate; and an orally acceptable carrier, such as glycerin. Also disclosed herein are methods of using the oral care composition.

Description

COLOR-CHANGING ORAL CARE COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 63 / 779,685, filed 28 March 2025, the contents of which are hereby incorporated herein by reference in their entirety.BACKGROUND

[0002] It is recommended that children should brush their teeth for at least 45-60 seconds, and adults for at least 90 to 120 seconds. Most people, especially children, do not brush their teeth for a sufficient period of time to obtain maximum benefit and may have difficulty accurately estimating the time necessary to brush the teeth.

[0003] Sensory signals such as visual cues may therefore play an important role in communicating key benefits to the consumer, including whether the length of brushing time has been adequate. For example, when using toothpaste there is typically no immediate signal that the product has worked as intended or done anything during use. A visual cue, such as the foam or the toothpaste changing color, e.g., from white to blue, could dramatically improve this perception and signal to users that the length of brushing time has been adequate.

[0004] Although pigments may be used in oral care compositions elsewhere, in the United States, only dye is allowed in oral care products. One problem of using dye, however, is that dyes are water-soluble and may leach out of films almost immediately upon addition to a formulation that contains water, causing unacceptable color bleeding. Therefore, formulating a dentifrice composition with water-soluble dye may be problematic. When the content of water, which is a highly polar solvent, is reduced, conventional thickeners such as carboxymethyl cellulose (CMC) tend to inadequately gel up. Non-aqueous formulations have been shown to exhibit progressive thickening over time, which prolongs the time period or even prevents the dentifrice from teaching a rheological steady state. If a formulation routinely increases in viscosity over time, dispensing of the formulation may become difficult, which will likely result in consumer dissatisfaction. The rheology of the formulation should also be adequate for pumping and handling during the manufacturing process.

[0005] Although dyes may be coated to slow color leaching, one problem faced with coated dyefilms is stabilizing the films so that they do not dissolve in the dentifrice yet they dissolve when exposed to water and brushing action. In a typical dentifrice, dye films may break down within 2-4 days, leaving the dye to bleed within the dentifrice.

[0006] Accordingly, there is a need for a color-changing oral care product wherein the color changes at a rate that signals the product is being used by the consumer efficaciously, e.g., to ensure a child has brushed adequately, but maintains separation of the color-changing dye from the remainder of the dentifrice during storage and up to the point of use by the consumer, while maintaining suitable stability and viscosity.BRIEF SUMMARY

[0007] This summary is intended merely to introduce a simplified summary of some aspects of one or more implementations of the present disclosure. Further areas of applicability of the present disclosure will become apparent from the detailed description provided hereinafter. This summary is not an extensive overview, nor is it intended to identify key or critical elements of the present teachings, nor to delineate the scope of the disclosure. Rather, its purpose is merely to present one or more concepts in simplified form as a prelude to the detailed description below.

[0008] Disclosed herein are novel compositions comprising a water-soluble film and an orally-acceptable carrier. The composition disclosed herein may be an oral care composition, such as a dentifrice, comprising (i) a water-soluble film comprising at least one cellulose polymer, at least one dye, and at least one coating (e.g., calcium carbonate); and (ii) an orally- acceptable carrier.

[0009] In certain embodiments, the orally- acceptable carrier is glycerin, and in certain embodiments, the glycerin may be present in the oral care composition in an amount ranging from about 20 wt% to about 90 wt%, such as from about 60 wt% to about 80 wt%, based on a total weight of the oral care composition. According to certain embodiments, the oral care composition contains less than about 40 wt% water, less than about 35 wt% water, less than about 25 wt% water, less than about 15 wt% water, less than about 10 wt% water, such as less than 8 wt% water, less than 5 wt%, less than 2 wt% water, or wherein the oral care composition is free of or substantially free of water (e.g., anhydrous).

[0010] In certain embodiments of the disclosure, the water-soluble film comprises at least two, such as at least three or three coatings (e.g., at least two, such as at least three or three calcium carbonate coatings). In certain embodiments, the dye is a water soluble dye, such as FD&C Blue#1 , for example Brilliant Blue or Aluminum Lake Blue.

[0011] In certain embodiments, the at least one cellulose polymer in the water-soluble film is selected from methylcellulose, hydroxypropylmethyl cellulose, hydroxyethylpropyl cellulose, hydroxybutylmethyl cellulose, carboxymethyl cellulose, and mixtures thereof, preferably hydroxypropylmethyl cellulose.

[0012] In embodiments of the disclosure, the oral care composition further comprises a polyethylene glycol / polypropylene glycol copolymer, and in certain embodiments, the polyethylene glycol / polypropylene glycol copolymer is present in the oral care composition in an amount ranging from about 1 wt% to about 15 wt%, such as about 5 wt% to about 10 wt%, based on a total weight of the oral care composition. In certain embodiments of the disclosure, the oral care composition further comprises at least one anticalculus agent, such as phosphates and polyphosphates, polyaminopropanesulfonic acid (AMPS), hexametaphosphate salts, zinc citrate trihydrate, polypeptides, polyolefin sulfonates, polyolefin phosphates, diphosphonates, and mixtures thereof, preferably tetrasodium pyrophosphate (TSPP). In certain embodiments, the anticalculus agent (e.g., TSPP) is present in the oral care composition in an amount ranging from about 0.1 wt% to about 5 wt%, such as from about 0.5 wt% to about 3 wt%, based on a total weight of the oral care composition. In certain embodiments, the oral care composition further comprises at least one thickening agent, such as sodium carboxymethyl cellulose (CMC), and in certain embodiments, the at least one thickening agent (e.g., CMC) is present in the oral care composition an amount ranging from about 0.1 wt% to about 2 wt%, such as from about 0.4 wt% to about 0.8 wt%, or about 0.6 wt%, based on a total weight of the oral care composition.

[0013] In certain embodiments of the disclosure, the oral care composition is free of sugar alcohols. In some embodiments, the oral composition is free of or substantially free of sorbitol.

[0014] According to various embodiments of the disclosure, the water-soluble film in the oral care composition is substantially dissolved after a period of greater than 30 seconds and less than 180 seconds of brushing, scrubbing, or agitation in the presence of water. In certain embodiments, the water-soluble film has a thickness ranging from about 1 to about 3 mils. In further embodiments, the at least one calcium carbonate coating comprises at least about 50 wt% of the water-soluble film, such as about 60 wt% to about 70 wt% of the water-soluble film, based on a total weight of the water-soluble film.

[0015] According to certain embodiments, the oral care composition and the water-soluble filmdisclosed herein are substantially stable at about 60 °C for at least one week, preferably for at least two weeks, or wherein the oral care composition and the water soluble-film are substantially stable at room temperature for at least one month, preferably for at least two months. In certain embodiments of the disclosure, the oral care composition has a water activity (aw) of less than about 0.5, such as an awranging from about 0.15 to about 0.25 or from about 0.1 to about 0.2.

[0016] According to certain embodiments, the water-soluble film is present in the oral care composition in an amount ranging from about 0.1 wt% to a about 1 wt%, such as about 0.2 wt% to about 5 wt%, or about 0.2 wt%, based on a total weight of the oral care composition.

[0017] In accordance with another aspect of the disclosure, provided herein is a method of cleaning teeth in an oral cavity, the method comprising brushing the teeth with the oral care composition disclosed herein, wherein brushing is continued at least until the water-soluble film releases substantially all of the dye into the orally-acceptable carrier. In certain embodiments of the methods disclosed herein, the brushing is continued for at least about 30 seconds, such as at least about 60 seconds.BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The features and advantages of the disclosure will be apparent from the following more detailed description of certain embodiments and as illustrated in the accompanying drawings in which:

[0019] FIG. 1 is a bar graph showing the water activity (aw) of each of the test formulations #1-5, as described in Example 1.

[0020] FIG. 2 is a bar graph showing the W value of the color change for each of the test formulations #1-5 after preparation at room temperature, after 1 week aging at 60 °C, and after 2 weeks aging at 60 °C, as described in Example 1.

