AU2013406042A1 - Regimen for providing smooth tooth feel - Google Patents

Abstract

The present invention provides a method of treating a tooth surface to provide smooth tooth feel benefits, comprising the steps: (a) contacting the tooth surface with a first composition comprising a water-insoluble calcium phosphate; and thereafter (b) contacting the tooth surface with a second composition comprising an organophosphate.

Description

WO 2015/074241 PCT/CN2013/087671 1 REGIMEN FOR PROVIDING SMOOTH TOOTH FEEL FIELD OF THE INVENTION The present invention relates to a method of treating tooth surface with a first composition 5 and then a second composition to provide a smooth tooth feel. BACKGROUND OF THE INVENTION Oral care products, such as toothpastes and mouth rinses, are routinely used by consumers as part of their oral care hygiene regimen. Oral care products are often formulated to provide 10 both therapeutic and cosmetic hygiene benefits. Therapeutic benefits include dental caries prevention, gingivitis prevention, and hypersensitivity control. Cosmetic benefits include control of plaque and calculus formation, removal and prevention of tooth stain, tooth whitening, breath freshening, and overall improvements in mouth feel impression which can be broadly characterized as mouth feel aesthetics. Smooth tooth surface or slick tooth feel is generally 15 considered as an important sign of thorough cleaning and effective delivery of these benefits. Abrasives, such as silica and calcium carbonate, are widely used in toothpastes to remove dental stains and polish the teeth, therefore smoothing the tooth surface and providing a slick tooth feel. However, the abrasion of abrasives on the tooth surface may lead to abrasive damages on dental enamel. Such abrasive damages include enamel loss (e.g., scratches, micro-cracks, etc.) 20 and enamel thinning, which may roughen the tooth surface and make it easier for undesirable bacteria to deposit and invade into the tooth and consequently result in enamel destruction. On the other hand, a pellicle film to which the dental stains affix usually forms on the surface of the dental enamel within minutes after teeth are cleaned by selective binding of glycoproteins from saliva. The slick tooth feel may diminish soon after the adhesion of the thin coating to the dental 25 enamel. Therefore, there is a need to solve this problem. There is a need to smooth the tooth surface without abrasive damage to dental enamel. There is also a need to restore the tooth surface smoothness even after enamel loss or thinning. Finally, there is a need to provide a long-lasting smoothing effect on the tooth surface. 30 SUMMARY OF THE INVENTION The present invention attempts to solve one or more of these problems. In one aspect, the present invention provides a method of treating a tooth surface, comprising the steps: WO 2015/074241 PCT/CN2013/087671 2 (a) contacting the tooth surface with a first composition comprising a water-insoluble calcium phosphate, wherein the water-insoluble calcium phosphate has a calcium to phosphorus molar ratio from 1:1 to 10:1; and thereafter (b) contacting the tooth surface with a second composition, wherein the second composition 5 comprises an organophosphate having the formula: 0 R-(-0X)a(0-Y) -P0 -Zi 0-Z2 wherein R is a hydrocarbyl comprising 4 to 22 carbon atoms; X and Y are each independently an alkylene comprising 2 to 4 carbon atoms; a and b are each independently an integer selected from 0 to 20, wherein a+b is in the range from 0 to 20; Z' and Z2 are each 10 independently selected from hydrogen, hydrocarbyl comprising 1 to 26 carbons preferably comprising one or more ether moieties, and a counter ion, provided that at least one of Z' and Z 2 is hydrogen or a counter ion. In another aspect, the present invention provides an oral care kit, comprising: (a) a first product containing a first composition, wherein the first composition comprises 15 0.01% to 99% by weight of a water-insoluble calcium phosphate having a calcium to phosphorus molar ratio from 1:1 to 10:1; (b) a second product containing a second composition, wherein the second product is a mouth rinse with a pH from 6 to 8 and a viscosity from 100 cps to 5000 cps, and wherein the second composition comprises 0.01% to 99% by weight of an organophosphate as defined above; 20 and (c) instructions instructing a user to first use the first product to contact a tooth surface and thereafter immediately use the second product to contact the tooth surface. In a further aspect, the present invention provides an oral care product comprising a first container and a second container, wherein the first container contains a first composition 25 comprising 0.0 1% to 99% by weight of a water-insoluble calcium phosphate which has a calcium to phosphorus molar ratio from 1:1 to 10:1, and the second container contains a second composition comprising 0.01% to 99% by weight of an organophosphate as defined above; and wherein the product optionally contains instructions instructing a user to dispense the first composition before the second composition is dispensed. 30 One aspect of the invention generally provides a sequential application system of a calcium WO 2015/074241 PCT/CN2013/087671 3 source followed by a specific organophosphate onto the tooth surface. Without wishing to be bound by theory, the first step of applying the calcium source is believed to seal micro-cracks or crevices in the tooth structure, and the second step of applying the specific organophosphate is believed to seal the calcium into the tooth structure. By this sequential application system, 5 perceptible and meaningful improvements are delivered to the tooth surface, by potentially providing new crystal growth at sites of enamel loss or thinning, restoring tooth surface smoothness and/or building up a uniform protection layer to prolong the tooth surface smoothness. These and other features, aspects, and advantages of the present invention will become 10 evident to those skilled in the art from the detailed description which follows. BRIEF DESCRIPTION OF THE DRAWINGS While the specification concludes with claims particularly defining and distinctly claiming the invention, it is believed that the invention will be better understood from the following 15 description of the accompanying figures. In the accompanying figures, Figs. 1(a) to 1(e) show property analysis of a tooth surface by Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) when the tooth surface is treated according to a specific embodiment of the present invention. Figs. 2(a) to 2(d) show Scanning Probe Microscopy (SPM) images of a tooth surface before 20 treatment, after etching with citric acid, after a first step of treatment and after a second step of treatment, according to a specific embodiment of the present invention. Figs. 3(a) to 3(d) show Scanning Probe Microscopy (SPM) images of a tooth surface before treatment, after etching with citric acid, after a first step of treatment and after a second step of treatment, according to a comparative embodiment. 25 Figs. 4(a) to 4(c) show Scanning Probe Microscopy (SPM) images of a tooth surface before treatment, after etching with citric acid, and after a one-step treatment, according to another comparative embodiment. Fig. 5 shows panel test results about slick tooth feel over time for 3 hours after treatment, according to a specific embodiment of the present invention as well as after treatment according 30 to comparative embodiments. DETAILED DESCRIPTION OF THE INVENTION The terms "oral composition" and "oral care composition" are used interchangeably herein, WO 2015/074241 PCT/CN2013/087671 4 and refer to a product, which in the ordinary course of usage, is not intentionally swallowed for purposes of systemic administration of particular therapeutic agents, but is rather retained in the oral cavity for a time sufficient to contact dental surfaces and/or oral tissues for purposes of topical administration. 5 The term "dentifrice", as used herein, includes paste, gel, liquid, powder or tablet formulations for cleaning teeth with the aid of a toothbrush unless otherwise specified. The dentifrice composition may be a single phase composition or may be a combination of two or more separate dentifrice compositions. The term "water-insoluble", as used herein, means having a low solubility in water or being 10 incapable of being fully dissolved in water. Specifically, a water-insoluble substance is intended to mean a substance which has a solubility at 20'C of less than 1 g/l and in particular of less than 1 mg/l. The term "water-soluble", as used herein, means having a high solubility in water or being capable of being fully dissolved in water. Specifically, a water-soluble substance is intended to 15 mean a substance which has a solubility at 20'C of no less than 1 g/l and in particular of no less than 10 g/l. The term "particle size", as used herein, refers to a volume based particle size measured by laser diffraction methods. Laser diffraction measures particle size distributions by measuring the angular variation in intensity of light scattered as a laser beam passes through a dispersed 20 particulate sample. Large particles scatter light at small angles relative to the laser beam and small particles scatter light at large angles. The angular scattering intensity data is then analyzed to calculate the size of the particles responsible for creating the scattering pattern, using the Mie theory of light scattering. The particle size is reported as a volume equivalent sphere diameter. The term "mean particle size" and "average particle size" are used interchangeably herein, and 25 refer to an average value of particle size distribution calculated based on the logarithmic scale. The terms "hydrocarbyl", "hydrocarbyl substituent" and "hydrocarbyl group" are used interchangeably herein, and refer to a univalent radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. Such a univalent radical can be classified as an aliphatic group, cyclic group, or combination of aliphatic and cyclic 30 groups (e.g., alkaryl and aralkyl groups). The term "aliphatic group" means a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example. The term "alkyl group" means a saturated linear or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, WO 2015/074241 PCT/CN2013/087671 5 octadecyl, amyl, 2-ethylhexyl, and the like. The term "alkenyl group" means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group. The term "alkynyl group" means an unsaturated, linear or branched hydrocarbon group with one or more carbon-carbon triple bonds. The term "cyclic group" means a closed ring 5 hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group. The term "alicyclic group" means a cyclic hydrocarbon group having properties resembling those of aliphatic groups. The term "aromatic group" or "aryl group" means a mono- or polynuclear aromatic hydrocarbon group. The term "viscosity", as mentioned herein, is measured using Brookfield viscometers with 10 cone and plate attachment. For viscosities in the range of 0-16000cps, the Brookfield DV-II viscometer with S02 plate is used. A 500ml sample of the composition is equilibrated at 25'C for three minutes before the readings are taken at 2.5 rpm. For viscosities greater than 16000cps and up to 33000cps, the Brookfield DV-I viscometer with S02 plate is used. A 500ml sample of the composition is equilibrated for 1 minute at 25'C before the readings are taken at 0.3 rpm. 15 The term "tooth" or its plural form "teeth", as used herein, refers to natural tooth as well as artificial tooth or dental prosthesis. Active and other ingredients useful herein may be categorized or described by their cosmetic and/or therapeutic benefit or their postulated mode of action or function. However, it is to be understood that the active and other ingredients useful herein can, in some instances, 20 provide more than one cosmetic and/or therapeutic benefit or function or operate via more than one mode of action. Therefore, classifications herein are made for the sake of convenience and are not intended to limit an ingredient to the particularly stated application or applications listed. As used herein, the articles including "a" and "an" when used in a claim, are understood to mean one or more of what is claimed or described. 25 As used herein, the terms "comprise", "comprises", "comprising", "include", "includes", "including", "contain", "contains", and "containing" are meant to be non-limiting, i.e., other steps and other sections which do not affect the end of result can be added. The above terms encompass the terms "consisting of' and "consisting essentially of'. As used herein, the words "preferred", "preferably" and variants refer to embodiments of the 30 invention that afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

