CN1201721C - Improved low-cost dentifrice composition - Google Patents
Improved low-cost dentifrice composition Download PDFInfo
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- CN1201721C CN1201721C CNB008185727A CN00818572A CN1201721C CN 1201721 C CN1201721 C CN 1201721C CN B008185727 A CNB008185727 A CN B008185727A CN 00818572 A CN00818572 A CN 00818572A CN 1201721 C CN1201721 C CN 1201721C
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- 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
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- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A61K8/21—Fluorides; Derivatives thereof
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- 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
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- 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
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- 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
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- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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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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Abstract
An improved low-cost dentifrice composition comprises from about 6 % to about 70 % of an abrasive polishing material, from about 0.5 % to about 4.5 % of a thickener, from about 0.5 % to about 45 % of a hexahydric humectant, from about 0.05 % to about 2.5 % of an anti-cavity agent, and at least about 30 % of water. The composition comprises less than about 10 % dihydric and trihydric alcohols, and has a viscosity of from about 8 to about 100 BKU.
Description
Invention field
The present invention relates to a kind of oral care composition.Especially, the present invention relates to a kind of low-cost dentifrice composition.
Background of invention
Good oral hygiene at least a portion is by using oral cavity composition, and for example dentifrice composition is brushed teeth and realized.Dentifrice composition has extensively been thought, and to improving oral hygiene be important, especially by reducing the formation of tooth decayed tooth incidence rate and tartar and tartar.These situations can cause diseases such as periodontitis and gingivitis owing to the oral cavity bacterial plaque causes.These diseases remain the main cause of adult's loss of tooth today.In addition, the worry of other oral hygienes, for example the enamel speckle of tooth and halitosis (halitosis) can be by the minimizings of often brushing teeth with dentifrice composition.
Introduce though many dentifrice compositions are existing, and the dentifrice of many types is on sale at present with other oral care compositions, but still needs exploitation to be used to promote the improvement product of oral hygiene.In addition, present dentifrice composition may need expensive composition or production technology.Therefore, these dentifrice compositions are for certain areas or some consumer's too expensive.Therefore need to improve the cost benefit of these products, do not render a service and do not reduce it, thereby its consumer for all income levels and all regions all more and more can be accepted.
Previous low-cost dentifrice composition contains the water of grinding agent, wetting agent, aqueous solvent, the binary at least about 15% and trihydroxylic alcohol and low content usually.Yet these dentifrice compositions do not contain the agent of anti-decayed tooth usually, because they are too expensive usually.Therefore, these low-cost dentifrice compositions may not provide required anti-decayed tooth protection.In addition, have high-load binary and trihydroxylic alcohol usually because it commercial be important, make dentifrice composition have acceptable physical property, for example the quality and the rheological equationm of state.Consumer usually needs acceptable dentifrice composition, it have smooth, can extrude and relative character such as sticking.
International Application No. WO 99/63959 discloses a kind of dentifrice composition, contains non-ionic block copolymer, surfactant, fluorion, binding agent and water, and wherein block copolymer is dihydroxylic alcohols or trihydroxylic alcohol.This dentifrice composition is with a kind of non-ionic block copolymer, anion or amphoteric surfactant and soil takes off in special binding agent-Strese Hofmann's hectorite., class or the fumed silica type mixes, and improves foaming capacity, not at reducing cost.
Therefore, the dentifrice composition of satisfied oral health need be provided in mode with low cost.
The invention summary
The present invention relates to a kind of low-cost dentifrice composition of improvement, contain the anti-decayed tooth agent of the six hydroxyl wetting agents of the thickening agent of the abrasive polishing materials of the 6%-70% that has an appointment, about 0.5%-4.5%, about 0.5%-45%, about 0.05%-2.5% and at least about 30% water.Compositions does not contain binary and trihydroxylic alcohol substantially, and has the viscosity of about 8-100BKU.In yet another aspect, the present invention also provides a kind of method of the human or animal's of cleaning dental surface, comprises step: with above-mentioned dentifrice composition contact dental surface.Of the present invention also have one aspect, a kind of dentifrice composition is provided, comprising: the silicon dioxide abrasive polishing materials of 6%-70%; The thickening agent of 0.5%-4.5% is selected from carboxymethyl cellulose, carbomer, xanthan gum and composition thereof; The six hydroxyl wetting agents of 5%-30% are selected from Sorbitol, xylitol, glucose and composition thereof; The sodium fluoride of 0.1%-1%; At least 30% water, wherein compositions does not contain binary and trihydroxylic alcohol substantially, and the viscosity of said composition is 15-50BKU.
Found now the present invention can provide a kind of effectively, stable and stimulate less compositions, it is produced easily and is with low cost.In addition, this improved dentifrice composition provides oral hygiene and/or has reduced decayed tooth, with present dentifrice composition effect quite or improvement arranged.In addition, fragrance release, the rheological equationm of state and/or the quality of improved dentifrice composition and existing dentifrice composition are quite or improve to some extent.