[0021] It should be understood that the various aspects are not limited to the compositions, arrangements, and instrumentality shown in the figures.DETAILED DESCRIPTION

[0022] For illustrative purposes, the principles of the present disclosure are described by referencing various exemplary embodiments thereof. Although certain embodiments are specifically described herein, one of ordinary skill in the art will readily recognize that the sameprinciples are equally applicable to and can be employed in other compositions and methods. Before explaining the disclosed embodiments in detail, it is to be understood that the disclosure is not limited in its application to the details of any particular embodiment disclosed herein. The terminology used herein is for the purpose of description and not of limitation.

[0023] All references cited herein are hereby incorporated by reference in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.

[0024] As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural references unless the context dictates otherwise. The singular form of any class of the ingredients refers not only to one chemical species within that class, but also to a mixture of those chemical species. The terms “a” (or “an”), “one or more” and “at least one” may be used interchangeably herein. The terms “comprising”, “including”, and “having” may be used interchangeably. The term “include” should be interpreted as “include, but are not limited to”. The term “including” should be interpreted as “including, but not limited to”.

[0025] As used herein, the term “or” is an inclusive operator, and is equivalent to the term “and / or,” unless the context clearly dictates otherwise. The term “based on” is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise. In the specification, the recitation of “at least one” of A, B, and C includes implementations containing A, B, or C, multiple examples of A, B, or C, or combinations of A / B, A / C, B / C, A / B / B / B / B / C, A / B / C, etc. In addition, the meaning of “in” includes “in” and “on.”

[0026] All physical properties that are defined hereinafter are measured at 20 °C to 25 °C (e.g., room temperature) unless otherwise specified.

[0027] As used herein, “oral care composition” refers to a composition that is delivered to the oral surfaces. The composition may be a product which, during the normal course of usage, is not, for the purpose of systemic administration of particular therapeutic agents, 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. Examples of an oral care composition include, but are not limited to, a toothpaste or a dentifrice, a mouthwash or a mouth rinse, powder (e.g., tooth powder), lozenge, mint, cream, strip or gum (e.g., chewing gum), a topical oral gel, a denture cleanser, and the like.

[0028] As used herein, the term “dentifrice” means paste, gel, strips, dissolvable ribbons or liquidformulations unless otherwise specified. Tn some embodiments, a dentifrice composition can be a combination of pastes, gels, or paste and gel. In some embodiments, a dentifrice composition is a toothpaste.

[0029] As used throughout, ranges are used as shorthand for describing each and every value that is within the range. It should be appreciated and understood that the description in a range format is merely for convenience and brevity, and should not be construed as an inflexible limitation on the scope of any embodiments or implementations disclosed herein. Accordingly, the disclosed range should be construed to have specifically disclosed all the possible subranges as well as individual numerical values within that range. As such, any value within the range may be selected as the terminus of the range. For example, description of a range such as from 1 to 5 should be considered to have specifically disclosed subranges such as from 1.5 to 3. from 1 to 4.5, from 2 to 5, from 3.1 to 5, etc., as well as individual numbers within that range, for example, 1, 2, 3, 3.2, 4, 5, etc. This applies regardless of the breadth of the range.

[0030] As used herein, by “substantially free” it is meant that the total amount of the respective ingredient is present in amounts less than 2% of the weight of the composition. As used herein, by “free” it is meant that the total amount of the respective ingredient is present in amounts less than 0.1% of the weight or undetectable by common laboratory equipment.

[0031] Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight. The amounts given are based on the active weight of the material.

[0032] Disclosed herein are oral care compositions comprising a base and dissolvable films, wherein the dissolvable film comprises at least one dye that provides a color change as compared to the base, wherein the color change may signal that a user has completed a sufficient period of use, e.g., brushing time. The dissolvable films disclosed herein may comprise a coated dye, such as a calcium carbonate coated dye, and the base may comprise glycerin.

[0033] It has been surprisingly and unexpectedly discovered that when dye is coated with a coating (such as an inorganic coating such as calcium carbonate) and incorporated into a film that may in turn be incorporated into an orally-acceptable carrier, the dye does not substantially leach from the film into the carrier until use, i.e., when diluted with saliva and / or subjected to mechanical forces such as brushing. The oral care compositions disclosed herein are stable upon storage, e.g., the dye does not substantially leach, migrate, or leak from the film into the vehicle, but is released uponintroduction into the oral cavity which, in some embodiments, provides a visible signal upon use. In certain embodiments, the user may continue brushing until the color change is observed, helping to indicate to the user that they have brushed for a sufficient period of time.

[0034] In certain embodiments, the oral care composition disclosed herein comprises flakes or strips of a water-dissolvable or water-soluble film comprised of a dye and a coating (e.g., calcium carbonate); and an orally- acceptable vehicle.Films

[0035] The films disclosed here may be formed from at least one film-forming polymer, such as film-forming polymers in the form of a polymer matrix comprising a cellulose polymer in which the coated dye may be entrained. The films disclosed herein may be single layer and pliable, meaning that the film will not easily tear or crack during normal manufacturing and handling.

[0036] The films disclosed herein may be prepared by any means known in the art. In certain embodiments, the coated dye and the filming-forming polymer(s) together with any other optional ingredients are dissolved in a compatible solvent to form a film-forming composition. Compatible solvents may include, for example, water alcohols such as ethanol, ethyl acetate, acetone, and mixtures thereof. The film-forming composition is then cast on a releasable carrier and dried to form a sheet of film material. The carrier material should have a surface tension that allows the film solution to spread evenly across the intended carrier width without soaking to form a destructive bond between the film carrier substrates. Examples of suitable carrier materials include glass, stainless steel, Teflon®, and polyethylene-impregnated paper. Drying of the film may be carried out at high temperature using a drying oven, drying terminal, vacuum drier, or any other suitable drying equipment that does not adversely affect the ingredients in the film.

[0037] The film may be any size, shape, and / or thickness that is suitable for use in an oral care composition, hi certain embodiments, the film thickness may range from about 1 to about 10 mils, such as about 1 to about 5 mils or about 2 to about 4 mils. The dried film disclosed herein may then be cut, punched, or ground into flakes or the desired shape, e.g., stars, circles, diamonds, squares, ribbons, hearts, and the like. In certain embodiments, the flakes may have a particle size ranging from about 10 to about 100 mesh, such as about 20 to about 60 mesh or about 30 to about 50 mesh.

[0038] In certain embodiments, the film may be present in the oral care composition disclosed herein an amount ranging from about 0.001 wt% to about 5 wt%, such as from about 0.01 wt% toabout 1 wt%, about 0.1 wt% to about 0.5 wt%, about 0.15 wt% to about 0.25 wt%, about 0.1 wt% to about 0.2 wt%, or about 0.2 wt%, based on a total weight of the oral care composition.Film Forming Polymers

[0039] The film in the oral care compositions disclosed herein comprise at least one film-forming polymer. In certain embodiments, the at least one film-forming polymer may be a cellulose polymer, such as a cellulose ether polymer, e.g., selected from alkylcellulose, e.g., methylcellulose; hydroxyalkyl cellulose, e.g., selected horn hydroxypropyl methyl cellulose, hydroxyethylpropyl cellulose, hydroxy butyl methyl cellulose, hydroxy propyl methyl cellulose, carboxymethyl cellulose; and mixtures thereof. In certain embodiments, the film-forming polymer is hydroxypropylmethyl cellulose (HPMC). In certain embodiments, the cellulose ether polymer is a low viscosity hydropropylmethyl cellulose, hr certain embodiments, the cellulose ether may be incorporated in the film matrix in amounts ranging from about 10% to about 60% by weight, such as from about 15 to about 40% by weight. Other film-forming polymers may also be used in addition to the cellulose ether, for example, polyvinyl acetate, starch, e.g., a pregelatinized starch, and the like. HPMC is available commercially, for example, from the Dow Chemical Company under the trade designation METHOCEL®.Dyes

[0040] The water-dissolvable or water-soluble films disclosed herein comprise at least one dye. The dye may be distinguishable in color from the orally acceptable vehicle of the oral care composition. In certain embodiments, the dye is a water-soluble dye. In this context, the term “water soluble” indicates that the dye has an aqueous solubility of at least about 10 g / L at 25 °C. Solubility may be determined in unbuffered distilled water. Triarylmethane dyes are examples of water-soluble dyes that may be used according to certain embodiments of the oral care compositions disclosed herein. In some embodiments, the dyes contemplated herein are anionic triphenylmethane dyes, such as diaminotriphenylmethane dyes containing from two to four sulphonate groups, such as those corresponding to the general Formula (1):Formula (I),in which Ri, R2, R3, and R4 are monovalent moieties that are each independently selected from hydrogen, hydroxyl, halogen (e.g., -Cl), and sulphonate (-SO3) groups, with the proviso that at least two of Ri, R2, R3, and R4 are sulphonate groups.

