WO2015172652A1 - Dentifrice compositions having improved fluoride ion stability or fluoride uptake - Google Patents
Dentifrice compositions having improved fluoride ion stability or fluoride uptake Download PDFInfo
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- WO2015172652A1 WO2015172652A1 PCT/CN2015/077636 CN2015077636W WO2015172652A1 WO 2015172652 A1 WO2015172652 A1 WO 2015172652A1 CN 2015077636 W CN2015077636 W CN 2015077636W WO 2015172652 A1 WO2015172652 A1 WO 2015172652A1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/24—Phosphorous; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
- A61K33/10—Carbonates; Bicarbonates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/345—Alcohols containing more than one hydroxy group
Definitions
- the present invention relates to dentifrice compositions having improved sustained monofluorophosphate ion levels overtime.
- Dentifrice compositions are well known for dental and oral hygiene care.
- High carbonate (e.g., >25 wt%) formulation chassis are cost effective for many markets and consumers. Fluoride and its benefits are well known (e.g., helping to prevent tooth decay) .
- Sodium monofluorophosphate as fluoride ion source is also generally a well known way to provide fluoride benefits through dentifrice.
- dentifrice formulations that maximize available sodium monofluorophosphate, especially as formulations age (e.g., through distribution channels and on shelf) .
- the present invention is based on a surprising discovery on the role of forming and maintaining the specific fluoride species whereby the degradation of the monofluorophosphate ion is significantly reduced. This is achieved through the use of calcium chelating agents, in combination a high carbonate and/or high water dentifrice compositions that create the desired fluoride species with both improved stability and performance over the shelf life of the product. Under alkali conditions the monofluorophosphate ions will dissociate accordingly to liberate free fluoride ions that complex with surface Ca 2+ ions on the calcium carbonate particle, further to that sodium monofluorophosphate may undergo slow hydrolysis.
- pyrophosphate salts can aid in reducing the formation of undesirable calcium fluoride within a calcium carbonate and sodium monofluorophosphate containing dentifrice compositions.
- the present invention identifies a means to deliver and maintain the desired fluoride species, whereby firstly there is minimal degradation of the monofluorophosphate ion species, and secondly monofluorophosphate ions that undergo degradation are maintained as free fluoride ion source, resulting in improved stability and performance in fluoride uptake. Too much calcium chelating agent, e.g., pyrophosphate salts can create consumer negatives around irritation of the soft tissue.
- One aspect of the invention provides a dentifrice composition
- a dentifrice composition comprising: (a) 25%to 60%, preferably 27%to 47%, of a calcium-containing abrasive by weight of the composition, preferably wherein the calcium-containing abrasive comprises calcium carbonate composition; (b) 0.0025%to 4.0%, preferably from 0.19%to 3.8%sodium monofluorophosphate by weight of the composition; (c) 0.001%to 4%calcium chelating agent by weight of the composition, preferably wherein the calcium chelating agent is a pyrophosphate ion, more preferably from 0.01%to 1.35%, yet more preferably from 0.1%to 1%, by weight of the composition; and (d) pH greater than 8.3.
- a dentifrice composition comprising: (a) 20%to 75%, preferably 50%to 60%, of water by weight of the composition; (b) 0.0025%to 4.0%, preferably from 0.19%to 3.8%sodium monofluorophosphate by weight of the composition; (c) 0.001%to 4%calcium chelating agent by weight of the composition, preferably wherein the calcium chelating agent is a pyrophosphate ion, more preferably from 0.01%to 1.35%, yet more preferably from 0.1%to 1%, by weight of the composition; and (d) pH greater than 8.3.
- the composition further comprises 25%to 60%, preferably 27%to 47%, of a calcium-containing abrasive by weight of the composition, preferably wherein the calcium-containing abrasive comprises calcium carbonate composition.
- Another aspect of the invention provides a dentifrice composition wherein a monofluorophosphate ion degrades less than 40%, more preferably less than 35%, and more preferably less than 30%after 14 days at 60°C relative to the monofluorophosphate ion in freshly prepared dentifrice composition.
- the composition comprises a percentage of degraded monofluorophosphate ion that remains as free fluoride ion after 14 days at 60°C is greater than 50%, or greater than 75%, preferably greater than 85%, more preferably greater than 90%.
- the composition contains greater than 3,660 parts per million (ppm) monofluorophosphate ion after 14 days at 60°C, preferably from 4,000 ppm to 8,000 ppm of monofluorophosphate ion, more preferably from 5,000 to 7,000 ppm of monofluorophosphate ion, yet more preferably from 5,500 to 7,000 ppm of monofluorophosphate ion after 14 days at 60°C.
- ppm 3,660 parts per million
- the composition contains greater than 3,260 parts per million (ppm) monofluorophosphate ion after 43 weeks at 30°C, preferably from 3,500 ppm to 11,000 pm of monofluorophosphate ion, more preferably greater than 4,000 ppm to 11,000 ppm, yet more preferably 5,000 ppm to 11,000 ppm, yet still more preferably from 6,000 ppm to 11,000 ppm monofluorophosphate ion after 43 weeks at 30°C.
- the calcium chelating agent is from 0.1%to less than 1.0%of a pyrophosphate salt by weight of the composition, preferably wherein the pyrophosphate is tetrasodium pyrophosphate.
- the dentifrice composition is a single phase composition.
- orally acceptable carrier means a suitable vehicle or ingredient, which can be used to form and/or apply the present compositions to the oral cavity in a safe and effective manner.
- compositions of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations of the invention described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.
- an effective amount means an amount of a compound or composition sufficient to induce a positive benefit, an oral health benefit, and/or an amount low enough to avoid serious side effects, i.e., to provide a reasonable benefit to risk ratio, within the sound judgment of a skilled artisan. In one embodiment, “effective amount” means at least 0.01%of the material, by weight of the composition, alternatively at least 0.1%.
- doctor as used herein means paste, gel, powder, tablets, or liquid formulations, unless otherwise specified, that are used to clean the surfaces of the oral cavity.
- teeth as used herein refers to natural teeth as well as artificial teeth or dental prosthesis.
- 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” .
- the words "preferred”, “preferably”and variants refer to embodiments of the 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.
- the calcium chelating agent is any pyrophosphate salt source.
- pyrophosphate salts useful in the present compositions include the dialkali metal pyrophosphate salts, tetraalkali metal pyrophosphate salts, and mixtures thereof.
- Disodium dihydrogen pyrophosphate (Na 2 H 2 P 2 O 7 ) , tetrasodium pyrophosphate (Na 4 P 2 O 7 ) , and tetrapotassium pyrophosphate (K 4 P 2 O 7 ) in their unhydrated as well as hydrated forms are the preferred species.
- Tetrasodium pyrophosphate salt is a preferred pyrophosphate salt in the compositions of the present invention.