WO 2015/074241 PCT/CN2013/087671 6 Sequential Aulication System In accordance with the present invention, a sequential application system is provided to treat the tooth surface. 5 In the first step (a), the tooth surface is contacted with a first composition comprising a water-insoluble calcium phosphate, wherein the water-insoluble calcium phosphate has a calcium to phosphorus molar ratio from 1:1 to 10:1. The water-insoluble calcium phosphate particles can deposit into micro-cracks and crevices, providing a source of calcium and phosphate ions for remineralization of the dental enamel. 10 In the second step (b), the tooth surface is further contacted with a second composition comprising the organophosphate as defined hereinabove. The organophosphate can form a protection layer on the tooth surface so as to seal the calcium and phosphate ions into the tooth structure. In a specific embodiment, contacting step (b) is initiated within 30 minutes, within 15 15 minutes, within 5 minutes, or immediately after the conclusion of contacting step (a). It is preferred that there is no intervening dental treatment step between step (a) and step (b). The contacting steps can be achieved by any oral care hygiene regimen, for example, selected from the group consisting of brushing, flossing, rinsing, plastering, attaching, and combinations thereof. Accordingly, the first composition and the second composition can be in 20 various forms to facilitate the oral care hygiene regimen. Such forms include but are not limited to toothpaste, tooth powder, tooth gel, dental floss, mouth rinse, chewable tablet, chewing gum, or strip or film for direct application or attachment to the tooth surface. In a specific embodiment, the first composition is a toothpaste composition and the second composition is a mouth rinse. In another specific embodiment, the first composition and the second composition are each 25 independently a mouth rinse. The contacting duration depends on the specific regimen and the specific composition form. For example, brushing with a toothpaste may be conducted from 1 to 5 minutes, rinsing with a mouth rinse may be conducted from 5 seconds to 2 minutes, and plastering with a strip or film may be conducted from 5 minutes to 60 minutes, preferably from 20 minutes to 40 minutes. 30 In a specific embodiment, contacting steps (a) and (b) each independently has a contacting duration from 5 seconds to 5 minutes; and contacting step (b) is initiated immediately after the conclusion of contacting step (a). In a specific embodiment, contacting step (a) is achieved by brushing the tooth surface with WO 2015/074241 PCT/CN2013/087671 7 a toothpaste comprising the first composition, and then contacting step (b) is immediately achieved by rinsing the tooth surface with a mouth rinse comprising the second composition. In another specific embodiment, contacting step (a) is achieved by rinsing the tooth surface with a first mouth rinse comprising the first composition, and then contacting step (b) is 5 immediately achieved by rinsing the tooth surface with a second mouth rinse comprising the second composition. The First Composition Tooth surfaces are constantly experiencing a loss and gain of minerals. This process is 10 partially kept in balance by the chemical composition of saliva and the extra-cellular fluid. Disruption of the tooth surface integrity can occur by acidic food and beverages, bacterial challenge and erosion by exaggerated tooth brushing or grinding of the teeth. These processes are accompanied by a demineralization of the exposed tooth surfaces leading to surface roughness. Therefore, according to the present invention, the first composition provides a source 15 of calcium and phosphate ions for remineralization of the dental enamel by depositing into micro-cracks and crevices in the tooth structure or on the tooth surface. In a specific embodiment, the first composition comprises a water-insoluble calcium phosphate, wherein the water-insoluble calcium phosphate has a calcium to phosphorus molar ratio from 1:1 to 10:1. 20 Calcium phosphate is the main mineral found in teeth. Tooth enamel is composed of almost ninety percent of hydroxyapatite which is a calcium phosphate mineral known as bone mineral. The water-insoluble calcium phosphate as used in the present invention can release and deliver small amounts of calcium and phosphate ions under physiological conditions for promoting remineralization of the tooth enamel. 25 It has also been found that a specific calcium to phosphorus molar ratio range is important for tooth health and remineralization of the tooth enamel. A ratio of calcium to phosphorus that is too high may not be effective in inhibiting caries of the crowns and/or tartar on teeth, while one that is too low may not be effective in inhibiting caries near the gum and/or may increase inflammatory tendencies such as pyorrhea and gingivitis. In a specific embodiment, the water 30 insoluble calcium phosphate has a calcium to phosphorus molar ratio from 1:1 to 5:1, or from 1:1 to 3:1, or from 1.5:1 to 2.5:1, or from 1.3:1 to 2:1. Suitable water-insoluble calcium phosphates useful in the present invention include, but are not limited to, apatite, calcium halide phosphate, dicalcium phosphate, tricalcium phosphate, WO 2015/074241 PCT/CN2013/087671 8 octacalcium phosphate, and mixtures thereof. In an embodiment, the apatite is selected from the group consisting of hydroxyapatite (Caio(PO 4