[0041] An example of a dye that may be used in embodiments of the present disclosure is FD&C Blue #1, also known as Brilliant Blue FCF (Blue 1) and aluminum lake blue, as well as other commercial names. Blue #1 corresponds to the general Formula (1) set forth above, wherein R2 is hydrogen, and Ri, R3, and R4 are sulphonate groups. FD&C Blue #1 is a colorant for foods and other substances to induce a color change. It is denoted by E number El 33 and has a color index of 42090. It has the appearance of a reddish-blue powder. It is soluble in water, and the solution has a maximum absorption at about 628 nanometers. It is a synthetic dye produced using aromatic hydrocarbons from petroleum. It is usually a disodium salt. The diammonium salt has CAS number [2650-18-2], Calcium and potassium salts are also known. Other exemplary dyes that may be used in the oral care compositions disclosed herein include red dyes such as FD&C Red #33, FD&C Red #40, and the like; yellow dyes such as FD&C Yellow #5, FD&C Yellow #46, FD&C Yellow #15, and the like; and green dyes such as FD&C Green #3; as well as other color dyes and mixtures of any two or more dyes.Coating

[0042] In some embodiments, the films comprising a dye as disclosed herein are coated, and in certain embodiments, the coating is an in organic coating. Any inorganic coating may be used in embodiments disclosed herein. In certain embodiments, the inorganic coating is an inorganic material suitable to conceal the color of the dye in an oral care composition. Non- limiting examples of inorganic coatings may include, for example, aluminum oxide, calcium carbonate, magnesium oxide, silicon monoxide, silicon dioxide, titanium dioxide, tin oxide, zinc oxide, calcium magnesium carbonate, magnesium carbonate, phosphate salts, pyrophosphate salts, and combinations thereof.

[0043] In certain embodiments, the coating is a calcium carbonate coating. Calcium carbonate (CaCCh), also known as chalk, is a white powder that can itself be used as a colorant due to its white properties. Calcium carbonate is also known for use in oral care compositions as an abrasive material. Additionally or alternatively, calcium carbonate can be used as a coating material to coat the water-soluble dye or dyes disclosed herein.

[0044] In some embodiments, the coating, e.g., calcium carbonate, covers substantially the entire surface of the film, such as the entire surface of the film flakes described above, wherein the film is optionally cut, punched, or ground into flakes or the desired shape, e.g., stars, circles, diamonds, squares, ribbons, hearts, and the like (collectively referred to herein as the film flakes). In certain embodiments, the entire surface of each film flake includes two opposed faces and two peripheral edge surfaces therebetween. In certain embodiments, the two opposed faces are coated with the coating, e.g., calcium carbonate, and in certain embodiments, the two opposed faces and the two peripheral edge surfaces are coated with the coating. In certain embodiments, the film flakes are coated once or at least once with the coating, and in certain embodiments, the film flakes are coated more than once with the coating, such as coated twice, three times, four times, five times, or six times. In certain embodiments of the disclosure, the coating and / or the film is free of or substantially free of titanium dioxide.

[0045] In certain embodiments, the at least one coating (e.g., calcium carbonate) comprises at least about 40 wt% of the total weight of the coated film, such as at least about 45 wt%, at least about 50 wt%, at least about 55 wt%, at least about 60 wt%, at least about 65 wt%, at least about 70 wt%, at least about 75 wt%. or at least about 80 wt%. In certain embodiments, the at least one coating (e.g., calcium carbonate) comprises from about 40 wt% to about 80 wt% of the total weight of thecoated film, such as from about 40 wt% to about 50 wt%, about 50 wt% to about 60 wt%, about 50 wt% to about 70 wt%, or about 60 wt% to about 70 wt%, based on a total weight of the coated film.

[0046] The oral care composition disclosed herein may contain an orally-acceptable carrier. In certain embodiments, the orally-acceptable carrier comprises or consists of a humectant. In certain embodiments, the orally-acceptable carrier comprises glycerin, and in certain embodiments, the orally-acceptable carrier is free of or substantially free of sorbitol. The oral care composition disclosed herein may, in certain embodiments, comprise water, and in certain embodiments, the oral care composition, and hence the orally-acceptable carrier, may be anhydrous.

[0047] For example, in certain embodiments of the disclosure, the oral care composition (and the orally-acceptable carrier) may comprise less that about less than 40 wt% water, less than 35 wt% water, less than 30 wt% water, such as less than, about 25 wt% water, less than about 15 wt% water, less than about 10 wt% water, less than about 9 wt% water, less than about 8 wt% water, less than about 7 wt%, less than about 6 wt% water, less than about 5 wt% water, less than about 4 wt% water, less than about 3 wt% water, less than about 2 wt% water, less than about 1 wt%, or 0 wt% water, based on a total weight of the composition. In certain embodiments, water may be present in the oral care composition disclosed herein an amount ranging from about 0 wt% to about 30 wt%, such as from about 0 wt% to about 15 wt%, about 0 wt% to about 10 wt%, about 0 wt% to about 9 wt%, 0 wt% to about 8 wt%, 0 wt% to about 7 wt%, 0 wt% to about 6 wt%, 0 wt% to about 5 wt%, 0 wt% to about 4 wt%, 0 wt% to about 3 wt%, 0 wt% to about 2 wt%, 0 wt% to about 1 wt%; about 0.5 wt% to about 10 wt%, about 0.5 wt% to about 5 wt%, about 0.5 wt% to about 4 wt%. about 0.5 wt% to about 3 wt%, about 0.5 wt% to about 2 wt%. or about 0.5 wt% to about 1 wt%, based on a total weight of the oral care composition.

[0048] In certain embodiments disclosed herein, the orally-acceptable carrier comprises glycerin. In certain embodiments, the orally-acceptable carrier, such as glycerin, in present in the oral care composition in an amount ranging from about 50 wt% to about 95 wt%, such as from about 55 wt% to about 90 wt%, about 60 wt% to about 85 wt%, about 65 wt% to about 80 wt%. about 66 wt% to about 75 wt%, about 66 wt% to about 70 wt%, about 67 wt% to about 70 wt%, such as about 67 wt%, about 68 wt%, about 70 wt%, or about 74 wt%, based on a total weight of the oral care composition.Additional Ingredients

[0049] In certain embodiments, the oral care compositions disclosed herein may contain additional optional ingredients traditionally used in formulating oral care compositions, such as toothpastes and other dentifrices. The oral care compositions described herein may also comprise one or more further agents such as those selected from: a fluoride ion source, abrasives, an anti-plaque agent, whitening agents, antibacterial agents, cleaning agents, flavoring agents, sweetening agents, adhesion agents, surfactants, foam modulators, pH modifying agents, humectants, mouth-feel agents, colorants, tartar control (anti-calculus) agents, polymers, saliva stimulating agents, nutrients, viscosity modifiers, anti- sensitivity agents, antioxidants, and combinations thereof.