- Tetrasodium pyrophosphate may be the anhydrous salt form or the decahydrate form, or any other species stable in solid form in the dentifrice compositions.
- the salt is in its solid particle form, which may be its crystalline and/or amorphous state, with the particle size of the salt preferably being small enough to be aesthetically acceptable and readily soluble during use.
- the amount of pyrophosphate salt, useful for providing the improved monofluorophosphate ( “MFP” ) delivery or maintenance of MFP species to enhance fluoride uptake, is from 0.01%to less than 1.5% by weight of the dentifrice composition, preferably from 0.1%to 1.4%, alternatively from 0.1%to 1.36%, more preferably from 0.2%to 1.2%, alternatively from 0.3%to 1.0%, alternatively from 0.1%to less than 1%, alternatively from 0.4%to 0.8%, alternatively combinations thereof, by weight of the composition. Any of the above mentioned pyrophosphate salts may be used.
- the pyrophosphate salts are described in more detail in Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 17, Wiley-Interscience Publishers (1982) .
- compositions of the present invention comprise herein from 45%to 75%, by weight of the composition of water.
- the composition includes from 40%to 70%, alternatively from 45%to 65%, alternatively from 40%to 60%, alternatively from 50%to 70%, alternatively from 50%to 60 %, alternatively from 45%to 55%, alternatively from 55%to 65%, alternatively from 50%to 60%, alternatively about 55%, alternatively combinations thereof, of water by weight of the composition.
- the water may be added to the formulation and/or may come into the composition from the inclusion of other ingredients.
- the water is USP water.
- compositions of the present invention comprise from 25%to 50%by weight of a calcium-containing abrasive, wherein the calcium-containing abrasive is selected from the group consisting of calcium carbonate, dicalcium phosphate, tricalcium phosphate, calcium orthophosphate, calcium metaphosphate, calcium polyphosphate, calcium oxyapatite, sodium carbonate, and combinations thereof.
- the calcium-containing abrasive is selected from the group consisting of calcium carbonate, dicalcium phosphate, tricalcium phosphate, calcium orthophosphate, calcium metaphosphate, calcium polyphosphate, calcium oxyapatite, sodium carbonate, and combinations thereof.
- the composition comprises from 25%to 60%, more preferably from 25%to 50%, even more preferably from 25%to 40%, yet even more preferably from 26%to 39%, alternatively from 27%to 47%, alternatively from 27%to 37%, alternatively from 30%to 35%, alternatively from 30%to 34%, alternatively combinations thereof, of a calcium-containing abrasive by weight of the composition.
- a further preferred composition contains calcium-containing abrasive at the previously indicated weight percentage, wherein the calcium-containing abrasive is a calcium carbonate, and wherein the calcium carbonate has: a D50 particle size range from 2 microns to 7 microns, preferably from 3 microns to 6 microns, more preferably from 3.4 microns to 5.8 microns; or D90 from 8 microns to 15 microns, preferably from 9 microns to 14 microns, more preferably from 9.2 microns to 13.5 microns; or D98 range from less than 28 microns, preferably from 1 micron to less than 27 microns, more preferably less than 26 microns or from 1 micron to less than 26 microns.
- the calcium carbonate has a particle size range at the aforementioned D50 and D90 ranges; even more preferably at the aforementioned D50, D90 and D98 ranges. Surprisingly, it is believed that having calcium carbonate at these aforementioned particle size distribution ranges may increase fluoride stability benefits. Fluoride stability may be measured as described in herein, and generally China’s National Standard Method GB8372-2008.
- D50 means, in particle size distribution measurements, the mass-median-diameter, considered to be the average particle size by mass. That is, the D50 is the size in microns that splits the distribution with half above and half below this diameter by mass.
- D90 similarly means the size in microns that splits 90 percent of the distribution below the D90 by mass.
- D98 means the size in microns that 98 percent of the distribution below the D98 by mass.
- the particle size of calcium carbonate (as a raw material) is measured by using a laser scattering particle sizing instrument (e.g., Bettersize BT9300H from DanDong Better Instrument, China) .
- a laser scattering particle sizing instrument e.g., Bettersize BT9300H from DanDong Better Instrument, China
- the laser scattering technique works by measuring the light diffracted from particulates as they pass through a laser beam. Particulates scatter light at an angle that is directly related to their size.
- the Bettersize BT9300H uses the light scattering pattern associated with a sample to calculate particle size distributions.
- ISO 13320-1-1999 are followed. Briefly, calcium carbonate raw material is pre-dispersed in deionized water (DI-water” ) . And a volume of calcium carbonate slurry is transferred to sampling cell, which is filled with DI-water as dispersion solution. The particles of calcium carbonate are well dispersed by re-circulation and ultrasonication while particle size
- the calcium-containing abrasive is calcium carbonate.
- the calcium-containing abrasive is selected from the group consisting of fine ground natural chalk, ground calcium carbonate, precipitated calcium carbonate, and combinations thereof.
- the calcium-containing abrasive is selected from fine ground natural chalk, ground calcium carbonate, and combinations thereof (at the aforementioned weight percentage ranges for calcium-containing abrasives; and having the aforementioned D50, D90, and D98 measurements) .
- Fine ground natural chalk is one of the more preferred calcium-containing abrasives useful in the present invention. It is obtained from limestone or marble. FGNC may also be modified chemically or physically by coating during milling or after milling by heat treatment. Typical coating materials include magnesium stearate or oleate. The morphology of FGNC may also be modified during the milling process by using different milling techniques, for example, ball milling, air-classifier milling or spiral jet milling. One example of natural chalk is described in WO 03/030850 having a medium particle size of 1 to 15 ⁇ m and a BET surface area of 0.5 to 3 m 2 /g.
- the natural calcium carbonate may have a particle size of 325 to 800 mesh, alternatively a mesh selected from 325, 400 600, 800, or combinations thereof; alternatively the particle size is from 0.1 to 30 microns, or from 0.1 to 20 microns, or from 5 to 20 microns.
- composition of the present invention is free or substantially free of silicate.
- compositions of the present invention may comprise polyethylene glycol (PEG) , of various weight percentages of the composition as well as various ranges of average molecular weights.
- PEG polyethylene glycol
- the compositions have from 0.1%to 15%, preferably from 0.2%to 12%, more preferably from 0.3%to less than 10%, yet more preferably from 0.5%to 7%, alternatively from 1%to 5%, alternatively from 0.5%to 10%, alternatively from 1%to 8%, alternatively from 1%to 4%, alternatively from 1%to 2%, alternatively from 2%to 3%, alternatively from 4%to 5%, or combinations thereof, of PEG by weight of the composition.
- the PEG is one having a range of average molecular weight from 100 Daltons to 1600 Daltons, preferably from 200 to 1000, alternatively from 400 to 800, alternatively from 500 to 700 Daltons, alternatively combinations thereof.