Those skilled in the art are after reading present disclosure and additional claim, and above-mentioned and other features, aspect, advantage and the variation of the present invention and embodiment as herein described are conspicuous, and within the scope of the claims.
Detailed Description Of The Invention
All percents, ratio and the ratio of this paper is that other has except the explanation in the weight of final dentifrice composition.All temperature be degree centigrade (℃), except as otherwise noted.The file of all references is this complete quoting for your guidance.Quoting any document does not admit to determine that with any can it relevant as the prior art of desired invention.
" alkyl " refers to straight or branched, saturated or undersaturated alkyl herein.Except as otherwise noted, more suitable alkyl is a saturated alkyl, or the unsaturated alkyl of the two keys of band, is with one or two pair key better.Term " alkyl " also comprises the moieties in the acyl group.
" comprise " herein and mean and to add other steps of not influencing final result and other compositions.This term comprise term " by ... form " and " mainly by ... composition ".
" effective dose " means a certain amount of chemical compound or compositions herein, its amount is enough brought significant benefits, particularly to the benefit of oral hygiene, but enough low, to prevent serious adverse, promptly be provided at those of skill in the art and rationally judge interior rational benefit risk ratio.
" dentifrice composition " means a kind of compositions herein, and its physical form is cream or gel-form composition, except as otherwise noted.Dentifrice composition can be any required aesthstic form, and for example dark striped, striated surface, multilamellar have the gel that surrounds cream, or its any combination.In addition, dentifrice composition can have the two-phase system, forms by being included in the applicator in the physically-isolated chamber then side by side two or more dentifrice compositions of feed.
" dihydroxylic alcohols " herein is meant a kind of molecule with two hydroxyls, comprises wetting agent commonly used, as Polyethylene Glycol, polypropylene glycol etc." trihydroxylic alcohol " is meant a kind of molecule with three hydroxyls herein, comprises for example glycerol of common humectants.Dihydroxylic alcohols and trihydroxylic alcohol are referred to as " binary and trihydroxylic alcohol " in this article.
" applicator " is meant pump, pipe or the container of any suitable dispensing dentifrice composition herein.
" do not contain substantially " herein and mean and in dentifrice composition, on purpose do not add this chemical compound as composition.Yet this term is not got rid of a spot of this chemical compound and may be existed as impurity, or exists with the content of general performance, cost and/or the stabilizing agent of not appreciable impact dentifrice composition.
Useful in the present invention all the components, for example active substance and other compositions can be classified and description by the binding mode of its dressing effect and/or therapeutic effect or its hypothesis.Yet be appreciated that active substance used herein and other compositions can provide more than one cosmetic and/or therapeutic effect in some cases, or work by more than one binding mode.Therefore, the classification of this paper for convenience of and carry out, be not in the application that a kind of component is limited in the purposes of special instruction or lists.
Abrasive polishing materials
The used abrasive polishing materials of the present invention can be selected from any not material of excessive tooth lapping matter.Abrasive polishing materials has less than about 23% calcium content preferable.Typical abrasive polishing materials comprises silicon dioxide (comprising gel and precipitate); Aluminium oxide; Phosphate (comprising orthophosphate, polymetaphosphate and pyrophosphate); And composition thereof.The more preferred example of the abrasive polishing materials that the present invention is used comprises silicon dioxide (will further describe hereinafter), two water orthophosphoric acid dicalcium, calcium pyrophosphate, tricalcium phosphate, poly-calcium metaphosphate, insoluble sodium hexametaphosphate, hydrated alumina, β calcium pyrophosphate, calcium carbonate, resin ground agent material (for example graininess condensation material of urea and formaldehyde) dicalcium phosphate, Alumina hydrate, insoluble Polymeric sodium metaphosphate. and other United States Patent (USP)s 3 as the submission on the 25th of in Decembers, 1962 such as Cooley, disclosed material in 070,510.Also can use the mixture of grinding agent.Though can use calcium carbonate in the present invention, it is not preferred, because it may be incompatible, as mentioned below with the agent of anti-decayed tooth; Therefore, in a preference, dentifrice composition does not contain calcium carbonate substantially.
Various types of silica dental also are highly preferred with grinding agent, because it has special cleaning of teeth and polishing action, and have not can the overmastication tooth enamel or the unique benefit of dentine.Silicon dioxide abrasive polishing materials of the present invention and other abrasive polishing materials have about 0.1-30 micron usually, the mean diameter between preferably about 5-15 micron, and have good fluoride compatibility (soluble fluoride ion promptly is provided).Abrasive polishing materials can be precipitated silica or silica gel, for example the silica xerogel described in the United States Patent (USP) 3,862,307 January 21 submitted to of the United States Patent (USP) 3,538,230 on March 2nd, 1970 submitted to such as Pader and DiGiulio1975.W.R.Grace ﹠amp preferably; Company, the silica xerogel that Davision Chemical Division sells with trade name " Syloid ".The preferred silicon dioxide of the sedimentary earth silicon material, particularly commodity " Zeodent 119 " by name sold with trade name " Zeodent " of J.M.Corporation also.Wason in the United States Patent (USP) of submitting to July 29 nineteen eighty-two 4,340,583 more detailed description be used for the type of the silica dental of dentifrice of the present invention with abrasive polishing materials.Dentifrice composition contains the 6%-70% that has an appointment, preferably about 10%-50%, and more preferably from about 15%-30% is in the abrasive polishing materials of dentifrice composition weight.
