WO2011103226A2 - Silica materials for reducing oral malodor - Google Patents
Silica materials for reducing oral malodor Download PDFInfo
- Publication number
- WO2011103226A2 WO2011103226A2 PCT/US2011/025141 US2011025141W WO2011103226A2 WO 2011103226 A2 WO2011103226 A2 WO 2011103226A2 US 2011025141 W US2011025141 W US 2011025141W WO 2011103226 A2 WO2011103226 A2 WO 2011103226A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silica material
- precipitated silica
- adduct
- metal
- zinc
- Prior art date
Links
Classifications
-
- 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
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
-
- 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
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- 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
- A61K8/27—Zinc; Compounds thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
-
- 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
- A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
-
- 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
- A61K2800/60—Particulates further characterized by their structure or composition
- A61K2800/61—Surface treated
- A61K2800/62—Coated
- A61K2800/621—Coated by inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- VSC volatile sulfur compounds
- the shift to gram-negative bacteria is typically accompanied by a depletion of carbohydrates and a rise in the pH level of saliva of from below about 6.5 to about 7.2.
- carbohydrates are depleted, gram-positive flora begin to lose fuel sources and are thus suppressed, while gram-negative flora become progressively more dominant.
- Gram- negative flora unlike gram-positive flora, are capable of breaking down proteins into short peptides and amino acids by proteolysis. Certain proteins, such as those containing cysteine and methionine residues, can be further broken down into VSCs.
- Solutions for oral malodor include mouthwash, chewing gums, breath strips, lozenges, mints, and toothpastes. Unfortunately, many of these products are incapable of reducing or preventing oral malodor for an extended period of time. Additionally, some of these products do little to prevent the exhalation of putrid VSCs. A need therefore exists for new compositions and methods for reducing oral malodor. These needs and other needs are satisfied by the present invention.
- silica materials comprising an adduct on at least a portion of a surface thereof.
- the silica materials are capable of binding volatile sulfur compounds (VSC)s and thereby reducing oral malodor.
- VSC volatile sulfur compounds
- dentifrice compositions oral care compositions comprising the silica materials, and methods of making and using the silica materials.
- Figure 1 is a diagram of the testing apparatus used to measure mercaptan absorption using the disclosed silica materials.
- Figure 2 is a plot of methyl mercaptan peak area vs. time obtained using the Comparative Example. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 3 is a plot obtained from a repeated time study using the Comparative Example, which includes an outlier point. The plot shows methyl mercaptan peak area vs. time; ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 4 is a plot from the repeated time study using the Comparative Example, which does not include the outlier point. The plot shows methyl mercaptan peak area vs. time; ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 5 is a plot of methyl mercaptan peak area vs. time obtained using Example 1A. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 6 is a plot from a repeated time study using Example 1A. The plot shows methyl mercaptan peak area vs. time. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 7 is a plot showing methyl mercaptan peak area vs. time obtained using Example IB. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 8 is a plot showing methyl mercaptan peak area vs. time obtained using Example 1C. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 9 is a plot showing methyl mercaptan peak area vs. time obtained using Example ID. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 10 is a plot showing methyl mercaptan peak area vs. time obtained using Example IE. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 11 is a plot showing headspace recoveries in the multi-dosing study for Examples 1A-E and Comparative Example, described below.
- the headspace recoveries are as follows: ⁇ - Example 1A; ⁇ - Example IB; A - Example 1C; X - Example ID; > ⁇ - Comparative Example; + - Example IE.
- Figure 12 is a plot of soluble concentration versus pH for Examples 1A-E. The samples are as follows: ⁇ - Example 1A; ⁇ - Example IB; A - Example 1C; X - Example ID; + - Example IE.
- each of the combinations A-E, A-F, B-D, B-E, B-F, C- D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
- any subset or combination of these is also specifically contemplated and disclosed.
- the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
- This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions.
- steps in methods of making and using the disclosed compositions are if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.
- mean particle size refers to the particle size for which 50% of the sample by number has a smaller size and 50% of the sample by number has a larger size.
- the present invention relates to silica materials that comprise an adduct, such as a transition metal, which are capable of absorbing VSCs and are thus useful for reducing oral malodor.
- the silica materials of the invention can be retained in the oral cavity of the mouth, which may enable VSC absorption over an extended period of time.
- the silica material has a mean particle size of from 1 to 15 microns and has an adduct present on at least a portion of its surface.
- the adduct is present on the surface of the silica particles in the silica material such that the adduct is available for interaction with VSCs, i.e., the adduct is exposed.
- a slurry of the silica material exhibits at least a 35% reduction, 45% reduction, or 50% reduction, in headspace in the VSC absorption test, i.e., the test described below in the Examples section under the heading "VSC Absorption Test” and "Multi-dosing Study.”
- the specific test for determining % headspace reduction (also referred to as “recovery") is the aqueous test described below under the heading "Multi- dosing Study.”
- the silica material of the invention has a mean particle size of 1 to 15 microns.
- the silica material has a mean particle size of greater than 5 microns to 15 microns, or for example, from 8 to 15 microns.
- Preferably, less than about 2% of the silica material of the invention has a particle size of greater than 44 microns.
- the adduct present on the silica material is preferably a metal adduct, such as a transition metal or post-transition metal.
- suitable metal adducts include zinc, tin, copper, strontium, aluminum, and mixtures thereof.
- the silica material is prepared by the addition of the adduct in the form of a water-soluble metal salt during the formation of precipitated silica material. Any metal salt that is soluble in acidic conditions would be suitable, such as metal nitrates, metal chlorides, metal sulfates, and the like.
- the silica material of the invention has a mean particle size of 1 to 15 microns and has a first and second adduct present on at least a portion of its surface, wherein the first and second adducts are different.