[0050] In certain embodiments, the oral care compositions disclosed herein further comprise at least one fluoride ion source. The at least one fluoride ion source may be optionally present in an amount providing a clinically efficacious amount of soluble fluoride ion to the oral care composition. A fluoride ion source may be useful, for example, as an anti-caries agent. Any orally acceptable particulated fluoride ion source can be used, including stannous fluoride, sodium fluoride, potassium fluoride, potassium monofluorophosphate, sodium monofluorophosphate, ammonium monofluorophosphate, sodium fluorosilicate, ammonium fluorosilicate, indium fluoride, amine fluoride such as olaflur (N'-octadecyltrimethylendiamine-N,N,N'-tris(2-ethanol)-dihydrofluoride), ammonium fluoride, titanium fluoride, hexafluorosulfate, and combinations thereof. Fluoride where present may be present in the oral care compositions at levels of, e.g., about 25 to about 25,000 ppm, for example about 50 to about 5000 ppm, about 750 to about 2,000 ppm for a consumer toothpaste product (e.g., 1000-1500 ppm, e.g., about 1000 ppm, e.g., about 1450 ppm). In some embodiments, fluoride is present from about 500 to about 3000 ppm, such as from about 100 to about 1000. from about 200 to about 500, or about 250 ppm fluoride ion. In some embodiments, the fluoride source provides fluoride ion in an amount of from 50 to 25,000 ppm (e.g., 750-7000 ppm, e.g., 1000-5500 ppm, e.g., about 500 ppm, 1000 ppm, 1100 ppm, 2800 ppm, 5000 ppm, or 25000 ppm). In some embodiments, the fluoride ion source is stannous fluoride. In some embodiments, the fluoride ion source is stannous fluoride which provides fluoride in an amount from 750-7000 ppm (e.g., about 1000 ppm, 1100 ppm, 2800 ppm, 5000 ppm). In some embodiments, the fluoride ion source is stannous fluoride which provides fluoride in an amount of about 5000 ppm. In some embodiments, the fluoride ion source is sodium fluoride which provides fluoride in an amount from 750-2000 ppm (e.g., about 1450 ppm). In some embodiments, the fluoride ion source is selected from sodium fluoride and sodiummonofluorophosphate and which provides fluoride in an amount from 1000 ppm-1500 ppm. In some embodiments, the fluoride ion source is sodium fluoride or sodium monofluorophosphate and which provides fluoride in an amount of about 1450 ppm. In some embodiments, stannous fluoride is the only fluoride ion source. Fluoride ion sources may be added to the compositions at a level of about 0.001 wt% to about 10 wt%, e.g., from about 0.003 wt% to about 5 wt%, 0.01 wt% to about 1 wt%, or about 0.05 wt%. 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% to 2 wt%, such as 0.1 wt% - 0.6 wt%, of the total composition weight (e.g., sodium fluoride or sodium monofluorophosphate).

[0051] In some embodiments, the oral care compositions comprise one or more abrasive particulates such as those useful, for example, as a polishing agent. Any orally- acceptable abrasive can be used, but type, fineness (particle size), and amount of abrasive should be selected so that tooth enamel is not excessively abraded in normal use of the composition. Examples of abrasive particulates that may be used include abrasives such sodium bicarbonate, insoluble phosphates (such as orthophosphates, polymetaphosphates and pyrophosphates including dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate and insoluble sodium polymetaphosphate), calcium phosphate (e.g., dicalcium phosphate dihydrate), calcium sulfate, natural calcium carbonate (CC), precipitated calcium carbonate (PCC), silica (e.g., hydrated silica or silica gels or in the form of precipitated silica or as admixed with alumina), iron oxide, aluminum oxide, aluminum silicate, calcined alumina, bentonite, other siliceous materials, perlite, plastic particles, e.g., polyethylene, and combinations thereof. The natural calcium carbonate abrasive may in certain embodiments be a finely ground limestone that may optionally be refined or partially refined to remove impurities. The material may have an average particle size of less than about 10 microns, e.g., about 3-7 microns, e.g., about 5.5 microns. For example, a small particle silica may have an average particle size (D50) of about 2.5-4.5 microns. Natural calcium carbonate may contain a high proportion of relatively large particles if not carefully controlled, which may unacceptably increase the abrasivity. Therefore, in certain embodiments, no more than 0.01 wt%. such as no more than 0.004 wt%, by weight of particles would not pass through a 325 mesh. Natural calcium carbonate has a strong crystalstructure and is thus much harder and more abrasive than precipitated calcium carbonate. The tap density for the natural calcium carbonate may be, for example, between 1 and 1.5 g / cc, e.g., about 1.2 g / cc or for example about 1.19 g / cc. There are different polymorphs of natural calcium carbonate, e.g., calcite, aragonite and vaterite. An example of a commercially available product suitable for use in certain embodiments of the disclosure includes VICRON® 25-11 FG from GMZ.

[0052] 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 certain embodiments disclosed herein, the particles may be small, e.g., having an average particle size of about 1-5 microns, and e.g., no more than about 0.1%, such as no more than about 0.05% by weight of particles that would not pass through a 325 mesh. The particles may for example have a D50 of about 3-6 microns, for example about 3.8-4.9, e.g., about 4.3; a D50 of about 1-4 microns, e.g., about 2.2-2.6 microns, e.g., about 2.4 microns, or a D10 of about 1-2 microns, e.g.. about 1.2-1.4, e.g., about 1.3 microns. The particles may have relatively high water absorption, e.g., at least 25 g / 100 g, e.g., 30-70 g / 100 g. Examples of commercially available products suitable for use include, for example, CARBOLAG® 15 Plus from Lagos Industria Quimica. 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, aluminum silicate, calcined alumina, bentonite or other siliceous materials, or combinations thereof are used. Examples of silica abrasives include, but are not limited to, precipitated or hydrated silicas having a mean particle size of up to about 20 microns (such as ZEODENT® 105 and ZEODENT® 1 14 marketed by J.M. Huber Chemicals Division, Havre de Grace, Md.); SYLODENT® 783 (marketed by Davison Chemical Division of W.R. Grace & Company); or SORBOSIL® AC 43 (from PQ Corporation). In some embodiments, an effective amount of a silica abrasive is about 10 wt% to about 30 wt%, e.g., about 20 wt%, by weight based on the total weight of the oral care composition. For example, the silica abrasive may be present in an amount selected from about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%. about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, or about 20 wt%, by weight based on the total weight of the oral care composition.

[0053] In some embodiments, the silica is synthetic amorphous silica (e.g., about 1 %-28% by weight or about 8%-25% by weight). In some embodiments, the silica abrasives are silica gels or precipitated amorphous silicas, e.g., silicas having an average particle size ranging from about 2.5 microns to about 12 microns.

[0054] In some embodiments, the oral care compositions disclosed herein comprise a whitening agent, e.g., a whitening agent selected from peroxides, metal chlorites, perborates, percarbonates, peroxyacids, hypochlorites, hydroxyapatite, or combinations thereof. Oral care compositions may comprise hydrogen peroxide or a hydrogen peroxide source, e.g., urea peroxide or a peroxide salt or complex, e.g., such as peroxyphosphate, peroxycarbonate, perborate, peroxysilicate, or persulphate salts; for example, calcium peroxyphosphate, sodium perborate, sodium carbonate peroxide, sodium peroxyphosphate, and potassium persulfate or hydrogen peroxide polymer complexes such as hydrogen peroxide -polyvinyl pyrrolidone polymer complexes.

[0055] In some embodiments, the oral care compositions disclosed herein comprise an effective amount of one or more antibacterial agents, for example an antibacterial agent selected from a CPC stannous salt complex (e.g., cetylpyridinium trichlorostanate), 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, magonol, ursolic acid, ursic acid, mom, 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), benzalkonium 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, chlorite salts; 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 oral care compositions disclosed herein in a total amount of fromabout 0.01 wt% to about 0.5 wt%, such as about 0.05 wt% to about 0.1 wt% or about 0.3%, by weight based on a total weight of the oral care composition.

[0056] In some embodiments, the oral care compositions disclosed herein may 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 weight based on the total weight of the oral care composition.

[0057] In some embodiments, the oral care compositions further 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.

[0058] Also encompassed within flavorants disclosed herein are ingredients that provide fragrance and / or other sensory effect in the mouth, including cooling or warming effects. Such ingredients illustratively may include menthol, carvone, methyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone, a-irisone, propenyl guaiethoi, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthan-3-carboxamine, N,2,3-trimethyl-2-isopropylbutanamide, 3-(l-menthoxy)-propane-l,2-diol, cinnamaldehyde glycerol acetal (CGA), menthone glycerol acetal (MGA) and the like. One or more flavorants are optionally present in the oral care compositions disclosed herein in an amount ranging 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%, and in some embodiments from about 0.01 wt% to about 1 wt%, from about 0.05 wt% to about 2 wt%, from about 0.1 wt% to about 2.5 wt%, and from about 0.1 wt% to about 0.5 wt%, by weight based on the total weight of the oral care composition.