Thickening agent
The used thickening agent of the present invention provides required stability as binding agent.The thickening agent that is used for dentifrice of the present invention can be selected from the thickening agent of inorganic gel formation, modified cellulose thickening agent, natural plant thickening agent, antibacterial glue thickening agent, synthetic property organic polymer thickening agent, blended natural thickener and composition thereof.The thickening agent that preferred inorganic gel forms comprises precipitation of silica thing, silicon dioxide aerosol, pyrogenic silica, colloidal magnesium aluminum silicate and composition thereof.Preferred modified cellulose thickening agent comprises carboxymethyl cellulose, hydroxyethyl-cellulose, methylol carboxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl carboxypropyl cellulose, methylcellulose, ethyl cellulose and composition thereof.These thickening agents are available from for example Aqualon Co., Hopewell, VA, USA; Jiangmen Fenghua Fine Chemical Industry Co.Ltd, Jiangmen City, China; With Zhangjiagang Xinguang Chemical Factory, Zhangjiagang City, China.Preferred natural plant thickening agent comprises Irish moss (carrageenin), Tragacanth, arabic gum, gum ghatti, acacia gum, locust bean gum, sodium alginate and composition thereof.Preferred antibacterial glue thickening agent is a Tragacanth.Preferred synthetic organic polymer thickening agent comprises polyacrylic acid, polyvinylpyrrolidone and composition thereof, more preferably acrylic acid crosslinked homopolymer, for example carbomer.Highly preferred carbomer comprises Carbopol series, BF Goodrich Co. especially, Calvert City, Kentucky, the Carbopol 956 that USA sells.The preferred natural thickener that mixes comprises agar-agar, pectin, gelatin and composition thereof.From effect, economy, safety and cost, even more preferred thickener is carboxymethyl cellulose, carbomer and composition thereof.
The contents level of thickening agent is about 0.5%-4.5%, preferred 0.5%-2.0%, more preferably from about 0.8%-1.5% (in adhesive composition weight).
Six hydroxyl wetting agents
This dentifrice composition contains six hydroxyl wetting agents therein, and it plays and prevents dentifrice composition in the ingress of air after-hardening, also gives dentifrice composition required sweet taste usually.Six hydroxyl wetting agents used herein have six hydroxyls, normally sugar or derived from sugar, though not necessarily.Six hydroxyl wetting agents can have linearity, branch or cyclic skeleton; Preferred six hydroxyl wetting agents have the cyclic skeleton of about 6 carbon atoms.Six hydroxyl wetting agents also can have one or more other functional groups, for example hydroxy-acid group, amine groups, acylamino-group, ester group and composition thereof.Preferred six hydroxyl wetting agents are selected from Sorbitol, xylitol, glucose and composition thereof, also Sorbitol preferably.These saccharides also can reduce formulation cost by reducing or eliminating the needs to optional sweeting agent.
Not accepting opinion limits, believe these six hydroxyls wetting agents, especially Sorbitol, xylitol, glucose and composition thereof interact with thickening agent as herein described, provide the ability of superb bound water, because they have the accessibility and the location of a plurality of hydroxyls.When increasing by six hydroxyl humectant content separately, these advantages do not exist according to another letter.This cooperative effect has reduced the needs to more expensive thickening agent and binary and trihydroxylic alcohol on the contrary, can also further reduce the preparation cost, and keep the acceptable rheological equationm of state of dentifrice composition and quality.These six hydroxyls wetting agents still are easy to obtain usually, with low cost, be safe almost all cases, and shockingly stable in being included in dentifrice composition of the present invention the time.
In addition, the high-hydrophilic that it is believed that these six hydroxyls wetting agents can directly improve the maintenance of taste of oil base flavouring system and the release of taste, thereby can use the flavoring agent of lower content.Because the normally highly distilled and expensive mixture of flavoring agent system, the preparation cost of this dentifrice composition can significantly reduce.Because oil base flavoring agent system is insoluble relatively in this hydrophilic compounds, more taste can directly be experienced by the dentifrice user.On the contrary, the oil base flavouring system can be partially or completely to be dissolved in binary and/or trihydroxylic alcohol, and for example in glycerol and the propylene glycol, they are used always in dentifrice composition; This has reduced the ability that flavouring system is experienced by the dentifrice user on the contrary, and has improved the preparation cost owing to comprising more high-load flavouring system.