- PEG is a water soluble linear polymer formed by the addition reaction of ethylene oxide to an ethylene glycol equivalent having the general formula: H- (OCH 2 CH 2 ) n -OH.
- One supplier of PEG is Dow Chemical Company under the brand name of CARBOWAX TM .
- the oral care compositions herein may include a sweetening agent.
- sweeteners such as saccharin, dextrose, sucrose, lactose, maltose, levulose, aspartame, sodium cyclamate, D-tryptophan, dihydrochalcones, acesulfame, sucralose, neotame, and mixtures thereof.
- Sweetening agents are generally used in oral compositions at levels of from 0.005%to 5%, by weight of the composition, alternatively 0.01%to 1%, alternatively from 0.1%to 0.5%, alternatively combinations thereof.
- the compositions may include an effective amount of an anti-caries agent.
- the anti-caries agent is a fluoride ion source.
- the fluoride ion may be present in an amount sufficient to give a fluoride ion concentration in the composition at 25°C, and/or in one embodiment can be used at levels of from about 0.0025%to about 5%by weight of the composition, alternatively from about 0.005%to about 2.0%by weight of the composition, to provide anti-caries effectiveness.
- suitable fluoride ion-yielding materials are disclosed in U. S. Patent Nos. 3,535,421, and 3,678,154.
- Representative fluoride ion sources include: stannous fluoride, sodium fluoride, potassium fluoride, amine fluoride, sodium monofluorophosphate, and zinc fluoride.
- the dentifrice composition contains a fluoride source selected from stannous fluoride, sodium fluoride, and mixtures thereof.
- the fluoride ion source is sodium monofluorophosphate, and wherein the composition more preferably comprises 0.0025%to 2%of the sodium monofluorophosphate by weight of the composition, alternatively from 0.5%to 1.5%, alternatively from 0.6%to 1.7%, alternatively combinations thereof.
- the dentifrice composition comprises from 1 parts per million (ppm) to 15,000 ppm, alternatively from 100 ppm to 8,000 ppm, alternatively from 5,000 ppm to 10,000 ppm, alternatively from 7,000 to 9,000 ppm, of monofluorophosphate (MFP) ion.
- ppm parts per million
- MFP monofluorophosphate
- the pH of the dentifrice composition may be greater than pH 7.8, preferably greater than pH 8.3, or from pH 8 to 13, or from pH 8.4 to 13, or more preferably from pH 9 to 12, alternatively greater than pH 8.5, alternatively greater than pH 9, alternatively from pH 9 to 11, alternatively from pH 9 to 10, or combinations thereof.
- a method for assessing pH of dentifrice is described. pH is measured by a pH Meter with Automatic Temperature Compensating (ATC) probe.
- the pH Meter is capable of reading to 0.001 pH unit.
- the pH electrode may be selected from one of the following (i) Orion Ross Sure-Flow combination: Glass body -VWR #34104-834/Orion #8172BN or VWR#10010-772/Orion #8172BNWP; Epoxy body -VWR #34104-830/Orion #8165BN or VWR#10010-770/Orion #8165BNWP; Semi-micro, epoxy body -VWR #34104-837/Orion #8175BN or VWR#10010-774/Orion #3175BNWP; or (ii) Orion PerpHect combination: VWR #34104-843/Orion #8203BN semi-micro, glass body; or (iii) suitable equivalent.
- the automatic temperature compensating probe is Fisher Scientific, Cat #13-620-16.
- a 25%by weight slurry of dentifrice is prepared with deionized water, and thereafter is centrifuged for 10 minutes at 15000 rotations-per-minute using a SORVALL RC 28S centrifuge and SS-34 rotor (or equivalent gravitational force, at 24149g force) .
- the pH is assessed in supernatant after one minute or the taking reading is stabilized.
- the electrode is washed with deionized water. Any excess water is wiped with a laboratory grade tissue. When not being used, the electrode is kept immersed in a pH 7 buffer solution or an appropriate electrode storage solution.
- the dentifrice compositions herein may include an effective amount of a pH modifying agent, alternatively wherein the pH modifying agent is a pH buffering agent.
- pH modifying agents refer to agents that can be used to adjust the pH of the dentifrice compositions to the above-identified pH range.
- pH modifying agents may include alkali metal hydroxides, ammonium hydroxide, organic ammonium compounds, carbonates, sesquicarbonates, borates, silicates, phosphates, imidazole, and mixtures thereof.
- Specific pH agents include monosodium phosphate (monobasic sodium phosphate) , trisodium phosphate (sodium phosphate tribasic dodecahydrate or “TSP” ) , sodium benzoate, benzoic acid, sodium hydroxide, potassium hydroxide, alkali metal carbonate salts, sodium carbonate, imidazole, pyrophosphate salts, sodium gluconate, lactic acid, sodium lactate, citric acid, sodium citrate, phosphoric acid.
- TSP trisodium phosphate tribasic dodecahydrate
- the dentifrice composition comprises: from 0.01%to 3%, preferably from 0.1%to 1%of TSP by weight of the composition; and from 0.001%to 2%, preferably from 0.01%to 0.3%of monosodium phosphate by weight of the composition.
- TSP and monosodium phosphate may also have calcium ion chelating activity and therefore provide some monofluorophosphate stabilization (in those formulations containing monofluorophosphate) .
- the dentifrice compositions herein may include a surfactant.
- the surfactant may be selected from anionic, nonionic, amphoteric, zwitterionic, cationic surfactants, or mixtures thereof.
- the composition may include a surfactant at a level of from about 0.1%to about 10%, from about 0.025%to about 9%, from about 0.05%to about 5%, from about 0.1%to about 2.5%, from about 0.5%to about 2%, or from about 0.1%to about 1%by weight of the total composition.
- anionic surfactants may include those described at US 2012/0082630 A1 at paragraphs 32, 33, 34, and 35.
- Non-limiting examples of zwitterionic or amphoteric surfactants may include those described at US 2012/0082630 A1 at paragraph 36; cationic surfactants may include those described at paragraphs 37 of the reference; and nonionic surfactants may include those described at paragraph 38 of the reference.
- the composition comprises 0.1%to 5%, preferably 0.1%to 3%, alternatively from 0.3%to 3%, alternatively from 1.2%to 2.4%, alternatively from 1.2%to 1.8%, alternatively from 1.5 %to 1.8%, alternatively combinations thereof, of the anionic surfactant sodium lauryl sulfate (SLS) by weight of the composition.
- SLS sodium lauryl sulfate
- the dentifrice compositions herein may include one or more thickening agents.
- a thickening agent may be used in an amount from about 0.01%to about 15%, or from about 0.1%to about 10%, or from about 0.1%to about 5%, by weight of the composition.
- Non-limiting examples may include those described in US 2008/0081023 A1 at paragraphs 134 to 137, and the references cited therein.