- a silica material can have a mean particle size of 1 to 5 microns, from greater than 5 microns to 15 microns, or from 8 to 15 microns.
- Examples of such silica materials include without limitation those having aluminum and zinc, aluminum and copper, zinc and tin, strontium and copper, or tin and strontium adducts both present on at least a portion of the surface of the silica.
- the silica material of the invention has a mean particle size of 1 to 15 microns and has an adduct present on at least a portion of its surface, wherein the adduct is present in an amount ranging from 0.025% to 10% by weight relative to the silica material as a whole, i.e. , metal adduct weight/(metal adduct weight + silica weight).
- the adduct is present in an amount ranging from 0.025% to 5%, from 0.025% to 3%, from 0.025% to 2%, or from 0.025% to 1% by weight relative to the silica material.
- the adduct is present in an amount ranging from 0.1% to 10%, 0.35% to 5%, or 1% to 3% by weight of the silica material.
- the silica material can include a variety of types of silicas, including precipitated silicas, fumed silica, silica gels, and the like.
- the silica material contains a precipitated silica and is prepared according to the following process. An aqueous solution of an alkali silicate, such as sodium silicate, is charged into a reactor equipped with mixing means adequate to ensure a homogeneous mixture.
- the alkali silicate solution in the reactor is preheated to a temperature of between about ambient temperature and 130 °C, preferably from about 50 to 100 °C, and more preferably from about 65°C and about 100°C, or from about 60 °C to about 90 °C.
- the alkali silicate solution can have an alkali silicate concentration of approximately 8.0 to 35 wt , such as from about 8.0 to about 20 wt .
- the alkali silicate can be a sodium silicate with a Si0 2 :Na 2 0 ratio of from about 1 to about 3.5, such as about 2.4 to about 3.4.
- the quantity of alkali silicate charged into the reactor is about 5 wt to 100 wt of the total silicate used in the batch.
- an electrolyte such as sodium sulfate solution or aluminum sulfate (Alum) solution, can be added to the reaction medium. Additionally, this mixing can be performed under high-shear conditions if desired.
- an aqueous solution of an acidulating agent or acid such as sulfuric acid
- an aqueous solution containing the same species of alkali silicate as is in the reactor such aqueous solution being preheated to a temperature of about 65°C to about 100°C.
- An adduct compound is added to the acidulating agent solution prior to the introduction of the acidulating agent solution into the reactor.
- the adduct compound is premixed with the acidulating agent solution in a concentration of mol. of adduct compound to L of acidulating agent solution of about 0.002 to about 0.185, preferably about 0.074 to about 0.150.
- an aqueous solution of the adduct compound can be used in place of the acid.
- the adduct compound can be a variety of metal compounds, including metal salts such as zinc(II) salts, tin(II) salts, iron(III) salts, copper(II) salts, and Alum. Specific examples include zinc(II) chloride, tin(II) chloride, iron(III) nitrate, copper(II) nitrate, and hydrated aluminum potassium sulfate.
- the acidulating agent solution preferably has a concentration of acidulating agent of about 6 to 35 wt , such as about 9.0 to about 20 wt . After a period of time the inflow of the alkali silicate solution is stopped and the acidulating agent solution is allowed to flow until the desired pH is reached.
- the reactor batch is allowed to age or "digest" for between 5 minutes to 30 minutes at a set digestion temperature, with the reactor batch being maintained at a constant pH.
- the reaction batch is filtered and washed with water to remove excess by-product inorganic salts until the wash water from the silica filter cake obtains a conductivity of less than about 2000 Because the conductivity of the silica filtrate is proportional to the inorganic salt by-product concentration in the filter cake, then by maintaining the conductivity of the filtrate to be less than 2000 ⁇ 8, the desired low concentration of inorganic salts, such as Na 2 SC>4 in the filter cake can be obtained.
- the silica filter cake is slurried in water, and then dried by any conventional drying techniques, such as spray drying, to produce adduct-treated precipitated silica material containing from about 3 wt to about 50 wt of moisture.
- the adduct-treated precipitated silica material can then be milled to obtain the desired particle size of between about 1 ⁇ to 15 ⁇ , from 1 ⁇ to 5 ⁇ , from greater than 5 ⁇ to 15 ⁇ , or from 8 ⁇ to 15 ⁇ .
- the present invention also relates to dentifrices comprising the disclosed silica materials.
- a "dentifrice composition” refers to a composition that can be used to maintain oral hygiene, for example by cleaning accessible surfaces of the teeth. Examples include toothpastes, liquid dentifrices, paste dentifrices, powdered dentifrices, and the like.
- dentifrices are those that, in addition to the silica material of the invention, comprise water, detergent, humectant, binder, flavoring agents, powdered abrasive, or combinations thereof as the ingredients.
- Dentifrice formulations can also comprise ingredients which must be dissolved prior to incorporation into the dentifrice formulation (e.g. anti-caries agents such as sodium fluoride, sodium phosphates, flavoring agents such as saccharin).
- the silica material of the invention can be present in the dentifrice composition in an amount generally ranging from 0.01 to 50%, from 0.01 to 30%, or from 0.01 to 25% by weight relative to the entire dentifrice composition. If the silica material of the invention is abrasive in nature, the amount can be from 0.05 to about 15% by weight. If the adduct- treated precipitated silica material is a viscosity modifier (thickening agent), the amount can be from 0.05 to about 10% by weight. However, the silica material of the invention can be present as an agent useful for reducing oral malodor.
- the amount may be within the range noted above within the dentifrice formulation, but the materials may not provide any appreciable degree of thickening or abrasivity to the dentifrice, but will provide oral malodor reduction benefits.
- Such formulations may also include potassium nitrate salts, as one example, of a suitable other desensitizing material, if desired.