Bound by theory not, it is believed that the combination acts synergistically of six hydroxyl wetting agents as herein described and thickening agent, the acceptable rheological equationm of state, aesthetic effect, stability and equal or better effect can be provided, and not need traditional high level (for example 15% or more) binary and trihydroxylic alcohol.Notice that as top these binary and trihydroxylic alcohol are normally expensive, therefore reduce or remove the preparation cost that these chemical compounds can significantly reduce dentifrice composition.Therefore, dentifrice composition of the present invention contains usually less than about 10%, preferably dihydroxylic alcohols between 0%-5% and trihydroxylic alcohol.Preferred, dentifrice composition of the present invention does not contain binary and trihydroxylic alcohol substantially.
Hexa-atomic wetting agent is usually with about 0.5%-45%, preferably about 5%-40%, and more preferably from about the level of 10%-35% (in dentifrice composition weight) exists.
The agent of anti-decayed tooth
Make formulator have bigger freedom owing to reduce or eliminate the minimizing of the preparation cost that dihydroxylic alcohols and trihydroxylic alcohol cause, comprise and/or provide the level of anti-decayed tooth agent in the dentifrice composition, and do not improve price.In some countries and regions, this can improve good, effectively oral hygiene nursing for a big chunk ordinary populace.The agent of anti-decayed tooth contains fluorion usually, preferred water-soluble fluoride.Fluorine ion source is to be used for the agent of anti-decayed tooth in the oral care composition to know.Fluorion is included in for this purpose many oral care compositions, particularly at dentifrice composition for example in the toothpaste.The patent that discloses these dentifrice compositions comprises Pader etc., the U.S. Patent No. 3,538,230 on November 3rd, 1970; Pader, 5 days U.S. Patent No. of JIUYUE in 1972 3,689,637; Colodney etc., the U.S. Patent No. 3,711,604 on January 16th, 1973; The U.S. Patent No. 3,911,104 that Harrison1975 submitted at October 7; Roberts etc., the U.S. Patent No. 3,935,306 that on January 27th, 1976 submitted to; With the Wason1977 U.S. Patent No. 4,040,858 on August 9.
Fluorion is used for tooth enamel have been played to take care of one's teeth and not to be subjected to eat into the effect of erosion.The material of various generation fluorions can be used as the source of this compositions soluble fluoride.At Briner etc., U.S. Patent No. 3,535,421 that on October 20th, 1970 submitted to and Widder etc. can find suitable product fluorion examples of material in the U.S. Patent No. 3,678,154 that on July 18th, 1972 submitted to.The fluorine ion source that is preferred for this paper comprises sodium fluoride, potassium fluoride, ammonium fluoride, sodium monofluorophosphate, stannous fluoride and composition thereof.Sodium fluoride is particularly preferred, and can be from Jinan Chemical Sub-factory, Jinan City, and Shandongprovince, China buys.Preferred dentifrice composition provides the about 50ppm-10 that contacts with dental surface, 000ppm, the more preferably from about fluorion of 100-3000ppm in compositions when using with transmission system of the present invention.These fluorions normally water by 3: 1 and dentifrice composition serosity are measured.Usually, the agent of the anti-decayed tooth of anti-decayed tooth agent, particularly fluorion will be about 2.5% with about 0.05%-, and preferably about 0.1%-is about 1%, and more preferably from about 0.1%-0.5% exists with the level of composition weight meter.
Yet, when with the agent of the anti-decayed tooth of fluorion conduct, must be noted that and reduce and Incompatible Substance, for example can be used as the interaction of the calcium carbonate of abrasive polishing materials.If therefore have fluorion, especially have under the situation of sodium fluoride dentifrice composition highly preferably not calciferous substantially.Though the anti-decayed tooth agent of fluoride ion is preferred, not fluorine-containing anti-decayed tooth agent known in the art, a hypophosphite monohydrate list sodium for example also can be separately or combine with the anti-decayed tooth agent of fluoride ion and to be used for the present invention.
Water
Dentifrice composition also contains the water of at least 30% (in dentifrice composition weight).As described herein and measurement, " water " comprises the water (being wetting agent solution, sweetener soln, surfactant solution etc.) from solution, but does not comprise bound water (promptly from the hydrate under the room temperature).Before adding dentifrice composition, water used herein passes through purification or distillation usually, to remove impurity.
Auxiliary compounds
Dentifrice composition can also contain one or more auxiliary compounds known in the art, is preferably selected from the auxiliary compounds of two water or three water wetting agents, buffer agent, peroxide source, alkali metal hydrogencarbonate source, anticalculus agent, surfactant, titanium oxide, antioxidant, coloring agent, flavouring system, sweeting agent, herbal medicinal product, antimicrobial and composition thereof.
The present invention can contain and reaches 10% two water or three water wetting agents, for example conventional those that use in dentifrice composition.Yet in preference, dentifrice composition contains the binary and the trihydroxylic alcohol of having an appointment between the 0%-5%.More preferably, dentifrice composition of the present invention does not contain binary and trihydroxylic alcohol substantially.Be used for suitable wetting agent of the present invention and comprise glycerol, Polyethylene Glycol, propylene glycol, other edible polyhydric alcohol and composition thereof, preferably glycerine, Polyethylene Glycol and composition thereof.