)

6

(OH)

2 ), fluorapatite (Caio(PO 4

)

6

F

2 ), chlorapatite (Caio(PO 4

)

6 Cl 2 ), bromapatite (Caio(PO 4

)

6 Br 2 ) and mixtures thereof. The water-insoluble calcium phosphate can be in any solid form, for example, substantially 5 spherical particles, agglomerates of smaller particles, rod-like particles, needle-like particles, fibroid particles or mixtures thereof. The water-insoluble calcium phosphate can be of any size which can deposit onto the tooth surface without impairing the spirit of the present invention. In a specific embodiment, the water-insoluble calcium phosphate has a particle size from 0.01, 0.5, 1, 2, or 4 to 5, 8, 10, 15 or 10 20 microns. According to the present invention, the geometry and size of the water-insoluble calcium phosphate particles can be optimized so that the various micro-cracks or crevices on the tooth surface are taken into account. The water-insoluble calcium phosphate is present in an amount from 0.01%, 0.05%, 0.1%, 15 0.50%, 1%, or 2% to 3%, 5%, 10%, 2 0%, 50%, or 9 9 %, by weight, of the first composition. In a specific embodiment, the first composition comprises 0.1% to 20%, by weight, of apatite. In a further specific embodiment, the first composition comprises 1% to 5%, by weight, of hydroxyapatite. The amount of the water-insoluble calcium phosphate can be adjusted to provide the desired technical and sensorial benefits while mitigating any side effects. In some medical or 20 clinical cases when the side effects do not matter much, the amount of the water-insoluble calcium phosphate can be up to 99%, by weight, of the first composition. The pH of the first composition can be in the range from 6, 7, or 8 to 9, 10, or 11. The pH can be achieved through a proper balancing of the calcium phosphate sources or by addition of an alkaline or acidic agent. Without wishing to be bound by theory, a relatively basic pH is 25 preferred because it is believed to stabilize the water-insoluble calcium phosphate from being dissolved. The Second Composition According to the present invention, the second composition comprises a specific 30 organophosphate compound. The organophosphate compound has a strong affinity for enamel surfaces, like teeth, and has a sufficient surface binding propensity to desorb pellicle proteins and remain affixed to enamel surfaces. Without wishing to be bound by any theory, it is believed that, when applied according to the present invention, the organophosphate compound adheres to the WO 2015/074241 PCT/CN2013/087671 9 teeth, with the phosphate groups binding the calcium in teeth and thus preventing loss of calcium from dissolution into acidic saliva. The organophosphate may also deposit a protective surface coating that prevents teeth from coming into direct contact with erosive acids or other harmful substances. 5 In particular, the second composition comprises an organophosphate having the formula: 0 R-(O-X)a(OY)gO-P-0-Zi O-Z2 wherein R is a hydrocarbyl comprising 4 to 22 carbon atoms; X and Y are each independently an alkylene comprising 2 to 4 carbon atoms; a and b are each independently an integer selected from 0 to 20, and a+b is in the range from 0 to 20; Z' and Z2 are each 10 independently selected from hydrogen, hydrocarbyl comprising 1 to 26 carbons preferably comprising one or more ether moieties, and a counter ion, provided that at least one of Z' and Z 2 is hydrogen or a counter ion. Examples of hydrocarbyl groups useful herein include, but are not limited to: (1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) 15 substituents, and aromatic-, aliphatic-, and alicyclic-substituted aromatic substituents, as well as cyclic substituents wherein the ring is completed through another portion of the molecule (e.g., two substituents together form an alicyclic radical) and equivalents thereof; (2) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups which, in the context of the description herein, do not alter the predominantly hydrocarbon substituent (e.g., halo (especially 20 chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy) and equivalents thereof; (3) hetero-substituents, that is, substituents which, while having a predominantly hydrocarbon character, in the context of this description, contain other than carbon in a ring or chain otherwise composed of carbon atoms and equivalents thereof. Hetero-atoms include sulfur, oxygen, nitrogen, and encompass substituents such as pyridyl, furyl, thienyl and 25 imidazolyl. In a specific embodiment, no more than two, preferably no more than one, non hydrocarbon substituent is present for every ten carbon atoms in the hydrocarbyl group. In a further specific embodiment, there is no non-hydrocarbon substituent in the hydrocarbyl group. The presence of the hydrocarbyl group is believed to impart to the compound a degree of hydrophobicity, so that the organophosphate can effectively form a hydrophobic layer on the tooth 30 surface. Such a hydrophobic layer can protect the enamel from erosive acidic challenges and stain WO 2015/074241 PCT/CN2013/087671 10 deposition, and provide good smooth feeling for a prolonged time. Some examples of the organophosphate include, but are not limited to, alkyl phosphates and alkyl (poly)alkoxy phosphates, such as lauryl phosphate (tradenames MAP 230K and MAP 230T commercially available from Croda, Snaith, UK); PPG5 ceteareth-10 phosphate (Crodaphos SG 5 commercially available from Croda, Snaith, UK); laureth-1 phosphate (tradenames MAP L210 commercially available from Rhodia, La DMfense, France, Phosten HLP-1 commercially available from Nikkol Chemical, Tokyo, Japan, or Sunmaep L commercially available from Sunjin Chemical, Korea); laureth-3 phosphate (tradenames MAP L130 commercially available from Rhodia, La DMfense, France, Foamphos L-3 commercially available from Alzo, NJ, U.S., or 10 Emphiphos DF 1326 commercially available from Huntsman Chemical, Texas, U.S.); laureth-9 phosphate (tradename Foamphos L-9 commercially available from Alzo, NJ, U.S.); trilaureth-4 phosphate (tradenames Hostaphat KL 340D commercially available from Clariant, Muttenz, Switzerland, or TLP-4 commercially available from Nikkol Chemical, Tokyo, Japan); C12-18 PEG 9 phosphate (tradename Crafol AP261 commercially available from Cognis, Ludwigshafen, 15 Germany); sodium dilaureth-10 phosphate (tradename DLP-10 commercially available from Nikkol Chemical, Tokyo, Japan). Particularly preferred organophosphates are those containing alkoxy groups, especially repeating alkoxy groups, (O-X)a(O-Y)b, in particular those containing 1 or more ethoxy, propoxy, isopropoxy, butoxy groups or combinations thereof. The presence of the alkoxy group is believed 20 to increase the solubility of the compound and balance the amphiphilicity of the compound, so that the hydrophilic phosphate head can "stick" to the tooth surface (given its charge) while the hydrophobic hydrocarbyl tail is extended to a long carbon chain. On the other hand, the presence of the alkoxy group can help diffusing substances away from the tooth surface. Additional suitable organophosphates may include alkyl mono glyceride phosphate, alkyl 25 sorbitan phosphate, alkyl methyl glucoside phosphate, alkyl sucrose phosphates, dextran phosphate, polyglucoside phosphate, alkyl polyglucoside phosphate, polyglyceryl phosphate, alkyl polyglyceryl phosphate, polyether phosphates and alkoxylated polyol phosphates. Some specific examples may include polyethylene glycol (PEG) phosphate, polypropylene glycol (PPG) phosphate, alkyl PPG phosphate, PEG/PPG phosphate, alkyl PEG/PPG phosphate, 30 PEG/PPG/PEG phosphate, dipropylene glycol phosphate, PEG glyceryl phosphate, polybutylene glycol (PBG) phosphate, PEG cyclodextrin phosphate, PEG sorbitan phosphate, PEG alkyl sorbitan phosphate, PEG methyl glucoside phosphate, and combinations thereof. The organophosphate may provide desired surface conditioning effects including: 1) WO 2015/074241 PCT/CN2013/087671 11 effective desorption of undesirably adsorbed pellicle proteins, in particular those associated with tooth stain binding, calculus development and attraction of undesirable microbial species, and 2) maintaining surface conditioning effects and control of pellicle film formation for extended periods following product use. The present compositions provide a protective surface coating by 5 binding calcium minerals within teeth (e.g., hydroxyapatite). The protective surface coating provides improved tooth surface characteristics by modifying surface hydrophilic and hydrophobic properties and improving resistance to dietary acid attack. The amount of the organophosphate in the second composition is an effective amount to provide the protection layer with good smooth feeling for some desired time. Preferably, the 10 protection will last for at least an hour after use of the composition. The organophosphate can be present in an amount effective to provide an increase of at least 10 degrees in water contact angle on the surface, with the hydrophobic character being maintained for a period of at least 5 minutes. In a specific embodiment, the organophosphate is present in an amount ranging from 0.01%, 0.02%, 0.03%, 0.050%, 0.07%, or 0.10% to 0.50%, 1%, 5%, 10%, 50%, or 99%, by weight, of the 15 second composition. The amount of the organophosphate can be adjusted to provide the desired technical and sensorial benefits while mitigating any side effects which the organophosphate compound may have, for example, an undesirable bitter or soapy taste. In some medical or clinical cases when the undesirable bitter or soapy taste is not a big consideration, the amount of the organophosphate can be up to 99%, by weight, of the second composition. 20 In a specific embodiment, the organophosphate is defined by: R is an alkyl comprising 8 to 16 carbon atoms; a+b is from 1 to 10; and Z' and Z2 are each independently selected from the group consisting of hydrogen and an alkali metal counter ion. Preferably, at least one of Z' and Z2 is an alkali metal counter ion selected from the group consisting of sodium ion and potassium ion; and wherein the second composition comprises 0.01% to 10 %, by weight, of the 25 organophosphate. Specifically, the organophosphate can be selected from the group consisting of sodium laureth-1 phosphate, sodium laureth-2 phosphate, sodium laureth-3 phosphate, sodium laureth-4 phosphate, potassium laureth-1 phosphate, sodium laureth-9 phosphate, sodium myreth-2 phosphate, sodium pareth- 1 phosphate and mixtures thereof. 30 In a specific embodiment, the second composition comprises 0.01% or 0.05% to 5% or 10%, by weight, of sodium laureth- 1 phosphate. The pH of the second composition can be in the range from 5, 6, or 6.5 to 7.5, 8 or 10. The pH of the second composition should not be too low since there is a possibility of the WO 2015/074241 PCT/CN2013/087671 12 organophosphate hydrolyzing in a strong acidic environment. Optional Components The first composition and the second composition of the present invention can each 5 independently contain a variety of optional conventional components useful in oral compositions to increase the benefits mentioned herein or provide additional benefits. Such optional components include, but are not limited to, a fluoride ion source, a thickening agent, a humectant, a surfactant, an antibacterial agent, a colorant, a flavorant, and some other conventional components. 10 A fluoride ion source, also called a water-soluble fluoride source, capable of providing free fluoride ions, can help accelerating remineralization by increasing local supersaturation with respect to fluoridated calcium phosphate deposition. Fluoride uptake or fluoridation refers to the acquisition of fluoride into tooth substrates resulting from topical treatments with fluoride agents. Teeth with increased remineralization and fluoride uptake exhibit superior resistance to acid 15 demineralization and therefore help prolong the smoothing effect on the tooth surface. The water-soluble fluoride source can be selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, amine fluoride, and mixtures thereof. In a specific embodiment, the second composition comprises a water-soluble fluoride source capable of providing from 50 ppm, 500 ppm, 1000 ppm, or 1500 ppm to 2000 ppm, 2500 ppm, 3000 ppm, 20 or 3500 ppm of free fluoride ions. In a further specific embodiment, the second composition comprises 0.005%, 0.01%, or 0.02% to 0.1%, 1%, or 5%, by weight, of sodium fluoride. In an even further specific embodiment, the first composition comprises 1% to 5%, by weight, of hydroxyapatite, and the second composition comprises 0.05% to 5%, by weight, of sodium laureth- 1 phosphate and 0.01 % to 1%, by weight, of sodium fluoride. 25 Thickening agents, also called thickeners, are generally used to increase the viscosity of a solution or liquid/solid mixture. According to the present invention, thickening agents can be incorporated to provide a consumer desirable consistency and tooth coating ability by adjusting the viscosity of the composition. The oral care composition of the present invention can have a viscosity ranging from 10cps, 50cps, 100cps, 500cps, 800cps, 1200cps, or 2000cps to 3000cps, 30 5000cps, 8000cps, 12000cps, 20000cps, 30000cps, or 45000cps, depending on the delivery form of the composition. In a specific embodiment, the first composition has a viscosity of 2000cps to 8000cps. In another specific embodiment, the second composition has a viscosity of 1200cps to 3000cps. Thicker composition tends to provide longer lasting benefits on the tooth surface.