[0059] In some embodiments, the oral care compositions disclosed herein further comprise at least one sweetener, useful for example to enhance taste of the composition. Sweetening agents among those disclosed herein may 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, glycerine, propylene glycol, polyethylene glycols, Poloxamer polymers such as Poloxamer R 407 or PLURONIC® F108 (both available from BASF Corporation), alkyl polyglycoside (APG), polysorbate, PEG40, castor oil, menthol, and mixtures thereof. One or more sweeteners are optionally present in the oral care composition disclosed herein in a total amount depending on the particular sweetener(s) selected, but typically from about 0.005 wt% to about 5 wt%, such as from about 0.005 wt% to about 0.2 wt%, or from about 0.05 wt% to about 0.1 wt%, by weight based on the total weight of the oral care composition.

[0060] In some embodiments, the oral care compositions may 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.

[0061] In some embodiments, the oral care compositions disclosed herein further comprise at least one surfactant. Any orally acceptable surfactant, most of which are anionic, cationic, zwitterionic, nonionic, or amphoteric, and mixtures thereof, can be used. Examples of suitable surfactants include taurates; water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of monosulfated monoglyceride of hydrogenated coconut oil fatty acids; higher alkyl sulfates such as sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl isoethionate, sodium laureth carboxylate and sodium dodecyl benzenesulfonate; alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate; higher alkyl sulfoacetates, such as sodium lauryl sulfoacetate; higher fatty acid esters of 1,2-dihydroxypropane sulfonate; and the substantially saturated higher aliphatic acyl amides of lower aliphatic amino carboxylic compounds, such as those having 12-16 carbons in the fatty acid, alkyl or acyl radicals; and the like. Examples of amides include N-lauryl sarcosine, and the sodium, potassium and ethanolamine salts of N-lauryl, N-myristoyl, or N-palmitoyl sarcosine. Examples of cationic surfactants include derivatives of aliphatic quaternary ammonium compounds having one longalkyl chain containing 8 to 18 carbon atoms such as lauryl trimethylammonium chloride, cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, diisobutylphenoxyethyldimethylbenzylammonium chloride, coconut alkyltrimethylammonium nitrite, cetyl pyridinium fluoride, and mixtures thereof. Suitable nonionic surfactants include without limitation poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, di alkyl sulfoxides and the like. Others include, for example, non-anionic polyoxyethylene surfactants, such as Poloxamer 407, Steareth 30, Polysorbate 20, and castor oil; and amphoteric surfactants such as derivatives of aliphatic secondary and tertiary amines having an anionic group such as carboxylate, sulfate, sulfonate, phosphate or phosphonate such as cocamidopropyl betaine (tegobaine), and cocamidopropyl betaine lauryl glucoside; condensation products of ethylene oxide with various hydrogen containing compounds that are reactive therewith and have long hydrocarbon chains (e.g., aliphatic chains of from 12 to 20 carbon atoms), which condensation products (ethoxamers) contain hydrophilic polyoxyethylene moieties, such as condensation products of poly (ethylene oxide) with fatty acids, fatty, alcohols, fatty amides and other fatty moieties, and with propylene oxide and polypropylene oxides. One or more surfactants are optionally present in the oral care compositions disclosed herein in an amount ranging from 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%, e.g., 1.5 wt%, by weight based on the total weight of the composition.

[0062] In some embodiments, the oral care compositions disclosed herein may further comprise at least one foam modulator, useful for example to increase the amount, thickness, or stability of foam generated by the oral care 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 may be optionally present in the oral care composition in an amount range from 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 weight based on the total weight of the composition.

[0063] In some embodiments, the oral care compositions disclosed herein further comprise at least one pH modifying agent. Such pH modifying agents include acidifying agents to lower pH, basifying agents to raise pH, and buffering agents to control pH within a desired range. Forexample, one or more pH modifying agents selected from acidifying, basifying and buffering agents can be included to provide a pH of 2 to 10, or in various illustrative embodiments, 2 to 8, 3 to 9, 4 to 8, 5 to 7, 6 to 10, 7 to 9, etc. Any orally acceptable pH modifying agent can be used, including without limitation carboxylic, phosphoric and sulfonic acids, acid salts (e.g., monosodium citrate, disodium citrate, monosodium malate, etc.), alkali metal hydroxides such as sodium hydroxide, carbonates such as sodium carbonate, bicarbonates such as sodium bicarbonate, sesquicarbonates, borates, silicates, bisulfates, phosphates (<?.g., monosodium phosphate, trisodium phosphate, monopotassium phosphate, dipotassium phosphate, tribasic sodium phosphate, sodium tripolyphosphate, phosphoric acid), imidazole, sodium phosphate buffer (e.g., sodium phosphate monobasic and disodium phosphate) citrates (e.g., citric acid, trisodium citrate dehydrate), pyrophosphates (sodium and potassium salts) and the like, and combinations thereof. One or more pH modifying agents are optionally present in the oral care compositions disclosed herein in an amount effective to maintain the composition in an orally-acceptable pH range. Compositions may have a pH that is either acidic or basic, e.g., from pH 4 to pH 5.5 or from pH 8 to pH 10. In some embodiments, the amount of buffering agent is sufficient to provide a pH of about 5 to about 9, such as about 6 to about 8, or about 7, when the composition is dissolved in water, a mouth rinse base, or a toothpaste base. Typical amounts of buffering agent may range from about 5 wt% to about 35 wt%, such as from about 10 wt% to about 30 wt%, or from about 15 wt% to about 25 wt%, by weight based on the total weight of the oral care composition.

[0064] In some embodiments, the oral care compositions further comprise at least one humectant. Any orally-acceptable humectant can be used, including without limitation polyhydric alcohols such as glycerin, sorbitol (optionally as a 70 wt% solution in water), propylene glycol, xylitol, low molecular weight polyethylene glycols (PEGs), and combinations thereof. The at least one humectant may also function as a sweetener in the oral care composition. In some embodiments, the oral care composition disclosed herein comprises from about 15 wt% to 70 wt%. such as from about 30 wt% to about 65 wt% by weight humectant, by weight based on the total weight of the oral care composition. Suitable humectants include edible polyhydric alcohols such as glycerin, sorbitol, xylitol, propylene glycol as well as other polyols and mixtures of these humectants. Mixtures of glycerin and sorbitol may be used in certain embodiments as the humectant component of the oral care compositions disclosed herein. One or more humectants are optionally present in a total amount ranging from about 1 wt% to about 70 wt%, for example from about 1 wt% to about50 wt%, from about 2 wt% to about 25 wt%, or from about 5 wt% to about 15 wt%, by weight based on the total weight of the oral care composition. In some embodiments, humectants, such as glycerin, are present in an amount that is at least about 20 wt%, e.g., about 20 wt% to about 40 wt%, e.g., about 25 wt% to about 35 wt%. In some embodiments, the oral composition is free or substantially free of any sugar alcohol. In some embodiments, the oral composition is free or substantially free of sorbitol.

[0065] In certain embodiments, the oral care composition disclosed herein may comprise at least one mouth-feel agent, including at least one thickening agent. Mouth-feel agents include materials imparting a desirable texture or other feeling during use of the composition. In some embodiments, the oral care compositions disclosed herein may comprise at least one thickening agent, useful for example to impart a desired consistency and / or mouth feel to the composition. Any orally-acceptable thickening agent can be used, including without limitation carbomers, also known as carboxyvinyl polymers, carrageenans, also known as Irish moss and more particularly i-carrageenan (iota-carrageenan), cellulosic polymers such as hydroxyethyl cellulose, and water-soluble salts of cellulose ethers (e.g., sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose), carboxymethylcellulose (CMC) and salts thereof, e.g., CMC sodium, natural gums such as karaya, xanthan, gum arabic and tragacanthin, colloidal magnesium aluminum silicate, colloidal silica, starch, polyvinyl pyrrolidone, hydroxyethyl propyl cellulose, hydroxybutyl methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl cellulose and amorphous silicas, and the like, hi one embodiment, the class of thickening or gelling agents includes a class of homopolymers of acrylic acid crosslinked with an alkyl ether of pentaerythritol or an alkyl ether of sucrose, or carbomers. Carbomers are commercially available from B. F. Goodrich as the CARBOPOL® series. Particularly preferred carbomers include CARBOPOL® 934, 940, 941, 956, 974P, and mixtures thereof. Silica thickeners such as DT 267 (from PPG Industries) may also be used. The one or more thickening agents are optionally present in the oral care compositions disclosed herein in an amount ranging from about 0.01 wt% to about 15 wt%, for example from about 0.1 wt% to about 10 wt%, or from about 0.2 wt% to about 5 wt%, by weight based on the total weight of the composition. Certain embodiments of the oral care compositions disclosed herein comprise sodium carboxymethyl cellulose (e.g., from about 0.5 wt% to about 1.5 wt%). In certain embodiments, thickening agents in an amount of about 0.5 wt% to about 5.0 wt% by weight of the total composition are used. Thickeners may be present in anamount of from about 1 wt% to about 15 wt%, such as from about 3 wt% to about 10 wt%, from about 4 wt% to about 9 wt%, from about 5wt % to about 8 wt%, for example about 5 wt%, about 6 wt%, about 7 wt%, or about 8 wt%.