The present invention contains buffer agent usually.If dentifrice composition is a two-phase system, buffer agent will be present in two kinds of dentifrice compositions.Buffer agent used herein refers to that the pH regulator that can be used for compositions arrives about 4-10, preferably about 4-8, the more preferably from about preparation in the 5.5-8 scope.These preparations comprise alkali metal hydroxide, carbonate, sesquicarbonate, borate, silicate, phosphate, imidazoles and composition thereof.Concrete buffer agent comprises mono phosphoric acid ester sodium, tertiary sodium phosphate, sodium hydroxide, potassium hydroxide, alkali carbonate, sodium carbonate, imidazoles, pyrophosphate, citric acid and sodium citrate.The consumption of buffer agent is about 0.01%-30%, preferably about 0.1%-10%, more preferably from about 0.3%-7% (in the weight of this compositions).Preferred reducing is mono phosphoric acid ester sodium, tertiary sodium phosphate, pyrophosphate, citric acid, sodium citrate and composition thereof.Surprised discovery is that dentifrice composition of the present invention needs high-load buffer salt unlike traditional dentifrice composition.Do not accept opinion and limit, it is believed that this can reduce the interference to glue, and reduce the oral cavity decayed tooth of user.
Pyrophosphate is as buffer agent.The pyrophosphate that is used for this compositions comprises two alkali metal pyrophosphates, four alkali metal pyrophosphates and composition thereof.Sodium acid pyrophosphate, the Sodium Acid Pyrophosphate (Na of anhydrous and hydrated form
2H
2P
2O
7), tetrasodium pyrophosphate (Na
4P
2O
7) and tetrapotassium pyrophosphate (K
4P
2O
7) be preferred material.In compositions of the present invention, pyrophosphate one of can three kinds of modes exists: the mixture of most of dissolved, most of undissolved or dissolving and undissolved pyrophosphate.
The compositions that mainly contains dissolved pyrophosphate refers to exist the compositions at least a pyrophosphate ion source.Free pyrophosphate ion exists with various protonation states, and pH decides on compositions.
The compositions that mainly contains insoluble pyrophosphate refers in the compositions no more than 20% in whole pyrophosphates preferably be less than 10% and be dissolved in said composition.Tetrasodium pyrophosphate salt and tetrapotassium pyrophosphate salt are preferred pyrophosphates in these compositionss, and wherein tetrasodium pyrophosphate salt is preferred.Tetrasodium pyrophosphate can be anhydrous salt form or ten water forms, or any other stable material that exists with solid-state form in dentifrice composition.Salt can be solid particulate form, and it can be crystalline state and/or amorphous state, and the particle diameter of salt is preferably enough little, the dissolving of can accepting aesthetically and in use be not difficult.The amount that is used to prepare the pyrophosphate of these compositionss is the effective dose of any control tartar.Some or all tetrasodium phosphates can be insoluble to product, and exist as the tetrasodium pyrophosphate granule.Different protonated states (HPO for example
2O
7 -3) pyrophosphate ion also may exist, on the pH of compositions with whether there is the dissolving of part tetrasodium pyrophosphate to decide.
Compositions can also contain the mixture of dissolving or undissolved pyrophosphate.Available any above-mentioned pyrophosphate.At Kirk ﹠amp; (third edition Wiley-IntersciencePublishers) has more detailed description in 17 volumes to " encyclopedia of chemical technology " of Othmer work.
The present invention can contain the peroxide source with whitening effect.Peroxide source is selected from hydrogen peroxide, calper calcium peroxide, urea peroxide and composition thereof.Preferred peroxide source is a urea peroxide.Following amount has been represented the peroxide material quantity, though peroxide source can contain the composition except the peroxide raw material.This compositions can contain the 0.01%-10% that has an appointment, preferably about 0.1%-5%, 0.2%-3% more preferably from about, even the peroxide source of 0.3%-0.8% (with composition weight meter) more preferably from about.
The present invention can also comprise alkali metal hydrogencarbonate.The alkali metal hydrogencarbonate water soluble, unless and be fixed, tend to release of carbon dioxide in the water system.Sodium bicarbonate (being also referred to as sodium bicarbonate) is preferred alkali metal hydrogencarbonate.Alkali metal hydrogencarbonate can also be as buffer agent.This compositions can contain the 0.5%-50% that has an appointment, preferably about 0.5%-30%, more preferably from about 2%-20%, the most preferably from about alkali metal hydrogencarbonate of 5%-18% (in Orally administered composition weight).
The known anticalculus agent that is used for dental care products comprises phosphate.Phosphate comprises pyrophosphate, condensed phosphate, polycondensation phosphonate ester and composition thereof.Pyrophosphate is one of dental care products of knowing the most.Be delivered to the pyrophosphate of tooth and condensed phosphate ion from pyrophosphate and condensed phosphate.The pyrophosphate that this compositions is used comprises two alkali metal pyrophosphates, four alkali metal pyrophosphates and composition thereof.The sodium acid pyrophosphate of anhydrous form and hydrated form, Sodium Acid Pyrophosphate (Na
2H
2P
2O
7), tetrasodium pyrophosphate (Na
4P
2O
7) and tetrapotassium pyrophosphate (K
4P
2O
7) be preferred material.Though can use above-mentioned any pyrophosphate of mentioning, tetrasodium pyrophosphate salt is preferred.For example Vitrafos and polycondensation nitranol are preferred.