- the dentifrice composition comprises at least one other component such as an abrasive other than the adduct-treated precipitated silica material, at least one thickening agent other than the adduct-treated precipitated silica material, at least one solvent, at least one preservative, at least one surfactant, or a combination thereof; wherein the silica material of the invention is present as an abrasive agent, thickening agent, or both, within the dentifrice.
- an abrasive other than the adduct-treated precipitated silica material at least one thickening agent other than the adduct-treated precipitated silica material, at least one solvent, at least one preservative, at least one surfactant, or a combination thereof
- the silica material of the invention is present as an abrasive agent, thickening agent, or both, within the dentifrice.
- the disclosed silica materials can be utilized alone as the abrasive in the dentifrice composition, or as an additive or co-abrasive with other abrasive materials discussed herein or known in the art. Any number of other conventional types of abrasive additives can be present within the dentifrice compositions of the invention.
- abrasive particles include, for example, precipitated calcium carbonate (PCC), ground calcium carbonate (GCC), chalk, bentonite, dicalcium phosphate or its dihydrate forms, silica gel (by itself, and of any structure), precipitated silica, amorphous precipitated silica (by itself, and of any structure as well), perlite, titanium dioxide, dicalcium phosphate, calcium pyrophosphate, alumina, hydrated alumina, calcined alumina, aluminum silicate, insoluble sodium metaphosphate, insoluble potassium metaphosphate, insoluble magnesium carbonate, zirconium silicate, particulate thermosetting resins and other suitable abrasive materials. Such materials can be introduced into the dentifrice compositions to tailor the polishing characteristics of the target formulation.
- PCC precipitated calcium carbonate
- GCC ground calcium carbonate
- chalk chalk
- bentonite dicalcium phosphate or its dihydrate forms
- silica gel by itself, and of any structure
- precipitated silica
- the dentifrice can also contain one or more organoleptic enhancing agents.
- Organoleptic enhancing agents include humectants, sweeteners, surfactants, flavorants, colorants and thickening agents, (also sometimes known as binders, gums, or stabilizing agents).
- Humectants serve to add body or "mouth texture" to a dentifrice as well as preventing the dentifrice from drying out.
- Suitable humectants include polyethylene glycol (at a variety of different molecular weights), propylene glycol, glycerin (glycerol), erythritol, xylitol, sorbitol, mannitol, lactitol, and hydrogenated starch hydrolyzates, and mixtures thereof.
- humectants are present in an amount from about 20 wt % to about 50 wt % of the dentifrice composition, for example 40 weight %.
- Sweeteners can be added to the dentifrice composition (e.g. , toothpaste) to impart a pleasing taste to the product.
- suitable sweeteners include saccharin (as sodium, potassium or calcium saccharin), cyclamate (as a sodium, potassium or calcium salt), acesulfame-K, thaumatin, neohesperidin dihydrochalcone, ammoniated glycyrrhizin, dextrose, levulose, sucrose, mannose, and glucose.
- Surfactants can be used in the dentifrice compositions of the invention to make the compositions more cosmetically acceptable.
- the surfactant is preferably a detersive material which imparts to the composition detersive and foaming properties.
- Suitable surfactants are safe and effective amounts of anionic, cationic, nonionic, zwitterionic, amphoteric and betaine surfactants such as sodium lauryl sulfate, sodium dodecyl benzene sulfonate, alkali metal or ammonium salts of lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate and oleoyl sarcosinate, polyoxyethylene sorbitan monostearate, isostearate and laurate, sodium lauryl sulfoacetate, N-lauroyl sarcosine, the sodium, potassium, and ethanolamine salts of N
- Sodium lauryl sulfate is a preferred surfactant.
- the surfactant is typically present in the oral care compositions of the present invention in an amount of about 0.1 to about 15% by weight, preferably about 0.3% to about 5% by weight, such as from about 0.3% to about 2.5%, by weight.
- Flavoring agents can also be added to dentifrice compositions. Suitable flavoring agents include, but are not limited to, oil of wintergreen, oil of peppermint, oil of spearmint, oil of sassafras, and oil of clove, cinnamon, anethole, menthol, thymol, eugenol, eucalyptol, lemon, orange and other such flavor compounds to add fruit notes, spice notes, etc. These flavoring agents generally comprise mixtures of aldehydes, ketones, esters, phenols, acids, and aliphatic, aromatic and other alcohols.
- Colorants can be added to improve the aesthetic appearance of the product. Suitable colorants include without limitation those colorants approved by appropriate regulatory bodies such as the FDA and those listed in the European Food and Pharmaceutical
- Thickening agents are useful in the dentifrice compositions to provide a gelatinous structure that stabilizes the toothpaste against phase separation.
- suitable thickening agents include silica thickener; starch; glycerite of starch; gums such as gum karaya (sterculia gum), gum tragacanth, gum arabic, gum ghatti, gum acacia, xanthan gum, guar gum and cellulose gum; magnesium aluminum silicate (Veegum); carrageenan; sodium alginate; agar-agar; pectin; gelatin; cellulose compounds such as cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, hydroxymethyl carboxypropyl cellulose, methyl cellulose, ethyl cellulose, and sulfated cellulose; natural and synthetic clays such as hectorite clays; and mixtures thereof.
- Typical levels of thickening agents or binders are
- Useful silica thickeners for utilization within a toothpaste composition include, as a non-limiting example, an amorphous precipitated silica such as ZEODENT 165 silica.
- amorphous precipitated silica such as ZEODENT 165 silica.
- Other preferred (though non- limiting) silica thickeners are ZEODENT 153, 163 and/or 167 and ZEOFREE, 177, and/or 265 silicas, all available from J. M. Huber
- Therapeutic agents can also be used in the compositions to provide for the prevention and treatment of dental caries, periodontal disease and temperature sensitivity.