WO 2015/074241 PCT/CN2013/087671 13 Thickening agents may also improve the suspension of insoluble ingredients to provide a stable and uniform composition. This is especially advantageous when the first composition comprising the water-insoluble calcium phosphate is a mouth rinse. Preferred thickening agents are selected from the group consisting of carboxyvinyl polymers, carrageenan, xanthan gum, 5 cellulosic polymers, hydroxyethyl cellulose, carboxymethyl cellulose, ammonium acryloyldimethyltaurate/vinylprrolidone copolymer, polyethylene oxide, acrylates/C10-30 alkyl acrylate crosspolymer, polyacrylic acid, cross-linked polyacrylic acid, polycarbophil, alginate, clay, glucose, pectin, gelatin, and combinations thereof. Colloidal magnesium aluminum silicate or finely divided silica can also be used as part of the thickening agent to further improve texture. 10 The thickening agent can be present in an amount from 0.01%, 0.1%, 0.2%, 0.3%, or 0.4% to 2%, 5 %, 8%, 10%, or 20%, by weight, of the first composition or the second composition. Humectants such as polyethylene glycols can also been used to modify viscosity and to provide a smooth feel to dentifrice compositions. Polyethylene glycols are available in a large range of average molecular weights and have different properties depending upon their average 15 molecular weights. The humectant serves to keep the oral composition, especially a toothpaste composition, from hardening upon exposure to air and give a moist feel to the mouth. Certain humectants can also impart a desirable sweet flavor to oral compositions such as mouth rinse and toothpaste. Suitable humectants for use in the present invention include edible polyhydric alcohols such as glycerin, sorbitol, xylitol, butylene glycol, polyethylene glycol, propylene glycol, 20 and mixtures thereof. The humectant is optionally present in an amount of 1%, 2%, 5%, or 8% to 15%, 25%, 50%, or 7 0%, by weight, of the first composition or the second composition. Surfactants are useful, for example, to make other components of the oral care composition more compatible with one another. This provides enhanced stability, helps in cleaning the dental surface through detergency, and provides foam upon agitation, e.g., during brushing with a 25 dentifrice composition of the invention. Any orally acceptable surfactant, most of which are anionic, nonionic or amphoteric, can be used. Suitable anionic surfactants include without limitation water-soluble salts of C8-20 alkyl sulfates, sulfonated monoglycerides of C8-20 fatty acids, sarcosinates, taurates and the like. Illustrative examples of these and other classes include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, 30 sodium lauryl isoethionate, sodium laureth carboxylate and sodium dodecyl benzenesulfonate. Suitable nonionic surfactants include without limitation poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, dialkyl sulfoxides and the like. Suitable amphoteric surfactants include WO 2015/074241 PCT/CN2013/087671 14 without limitation derivatives of C8-20 aliphatic secondary and tertiary amines having an anionic group such as carboxylate, sulfate, sulfonate, phosphate or phosphonate. A suitable example is cocoamidopropyl betaine. The surfactant is optionally present in an amount of 0.01%, 0.05%, or 0.1% to 2 %, 5%, or 10%, by weight, of the first composition or the second composition. 5 Antibacterial agents useful in the present invention include but are not limited to water insoluble non-cationic antibacterial agents and water soluble antibacterial agents such as quaternary ammonium salts and bis-biquanide salts. Triclosan monophosphate is an additional water soluble antibacterial agent. In some preferred embodiments, the antibacterial agent is selected from the group consisting of cetylpyridinium halide, domiphen halide, a stannous ion 10 source, a zinc ion source, a copper ion source, and mixtures thereof. These antibacterial agents may be present at levels of from 0.01%, 0.05%, 0.1%, or 0.2% to 0.5%, 1.0%, 1.