[0066] In some embodiments, the oral care compositions disclosed herein further comprise at least one colorant in addition to the dye(s) in the film. Colorants herein include pigments, dyes, lakes and agents imparting a particular luster or reflectivity such as pearling agents, hr various embodiments, colorants are operable to provide a white or light-colored coating on a dental surface, to act as an indicator of locations on a dental surface that have been effectively contacted by the composition, and / or to modify appearance, in particular color and / or opacity, of the composition to enhance attractiveness to the consumer. Any orally acceptable colorant can be used, including FD&C dyes and pigments, talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium aluminum silicate, silica, titanium dioxide, zinc oxide, red, yellow, brown and black iron oxides, ferric ammonium ferrocyanide, manganese violet, ultramarine, titaniated mica, bismuth oxychloride, and mixtures thereof. One or more colorants are optionally present in the oral care composition in an amount ranging 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 weight based on the total weight of the oral care composition.

[0067] In some embodiments, the oral care composition disclosed herein further comprises an anti-calculus (tartar control) agent. Suitable anti-calculus agents include, but are not limited to: phosphates and polyphosphates, polyaminopropane sulfonic acid (AM PS), 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, and phosphonoalkane carboxylic acids. Useful inorganic phosphate and polyphosphate salts include monobasic, dibasic and tribasic sodium phosphates. Soluble pyrophosphates may be useful anticalculus agents. The pyrophosphate salts can be any of the alkali metal pyrophosphate salts. In certain embodiments, salts include tetra alkali metal pyrophosphate, dialkali metal diacid pyrophosphate, trialkali metal monoacid pyrophosphate and mixtures thereof, wherein the alkali metals are sodium or potassium. The pyrophosphates may also contribute to preservation of the compositions by lowering water activity. Exemplary pyrophosphates may include tetrasodium pyrophosphate (TSPP), tetrapotassium pyrophosphate, sodium tripolyphosphate,tetrapolyphosphate, sodium trimetaphosphate, sodium hexametaphosphate and mixtures thereof. The salts may be useful in both their hydrated and / or unhydrated forms. An effective amount of pyrophosphate salt that may be included in the oral care compositions disclosed herein is generally enough to provide least about 0.1 wt% pyrophosphate ions, e.g., from about 0.1 wt% to about 3 wt%, e.g., from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, or from about 0.2 wt% to about 0.5 wt%.

[0068] Other useful tartar control agents may include polymers and co-polymers. In some embodiments, the oral care compositions include one or more polymers, such as polyethylene glycols, polyvinyl methyl ether maleic acid copolymers, polysaccharides (e.g., cellulose derivatives, for example carboxymethyl cellulose, or polysaccharide gums, for example xanthan gum or carrageenan gum). Acidic polymers, for example polyacrylate gels, may be provided in the form of their free acids or partially or fully neutralized water-soluble alkali metal (e.g., potassium and sodium) or ammonium salts. Certain embodiments include 1:4 to 4:1 copolymers of maleic anhydride or acid with another polymerizable ethylenically unsaturated monomer, for example, methyl vinyl ether (methoxyethylene), having a molecular weight (MW) of about 30,000 to about 1,000,000, polyvinyl methyl ether / maleic anhydride (PVM / MA) copolymers such as GANTREZ® (e.g., GANTREZ® S-97 polymer). In some embodiments, the PVM / MA copolymer comprises a copolymer of methyl vinyl ether / maleic anhydride, wherein the anhydride is hydrolyzed following copolymerization to provide the corresponding acid. In some embodiments, PVM / MA copolymer has an average molecular weight of about 30,000 to about 1,000,000, e.g., about 300,000 to about 800,000, e.g., wherein the anionic polymer is optionally present in an amount of about 1 wt% to about 5 wt%. e.g., about 2 wt%, by weight based on the total weight of the composition. In some embodiments, the anti-calculus agent is present in the oral care composition disclosed herein in an amount ranging from 0.2 wt% to 0.8 wt%; such as from about 0.3 wt% to 0.7 wt%; from about 0.4 wt% to about 0.6 wt%; or about 0.5 wt%, by weight based on the total weight of the composition. Copolymers are available for example as GANTREZ® AN 139 (MW 500,000), AN 1 19 (MW 250,000) and S-97 Pharmaceutical Grade (MW 70,000), from GAF Chemicals Corporation. Other operative polymers include those such as the 1:1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vinyl-2-pyrollidone, or ethylene, the latter being available for example as Monsanto EMA No. 1 103, MW 10,000 and EMA Grade 61. and 1:1 copolymers of acrylic acid with methyl or hydroxyethyl methacrylate, methyl or ethyl acrylate, isobutyl vinylether or N-vinyl-2-pyrrolidone. Suitable generally are polymerized olefinically or ethylenically unsaturated carboxylic acids containing an activated carbon-to-carbon olefinic double bond and at least one carboxyl group, that is. an acid containing an olefinic double bond which readily functions in polymerization because of its presence in the monomer molecule either in the alphabeta position with respect to a carboxyl group or as part of a terminal methylene grouping. Illustrative of such acids are acrylic, methacrylic, ethacrylic, alpha-chloroacrylic, crotonic, beta-acryloxy propionic, sorbic, alpha-chlorsorbic, cinnamic, beta-styrylacrylic, muconic, itaconic, citraconic, mesaconic, glutaconic, aconitic, alpha-phenylacrylic, 2-benzyl acrylic, 2-cyclohexylacrylic, angelic, umbellic, fumaric, maleic acids and anhydrides. Other different olefinic monomers copolymerizable with such carboxylic monomers include vinylacetate, vinyl chloride, dimethyl maleate and the like. Copolymers may contain sufficient carboxylic salt groups for water-solubility. A further class of polymeric agents includes a composition containing homopolymers of substituted acrylamides and / or homopolymers of unsaturated sulfonic acids and salts thereof, in particular where polymers are based on unsaturated sulfonic acids selected from acrylamidoalykane sulfonic acids such as 2-acrylamide 2 methylpropane sulfonic acid having a molecular weight of about 1,000 to about 2,000,000. Another useful class of polymeric agents may include polyamino acids, such as those containing proportions of anionic surface-active amino acids such as aspartic acid, glutamic acid and phosphoserine.

[0069] In some embodiments, the oral care compositions disclosed herein further 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.

[0070] In some embodiments, the oral care compositions disclosed herein further comprise at least one nutrient. Suitable nutrients include vitamins, minerals, amino acids, and mixtures thereof. Vitamins include Vitamins C and D, miamine, riboflavin, calcium pantothenate, niacin, folic acid, nicotinamide, pyridoxine, cyanocobalamin, para-aminobenzoic acid, bioflavonoids, and mixtures thereof. Nutritional supplements include amino acids (such as L-tryptophane, L-lysine, methionine, threonine, levocamitine and L-camitine), lipotropics (such as choline, inositol, betaine, and linoleic acid), and mixtures thereof.