- therapeutic agents include fluoride sources, such as sodium fluoride, sodium monofluorophosphate, potassium monofluorophosphate, stannous fluoride, potassium fluoride, sodium fluorosilicate, ammonium fluorosilicate and the like; condensed phosphates such as tetrasodium pyrophosphate, tetrapotassium pyrophosphate, disodium dihydrogen pyrophosphate, trisodium monohydrogen pyrophosphate; tripolyphosphates, hexametaphosphates, trimetaphosphates and pyrophosphates; antimicrobial agents such as triclosan, bisguanides, such as alexidine, chlorhexidine and chlorhexidine gluconate; enzymes such as papain, bromelain, glucoamy
- Preservatives can also be added to the compositions of the present invention to prevent bacterial growth.
- Suitable preservatives approved for use in oral compositions such as methylparaben, propylparaben and sodium benzoate can be added in safe and effective amounts.
- the dentifrices disclosed herein can also contain a variety of additional ingredients such as desensitizing agents, healing agents, other caries preventative agents,
- chelating/sequestering agents vitamins, amino acids, proteins, other anti-plaque/anti- calculus agents, opacifiers, antibiotics, anti-enzymes, enzymes, pH control agents, oxidizing agents, antioxidants, and the like.
- Water typically provides the balance of the composition in addition to the additives mentioned above.
- the water is preferably deionized and free of impurities.
- the dentifrice will usually comprise from about 5 wt % to about 70 wt % of water, for example 5 wt % to 35 wt , such as 11 wt % water.
- silica materials of the invention can also be incorporated into a variety of other oral care compositions, including breath strips, gums, such as chewing gums, mouthwashes, mouth rinses, confections (e.g., lozenges, pressed tablets, hard candies, etc.), edible films, mouthsprays, and teeth whitening strips.
- breath strips including breath strips, gums, such as chewing gums, mouthwashes, mouth rinses, confections (e.g., lozenges, pressed tablets, hard candies, etc.), edible films, mouthsprays, and teeth whitening strips.
- a specific example is a method of reducing oral malodor in a subject, such as a human, by administering the silica material or dentifrice to the oral cavity of the subject, thereby reducing oral malodor in the subject.
- the disclosed materials and dentifrices are effective at reducing VSC levels in an atmosphere (see Examples below), and thus are effective at reducing oral malodor given that VSCs cause oral malodor.
- the subject which accepts the silica material or the dentifrice of the invention has a need for treatment, i.e., the subject has oral malodor.
- the silica material or dentifrice can be used for prophylactic treatment, i.e. , given to a subject such as a human that does not necessarily suffer from oral malodor at the time of administration.
- prophylactic treatment i.e. , given to a subject such as a human that does not necessarily suffer from oral malodor at the time of administration.
- the test below under the heading "Mult-dosing Study in Aqueous Conditions" can be used to show such a reduction, i.e. , using a vapor sample collected from the oral cavity of the subject..
- known methods in the art such as smell tests wherein oral cavity vapor samples from the subject are evaluated before and after administration, can also be used to show a reduction in oral malodor.
- a method for reducing oral malodor comprising the steps of a) providing a composition suitable for oral administration comprising the disclosed silica material; and b) administering the composition to a subject having the presence of VSCs in their mouth, thereby allowing the silica material of the composition to absorb the VSCs and in turn reduce the subject's oral malodor.
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- a sulfuric acid/zinc(II) chloride solution 11.4%, 1.078 g/mL sulfuric acid containing 0.077 mol ZnCl 2 /L acid
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- a sulfuric acid/tin(II) chloride solution 11.4%, 1.078 g/mL sulfuric acid containing 0.042 mol SnCl 2 -2H 2 0/L acid
- 82.4 mL/min and 24.8 mL/min were then simultaneously added at 82.4 mL/min and 24.8 mL/min, respectively, for 47 minutes. After 47 minutes, the flow of silicate was stopped, and the pH was adjusted to 5.5 with continued flow of acid.
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- a sulfuric acid/copper(II) nitrate solution 11.4%, 1.078 g/mL sulfuric acid containing 0.077 mol Cu(N0 3 )2-2.5H 2 0/L acid
- 82.4 mL/min and 24.8 mL/min were then simultaneously added at 82.4 mL/min and 24.8 mL/min, respectively, for 47 minutes. After 47 minutes, the flow of silicate was stopped, and the pH was adjusted to 5.5 with continued flow of acid.
- 67 L of silicate (19.5%, 1.180 g/mL, 3.32 MR) and 167 L of water were added to a 400 gallon reactor and heated to 87 °C with recirculation at 30 HZ and stirring at 60 RPM.
- Silicate (19.5%, 1.180 g/mL, 3.32 MR) and a sulfuric acid/alum solution (17.1%, 1.12 g/mL sulfuric acid containing 0.22 mol Alum/L acid) were then simultaneously added at 12.8 L/min and 3.9 L/min, respectively, for 47 minutes. After 47 minutes, the flow of silicate was stopped, and the pH was adjusted to 5.5 with continued flow of acid.
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- silicate 13.3%, 1.112 g/mL, 3.32 MR
- sulfuric acid 11.4%, 1.078 g/mL
- the flow of silicate was stopped, and the pH was adjusted to 5.5 with continued flow of acid. Once a pH 5.5 was reached, the batch was allowed to digest for 10 minutes at 90 °C and was then dropped.
- Median particle size can be determined using a Model LA-930 (or LA-300 or an equivalent) laser light scattering instrument available from Horiba Instruments, Boothwyn, Pa.
- moisture corrected water AbC value by the following equation. water absorbed(cc) + %moisture
- the pH of the silica materials can be determined by any conventional pH sensitive electrode.
- Example 1A-1E and the Comparative Example were evaluated for their ability to absorb mercaptan (CH 3 SH) using the apparatus shown in Figure 1.