2 % or 1.5%, by weight, of the first composition or the second composition. Colorants herein include pigments, dyes, lakes and agents imparting a particular luster or reflectivity such as pearling agents. A colorant can serve a number of functions, including for 15 example 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 user. Any orally acceptable colorant can be used, including but not limited to talc, mica, magnesium carbonate, calcium carbonate, magnesium silicate, magnesium 20 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 the like. Flavorants are useful for example to enhance taste of the composition. Any orally acceptable natural or synthetic flavorant can be used, including but not limited to vanillin, sage, 25 marjoram, parsley oil, spearmint oil, cinnamon oil, oil of wintergreen (methylsalicylate), peppermint oil, clove oil, bay oil, anise oil, eucalyptus oil, citrus oils, fruit oils and essences including those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, pineapple, etc., bean- and nut-derived flavors such as coffee, cocoa, cola, peanut, almond, etc., adsorbed and encapsulated flavorants and the like. Also encompassed 30 within flavorants herein are ingredients that provide fragrance and/or other sensory effect in the mouth, including cooling or warming effects. Such ingredients illustratively include menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone, a-irisone, propenyl guaiethol, thymol, linalool, benzaldehyde, cinnamaldehyde, N- WO 2015/074241 PCT/CN2013/087671 15 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. 5 Oral Care Kit and Product The present invention also provides any form of kit and product comprising the first composition and the second composition as discussed above. In some embodiments, the oral care kit comprises: (a) a first product containing a first composition, wherein the first composition comprises 10 0.01% to 99%, by weight, of a water-insoluble calcium phosphate having a calcium to phosphorus molar ratio from 1:1 to 10:1; (b) a second product containing a second composition, wherein the second product is a mouth rinse with a pH from 6 to 8 and a viscosity from 100 cps to 5000 cps, and wherein the second composition comprises 0.01% to 99%, by weight, of an organophosphate as defined 15 above; and (c) instructions instructing a user to first use the first product to contact a tooth surface and thereafter immediately use the second product to contact the tooth surface. In some embodiments, the kit further includes an applicator to apply the first and/or second compositions to the tooth surface, for example, a syringe-type applicator for depositing a 20 composition on the tooth surface or an applicator in the shape of a semicircular trough for use in applying composition to the tooth surface. The kit may also optionally include instructions on the use of an applicator in applying the composition to a tooth surface. In a specific embodiment, the first product and the second product can be physically separated, each independently as any suitable form, for example, as a liquid form or a dry powder. 25 When the composition provided is a dry powder, the composition may be reconstituted by the addition of a suitable solvent, which may also be included in the kit. In embodiments where a liquid form is provided, the composition may be concentrated or ready to use. In a specific embodiment, the first product and the second product are each independently a mouth rinse. 30 In some embodiments, the present invention intends to provide a single oral care product comprising a first container and a second container, wherein the first container contains a first WO 2015/074241 PCT/CN2013/087671 16 composition comprising 0.01% to 99%, by weight, of a water-insoluble calcium phosphate which has a calcium to phosphorus molar ratio from 1:1 to 10:1, and the second container contains a second composition comprising 0.01% to 99%, by weight, of an organophosphate as defined above. The product may optionally contain instructions instructing a user to dispense the first 5 composition before the second composition is dispensed. In a specific embodiment, the single oral care product further comprises instructions instructing a user to first dispense the first composition from the first container to contact a tooth surface and thereafter dispense the second composition from the second container to contact the tooth surface for every use. 10 In another specific embodiment, the single oral care product further comprises a pump which pumps the first composition from the first container upon a first actuation and pumps the second composition from the second container upon a second actuation for every treatment regimen use. 15 EXAMPLES The following examples further describe and demonstrate embodiments within the scope of the present invention. These examples are given solely for the purpose of illustration and are not meant to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the present invention. 20 The first composition Table 1 shows examples of the first composition according to the present invention in the form of mouth rinses. The preparation process is as follows: add glycerin and polymers to a first mixing vessel, mixing until well dispersed to get Premix 1; add water (10% of the total amount), 25 flavors & sensates, hydroxyapatite, sweeteners, liquid preservatives, surfactants, and colorants & aesthetics to a second mixing vessel, mixing until well dispersed and homogenous to get Premix 2; add water (90% of the total amount), solid preservatives, and thickening agents to a main mixing tank, mixing until homogenous to get a main mix; add Premix 1 to the main mix, mixing until well dispersed; add 25% of the total sodium hydroxide (if applicable) to the main mix, 30 mixing until homogenous; add Premix 2 to the main mix, mixing until well dispersed and homogenous; and add the rest of the sodium hydroxide until the pH is 7.