- the composition comprises a linear sulfated polysaccharide as a thickening agent.
- Carrageenans or carrageenins are one example of a linear sulfated polysaccharide.
- carrageenans can vary based upon the degree of sulfation that include: Kappa-carrageenan, Iota-carrageenan, and Lambda-carrageenan. Combinations of carrageenans can be used.
- the composition contains from 0.1%to 3%of a linear sulfated polysaccharides by weight of the composition, preferably from 0.5%to 2%, alternatively from 0.6%to 1.8%, alternatively combinations thereof.
- Iota-carrageenan is used.
- the composition comprises a silica agent, preferably a thickening silica obtained from sodium silicate solution by destabilizing with acid as to yield very fine particles.
- a silica agent preferably a thickening silica obtained from sodium silicate solution by destabilizing with acid as to yield very fine particles.
- a commercially available example is branded silicas from Huber Engineered Materials (e.g., 103, 124, 113 115, 163, 165, 167) .
- the composition comprising from 0.5%to 5%by weight of the composition of a silica agent, preferably from 1%to 4%, alternatively from 1.5%to 3.5%, alternatively from 2%to 3%, alternatively from 2%to 5%, alternatively from 1%to 3%, alternatively combinations thereof by weight of the composition.
- the composition comprises a carboxymethyl cellulose ( “CMC” ) .
- CMC is prepared from cellulose by treatment with alkali and monochloro-acetic acid or its sodium salt. Different varieties are commercially characterized by viscosity.
- One commercially available example is Aqualon TM branded CMC from Ashland Special Ingredients (e.g., Aqualon TM 7H3SF; Aqualon TM 9M3SF Aqualon TM TM9A; Aqualon TM TM12A) .
- the composition contains from 0.1%to 3%of a CMC by weight of the composition, preferably from 0.5%to 2%, alternatively from 0.6%to 1.8%, alternatively combinations thereof by weight of the composition.
- the thickener agents may comprise liner sulfated polysaccharide (e.g., carrageenans) , CMC, and preferably also a thickening silica for purposes of cost savings while achieving the right balancing of viscosity and elasticity.
- liner sulfated polysaccharide e.g., carrageenans
- the composition comprises a thickener comprising: (a) 0.01%to less than 1.4 %, preferably from 0.1 %to 1.3%, more preferably from 0.5%to 1.3%of a carrageenan by weight of the dentifrice composition; and (b) greater than 0.4 %to 2 %, preferably from 0.5%to 1.8%, more preferably from 0.6%to 1.8%of a carboxymethyl cellulose (CMC) by weight of the dentifrice composition.
- the aforementioned thickener further comprises 0.5%to 5%, preferably 1%to 4%, of a thickening silica by weight of the dentifrice composition.
- compositions herein may be substantially free or free of humectants, alternatively contain low levels of humectants.
- humectant for the purpose of present invention, includes edible polyhydric alcohols such as glycerin, sorbitol, xylitol, butylene glycol, propylene glycol, and combinations thereof.
- the humectant is selected from sorbitol, glycerin, and combinations thereof.
- the humectant is sorbitol.
- the composition comprises from 0%to less than 20%of humectants by weight of the composition, preferably from 0%to 10%, alternatively from 0%to 5%, alternatively from 0%to 3%, alternatively from 0%to 2%, alternatively from 0%to 1%, alternatively less than 20%, or less than 19%, 18%, 15%, 12%, 8%, 7%, 6%, 4%, 3%, 2%, 1%, or less than 0.5%; or greater than 1%, or greater than 2%, 5%, 10%, or 15%; or combinations thereof, by weight of the composition.
- the composition contains less than 20%of sorbitol by weight of the composition.
- compositions of the present invention comprise a humectant, preferably from 1%to 15%by weight of the composition.
- compositions herein may include a colorant.
- Titanium dioxide is one example of a colorant. Titanium dioxide is a white powder which adds opacity to the compositions. Titanium dioxide generally can comprise from about 0.25%to about 5%, by weight of the composition.
- compositions herein may include from about 0.001%to about 5%, alternatively from about 0.01%to about 4%, alternatively from about 0.1%to about 3%, alternatively from about 0.5%to about 2%, alternatively 1%to 1.5%, alternatively 0.5%to 1%, alternatively combinations thereof, of a flavorant composition by weight of the composition.
- flavorant composition is used in the broadest sense to include flavor ingredients, or sensates, or sensate agents, or combinations thereof.
- Flavor ingredients may include those described in US 2012/0082630 A1 at paragraph 39; and sensates and sensate ingredients may include those described at paragraphs 40 –45, incorporated herein by reference. Excluded from the definition of flavorant composition is “sweetener” (as described above) .
- a method for assessing free fluoride ion (also known as ionic fluoride) in dentifrice is described.
- Free fluoride ion is measured by an ion-selected electrode (ISE) .
- ISE ion-selected electrode
- An example of a fluoride ion meter is from SARTORIUS PP-50. The meter may be fitted with a Fluoride-Specific ion electrode with Single-Junction Reference electrode. An example of such an electrode is from Orion Research, Inc. , Cat. No. 9609BNWP. Equivalents of the meter and electrodes may also be used.
- the dentifrice sample for free fluoride assessment is prepared by using a balance that is accurate to the 0.0001 gram (g) .
- the aforementioned citrate buffer solution is prepared by dissolving 200 g sodium citrate in a 2000 mL glass beaker, 120 mL glacial acetic acid, 120 g sodium chloride, and 60 g NaOH, all with deionized water until a total volume of about 1800mL is achieved; and adjusting the pH to 5.0 ⁇ 5.5, and finally diluting the pH adjusted solution to a final volume of 2000 mL with deionized water.
- Fluoride Ion working standards preparation is described.
- the fluoride standard curve is prepared as inputs, which is also used for ISE calibration on the fluoride ion test.
- a fluoride stock solution ( ⁇ 100 ppm) is prepared by weighing 0.1116 g NaF reference standard in a 100 mL polyethylene bottle. Water is added until the weight is 100 g. 10 g of this solution is then weighed out, with water added until a total weight of 50 g is achieved.
- Fluoride Ion standards are prepared by a Fluoride stock solution as described. The Fluoride stock solution (see table below for target weights) is weighed into individual tared 100mL plastic bottles. Without re-taring the bottle, buffer solution is added to the bottle, and then water is weighed into the same bottle to obtain a total solution weight of approximately 50 grams. The resulting solution is mixed well.
- the Ion Chromatograph Instrument can be from DIONEX IC3000, fitted with an AS12A column and Guard 2mm (P/N: 046055/046056) ; and AS14 column and Guard 4mm (P/N: 046124/046134) .
- the instrument is also fitted with a 2 mm and a 4 mm Anion Self-regenerator Suppressor (P/N: 064555, and P/N: 064554, respectively) .