- the method involves evacuating a set of flasks (250-mL) in parallel and charging them with the desired test gas, in this case methyl mercaptan (CH 3 SH, 1.09 ppm, balance N 2 , Air Liquide America, P/N 01020002400TCL).
- Flask 1 contains the material of interest
- flask 2 contains a charge of nitrogen (Airgas, UHPG used for purging the gas sampling syringe)
- flask 3 is a blank control reference.
- test gas control valve was turned to the off position, ball valve 1 was opened and the system was evacuated for another 2 minutes. At this time, the stopcocks for flasks 1 and 3 were closed on the vacuum side, followed by closure of ball valve 1. The test gas control valve was then opened to the test gas cylinder and the system charged with test gas to 2 psi. The test gas side stopcocks for flasks 1 and 3 were then closed followed by the test gas control valve. The system is now charged with test gas and evaluation can begin.
- Figures 2-10 show the resulting reduction curves for each respective sample over time.
- Figure 1 is a diagram of the testing apparatus used to measure mercaptan absorption using the disclosed silica materials.
- Figure 2 is a plot of methyl mercaptan peak area vs. time obtained using the Comparative Example. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 3 is a plot obtained from a repeated time study using the Comparative Example, which includes an outlier point. The plot shows methyl mercaptan peak area vs. time; ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 4 is a plot from another repeated time study using the Comparative Example, which does not include the outlier point.
- the plot shows methyl mercaptan peak area vs. time; ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 5 is a plot of methyl mercaptan peak area vs. time obtained using Example 1A. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 6 is a plot from a repeated time study using Example 1A. The plot shows methyl mercaptan peak area vs. time. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 7 is a plot showing methyl mercaptan peak area vs. time obtained using Example IB. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 8 is a plot showing methyl mercaptan peak area vs. time obtained using Example 1C. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 9. is a plot showing methyl mercaptan peak area vs. time obtained using Example ID. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Figure 10. is a plot showing methyl mercaptan peak area vs. time obtained using Example IE. ⁇ represents percent remaining and ⁇ represents percent reduction.
- Example 1A and Example ID samples had the greatest reduction in methyl mercaptan with -90% and 100% reduction, respectively.
- the remaining samples had the following methyl mercaptan reduction percentages: Example 1C (-65%), Example IB (-54%), Example IE (-40%) and
- the testing method was altered to reduce sources of error that could arise from inconsistent flask volumes, irregular evacuations and/or test gas dosing.
- the samples were run in a rotation, evaluating two samples at a time with the third flask acting as a blank control.
- flask 1 would contain test slurry 1
- flask 2 would contain test slurry 2
- flask 3 would contain the blank.
- the apparatus was reset with flask 1 containing the blank, flask 2 test slurry 1 and flask 3 test slurry 2.
- the final rotation would be flask 1 containing test slurry 2, flask 2 containing the blank, and flask 3 containing test slurry 1.
- the sample and control peak areas were averaged over all rotations, with the standard deviation and relative standard deviation (RSD) calculated to monitor the reliability of the test.
- RSS standard deviation and relative standard deviation
- Example 1A Example IB
- Example 1C Example ID
- Example ID Example ID
- Example ID has the greatest adsorptive capacity for methyl mercaptan, preventing headspace formation out to 6 dosings.
- Examples 1A, IB and IE show the next best performance out to 2 dosings before coalescing with Examples 1C and Comparative Example. The individual data points are listed in Table 5. [0086] Table 5. Data from multi-dosing study.
- Example 1A Given that the 5% pH for these samples are all pH >8.0, there is little to no soluble metal ions present in solution. However, there is a significant release of soluble metal ions for Example 1A and Example ID at around pH 5.0. This also corresponds to the low point of the Stephen curve, which maps the pH in the oral cavity over time after an initial carbohydrate introduction. The use of the Example 1A would allow for the release of Zn ions after a challenge to the oral cavity, thereby inhibiting bacterial growth or acting as an anti-microbial agent.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2012008830A MX2012008830A (en) | 2010-02-19 | 2011-02-17 | Silica materials for reducing oral malodor. |
JP2012554011A JP2013520430A (en) | 2010-02-19 | 2011-02-17 | Silica material to reduce bad breath |
CN2011800088483A CN102821740A (en) | 2010-02-19 | 2011-02-17 | Silica materials for reducing oral malador |
EP11713393A EP2536388A2 (en) | 2010-02-19 | 2011-02-17 | Silica materials for reducing oral malodor |
KR1020127024096A KR20130008549A (en) | 2010-02-19 | 2011-02-17 | Silica materials for reducing oral malodor |