Kirk ﹠amp; In " encyclopedia of chemical technology " [third edition, Wiley-IntersciencePublishers (1982)] 17 volumes of Othmer work pyrophosphate has been described in more detail.Other anticalculus agent comprise Parran ﹠amp; Sakkab is disclosed pyrophosphate or condensed phosphate in the U.S. Patent No. of submitting on May 20th, 1,986 4,590,066; U.S. Patent No. 3,429,963 that Shedlovsky submitted on February 25th, 1969 and Chang in the U.S. Patent No. 4,304,766 that December in 1981 was submitted on the 8th, Benedict; Sunberg is disclosed polyacrylate and other Merlon in the U.S. Patent No. of submitting on April 28th, 1,987 4,661,341; Benedict, Bush ﹠amp; Sunberg is disclosed poly-epoxy succinic acid in the U.S. Patent No. of submitting on July 11st, 1,989 4,846,650; The British patent No.490 that submits to February 15 nineteen thirty-seven, disclosed ethylenediaminetetraacetic acid in 384; Widder ﹠amp; The U.S. Patent No. 3,678,154 that Briner submitted on July 18th, 1972 discloses nitrilotriacetic acid(NTA) and relevant chemical compound; The U.S. Patent No. 3,737,533 that Francis submitted on June 5th, 1973, Ploger, Schmidt-Dunker; U.S. Patent No. 3,988,443 and Degenhardt that Gloxhuber submitted on October 26th, 1976; Kozikowski discloses the polycondensation phosphonate ester in the U.S. Patent No. of submitting on October 31st, 1,989 4,877,603.Tartar phosphate comprises potassium pyrophosphate and sodium; Sodium tripolyphosphate, bisphosphonates, ethane-1-hydroxyl-1 for example, 1-bisphosphonates, 1-azepan-1,1-bisphosphonates and linear di 2 ethylhexyl phosphonic acid Arrcostab; Linear carboxylic acid and Zinc sodium citrate..
The anticalculus agent that can replace or use in conjunction with pyrophosphate comprises known material, for example synthetic anionic polymer, the copolymer (as Gantrez) that comprises polyacrylate and maleic anhydride or maleic acid and methyl vinyl ether, for example in the U.S. Patent No. 4 of Gaffar etc., 627,977 introductions; And as poly-aminopropanesulfonic acid (AMPS), three hydration zinc citrates, poly phosphate (tripolyphosphate for example; The hempa acid esters), bisphosphonates (EHDP for example; AHP), polypeptide (for example poly-aspartate and polyglutamic acid) and composition thereof.
This compositions also can comprise surfactant, is commonly referred to foaming agent.Suitable surfactant be those quite stables and can be in wide pH scope blistered preparation.Surfactant can be anion, nonionic, both sexes, amphion, cation or its mixture.Be used for anion surfactant of the present invention and be included in the water soluble salt of sulfonic-glycerol monoesters that alkyl has the water solublity alkyl sulfate (for example alkyl sodium sulfate) of 8-20 carbon atom and has the fatty acid of 8-20 carbon atom.Dodecyl sodium sulfate and cocoyl monoglyceride sodium sulfonate are the type examples of anionic surfactants.As an example, dodecyl sodium sulfate can be available from the Rhodia Specialty Chemical Wuxi Company of Jiangsu Province, China Wuxi City.Other suitable anion surfactants are sarcosinates, for example sodium lauroyl sarcosine, taurate, lauryl alcohol sulfoacetic acid sodium, lauroyl sodium isethionate, lauryl alcohol sodium carbonate and dodecylbenzene sodium sulfonate.Also can use the mixture of anion surfactant.Agricola etc. disclose many suitable anion surfactants in the U.S. Patent No. of submitting on May 25th, 1,976 3,959,458.But spendable non-ionic surface active agent broad sense is defined as by condensed epoxy alkyl (being hydrophilic under the natural situation) and the chemical compound that has basic hydrophobic compound (can be aliphatic series or alkyl aromatic under natural situation) to produce in the compositions of the present invention.The example of suitable non-ionic surface active agent comprises poloxamer (selling with trade name Pluronic), poly(ethylene oxide), poly(ethylene oxide) sorbitan ester (trade name with Tweens is sold), aliphatic alcohol ethyl oxide, the polyethylene oxide condensation compound of alkylphenol, living product is drilled in reflection product condensation by oxirane and expoxy propane and ethylenediamine, the epoxide of aliphatic alcohol, the long chain tertiary amine oxide, the long chain tertiary phosphine oxide, the mixture of long-chain dialkyl sulphoxide and these materials.Be used for the derivant that amphoteric surfactant of the present invention can broadly be described as aliphatic secondary amine and tertiary amine, wherein aliphatic group can be a straight or branched, one of them aliphatic substituent group contains 8-18 the carbon atom of having an appointment, an aliphatic substituent group contains the anionic water-soluble group, for example carbonate, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.Other suitable amphoteric surfactantes are betaines, particularly the cocamidopropyl propyl amide betaine.Also can use the mixture of amphoteric surfactant.Manyly in nonionic that these are suitable and the amphoteric surfactant in equaling United States Patent (USP) 4,051,234 that JIUYUE in 1977 submitted on the 27th, describes to some extent Gieske.The present invention contains one or more surfactants usually, each about 0.25%-12% of its content, preferably about 1%-10% and 1%-8% (with composition weight meter) more preferably from about.