WO 2015/074241 PCT/CN2013/087671 17 Table 1 Ingredients Al A2 A3 A4 A5 A6 A7 A8 Water 77.744 77.674 75.244 79.244 76.279 78.404 77.654 79.154 Glycerin 18.000 18.000 18.000 18.000 18.000 18.000 18.000 18.000 Methylparaben 0.020 0.020 0.020 0.020 0.020 0.020 0.020 0.020 Propylparaben 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Benzyl Alcohol 1.000 0.900 1.000 1.000 0.900 0.900 0.900 0.900 Aristoflex AVC 0.500 - 0.500 0.500 - - - Carbopol ETD2020 - 0.200 - - 0.250 0.125 0.125 0.125 Polyox WSR1105 - 0.200 - - 1.000 0.500 0.500 0.500 Vitamin E Acetate - 0.070 - - 0.070 0.070 0.070 0.070 Bio-Gel HTP) 2.500 - 5.000 1.000 - - - nanoXIM.Care powder 2 ) - 2.500 - - 3.000 1.500 2.250 0.750 Sodium Saccharin 0.013 0.013 0.013 0.013 0.013 0.013 0.013 0.013 Sucralose 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 Peppermint 92 180 Blend 0.100 - 0.100 0.100 - - - Starburst Peppermint - 0.100 - - 0.120 0.120 0.120 0.120 Sodium Hydroxide - 0.200 0.200 0.200 0.200 0.200 Titanium Dioxide 0.100 0.100 0.100 0.100 0.050 0.050 0.050 0.050 Poloxamer 407 0.010 0.010 0.010 0.010 0.010 0.010 0.010 0.010 Candurin Silver Lustre - - - - 0.075 0.075 0.075 0.075 Total 100 100 100 100 100 100 100 100 1 Hydroxyapatite supplied by Bio-Rad, Hercules, CA, USA 2) Hydroxyapatite supplied by Fluidinova, Moreira da Maia, Portugal 5 As a mouth rinse, appropriate viscosity will suspend the hydroxyapatite uniformly in the composition and facilitate proper contact and retention of the composition on the tooth surface. The first compositions, Al to A8, have a viscosity of 2580 cps, 7690 cps, 5072 cps, 2600 cps, 29433 cps, 132 cps, 220 cps, and 116 cps, respectively. 10 Table 2 shows examples of the first composition according to the present invention in the form of toothpastes. The preparation process is as follows: add water, humectants, part of flavor, colorant, buffer and active to a main mixing tank of 35'C, mixing well and ensuring all the ingredients have dissolved or been well dispersed; add thickening agents and sweetener into the main mixing tank, mixing and homogenizing until well dispersed and homogeneous; add 15 abrasives, mixing and homogenizing until well dispersed and homogeneous; deaerate; add surfactant solution, rest part of flavor to the main mixing tank, mixing and homogenizing until WO 2015/074241 PCT/CN2013/087671 18 homogeneous; de-aerate; pump out and cool the batch to less than 40'C. Table 2 Ingredients A9 AlO All A12 A13 Sorbitol solution (70%) 22.169 40.370 40.500 - 23.000 Sodium fluoride 0.321 0.234 - - Water purified 45.000 33.096 22.950 - 44.170 Silica abrasive 15.000 12.500 17.000 17.000 15.000 Sodium Lauryl Sulfate (28%) 7.000 5.000 5.000 3.500 5.000 Sodium Carboxymethyl Cellulose 1.400 1.300 1.300 - 1.500 Carrageenan - 0.700 0.700 0.600 Carbomer 956 0.400 - - - 0.500 Sodium saccharin 0.280 0.300 0.300 0.300 0.280 Xanthan gum 0.250 - - 0.250 0.250 Titanium dioxide 0.250 0.500 0.525 0.400 0.250 Flavor 0.900 1.000 0.900 1.000 1.000 Sodium hydroxide 32% 3.750 - - 3.750 Mica 0.280 - - 0.500 0.300 Bio-Gel HTP) 3.000 7.500 5.000 nanoXIM.Care powder 2 ) 5.000 10.000 Glycerin - - - 41.950 Sodium polyphosphate - - - 13.000 Sodium citrate - - 0.150 - Sodium gluconate - 1.064 - - Zinc citrate - 0.955 0.375 - Hydroxyethyl Cellulose - 0.300 0.300 - Stannous chloride - 1.160 - - Propylene glycol - - - 7.000 Polyethylene glycol - - - 7.000 Total 100 100 100 100 100 1) Hydroxyapatite supplied by Bio-Rad, Hercules, CA, USA 5 2) Hydroxyapatite supplied by Fluidinova, Moreira da Maia, Portugal The second composition Table 3 shows examples of the second composition according to the present invention in the form of mouth rinses. The preparation process is the same as that for the first compositions in 10 the form of mouth rinses, except that no hydroxyapatite is added in the Premix 2 and that sodium fluoride and organophosphate are added along with water (90% of the total amount), solid preservatives, and thickening agents to get a main mix.