BR112012020740A BR112012020740A2 (en) | 2010-02-19 | 2011-02-17 | silica materials to reduce bad breath |
ES11713393T ES2399414T1 (en) | 2010-02-19 | 2011-02-17 | Silica materials to reduce mouth odor |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US30599810P | 2010-02-19 | 2010-02-19 | |
US61/305,998 | 2010-02-19 | ||
US13/026,864 | 2011-02-14 | ||
US13/026,864 US20110206749A1 (en) | 2010-02-19 | 2011-02-14 | Silica materials for reducing oral malador |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2011103226A2 true WO2011103226A2 (en) | 2011-08-25 |
WO2011103226A3 WO2011103226A3 (en) | 2012-05-03 |
Family
ID=44476690
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/025141 WO2011103226A2 (en) | 2010-02-19 | 2011-02-17 | Silica materials for reducing oral malodor |
Country Status (10)
Country | Link |
---|---|
US (2) | US20110206749A1 (en) |
EP (1) | EP2536388A2 (en) |
JP (1) | JP2013520430A (en) |
KR (1) | KR20130008549A (en) |
CN (1) | CN102821740A (en) |
BR (1) | BR112012020740A2 (en) |
DE (1) | DE11713393T1 (en) |
ES (1) | ES2399414T1 (en) |
MX (1) | MX2012008830A (en) |
WO (1) | WO2011103226A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014078066A3 (en) * | 2012-11-19 | 2014-09-25 | J.M. Huber Corporation | Treated silicas and metal silicates for improved cleaning in dentifrice |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX354968B (en) | 2013-12-20 | 2018-03-27 | Colgate Palmolive Co | Tooth whitening oral care product with core shell silica particles. |
CA2927403C (en) | 2013-12-20 | 2023-01-10 | Colgate-Palmolive Company | Core shell silica particles and use for malodor reduction |
HUE050377T2 (en) | 2015-09-28 | 2020-11-30 | Evonik Operations Gmbh | Silica-based antimicrobial oral compositions |
CN108840342B (en) * | 2018-07-24 | 2019-04-30 | 广州市飞雪材料科技有限公司 | A kind of Silica Using for Toothpaste and preparation method thereof having anti-microbial property |
Family Cites Families (73)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3122483A (en) * | 1960-07-21 | 1964-02-25 | Block Drug Co | Strontium ion toothpaste |
US3934001A (en) * | 1965-12-07 | 1976-01-20 | Lever Brothers Company | Oral compositions containing germicidally active plastic powders |
US3988162A (en) * | 1972-09-06 | 1976-10-26 | J. M. Huber Corporation | Amorphous precipitated silica products and method for their production |
US3967563A (en) * | 1973-10-03 | 1976-07-06 | J. M. Huber Corporation | Process for producing precipitated thickener silica |
US4191742A (en) * | 1974-05-22 | 1980-03-04 | J. M. Huber Corporation | Amorphous precipitated siliceous pigments and methods for their production |
US4122160A (en) * | 1974-10-31 | 1978-10-24 | J. M. Huber Corporation | Toothpaste compositions containing improved amorphous precipitated silicas |
US4040858A (en) * | 1974-10-31 | 1977-08-09 | J. M. Huber Corporation | Preparation of precipitated silicas having controlled refractive index |
US4187288A (en) * | 1975-01-28 | 1980-02-05 | Colgate Palmolive Company | Modified abrasive system for dentifrices |
US4336245A (en) * | 1975-03-12 | 1982-06-22 | J. M. Huber Corporation | Novel precipitated siliceous products and methods for their use and production |
US4280822A (en) * | 1978-09-28 | 1981-07-28 | J. M. Huber Corporation | Method for production of abrasive composition for use in toothpaste |
US4244707A (en) * | 1978-09-28 | 1981-01-13 | J. M. Huber Corporation | Abrasive composition for use in toothpaste |
EP0092929B2 (en) * | 1982-04-20 | 1991-05-02 | Beecham Group Plc | Oral hygiene compositions |
US4557916A (en) * | 1984-10-22 | 1985-12-10 | J. M. Huber Corporation | Synthetic calcium silicates and methods of preparation |
US4562065A (en) * | 1984-12-11 | 1985-12-31 | Colgate-Palmolive Company | Astringent dentifrice |
JPS63146809A (en) * | 1986-12-10 | 1988-06-18 | Kao Corp | Composition for oral cavity |
US4863722A (en) * | 1987-01-28 | 1989-09-05 | Jeffrey Martin, Inc. | Dentifrice compositions |
FR2646665B1 (en) * | 1989-05-03 | 1991-11-29 | Rhone Poulenc Chimie | SILICA FOR TOOTHPASTE COMPOSITIONS COMPATIBLE IN PARTICULAR WITH METAL CATIONS |
FR2622565B1 (en) * | 1987-11-04 | 1990-11-09 | Rhone Poulenc Chimie | SILICA FOR TOOTHPASTE COMPOSITIONS COMPATIBLE IN PARTICULAR WITH ZINC |
US5286478A (en) * | 1987-11-04 | 1994-02-15 | Rhone-Poulenc Chimie | Dentifrice-compatible silica particulates |
FR2632185B1 (en) * | 1988-06-01 | 1992-05-22 | Rhone Poulenc Chimie | SILICA FOR TOOTHPASTE COMPOSITIONS COMPATIBLE IN PARTICULAR WITH ZINC |
US5015467A (en) * | 1990-06-26 | 1991-05-14 | The Procter & Gamble Company | Combined anticalculus and antiplaque compositions |
ES2071336T3 (en) * | 1990-10-25 | 1995-06-16 | Boots Co Plc | Mouthwash |
US5503840A (en) * | 1991-08-09 | 1996-04-02 | E. I. Du Pont De Nemours And Company | Antimicrobial compositions, process for preparing the same and use |
DE4293451T1 (en) * | 1991-09-13 | 1994-09-08 | Gillette Canada | Polymer particles for dental applications |
IT1256702B (en) * | 1992-12-17 | 1995-12-12 | Giovanni Antonini | ADJUVANT PROTEIN FORMULATION IN THE PREVENTION AND TREATMENT OF PERIODONTITES AND OTHER BACTERIAL PATHOLOGIES OF THE ORAL CABLE. |
US5330748A (en) * | 1993-05-19 | 1994-07-19 | Church & Dwight Co., Inc. | Dentifrices containing zinc oxide particles |