Titanium dioxide also can be added in the dentifrice composition.Titanium dioxide is a kind of white powder, can increase the opacity of compositions.Titanium dioxide accounts for about 0.1%-5% of composition weight usually.
It is useful that antioxidant is generally believed in compositions of the present invention, and can be included in wherein.Antioxidant be disclosed in Cadenas and Packer's "
The antioxidant handbook(1996, Marcel Dekker Inc.) waits in the article.The polyphenoils that can be included in oral care composition of the present invention or the material includes, but is not limited to vitamin E, ascorbic acid (vitamin C), uric acid, carotenoid, vitamin A, flavonoid, medical herbs polyphenoils, Mai Laning, amino indole, thioctic acid and composition thereof.Microorganism E and C are preferred, have required about 0.01%-0.10%, preferably the level of about 0.01%-0.05%.
Also can in this compositions, add one or more coloring agent.Coloring agent can be the aqueous solution form, preferably the aqueous solution of 1% coloring agent.Color solution accounts for about 0.01%-5% of composition weight usually.
Also can in compositions, add flavouring system.Suitable flavoring agent composition comprises tea Herba Menthae, wintergreen oil, Oleum menthae, Oleum Menthae Rotundifoliae, Herba Medicaginis bud oil, Mentholum, anethole, methyl salicylate, eucalyptole, Cortex Cinnamomi, menthyl acetate, Salvia japonica Thunb., eugenol, parsley oil, oxazine, α-Zi Luotong, Adeps Bovis seu Bubali, Fructus Citri Limoniae, orange, 1-ethoxy-2-hydroxy-4-propenyl benzene, Cortex cinnamomi japonici (Ramulus Cinnamomi), Rhizoma et radix valerianae, ethyl Rhizoma et radix valerianae, heliotropine, 4-cis-enanthaldehyde, diacetyl methyl-to tert-butyl-phenyl ethyl ester and composition thereof.The non-limitative example of commercially available flavouring system comprises those Sino-U.S. international essence (Internationd Flavors and Fragrances, USA ﹠amp; China) flavouring system of selling with the trade name of " Smoothmint ", " Ultimint " and " Icy Mint ".The coolant of preferred this compositions is to menthane carbosamided dose, for example N-ethyl-to terpane-3-Methanamide (commercial being called " WS-3 ") and composition thereof.The flavoring agent system uses with the content of about 0.001%-5% (with composition weight meter) in compositions usually.
Can in this compositions, add sweeting agent, for example glucide, glucose, sucrose, lactose, mannose, levulose, aspartame, ring sodium sulfonate, D-tryptophan, dihydrochalcone, acesulfame potassium and composition thereof.Sweeting agent uses with the content of about 0.005%-5% (with composition weight meter) usually in toothpaste.
Can use herbal medicinal product in the compositions of this paper, include but not limited to gold thread extract, Flos Lonicerae extract and composition thereof, its content is about 0.01%-0.05%.It is believed that these herbal medicinal products provide antibacterial efficacy.
Though optional, in dentifrice composition of the present invention, can there be traditional antimicrobial.Yet because they are expensive, and the present invention do not have them to show surprising stability yet, and preference of the present invention does not contain traditional antimicrobial substantially.A kind of preferred traditional antimicrobial is 5-chloro-2-(2, the 4-dichlorophenoxy)-and phenol, be commonly referred to triclosan, in " The Merck Index " [11 editions (1989)], p.1529 (input number 9573), in U.S. Patent No. 3,506,720 and Beecham Group, PLC, the european patent application No.0 that published on January 7th, 1988 describes in 251,591 to some extent.Other concrete antimicrobials comprise chlohexidine, a phosphonic acids triclosan and a quintessence oil, comprise thymol, geraniol, carvacrol, citral, hinokitiol, eucalyptole and composition thereof.At Parran, Jr. etc. disclose triclosan and this type of other preparations in the United States Patent (USP) 4,894,220 that submit to January 16 nineteen ninety such as United States Patent (USP) 5,015,466 that on May 14th, 1991 submitted to and Nabi.These preparations can about 0.01%-1.5% (with composition weight meter) contents level exist.