- a dentifrice sample is prepared for MFP ion level assessment. A balance that is accurate to the 0.0001 gram (g) is used. 20g of dentifrice is weighed into a tared 100 mL plastic beaker and then gradually 50mL of deionized water is added, while a magnetic stir bar is stirring in the plastic beaker, until the dentifrice is a completely disperse solution. The entire solution is gently transferred to a 100mL plastic volumetric flask as to avoid generating foam (so the volume can be measured accurately) , and deionized water is added to reach a total volume of 100 mL, and then the solution shaken manually to form a slurry.
- the formed slurry is then transferred into 10 mL centrifuge tubes, and centrifuged for 10 minutes at 15000 roations-per-minutes (RPM) (at 24149g) at ambient temperature. Thereafter, 5 g of supernatant is weighed, and then an Eluent Preparation (2.0 mM NaCO 3 and 2.5 mM NaHCO 3 ) is added so that the total weight of superntatent and Eluent Preparation is 50 g, and then resulting solution is mixed well in a 100 plastic beaker. The mixed solution is filtered with a with 0.20 um nylon membrane (e.g., Millipore NYLON filter device, 0.20 um pores, Cat. No. SLGN033NB) . The filtered solution is injected in either the AS12A or AS14 chromatography column for separation. Results are calculated based on monofluorophosphate standards.
- RPM 15000 roations-per-minutes
- MFP Ion stock preparation ( ⁇ 1000 ppm) is prepared by weighing 0.15g of Sodium MFP into a 100mL volumetric flask and adding water to a final weight of 100 g, and then mix well. Determine the actual concentration of the stock solution by using the formula listed below, (wherein the purity of the Sodium MFP raw material must be established prior to its use) .
- the preparation of MFP working standards is descirbed.
- the MFP stock solution (see table below for target weights) is weighed into individual tared 100mL plastic bottles. Without re-taring the plastic bottle, eluent is added to the plastic bottle to obtain a total solution weight of approximately 100 grams, and the solution is mixed well.
- ISE ion-selective electrode
- An example of a fluoride ion meter is SARTORIUS PP-50, but an equivalent may be used.
- the ion meter may be fitted with a fluoride-specific ion electrode with a single-junction reference electrode by Orion Research Inc. , Cat. No. 9609BNWP, but an equivalent may be used.
- the sample is prepared by using a balance that is accurate to the 0.0001 gram (g) .
- the aforementioned citrate buffer solution is prepared by dissolving 100 g of sodium citrate, 60 mL of glacial acetic acid, 60 g of NaCl, and 30g of NaOH, all with water, adjusting the pH to 5.0 ⁇ 5.5, and diluting the citrate buffer solution with deionized water until a total volume of 1000 mL is achieved. Turning back to the sample solution, the entire 50 mL solution is transferred to a 50 mL plastic beaker and the fluoride level is assessed based on a fluoride standared curve using the fluoride ion meter and electrode described.
- the standard fluoride curve (w/w %) is prepared by accurately measuring 0.5 mL, 1.0 mL, 1.5 mL, 2.0 mL, and 2.5 mL fluoride ion standard solutions (100 mg/kg) into five respective 50 mL plastic measuring flasks. 5mL of citrate buffer solution (made as previously described above) into each respective flask, and then diluting each solution to the scale with deionized water. Thereafter, each solution is transferred into a 50 mL plastic beaker respectively, measuring potential E under magnetic agitation, recording potential values, and drawing E-logc (wherein “c” is a concentration) standard curve.
- Fluoride Uptake i.e., total fluoride that is bound within the tooth enamel
- Enamel specimens are prepared by cutting 4 mm cores (chips) from extracted, human maxillary incisors using a diamond core drill. Chips are mounted in 1/4 inch diameter Lucite rods (Beijing Mengzhijie M&E Engineering Technology Co. , Ltd. ) with dental acrylic (Shanghai New Century Dental Materials Co. , Ltd. ) covering all sides except the lingual surface. Course polishing of the surface with 600 grit silicon carbide-water slurry is used to remove approximately 50 microns of the outer enamel. Specimens are then polished for 30 minutes with gamma alumina (40-10076, BUEHLER) to a mirror finish.
- gamma alumina 40-10076, BUEHLER
- each chip After sonicating and rinsing with deionized water, each chip is exposed to 25 mL of demineralization solution (0.025M/L lactic acid, 2 x 10-4 MHDP (MethaneHydroxy Diphosphonate) , pH 4.5) for 32 hours at 23°C for the formation of initial carious lesions. After removal from the demineralization solution, the chips are carefully rinsed in deionized water. Each chip is assessed through visual inspection (10 x magnifications) to ensure enamel is free of surface imperfections. Chips are randomly placed into treatment groups (at 5 chips per treatment group) . Early carious lesion with slight mineral loss is necessary for the fluoride uptake test to assess the absorption of the fluoride ion.
- demineralization solution 0.025M/L lactic acid, 2 x 10-4 MHDP (MethaneHydroxy Diphosphonate) , pH 4.5
- Dentifrice treatments are prepared by thoroughly mixing 8 grams of the subject dentifrice sample with 24 g of fresh pooled human saliva to form a slurry. The saliva is utilized within 2 hours of collection. Slurries are centrifuged for 10 minutes at 10,000 rotations per minute (12,096 g) and the supernatant removed. Each treatment group of specimens is exposed to 20 mL of supernatant for 30 minutes with constant stirring with a magnetic stir bar. Following the treatment, specimens are thoroughly rinsed with deionized water and then analyzed for fluoride content. A microdrill biopsy technique is used to assess each dentifrice sample’s ability to deliver fluoride to the demineralized enamel.
- Specimens are mounted on the micro drill stage and sampled using a modified carbide dental bur.
- the biopsy technique removes a small portion of the chip, leaving behind a cylinder with the approximate dimensions 30-50 ⁇ m diameter and a constant 50 ⁇ m height.
- the powder removed is dissolved in 66.7 ⁇ l 0.5M HClO 4 .
- buffered and pH adjusted with 133.4 ⁇ l Total Ionic Strength Adjustment Buffer e.g., TISAB II
- 0.5N NaOH solution (1: 1 value ratio
- Example 1 has 1.10 wt%of sodium monofluorophosphate and 0.60 wt%of tetrasodium pyrophosphate and is at pH of 9.4.
- Controls (A, B, C) also have sodium monofluorophosphate (of varying levels) , but no tetrasodium pyrophosphate and a pH lower than 9.4.
- Example 1 assessed the monofluorophosphate (MFP) ion and soluble fluoride ion, on a parts-per-million (ppm) basis for Examples 1 and 5 (Control D) at an initial theoretical level and after 14 days at 60°C temperature; and after 43 weeks at 30°C.