US5302373A (en) * | 1993-06-10 | 1994-04-12 | Church & Dwight Co., Inc. | Liquid mouthwash containing a particulate bicarbonate suspension |
BR9508360A (en) * | 1994-06-06 | 1997-10-28 | Block Drug Co | Composition and method for treating hypersensitive teeth by submicron particles |
US5660817A (en) * | 1994-11-09 | 1997-08-26 | Gillette Canada, Inc. | Desensitizing teeth with degradable particles |
JP3502390B2 (en) * | 1994-12-07 | 2004-03-02 | サンメディカル株式会社 | Dental composition for dentin hypersensitivity |
CA2165013C (en) * | 1994-12-13 | 2004-01-06 | Nobuo Nakabayashi | Dental composition for relieving dentin hypersensitivity |
US5562939A (en) * | 1995-01-27 | 1996-10-08 | Bush Boake Allen Inc. | Method of suspending inclusions and compositions produced thereby |
US5589159A (en) * | 1995-04-11 | 1996-12-31 | Block Drug Company Inc. | Dispersible particulate system for desensitizing teeth |
ZA962939B (en) * | 1995-04-12 | 1997-10-13 | Quest Int | Oral care compositions. |
US6099315A (en) * | 1996-09-20 | 2000-08-08 | Block Drug Company, Inc. | Applicator tip for desensitizing agents and method |
US5885551A (en) * | 1997-08-01 | 1999-03-23 | Smetana; Alfred J. | Treatment for dentinal hypersensitivity |
US6077341A (en) * | 1997-09-30 | 2000-06-20 | Asahi Glass Company, Ltd. | Silica-metal oxide particulate composite and method for producing silica agglomerates to be used for the composite |
EP0933078A3 (en) * | 1997-12-10 | 2000-02-09 | Degussa-Hüls Aktiengesellschaft | Precipitated silica containing active substance |
US20020168324A1 (en) * | 1998-01-20 | 2002-11-14 | Frederic Amiche | Silica microbeads with sensory properties in the mouth, process for preparing them and toothpaste compositions containing them |
US6464963B1 (en) * | 1998-04-23 | 2002-10-15 | Colgate Palmolive Company | Desensitizing dentifrice containing potassium and tin salts |
GB9810806D0 (en) * | 1998-05-21 | 1998-07-22 | Boots Co Plc | Odour absorbing agent |
US6096292A (en) * | 1998-07-28 | 2000-08-01 | Block Drug Company, Inc. | Polymeric desensitizing compositions |
US6169118B1 (en) * | 1998-11-12 | 2001-01-02 | Block Drug Company, Inc. | Flavor blend for masking unpleasant taste of zinc compounds |
US6241972B1 (en) * | 1999-02-19 | 2001-06-05 | Block Drug Company, Inc. | Oral care formulation for the treatment of sensitivity teeth |
US6861048B2 (en) * | 1999-04-08 | 2005-03-01 | Warner-Lambert Company | Dentifrice compositions having reduced abrasivity |
JP2000319153A (en) * | 1999-05-13 | 2000-11-21 | Lion Corp | Composition for oral cavity |
US6436370B1 (en) * | 1999-06-23 | 2002-08-20 | The Research Foundation Of State University Of New York | Dental anti-hypersensitivity composition and method |
KR100488609B1 (en) * | 1999-08-16 | 2005-05-11 | 피큐 홀딩, 인코포레이티드 | Sulfur adsorbent for reducing onion or garlic breath odor |
EP1227781B9 (en) * | 1999-10-28 | 2006-03-08 | 3M Innovative Properties Company | Dental materials with nano-sized silica particles |
US6572693B1 (en) * | 1999-10-28 | 2003-06-03 | 3M Innovative Properties Company | Aesthetic dental materials |
GB2363386B (en) * | 2000-06-16 | 2004-07-28 | Chesham Chemicals Ltd | Fluid gel comprising xanthan and non-gelling polysaccharides |
US20070059257A1 (en) * | 2000-08-18 | 2007-03-15 | Block Drug Company, Inc. | Dentinal composition for hypersensitive teeth |
EP1333796A4 (en) * | 2000-10-13 | 2004-12-01 | Block Drug Co | Anhydrous dentifrice formulations for the delivery of incompatible ingredients |
US6447756B1 (en) * | 2000-11-08 | 2002-09-10 | Colgate Palmolive Company | Desensitizing dual component dentifrice |
JP3715895B2 (en) * | 2001-01-19 | 2005-11-16 | 株式会社太平洋 | Method for producing plant extract powder and composition for oral cavity containing plant extract powder produced by this method |
US6416745B1 (en) * | 2001-05-03 | 2002-07-09 | Block Drug Company, Inc. | Dental composition for treating hypersensitive teeth |
US7578997B2 (en) * | 2002-04-30 | 2009-08-25 | Kimberly-Clark Worldwide, Inc. | Metal ion modified high surface area materials for odor removal and control |
KR100471715B1 (en) * | 2002-07-12 | 2005-03-08 | 주식회사 서흥캅셀 | Composition or preparation for removing oral smell |
US6953817B2 (en) * | 2002-08-05 | 2005-10-11 | Colgate-Palmolive Company | Dual component dentinal desensitizing dentifrice |
US20050063928A1 (en) * | 2003-09-18 | 2005-03-24 | Withiam Michael C. | Compositions comprising odor neutralizing metal oxide silicates |
MXPA06006704A (en) * | 2003-12-19 | 2007-01-19 | Novamin Technology Inc | Compositions and methods for preventing or reducing plaque and/or gingivitis using a bioactive glass containing dentifrice. |
DE102004026433A1 (en) * | 2004-05-29 | 2005-12-22 | Schott Ag | Nanoglass powder and its use |
JP2006021981A (en) * | 2004-07-05 | 2006-01-26 | Taiyo Machinery Co Ltd | Method for producing artificial zeolite using frp waste material and artificial zeolite produced by the same |
US7229690B2 (en) * | 2004-07-26 | 2007-06-12 | Massachusetts Institute Of Technology | Microspheres including nanoparticles |
DE102004050954A1 (en) * | 2004-10-18 | 2006-04-20 | Henkel Kgaa | Smoothing and anti-malodour oral and dental care and cleaning products |
US7731110B2 (en) * | 2005-06-29 | 2010-06-08 | J.M. Huber Corporation | Method for making precipitated silica compositions and products thereof |
ES2326382T3 (en) * | 2006-03-22 | 2009-10-08 | The Procter And Gamble Company | ORAL COMPOSITIONS OF CINC. |