WO 2015/074241 PCT/CN2013/087671 19 Table 3 Ingredients Bi B2 B3 B4 B5 B6 B7 Water 80.014 80.144 79.914 79.729 79.364 79.794 79.704 Glycerin 18.000 18.000 18.000 18.000 18.000 18.000 18.000 Methylparaben 0.020 0.020 0.020 0.020 0.020 0.020 0.020 Propylparaben 0.005 0.005 0.005 0.005 0.005 0.005 0.005 Benzyl Alcohol 1.000 0.900 1.000 0.900 0.800 0.900 0.900 Aristoflex AVC 0.400 - 0.500 - - - Carbopol ETD2020 - 0.150 - 0.150 0.350 0.200 0.175 Polyox WSR1105 - - - 0.200 0.150 0.200 0.200 Vitamin E Acetate - 0.070 - 0.070 0.070 0.070 0.070 Sodium Fluoride - 0.050 - 0.020 0.050 0.050 0.020 MAP L213S 3 ) 0.330 - 0.330 0.660 - 0.330 Foamphos L-9 4 ) - 0.330 0.330 - 0.330 Sodium Saccharin 0.013 0.013 0.013 0.013 0.013 0.013 0.013 Sucralose 0.008 0.008 0.008 0.008 0.008 0.008 0.008 Peppermint 92 180 Blend 0.100 - 0.100 0.100 0.100 - 0.100 Starburst Peppermint - - - - - 0.100 Polar Mint Diluted - - - 0.120 - - 0.120 Sodium Hydroxide - 0.200 - 0.200 0.200 0.200 0.200 Titanium Dioxide 0.100 0.100 0.100 0.050 0.100 0.100 0.050 Candurin Silver Lustre - - - 0.075 - - 0.075 Timica Extra Bright - - - - 0.100 - Poloxamer 407 0.010 0.010 0.010 0.010 0.010 0.010 0.010 Total 100 100 100 100 100 100 100 3) Laureth- 1 phosphate supplied by Rhodia, pre-neutralized 4) Laureth-9 phosphate supplied by Alzo, neutralized with NaOH 5 The second compositions, B3 to B7, have a viscosity of 3072 cps, 1376 cps, 216.5 cps, 1408 cps, and 2616 cps, respectively. BI and B2 are not measured. Table 4 shows examples of the second composition according to the present invention in the form of nonabrasive tooth gels. Preparation process is as follows: add mineral 10 oil/petrolatum/Versagel, humectants, part of flavor, and colorant to a main mixing tank of 35'C, mixing well and ensuring all the ingredients have dissolved or been well dispersed; add organophosphate and sweetener into the main mixing tank, mixing and homogenizing until well dispersed and homogeneous; deaerate; add surfactant solution, rest part of flavor to the main mixing tank, mixing and homogenizing until homogeneous; deaerate; pump out and cool the WO 2015/074241 PCT/CN2013/087671 20 batch to less than 40 0 C. Table 4 Ingredients B8 B9 BIO B11 B12 MAP L-130') 13.330 - - Foamphos L-36) - 8.000 - MAP 230K 7 - - 10.000 DLP-108) - - 5.000 Crodaphos SG 9 ) - - - - 2.000 Glycerin 20.000 13.000 22.000 35.000 Flavor 2.000 2.000 2.000 2.000 1.000 Saccharin 0.500 0.500 0.500 0.500 2.000 Polyethylene oxide 2.000 2.000 2.000 2.000 Carbomer 956 0.500 0.500 0.500 0.500 Mineral Oil - - - 55.000 Petrolatum 61.670 64.000 63.000 - Versagel - - - - 95.000 Total 100 100 100 100 100 5) Laureth-3 phosphate supplied by Rhodia, neutralized with NaOH 5 6) Laureth-3 phosphate supplied by Alzo, neutralized with NaOH 7) Potassium C 12/13 phosphate supplied by Croda 8) Sodium diLaureth- 10 phosphate supplied by Nikkol Chemical 9) PPG5 Ceteareth- 10 phosphate supplied by Croda, neutralized with NaOH 10 Sequential application system One of the first compositions as shown in Tables 1 and 2 and one of the second compositions as shown in Tables 3 and 4 can be combined into a sequential oral application treatment regimen. Examples of sequential compositions according to the present invention are shown in Table 5. 15 Table 5 Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 The first composition A2 A3 A5 A7 A9 All A12 The second composition B6 B8 B1 B10 B3 B7 B12 The compositions in the form of mouth rinses are applied to the tooth surface by swishing and gargling 20ml of the mouth rinse in the mouth for 30 seconds and then spitting out. In the 20 application where the subject composition is too viscous or too thick to be swished or gargled in WO 2015/074241 PCT/CN2013/087671 21 the mouth, suitable applicators such as a swab can be used to apply (e.g., spread or daub) the composition onto the tooth surface. The compositions in the form of toothpastes are applied to the tooth surface by brushing with a toothbrush for 2 minutes. 5 The compositions in the form of tooth gels are applied to the tooth surface by applying the gels evenly into a mouth tray and putting the mouth tray onto the teeth for 10 minutes. Efficacy measurement Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) 10 QCM-D is a very sensitive mass balance technique allowing simultaneous measurement of adsorption kinetics and viscoelastic properties of an adsorbing layer. In QCM-D, a quartz crystal is excited to oscillate at its fundamental resonant frequency by the application of AC voltage across the crystal. A material adsorbed onto the surface of the crystal causes the resonant frequency to change, which is proportional to the mass of the 15 adsorbed film. The damping/dissipation of the crystal's oscillation by the film can be measured, allowing for the determination of the viscoelasticity of the film. AD = Edissipation/ 2 7u Estored wherein D is the energy dissipated per oscillation divided by the total energy stored in the crystal. 20 A large value for AD indicates that a soft, easily deformed material is attached to the crystal. A rigid material leads to a small AD. Figs. 1(a) to 1(e) show the QCM-D data for a tooth surface treated with Ex. 1 of the present invention. Three steps, in sequential order, are followed to treat the test tooth surface. The first step is 25 to rinse the tooth surface with deionized water. The second step is to rinse the tooth surface with the first composition, A2. The third step is to further rinse the tooth surface with the second composition, B6. The three columns in each of Figs. 1(a) to 1(e) represent the QCM-D test results after each step. It can be seen from the QCM-D data that, before the treatment according to the present 30 invention, no adsorbed layer is formed on the tooth surface. After treatment with the first composition, a layer displaying viscoelastic properties is adsorbed onto the tooth surface. After further treatment with the second composition, the adsorbed layer is strengthened by increased mass, density, and thickness.

WO 2015/074241 PCT/CN2013/087671 22 Scanning Probe Microscopy (SPM) Scanning probe microscopy is used to produce topographic images of a surface with nano scale resolution. In this technique, the deflection of a microfabricated cantilever spring is 5 monitored as it is raster scanned over the surface in question. Surface roughness analysis allows for quantitative measurements of topographical features as a function of surface modification. Figs. 2(a) to 2(d) show the changes of an enamel surface when it is treated with Ex. 1 of the present invention. Fig. 2(a) shows a rough enamel surface prior to treatment (i.e., control). Fig. 2(b) shows that the enamel surface is further roughened by being etched with citric acid. Fig. 2(c) 10 shows a slightly smoother enamel surface but with some insoluble components (large particles) deposited after the treatment with the first composition, A2. It is believed that the hydroxyapatite has been deposited onto the surface. Fig. 1(d) shows a smooth enamel surface after subsequent treatment with the second composition, B6. In comparison, Figs. 3(a) to 3(d) show the enamel surface changes when treated with the 15 same compositions in Ex. 1 of the present invention but in a different sequence. In other words, the comparative enamel surface is treated by the second composition, B6, followed by the first composition, A2. Fig. 3(a) shows a rough enamel surface prior to treatment (i.e., control). Fig. 3(b) shows a similarly roughened enamel surface as Fig. 2(b) after being etched with citric acid. Fig. 3(c) shows a much smoother enamel surface than Fig. 2(c) after the treatment with the 20 second composition, B6. However, after the two-step treatment of the second composition, B6, followed by the first composition, A2, Fig. 3(d) shows an enamel surface rougher than that shown in Fig. 2(d). In Fig. 3(d), the raised or depressed areas can be up to a depth of 20nm, compared to only 1Onm in Fig. 2(d). SPM images are also taken to show the enamel surface changes after a regular treatment 25 with an Oral B® Pro-Expert dentifrice (produced on March 18, 2011 in the US). The Oral B® Pro-Expert dentifrice does not contain the first composition or the second composition as defined in the present invention. Fig. 4(a) shows a rough enamel surface prior to treatment. Fig. 4(b) shows a further roughened enamel surface by being etched with citric acid. Fig. 4(c) shows the enamel surface after the dentifrice treatment, which is almost as rough as the etched enamel 30 surface. It can be seen that the dentifrice treatment hardly changes the enamel surface smoothness. Overall, SPM data shows that the treatment according to the present invention makes the tooth surface much smoother.