- Example 1 provided superior results compared to Example 5 given the lower percent drop of MFP ion and Soluble Fluoride ion at the 14 days and 43 week time points.
- the term “theoretical level” is referring to the amount of MFP ion and Soluble Fluoride Ion calculated from a freshly prepared sample (i.e., the formulation having no opportunity for degradation) .
- the intent of the shorter storage time period at higher temperature is to accelerate the equilibrium and any degradation kinetics.
- the data demonstrates that the presence of humectant (e.g., 16.8 wt%of sorbitol) in Control D may impact the results negatively.
- the dentifrice composition of the present invention is free of polyol, especially glycerol or sorbitol.
- Table 3 below assesses the free fluoride ion and monofluorophosphate (MFP) ion on a parts-per-million (ppm) basis of subject dentifrice formulation at the accelerated stability storage conditions (at 60°C for 14 days) .
- the term “theoretical level” is referring to the amount of MFP ion and elemental fluoride calculated from a freshly prepared sample (i.e., the formulation having no opportunity for degradation) .
- the MFP ion degradation for the inventive Example 1 is significantly lower vs. the other control examples.
- the MFP at accelerated storage conditions has 25%degradation, where as all other controls show greater than 50%degradation of MFP ion.
- the resultant degraded MFP ion in Example 1 is maintained predominantly as free fluoride ion, based on a mass balance of theoretical level vs. the measured free fluoride.
- Example 1 the predominant fluoride species of the degraded MFP ion in Example 1 is maintained as free fluoride ion (i.e., non-complexed fluoride) .
- free fluoride ion i.e., non-complexed fluoride
- all other Example controls have both a significantly higher MFP degradation rate /percentage and the free fluoride ion of the degraded MFP is relatively low.
- One aspect of the invention provides a dentifrice composition wherein the monofluorophosphate ion degrades less than 40%, more preferably less than 35%, and more preferably less than 30%, alternatively from 1%to 40%, alternatively from 5%to 30%, alternatively combinations thereof, after 14 days at 60°C relative to the monofluorophosphate ion in freshly prepared dentifrice composition.
- Another aspect of the invention provides a dentifrice composition wherein a percentage of degraded monofluorophosphate ion that remains as free fluoride ion after 14 days at 60°C is greater than 50%, or greater than 75%, preferably greater than 85%, more preferably greater than 90%, alternatively greater than 95%, alternatively from 75%to 100%, alternatively from 80%to 99%, alternatively from 80%to 98%, alternatively combinations thereof.
- Another aspect of the invention provides a dentifrice composition wherein the composition contains greater than 3,660 parts per million (ppm) monofluorophosphate ion after 14 days at 60°C, preferably from 4,000 ppm to 8,000 ppm of monofluorophosphate ion, more preferably from 5,000 to 7,000 ppm of monofluorophosphate ion, yet more preferably from 5,500 to 7,000 ppm, alternatively combinations thereof, of monofluorophosphate ion after 14 days at 60°C.
- ppm 3,660 parts per million
- Another aspect of the invention provides a dentifrice composition wherein the composition contains greater than 3,260 parts per million (ppm) monofluorophosphate ion after 43 weeks at 30°C, preferably from 3,500 ppm to 11,000 pm of monofluorophosphate ion, more preferably greater than 4,000 ppm to 11,000 ppm, yet more preferably 5,000 ppm to 11,000 ppm, yet still more preferably from 6,000 ppm to 11,000 ppm, alternatively combinations thereof, monofluorophosphate ion after 43 weeks at 30°C.
- ppm 3,260 parts per million
- Yet still another aspect of the invention provides for the use of a linear sulphated polysaccharide, preferably a carrageenan, to provide improved fluoride ion stability.
- Table 4 demonstrates that a carrageenan containing dentifrice formulation is better at fluoride ion stability than two control formulations.
- Examples 6, 7 and 8 as described by the formulation components of Table 1, are briefly summarized.
- Example 6 contains Iota-carrageenan at 1.4 wt%.
- Example 6 and Example 7 formulations do not have any carrageenan.
- Example 6 and Example 8 formulations both have slightly more sodium carboxymethyl cellulose (CMC) and thickening silica than Example 6, but notably Example 8 also has tetra sodium pyrophosphate (TSPP) .
- CMC carboxymethyl cellulose
- TSPP tetra sodium pyrophosphate
- Example 7 does not contain carrageenan, but does contain tetrasodium pyrophosphate (TSPP) .
- Control D notably containing 0.01%TSPP by weight of the composition.
Abstract
Description
Claims (15)
- A dentifrice composition comprising:(a) 25%to 60%of a calcium-containing abrasive by weight of the composition, wherein the calcium-containing abrasive comprises calcium carbonate;(b) 20%to 75%of water by weight of the composition(c) 0.0025%to 4.0%of a sodium monofluorophosphate by weight of the composition;(d) 0.001%to 4%of a calcium chelating agent by weight of the composition, wherein the calcium chelating agent is a pyrophosphate ion; and(e) pH is greater than 8.3.
- The composition of claim 1, wherein the composition comprises 27%to 47%of the calcium carbonate composition, and the pyrophosphate ion is from 0.01%to 1.35%by weight of the composition.
- The composition of claim 1 or 2, wherein the calcium carbonate is selected from fine ground natural chalk, ground calcium carbonate, and combinations thereof, and wherein the calcium carbonate has a D50 from 2 microns to 7 microns, preferably the D50 is from 3 microns to 6 microns.
- The composition of claim 1, 2, or 3, wherein an monofluorophosphate ion degrades less than 40%, more preferably less than 35%, and more preferably less than 30%after 14 days at 60℃ relative to the monofluorophosphate ion in freshly prepared dentifrice composition.
- The composition of claim 4, wherein a percentage of degraded monofluorophosphate ion that remains as free fluoride ion after 14 days at 60℃ is greater than 50%, preferably greater than 75%, more preferably greater than 85%, yet more preferably greater than 90%.
- The composition of claim 1, 2, 3, 4 or 5, wherein the composition contains greater than 3,660 parts per million (ppm) monofluorophosphate ion after 14 days at 60℃, preferably from 4,000 ppm to 8,000 ppm of monofluorophosphate ion, more preferably from 5,000 to 7,000 ppm of monofluorophosphate ion, yet more preferably from 5,500 to 7,000 ppm of monofluorophosphate ion after 14 days at 60℃.
- The composition of claim 1, 2, 3, 4 or 5, wherein the composition contains greater than 3,260 parts per million (ppm) monofluorophosphate ion after 43 weeks at 30℃, preferably from 3,500 ppm to 11,000 pm of monofluorophosphate ion, more preferably greater than 4,000 ppm to 11,000 ppm, yet more preferably 5,000 ppm to 11,000 ppm, yet still more preferably from 6,000 ppm to 11,000 ppm monofluorophosphate ion after 43 weeks at 30℃.