US20080160053A1 (en) * | 2006-12-27 | 2008-07-03 | Mcgill Patrick | High electrolyte additions for precipitated silica material production |
US8628755B2 (en) * | 2007-01-30 | 2014-01-14 | Colgate-Palmolive Company | Dentifrice containing zinc ions and polyphosphate ions |
AR071809A1 (en) * | 2008-05-16 | 2010-07-14 | Colgate Palmolive Co | ORAL COMPOSITIONS AND THEIR USES |
PL2246031T3 (en) * | 2008-06-10 | 2017-11-30 | The Procter & Gamble Company | Stannous chloride and Silica compositions |
US20100047742A1 (en) * | 2008-08-25 | 2010-02-25 | Pitcock Jr William Henry | Tubule-blocking silica materials for dentifrices |
US20100189663A1 (en) * | 2009-01-24 | 2010-07-29 | Gallis Karl W | Mouth rinse compositions including chemically modified silica or silicate materials for sustained delivery to tooth surfaces |
-
2011
- 2011-02-14 US US13/026,864 patent/US20110206749A1/en not_active Abandoned
- 2011-02-17 ES ES11713393T patent/ES2399414T1/en active Pending
- 2011-02-17 KR KR1020127024096A patent/KR20130008549A/en not_active Application Discontinuation
- 2011-02-17 EP EP11713393A patent/EP2536388A2/en not_active Withdrawn
- 2011-02-17 MX MX2012008830A patent/MX2012008830A/en not_active Application Discontinuation
- 2011-02-17 WO PCT/US2011/025141 patent/WO2011103226A2/en active Application Filing
- 2011-02-17 JP JP2012554011A patent/JP2013520430A/en active Pending
- 2011-02-17 CN CN2011800088483A patent/CN102821740A/en active Pending
- 2011-02-17 DE DE11713393T patent/DE11713393T1/en active Pending
- 2011-02-17 BR BR112012020740A patent/BR112012020740A2/en not_active Application Discontinuation
-
2014
- 2014-05-29 US US14/289,717 patent/US20140271749A1/en not_active Abandoned
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014078066A3 (en) * | 2012-11-19 | 2014-09-25 | J.M. Huber Corporation | Treated silicas and metal silicates for improved cleaning in dentifrice |
CN104781189A (en) * | 2012-11-19 | 2015-07-15 | J.M.休伯有限公司 | Treated silicas and metal silicates for improved cleaning in dentifrice |
KR20150084787A (en) * | 2012-11-19 | 2015-07-22 | 제이. 엠. 후버 코포레이션 | Treated silicas and metal silicates for improved cleaning in dentifrice |
US9186307B2 (en) | 2012-11-19 | 2015-11-17 | J.M. Huber Corporation | Treated silicas and metal silicates for improved cleaning in dentifrice |
CN104781189B (en) * | 2012-11-19 | 2017-02-22 | J.M.休伯有限公司 | Treated silicas and metal silicates for improved cleaning in dentifrice |
RU2613924C2 (en) * | 2012-11-19 | 2017-03-22 | Джей.Эм. ХЬЮБЕР КОРПОРЕЙШН | Processed silicon oxides and metal silicates for improved cleaning in dental care means |
KR102126825B1 (en) * | 2012-11-19 | 2020-06-25 | 에보니크 오퍼레이션즈 게엠베하 | Treated silicas and metal silicates for improved cleaning in dentifrice |
Also Published As
Publication number | Publication date |
---|---|
WO2011103226A3 (en) | 2012-05-03 |
DE11713393T1 (en) | 2013-05-23 |
US20140271749A1 (en) | 2014-09-18 |
EP2536388A2 (en) | 2012-12-26 |
JP2013520430A (en) | 2013-06-06 |
CN102821740A (en) | 2012-12-12 |
BR112012020740A2 (en) | 2016-04-26 |
ES2399414T1 (en) | 2013-04-01 |
KR20130008549A (en) | 2013-01-22 |
MX2012008830A (en) | 2012-11-29 |
US20110206749A1 (en) | 2011-08-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2726086C (en) | Stannous chloride compositions | |
US20140271749A1 (en) | Silica Materials for Reducing Oral Malodor | |
AU2019287467B2 (en) | Dentifrice formulations having spherical stannous compatible silica particles for reduced RDA | |
US20210024359A1 (en) | Spherical silica for tubule occlusion | |
US20090297459A1 (en) | Transparent silica gel/precipitated silica composite materials for dentifrices | |
EP3807217B1 (en) | Spherical stannous compatible silica particles for reduced rda | |
EP2549975A2 (en) | Antimicrobial silica composites | |
US20150209252A1 (en) | Heat Treated Silica for Improved Dentifrice | |
US9220667B2 (en) | Stannous chloride compositions | |
JP2024506057A (en) | Oral care compositions containing peroxides and compatible abrasives | |
JP7295280B2 (en) | Oral care composition containing stannous ions | |
US10857078B2 (en) | Powder oral hygiene compositions and methods for their manufacture | |
WO2023227642A1 (en) | Spherical calcium silicate | |
CN113164337A (en) | Oral care compositions with improved tin compatibility |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180008848.3 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11713393 Country of ref document: EP Kind code of ref document: A2 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012554011 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2012/008830 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1201004121 Country of ref document: TH |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2011713393 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011713393 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 8027/DELNP/2012 Country of ref document: IN |
|
ENP | Entry into the national phase |
Ref document number: 20127024096 Country of ref document: KR Kind code of ref document: A |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112012020740 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112012020740 Country of ref document: BR Kind code of ref document: A2 Effective date: 20120817 |