[0071] In some embodiments, the oral care compositions disclosed herein may further compriseat least one viscosity modifier, useful for example to help inhibit settling or separation of ingredients or to promote re-dispersibility upon agitation of a liquid oral care composition. Any orally acceptable viscosity modifier can be used, including without limitation, mineral oil, petrolatum, clays and organo-modified clays, silicas and the like. One or more viscosity modifiers may optionally be present in the oral care composition in an amount ranging from about 0.01 wt% to about 10 wt%, for example from about 0.1 wt% to about 5 wt%, by weight based on the total weight of the oral care composition.

[0072] In some embodiments, the oral care compositions disclosed herein further comprise at least one antisensitivity agent, 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 antisensitivity agents may be added to the oral care composition in any effective amount, 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.

[0073] In some embodiments, the oral care compositions disclosed herein further comprise an antioxidant. Any orally acceptable antioxidant can be used, including butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), vitamin A, carotenoids, co-enzyme Q10, PQQ, Vitamin A, Vitamin C, Vitamin E, anethole-dithiothione, flavonoids, polyphenols, ascorbic acid, herbal antioxidants, chlorophyll, melatonin, and mixtures thereof.

[0074] In some embodiments, the oral care compositions disclosed herein further comprise a source of calcium and phosphate selected from (i) calcium-glass complexes, e.g., calcium sodium phosphosilicates, and (ii) calcium-protein complexes, e.g., casein phosphopeptide-amorphous calcium phosphate, a soluble calcium salt, e.g., selected from calcium sulfate, calcium chloride, calcium nitrate, calcium acetate, calcium lactate, and combinations thereof.

[0075] In some embodiments, the oral care compositions disclosed herein further comprise water. The amount of water may depend on the form of the oral care composition, e.g., as a mouthwash, a dentifrice, a film, a gel, a paste, etc. In certain embodiments of the disclosure, the oral care composition disclosed herein may be anhydrous (e.g., about 0 wt% or less than about 0.01 wt% water), and in certain embodiments, the oral care composition may contain water in an amount less than about 5 wt%, such as less than about 4 wt%, less than about 3 wt%, less than about 1 wt%, or less than about 0.5 wt%, by weight relative to the total weight of the composition. In certain embodiments, the oral care composition may contain water in an amount ranging fromabout 5 wt% to about 40 wt%, e.g., from about 10 wt% to about 35 wt%, such as about 15 wt%, about 25 wt%, about 30%, and about 35 wt% or more of water, based on a total weight of the oral care composition.

[0076] Also disclosed herein are methods of using the oral care composition disclosed herein. The methods disclosed herein may comprise contacting the oral care composition with water. The methods may also include contacting the surface of the teeth with the oral care composition. Contacting the surface of the teeth with the oral care composition may include disposing the oral care composition (e.g., toothpaste) on a toothbrush and brushing the teeth with the toothbrush. In certain embodiments, the methods disclosed herein may include contacting the surface of the teeth with the oral care composition by contacting the oral care composition with the oral cavity, e.g., in the form of a mouth rinse or mouthwash. The oral care composition may be applied and / or contacted with the surfaces of the teeth at predetermined intervals. For example, a daily basis, at least once a day, twice a day, or more, for multiple days, or alternatively every other day. In another example, the oral care composition may be applied and / or contacted with the surfaces of the teeth at least once a day, at least once every two days, at least once every three days, at least once every five days, at least once a week, at least once every two weeks, or at least once a month. The oral care composition thereof may be utilized for up to 2 weeks, up to 3 weeks, up to 4 weeks, up to 6 weeks, up to 8 weeks, or greater.

[0077] In certain embodiments disclosed herein, the method comprises applying the oral care composition to the oral cavity for about 10 seconds to about 30 minutes, such as about 15 seconds to about 25 minutes, about 20 seconds to about 15 minutes, about 25 seconds to about 5 minutes, about 30 seconds to about 2 minutes, about 45 seconds to about 90 seconds, about 1 minute to about 2 minutes, or about 1 minute to about 90 seconds. In certain embodiments, the method comprises applying to oral care composition to the oral cavity for a sufficient period of time to allow the film to release the coated dye into the orally-acceptable earner, thereby changing the color of the orally-acceptable carrier. According to certain embodiments of the disclosure, the oral care composition is applied to the oral cavity in an amount of about 0.1 to about 3 grams.

[0078] In certain aspects, provided herein are methods of using an oral care composition as disclosed herein. The methods disclosed herein comprise administering the oral care composition to the oral cavity of a subject, e.g., by applying the oral care composition to the teeth of the subject. In certain embodiments, the oral care composition is exposed to an aqueous environment, e.g., byadding water to the oral care composition, prior to administration. Tn certain embodiments, the oral care composition is exposed to an aqueous environment, e.g., by saliva or by the addition of water into the mouth during the administration process.

[0079] In certain embodiments disclosed herein, the oral care composition has a water activity (aw) of less than about 1, such as less than about 0.5. In certain embodiments, the oral care composition has a water activity of less than about 0.45. less than about 0.4, less than about 0.35. less than about 0.3, less than about 0.25, less than about 0.2, or less than about 0.15. In certain embodiments, the oral care composition has a water activity ranging from about 0.1 to about 1, such as from about 0.1 to about 0.5, about 0.15 to about 0.3, or any range or subrange therebetween. Water activity (or aw) correlates to the association between various non-aqueous constituents and solids, and is a measure of the energy status of the water in a system. It is defined as the vapor pressure of a liquid divided by that of pure water at the same temperature. Therefore, pure distilled water has a water activity of exactly one. Total water content is related to water activity, but it is also influenced by the presence of compounds such as humectants that may interact strongly with water and reduce the vapor pressure of the composition.

[0080] In certain embodiments disclosed herein, the oral care composition has a W* value, such as W* initial value, a W* value after 1 week aging at 60 °C, or a W* value after 2 weeks aging at 60 °C, of less than about 75, such as less than about 70, less than about 65, less than about 60, less than about 55, less than about 50, less than about 45, less than about 40, or less than about 35. In certain embodiments, the oral care composition has a W* value, such as W* initial value, a W* value after 1 week aging at 60 °C, or a W* value after 2 weeks aging at 60 °C, ranging from about 30 to about 75, such as from about 30 to about 65, about 30 to about 60, about 30 to about 55, about 30 to about 50, about 30 to about 45, or about 30 to about 40.

[0081] In certain embodiments, the W* value may be calculated using the formula: W* = (a*2+ b*2+ (L*-100)2)1 / 2. Measurements may be taken, for example, with a Spectroshade Micro instrument manufactured by Medical High Technology (MHT). Before measuring the baseline optical properties of a formulation, the instrument may calibrated per the manufacturer’s instructions. To take a measurement, the instrument is positioned so that the formulation is in the instrument's field of vision and then the image is captured. This may be repeated for each measurement.

[0082] The measurement scale is the CIE L*a*b* (CIELAB) scale developed by the InternationalCommission on Illumination (CIE). CIELAB is an opponent color system based on the fact that retinal color stimuli are translated into distinctions between light and dark, red and green, and blue and yellow. CIELAB indicates these values with three axes: L*, a*, and b*. The L value indicates the lightness of a color, where L=0 is black and L=100 is white. AL = Lfinai - Lilial. Thus, a larger positive AL value corresponds to a whiter formulation. The a value ranges between +a = magenta and -a = green. The b value ranges between +b = yellow and -b = blue. The W value incorporates the L, a and b values to describe how close the measured color is to true white, where W* = (a2+ b2+ (L*-100)2)1 / 2. A larger negative AW value corresponds to a whiter formulation.EXAMPLES

[0083] The examples and other implementations described herein are exemplary and not intended to be limiting in describing the full scope of compositions and methods of this disclosure. Equivalent changes, modifications and variations of specific implementations, materials, compositions and methods may be made within the scope of the present disclosure, with substantially similar results.Example 1 - Dentifrice Compositions Containing Color-Changing Strips

[0084] Test dentifrice compositions were prepared containing regulatory-approved Blue 1 aluminum lake dye. Each color-changing strip was coated three times with calcium carbonate to prevent color leaching, and the coated strips were added to the formulations. The dentifrice formulations that were prepared are shown in Table 1 below.