- The composition according to any one of any of the preceding claims, wherein calcium chelating agent is from 0.1%to less than 1.0%of a pyrophosphate salt by weight of the composition, preferably wherein the pyrophosphate is tetrasodium pyrophosphate.
- The composition according to any one of the preceding claims, wherein the pH is greater than 8.5, preferably the pH is from 9 to 12.
- The composition according to any one of any of the proceeding claims, further comprising from 0.01%to 7%, preferably from 0.1%to 6%of a linear sulfated polysaccharide by weight of the composition, preferably wherein the linear sulfated polysaccharide is a carrageenan.
- The composition of 10, further comprising 0.5%to 2%of a carboxymethyl cellulose.
- The composition according to any one of the preceding claims, further comprising from 0.5%to less than 10%preferably from 1%to 8%of polyethylene glycol (PEG) by weight of the composition, wherein more preferably the PEG is selected a molecular weight range from PEG 200 to PEG 600.
- The composition according to any one of the preceding claims, further comprising 0.01%to 0.11%, preferably 0.02%to 0.10%, more preferably 0.03%to 0.09%of a paraben by weight of the composition, preferably wherein the paraben is selected from methyl paraben, propyl paraben, or combinations thereof.
- The composition according to any one of the preceding claims, which is substantially free of glycerin and sorbitol, and wherein the water is from 50%to 60%by weight of the composition.
- A method of treating tooth enamel comprising the step of contacting teeth with the dentifrice composition according to any one of preceding claims.
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BR112016025278-0A BR112016025278B1 (en) | 2014-05-15 | 2015-04-28 | toothpaste composition |
MX2016015016A MX363627B (en) | 2014-05-15 | 2015-04-28 | Dentifrice compositions having improved fluoride ion stability or fluoride uptake. |
CN201580024477.6A CN106456463B (en) | 2014-05-15 | 2015-04-28 | Dentifrice compositions with improved fluoride ion stability or fluoride uptake |
EP15793035.5A EP3142631B1 (en) | 2014-05-15 | 2015-04-28 | Dentifrice compositions having improved fluoride ion stability or fluoride uptake |
CA2946205A CA2946205C (en) | 2014-05-15 | 2015-04-28 | Dentifrice compositions having improved fluoride ion stability or fluoride uptake |
US14/700,196 US20150328093A1 (en) | 2014-05-15 | 2015-04-30 | Dentifrice Compositions Having Improved Fluoride Ion Stability or Fluoride Uptake |
US14/830,839 US10039697B2 (en) | 2014-05-15 | 2015-08-20 | Dentifrice compositions having improved fluoride ion stability or fluoride uptake |
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Publication number | Priority date | Publication date | Assignee | Title |
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Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015172348A1 (en) | 2014-05-15 | 2015-11-19 | The Procter & Gamble Company | Dentifrice compositions having dental plaque mitigation or improved fluoride uptake |
WO2017079952A1 (en) * | 2015-11-13 | 2017-05-18 | The Procter & Gamble Company | Dentifrice compositions with improved consumer experience |
WO2017079953A1 (en) | 2015-11-13 | 2017-05-18 | The Procter & Gamble Company | Dentifrice compositions with improved fluoride stability |
MX2018005911A (en) | 2015-11-13 | 2019-04-04 | Procter & Gamble | Dentifrice compositions with improved fluoride uptake. |
CN108348414A (en) | 2015-11-13 | 2018-07-31 | 宝洁公司 | The dentifrice composition absorbed with Difluoride source and improved fluoride |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1237894A (en) * | 1996-11-21 | 1999-12-08 | 普罗克特和甘保尔公司 | Dentifrice compositions containing polyphosphate and fluoride |
CN101330900A (en) * | 2005-12-20 | 2008-12-24 | 宝洁公司 | Oral care compositions comprising zinc and phytate |
WO2013034421A2 (en) * | 2011-09-08 | 2013-03-14 | Unilever N.V. | Tooth remineralizing dentifrice |
WO2013094312A1 (en) * | 2011-12-20 | 2013-06-27 | ライオン株式会社 | Dentrifice composition |
Family Cites Families (46)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL254647A (en) * | 1959-08-07 | |||
US4046872A (en) | 1974-04-29 | 1977-09-06 | Colgate Palmolive Company | Dental cream |
US4283385A (en) | 1980-05-09 | 1981-08-11 | Richardson-Merrell Inc. | Dentifrices with improved soluble fluoride availability |
ATE28398T1 (en) | 1982-04-20 | 1987-08-15 | Beecham Group Plc | AGENTS FOR ORAL HYGIENE. |
US4701319A (en) | 1984-09-14 | 1987-10-20 | The Procter & Gamble Company | Toothpaste compositions |
US4678662A (en) | 1985-10-09 | 1987-07-07 | Monsanto Company | Pyrophosphate coating process for calcium carbonate dental abrasives |
US4828849A (en) | 1988-01-14 | 1989-05-09 | Warner-Lambert Company | Surfactant inhibition of dental plaque |
BR9813677A (en) * | 1997-12-18 | 2000-10-03 | Unilever Nv | Composition for oral care, and use of a fully neutralized polyacrylic acid |
CN1154470C (en) | 1998-03-06 | 2004-06-23 | Fmc有限公司 | High moisture toothpaste |
FR2785534A1 (en) | 1998-11-09 | 2000-05-12 | Rhodia Chimie Sa | FLUORINATED TOOTHPASTE COMPOSITION COMPRISING FLUORINE-COMPATIBLE ABRASIVE PARTICLES OF CALCIUM MATERIAL |
KR100401957B1 (en) | 2000-12-27 | 2003-10-17 | 주식회사 태평양 | A method for stabilization of fluorinion in oral compositions containing calcium carbonate as polishing agent and oral composition containing of fluorinion stabled thereby |
US20040120902A1 (en) | 2001-04-24 | 2004-06-24 | Wernett Patrick Clinton | Fluoride compatible calcium carbonate |
DE60232597D1 (en) | 2001-10-01 | 2009-07-23 | Lion Corp | METHOD OF BLEACHING TEETH; DENTAL COMPOSITION AND TOOTHBAR SET |
WO2003030850A1 (en) | 2001-10-02 | 2003-04-17 | Unilever N.V. | Oral composition comprising fine ground natural chalk |