WO 2015/074241 PCT/CN2013/087671 23 Sensory Panel Test (DPP) A sensory panel test for slick tooth feeling is conducted by a Descriptive Profile Panel (DPP) comprised of 10 individuals who have been screened for above average sensory acuity and ability 5 to describe sensations of slick tooth feeling. The panelists are trained on oral care product specific attributes via Spectrum(TM) methodology and have the unique ability to evaluate oral care products on an attribute by attribute basis without regard to personal preference or bias. In this test, panelists use the products as directed and evaluate the products against their standard 3 hour clean mouth feel ballot (including a slick teeth measure) for 3 hours after use. Panelists also 10 provide descriptive analysis and additional voluntary comments to call out any other sensory attributes. Each attribute is measured on a 0-30 scale with defined intervals that are no longer then 15 minutes. After the first hour, panelists drink 8 oz / 236.59 mL of a carbonated beverage (one of Coca-Cola*, Caffeine Free Coca-Cola*, Diet Coke®, and Caffeine Free Diet Coke®) with continued evaluation. 15 The products involved in this panel test include: the first composition (A2) only; the second composition (B6) only; a sequential application system of A2 followed by B6 according to Ex. 1 of the present invention; a sequential application system of B6 followed by A2; and BioRepair* mouthwash (containing a hydroxyapatite variant, produced on June 11, 2011 in British). As shown in Fig. 5, the sequential application system of A2 followed by B6 according to the 20 present invention provides the best slick tooth feel over time. Although the sequential application system of B6 followed by A2 provides a comparable slick tooth feel immediately after the treatment, the values for slick tooth feel drop down quickly within 10 minutes after the treatment. 20 minutes after the sequential treatment of B6 followed by A2, the values for slick tooth feel is much lower than those obtained by the sequential treatment according to the present 25 invention, and even lower than those obtained by individual treatment with A2 or B6 only. BioRepair@ mouthwash is a commercial product comprising zinc hydroxyapatite. It can be seen from Fig. 5 that both the immediate and the long-lasting slick tooth feel evaluations are well below those obtained by the sequential treatment according to the present invention. 30 Unless otherwise indicated, all percentages, ratios, and proportions are calculated based on the weight of the total composition. All temperatures are in degrees Celsius ('C) unless otherwise indicated. All measurements made are at 25'C, unless otherwise designated. All component or composition levels are in reference to the active level of that component or WO 2015/074241 PCT/CN2013/087671 24 composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources. It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations 5 were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein. 10 The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm." 15 Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other 20 reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern. While particular embodiments of the present invention have been illustrated and described, 25 it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (20)

1. A method of treating a tooth surface comprising the steps: (a) contacting the tooth surface with a first composition comprising a water-insoluble calcium phosphate, wherein the water-insoluble calcium phosphate has a calcium to phosphorus molar ratio from 1:1 to 10:1; and thereafter (b) contacting the tooth surface with a second composition, wherein the second composition comprises an organophosphate having the formula: 0 R-(O-X)a(O-Y)-O-P--O-Z' o--z 2 wherein R is a hydrocarbyl comprising 4 to 22 carbon atoms; X and Y are each independently an alkylene comprising 2 to 4 carbon atoms; a and b are each independently an integer selected from 0 to 20, and a+b is in the range from 0 to 20; Z' and Z2 are each independently selected from hydrogen, hydrocarbyl comprising 1 to 26 carbons, and a counter ion, provided that at least one of Z' and Z 2 is hydrogen or a counter ion.

2. The method of claim 1, wherein the contacting step (b) is initiated within 15 minutes after the conclusion of contacting step (a).

3. The method of claim 2, wherein the water-insoluble calcium phosphate is selected from the group consisting of apatite, calcium halide phosphate, dicalcium phosphate, tricalcium phosphate, octacalcium phosphate, and mixtures thereof.

4. The method of claim 3, wherein the first composition comprises 0.1% to 20% by weight of apatite.

5. The method of claim 4, wherein the first composition comprises 1% to 5% by weight of hydroxyapatite.

6. The method of claim 2, wherein the organophosphate is defined by: R is an alkyl comprising 8 to 16 carbon atoms; a+b is from 1 to 10; and Z' and Z 2 are each independently selected from WO 2015/074241 PCT/CN2013/087671 26 the group consisting of hydrogen and an alkali metal counter ion.

7. The method of claim 6, wherein at least one of Z' and Z2 is an alkali metal counter ion selected from the group consisting of sodium ion and potassium ion; and wherein the second composition comprises 0.01% to 10 % by weight of the organophosphate.

8. The method of claim 7, wherein the organophosphate is selected from the group consisting of sodium laureth-1 phosphate, sodium laureth-2 phosphate, sodium laureth-3 phosphate, sodium laureth-4 phosphate, potassium laureth- 1 phosphate, sodium laureth-9 phosphate, sodium myreth 2 phosphate, sodium pareth- 1 phosphate and mixtures thereof.

9. The method of claim 8, wherein the second composition comprises 0.05% to 5 % by weight of sodium laureth- 1 phosphate.

10. The method of claim 2, wherein the second composition further comprises a water-soluble fluoride source.

11. The method of claim 10, wherein the water-soluble fluoride source is selected from the group consisting of sodium fluoride, stannous fluoride, sodium monofluorophosphate, amine fluoride, and mixtures thereof; wherein the first composition comprises 0.1% to 20% by weight of hydroxyapatite; and wherein the second composition comprises 0.01% to 10% by weight of sodium laureth- 1 phosphate.

12. The method of claim 2, wherein the first composition is a toothpaste composition, and the second composition is a mouth rinse.

13. The method of claim 2, wherein the first composition and the second composition are each a mouth rinse.

14. The method of claim 2, wherein the second composition is a mouth rinse, with a viscosity from 100 cps to 5000 cps.

15. The method of claim 2, wherein the first composition has a pH from 7 to 10. WO 2015/074241 PCT/CN2013/087671 27

16. The method of claim 2, wherein the second composition has a pH from 6 to 8.

17. The method of claim 2, wherein the contacting steps (a) and (b) each independently has a contacting duration from 5 seconds to 5 minutes; and the contacting step (b) is initiated immediately after the conclusion of the contacting step (a).

18. The method of claim 17, wherein the first composition is a mouth rinse comprising 1% to 5 % by weight of hydroxyapatite, and the second composition is a mouth rinse comprising 0.05% to 5% by weight of sodium laureth-1 phosphate and 0.01% to 1% by weight of a sodium fluoride; and wherein the second composition has a pH from 6.5 to 7.5 and a viscosity from 1000 cps to 3000 cps.

19. An oral care kit, comprising: (a) a first product containing a first composition, wherein the first composition comprises 0.01% to 99% by weight of a water-insoluble calcium phosphate having a calcium to phosphorus molar ratio from 1:1 to 10:1; (b) a second product containing a second composition, wherein the second product is a mouth rinse with a pH from 6 to 8 and a viscosity from 100 cps to 5000 cps, and wherein the second composition comprises 0.01% to 99% by weight of an organophosphate having the formula: 0 II R-(O-X)a(0-Y)bO P-O-Z o-z 2 wherein R is a hydrocarbyl comprising 4 to 22 carbon atoms; X and Y are each independently an alkylene comprising 2 to 4 carbon atoms; a and b are each independently an integer selected from 0 to 20, and a+b is in the range from 0 to 20; Z' and Z2 are each independently selected from hydrogen, hydrocarbyl comprising 1 to 26 carbons, and a counter ion, provided that at least one of Z' and Z 2 is hydrogen or a counter ion; and (c) instructions instructing a user to first use the first product to contact a tooth surface and thereafter immediately use the second product to contact the tooth surface.

20. An oral care product comprising a first container and a second container, wherein the first WO 2015/074241 PCT/CN2013/087671 28 container contains a first composition comprising 0.01% to 99% by weight of a water-insoluble calcium phosphate which has a calcium to phosphorus molar ratio from 1:1 to 10:1, and the second container contains a second composition comprising 0.01% to 99% by weight of an organophosphate having the formula: 0 II R-(Q-X)B(O-Y)b-O-P-O-Z' o-z 2 wherein R is a hydrocarbyl comprising 4 to 22 carbon atoms; X and Y are each independently an alkylene comprising 2 to 4 carbon atoms; a and b are each independently an integer from 0 to 20, and a+b is in the range from 0 to 20; Z' and Z2 are each independently selected from hydrogen, hydrocarbyl comprising I to 26 carbons, and a counter ion, provided that at least one of Z' and Z 2 is hydrogen or a counter ion.