[0085] Table 1 - Dentifrice Test FormulationsTest Test Test Test TestIngredient#1 #2 #3 #4 #5Sorbitol, 70%68.00 — — — —solutionWater 12.36 12.36 6.36 — —Sodium CMC 0.60 0.60 0.60 — —Tetrasodium0.50 0.50 0.50 0.50 3.00pyrophosphate3x coated dye strips 0.20 0.20 0.20 0.20 0.20Glycerin — 68.00 74.00 67.46 69.96PEG / PPG 116 / 66— — — 10.00 5.00CopolymerFumed silica — — — 1.75 1.75PVP — — — 1.75 1.75Silicas, SLSpowder, flavor,18.34 18.34 18.34 18.34 18.34NaF, PEG-600, NaSaccharinTotal: 100 100 100 100 100% Total Water in a32.76 12.36 6.36 — —formulation

[0086] The water activity of each of the test formulations was measured, and formulae with lower water levels or no water showed lower readings, which is consistent with the observation of reduced color leaching of the dye. The results are shown in FIG. 1 and in Table 2 below.

[0087] Table 2 - Water Activity (aw) of Test Formulations #1-5Test awFormulation#1 0.8307#2 0.4044#3 0.2772#4 0.1837#5 0.2022

[0088] The samples were evaluated cosmetically using the CIELAB scale on a Spectroshade from MHT. The L*, a*, and b* values were used to calculate a W value initially at room temperature (W initial), after 1 week aging at 60 °C, and after 2 weeks aging at 60 °C. W* was calculated using the formula: W* = (a*2+ b*2+ (L*-100)2)1 / 2. The results are shown in FIG. 2 and in Tables 3-5 below.

[0089] Table 3 - W* initial value of Test Formulations #1-5Test L* a* b* w*Formulation initial#1 29.2 -29.1 -9.9 77.2#2 53.7 -20.5 -2.2 50.7#3 46.7 -7.7 -7.2 54.3#4 66.1 -6.7 -4.6 34.9#5 67.8 -3.0 -6.3 32.9

[0090] Table 4 - W* value of Test Formulations #2-5 after 1 week at 60 °CTest L* a* b* w*Formulation 1 wk / 60 °C#2 45.6 -34.2 -16.8 66.4#3 44.8 -13.5 -16.7 59.2#4 61.9 -11.0 -10.6 41#5 65.4 -10.3 -8.7 37.1

[0091] Table 5 - W value of Test Formulations #2-5 after 2 weeks at 60 °CTest L* a* b* w*Formulation 2 wks / 60 °C#2 42.4 -32.6 -17.1 68.4#3 45.3 -13.4 -13.6 57.9#4 62.1 -12.3 -10.2 41.1#5 66.3 -11.8 -7.2 36.4

[0092] As shown, the results demonstrate that Test #1 (high water, sorbitol-based formulation) shows complete dissolution of the strips within 2 to 3 days at room temperature, and the formulation turned all blue in color. The formulae with lower water levels or no water showed very minimal leaching of color from the strips over time.

[0093] The present disclosure has been described with reference to exemplary implementations. Although a limited number of implementations have been shown and described, it will be appreciated by those skilled in the art that changes may be made in these implementations without departing from the principles and spirit of the preceding detailed description. It is intended that the present disclosure be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.

Claims

CLAIMSWhat Is Claimed Is:

1. An oral care composition comprising:(i) a water-soluble film comprising at least one cellulose polymer, at least one dye, and at least one coating; and(ii) an orally- acceptable carrier;wherein the composition contains less than about 40 wt% of water.

2. The oral care composition of claim 1, wherein the at least one coating is an inorganic material selected from calcium carbonate, aluminum oxide, magnesium oxide, silicon monoxide, silicon dioxide, titanium dioxide, tin oxide, zinc oxide, calcium magnesium carbonate, magnesium carbonate, phosphate salts, pyrophosphate salts, and combinations thereof.

3. The oral care composition according to claim 1 or 2, wherein the at least one coating is calcium carbonate.

4. The oral care composition according to any one of the preceding claims, wherein the orally-acceptable earner is glycerin.

5. The oral care composition according to any one of the preceding claims, wherein the orally -acceptable carrier is present in an amount ranging from about 20 wt% to about 90 wt%, such as from about 60 wt% to about 80 wt%, based on a total weight of the oral care composition.

6. The oral care composition of any one of the preceding claims, wherein the oral care composition contains less than about 35 wt% water, less than 25 wt% water, 15 wt% water, 10 wt% water, less than 8 wt% water, less than 5 wt%, less than 2 wt% water, or wherein the oral care composition is substantially free or free of water.

7. The oral care composition of any one of the preceding claims, wherein the water-soluble film comprises at least two or at least three calcium carbonate coatings, such as three calcium carbonate coatings.

8. The oral care composition of any one of the preceding claims, wherein the dye is a water soluble dye, such as FD&C Blue #1. for example Brilliant Blue or Aluminum Lake Blue.

9. The oral care composition of any one of the preceding claims, wherein the at least one cellulose polymer is selected from methylcellulose, hydroxypropylmethyl cellulose, hydroxyethylpropyl cellulose, hydroxybutylmethyl cellulose, carboxymethyl cellulose, and mixtures thereof, preferably hydroxypropylmethyl cellulose.

10. The oral care composition of any one of the preceding claims, further comprising a polyethylene glycol / polypropylene glycol copolymer.

11. The oral care composition of claim 8, wherein the polyethylene glycol / polypropylene glycol copolymer is present in an amount ranging from about 1 wt% to about 15 wt%, such as about 5 wt% to about 10 wt%, based on a total weight of the oral care composition.

12. The oral care composition of any one of the preceding claims, further comprising at least one anticalculus agent, such as phosphates and polyphosphates, polyaminopropanesulfonic acid (AMPS), hexametaphosphate salts, zinc citrate trihydrate, polypeptides, polyolefin sulfonates, polyolefin phosphates, diphosphonates, and mixtures thereof, preferably tetrasodium pyrophosphate (TSPP).

13. The oral care composition of claim 10, wherein the at least one anticalculus agent is present in an amount ranging from about 0.1 wt% to about 5 wt%, such as from about 0.5 wt% to about 3 wt%, based on a total weight of the oral care composition.

14. The oral care composition of any one of the preceding claims, further comprising at least one thickening agent, such as sodium carboxymethyl cellulose (CMC).

15. The oral care composition of claim 12, wherein the at least one thickening agent is present in an amount ranging from about 0.1 wt% to about 2 wt%, such as from about 0.4 wt% to about 0.8 wt%, or about 0.6 wt%, based on a total weight of the oral care composition.

16. The oral care composition according to any one of the preceding claims, wherein the oral care composition is free of or substantially free of sorbitol.

17. The oral care composition according to any one of the preceding claims, wherein the water-soluble film is substantially dissolved after a period of greater than 30 seconds and less than 180 seconds of brushing, scrubbing, or agitation in the presence of water.

18. The oral care composition according to any one of the preceding claims, wherein the at least one calcium carbonate coating comprises at least about 50 wt% of the water-soluble film, such as about 60 wt% to about 70 wt% of the water-soluble film, based on a total weight of the water-soluble film.

19. The oral care composition according to any one of the preceding claims, wherein the oral care composition and the water-soluble film are substantially stable at about 60 °C for at least one week, preferably for at least two weeks, or wherein the oral care composition and the water solublefilm are substantially stable at room temperature for at least one month, preferably for at least two months.

20. The oral care composition according to any one of the preceding claims, wherein the oral care composition has a water activity (aw) of less than about 0.

5. such as an awranging from about 0.15 to about 0.25 or from about 0.1 to about 0.2.

21. The oral care composition according to any one of the preceding claims, wherein the water-soluble film is present in the oral care composition in an amount ranging from about 0.1 wt% to a about 1 wt%. such as about 0.2 wt% to about 5 wt%, or about 0.2 wt%, based on a total weight of the oral care composition.

22. A method of cleaning teeth in an oral cavity comprising brushing the teeth with the oral care composition according to any one of claims 1-21, wherein brushing is continued at least until the water-soluble film releases substantially all of the dye into the orally-acceptable carrier.

23. The method of claim 22, wherein the brushing is continued for at least about 30 seconds, such as at least about 60 seconds.

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