JP4247116B2 (en) * | 2001-10-25 | 2009-04-02 | 花王株式会社 | Dentifrice |
US6723304B2 (en) | 2001-11-13 | 2004-04-20 | Noville, Inc. | Oral care compositions comprising diglycerol |
JP4800576B2 (en) | 2001-11-28 | 2011-10-26 | ザ プロクター アンド ギャンブル カンパニー | Dentifrice composition comprising a stable low aqueous phase comprising polyphosphate and an ionic active ingredient |
JP3868293B2 (en) | 2001-12-28 | 2007-01-17 | 松下電器産業株式会社 | Semiconductor integrated circuit |
US20040131560A1 (en) | 2002-10-04 | 2004-07-08 | The Procter & Gamble Company | Oral compositions and use thereof |
EP1608327A2 (en) | 2003-03-14 | 2005-12-28 | Smithkline Beecham Corporation | Compositions and methods for preventing dental stain |
US20080230298A1 (en) | 2003-09-18 | 2008-09-25 | Robert Michael Buch | Method of Applying Oral Compositions |
US7135163B2 (en) * | 2003-10-16 | 2006-11-14 | Church & Dwight Co., Inc. | Prevention of crystal formation in toothpaste |
GB2408933A (en) | 2003-12-12 | 2005-06-15 | Reckitt Benckiser Healthcare | Antimicrobial composition |
US20090202453A1 (en) * | 2004-08-03 | 2009-08-13 | Hindustan Lever Limited | Oral Composition |
US20060134020A1 (en) | 2004-12-21 | 2006-06-22 | Robinson Richard S | Anti-caries oral care composition with a chelating agent |
US7803353B2 (en) | 2006-03-29 | 2010-09-28 | The Procter & Gamble Company | Oral care compositions having improved consumer aesthetics and taste |
MX2008013710A (en) | 2006-04-26 | 2008-11-04 | Unilever Nv | Toothpaste. |
US8865192B2 (en) | 2006-07-07 | 2014-10-21 | The Procter & Gamble Co | Flavor oils with reduced sulfur content and use in oral care compositions |
AU2006349144C1 (en) | 2006-10-02 | 2013-10-31 | The Procter & Gamble Company | Stannous oral care compositions |
CN101848694A (en) | 2007-11-09 | 2010-09-29 | 宝洁公司 | Oral stannous compositions |
RU2010139833A (en) * | 2008-04-28 | 2012-06-10 | Дзе Проктер Энд Гэмбл Компани (US) | ORGANIC CARE COMPOSITIONS |
WO2010059289A1 (en) | 2008-11-20 | 2010-05-27 | The Procter & Gamble Company | Personal care compositions providing enhanced cooling sensation |
US20120020897A1 (en) | 2009-04-02 | 2012-01-26 | Colgate-Palmolive Company | Dentifrice composition |
TW201109022A (en) * | 2009-06-03 | 2011-03-16 | Colgate Palmolive Co | Borinic compositions |
CN102471386B (en) | 2009-08-07 | 2015-12-16 | Fmc有限公司 | Carrageenan product and production method thereof and application |
MX351181B (en) | 2009-09-11 | 2017-10-02 | The Procter & Gamble Company Star | Methods and compositions for hydrophobic modification of oral cavity surfaces. |
CN101690699A (en) | 2009-09-29 | 2010-04-07 | 广东名臣有限公司 | Teeth-cleaning whitening toothpaste composition |
RU2561587C2 (en) * | 2010-06-01 | 2015-08-27 | Колгейт-Палмолив Компани | Compositions for oral cavity care, resistant to microbial growth |
MX2012014447A (en) | 2010-06-17 | 2013-02-07 | Unilever Nv | Oral care compositions. |
KR101693732B1 (en) | 2010-10-25 | 2017-01-09 | (주)아모레퍼시픽 | Oral composition containing polyethylene glycol for improving preparation stability |
CN102283795A (en) | 2011-08-22 | 2011-12-21 | 昆明振华制药厂有限公司 | Propolis toothpaste and preparation method thereof |
CN102283794B (en) | 2011-08-22 | 2013-07-24 | 昆明振华制药厂有限公司 | Toothpaste including radix notoginseng and propolis and preparation method thereof |
WO2013033090A1 (en) | 2011-09-01 | 2013-03-07 | The Procter & Gamble Company | Oral care compositions with improved rheology |
US20130344120A1 (en) | 2012-06-21 | 2013-12-26 | Douglas Craig Scott | Mouth Rinse Emulsions |
BR112016013195A2 (en) * | 2013-12-16 | 2017-09-19 | Colgate Palmolive Co | COMPOSITIONS FOR ORAL HYGIENE COMPRISING CALCIUM CARBONATE AND CLAY |
CN105813618B (en) * | 2013-12-16 | 2019-03-29 | 高露洁-棕榄公司 | Oral care composition comprising calcium carbonate and silica |
-
2014
- 2014-05-15 WO PCT/CN2014/077555 patent/WO2015172354A1/en active Application Filing
-
2015
- 2015-04-28 MX MX2016015016A patent/MX363627B/en unknown
- 2015-04-28 CN CN201580024477.6A patent/CN106456463B/en active Active
- 2015-04-28 CA CA2946205A patent/CA2946205C/en active Active
- 2015-04-28 EP EP15793035.5A patent/EP3142631B1/en active Active
- 2015-04-28 BR BR112016025278-0A patent/BR112016025278B1/en active IP Right Grant
- 2015-04-28 WO PCT/CN2015/077636 patent/WO2015172652A1/en active Application Filing
- 2015-04-30 US US14/700,196 patent/US20150328093A1/en not_active Abandoned
- 2015-05-14 AR ARP150101514A patent/AR100456A1/en unknown
- 2015-08-20 US US14/830,839 patent/US10039697B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1237894A (en) * | 1996-11-21 | 1999-12-08 | 普罗克特和甘保尔公司 | Dentifrice compositions containing polyphosphate and fluoride |
CN101330900A (en) * | 2005-12-20 | 2008-12-24 | 宝洁公司 | Oral care compositions comprising zinc and phytate |
WO2013034421A2 (en) * | 2011-09-08 | 2013-03-14 | Unilever N.V. | Tooth remineralizing dentifrice |
WO2013094312A1 (en) * | 2011-12-20 | 2013-06-27 | ライオン株式会社 | Dentrifice composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017079954A1 (en) | 2015-11-13 | 2017-05-18 | The Procter & Gamble Company | Dentifrice compositions with improved fluoride stability |
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MX363627B (en) | 2019-03-28 |
BR112016025278A2 (en) | 2017-08-15 |
US20160317406A1 (en) | 2016-11-03 |
CN106456463A (en) | 2017-02-22 |
WO2015172354A1 (en) | 2015-11-19 |
EP3142631A4 (en) | 2017-12-13 |
US20150328093A1 (en) | 2015-11-19 |
US10039697B2 (en) | 2018-08-07 |
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CA2946205C (en) | 2019-01-29 |
BR112016025278B1 (en) | 2021-03-16 |
EP3142631B1 (en) | 2019-10-23 |
CN106456463B (en) | 2020-05-19 |
MX2016015016A (en) | 2017-04-11 |
CA2946205A1 (en) | 2015-11-19 |
EP3142631A1 (en) | 2017-03-22 |
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