Other antimicrobials also comprise water-fast nonionic antimicrobial, for example halogenated diphenyl ether, oxybenzene compound, comprise phenol ex hoc genus anne thing, monoalkyl, poly-alkyl and aromatics halobenzene phenol, resorcinol and derivant thereof, biphenol chemical compound and halogenated N-phenylsalicylamide, benzene methyl and halogenated carbanilide.Other water soluble antimicrobials also comprise quaternary ammonium salt and bis-biguanide (bis-biquanide) salt etc.One phosphoric acid triclosan also is suitable water soluble antimicrobials.The quaternary ammonium salt preparation is included in that one or two substituent group of tool has about 8-20 on the quaternary nitrogen, the carbon chain lengths (normally alkyl) of common about 10-18 carbon atom, and remaining substituent group (normally alkyl or benzyl) has less carbon number, for example about 1-7 carbon atom, normally methyl or ethyl.Bromination dodecyl trimethyl ammonium, chlorination four decyl pyridines, domiphen bromide, chlorination N-four decyls-4-ethylpyridine, bromododecane base dimethyl (2-phenoxy group ethyl) ammonium, chloro benzyl dimethyl octadecyl ammonium, cetylpyridinium chloride, quaternised 5-amino-1,3-two (2-ethyl-hexyl)-5-methyl piperidine, benzalkonium chloride, benzethonium chloride and methyl benzethonium chloride are the examples of typical quaternary ammonium salt antiseptic.Other chemical compounds for example two [4-(R-amino)-1-pyridine] alkane are open in the United States Patent (USP) 4,206,215 that Bailey1980 submitted at June 3.Also can comprise stannous salt, for example inferior stannum of ditin diphosphate and gluconic acid and other antimicrobials are as Diglycocol copper, cupric glycinate, zinc citrate and zinc lactate.Also available enzyme comprises endoglycosidase, carase, dextranase, mutase (mutanase) and composition thereof.These preparations are at Norris etc., July 26 nineteen sixty, and United States Patent (USP) 2,946,725 and at Gieske etc., have disclosedly in 27 days the United States Patent (USP) of JIUYUE in 1977 4,051,234, be incorporated herein for your guidance.
What also be suitable as antimicrobial herein is phthalic acid and salt thereof, include but not limited to United States Patent (USP) 4 on February 19th, 1991,994, those disclosed in 262, preferred Potassium Hydrogen Phthalate magnesium, chlohexidine (No. 2090, Merk Index), alexidine (Merk Index, No. 222), triocil (Merck Index, No. 4624), Sanguinarine (Merck Index, No. 8320); Benzalkonium chloride (Merck Index, No. 1066), N-phenylsalicylamide (Merck Index, No. 8299), domiphen bromide (Merck Index, No. 3411), cetylpyridinium chloride (CPC) (Merck Index, No. 2024), chlorination four decyl pyridines (TPC), chlorination N-four decyls-4-ethylpyridine (TDEPC), octene pyridine (octenidine), delmopinol, octapinol and other pyridine derivates, fungus (nicin) prepared product, zinc/stannous ion preparation, antibiotic (augmentin for example, the amoxicillin, tetracycline, doxycycline, minocycline and metronidazole) and the analog and the salt of above-mentioned substance, methyl salicylate, hydrogen peroxide, chlorous acid slaine and composition thereof.
Using method
In enforcement of the present invention, user only needs the dentifrice of this paper is coated onto the dental surface of human or animal's desired location, obtains required effect, for example brightens, breath freshening, decayed tooth prevention, pain relief, dental bed health, tartar control etc.Compositions also can be used for other oral surfaces, for example on gingiva or the mucosal tissue, though believe that effect is best when dentifrice composition is used for tooth.Dentifrice composition can directly or indirectly contact with tooth and/or oral surfaces; Yet the preferred dentifrice composition that directly uses.Available any method, but preferably coat dentifrice composition with toothbrush.
Manufacture method
Dentifrice composition can form with the method and the technology of this area routine.For example can in pure water, add six hydroxyl wetting agents and any optional binary and trihydroxylic alcohol, and in blender with about 2 minutes of anti-decayed tooth agent homogenize.Can add sweeting agent, antimicrobial and other auxiliary compounds (except flavoring agent system, surfactant and titanium dioxide) then, homogenized mix is 10 minutes again.Under the vacuum of about 0.1-0.2 crust, in mixture, added thickening agent and titanium dioxide then, remove air bubble through about 20 minutes.Add surfactant then, vacuum homogenize 15-30 minute forms final dentifrice composition.Then dentifrice composition is contained in independently applicator, for example in the dentifrice tube, with transportation and sale.
Final dentifrice composition has about 8-100BKU usually, preferably about 15-80BKU, the more preferably from about viscosity of 15-50BKU." BKU " used herein is viscosity unit, and this viscosity is the Brookfield viscometer, and 1/2RVT type (1/2 spring strength) has Brookfield " Helipath " support.Axle is conventional " E-series " T oblique crank Z.Viscometer is placed on the Helipath support, smooth with spirit level.The E axle is fixed, and viscometer schedules 2.5RPM when operation.After 10 minutes, temperature stabilization is measured viscosity in the time of 25 ℃.Commercial acceptable dentifrice composition has the aesthetic features of the acceptable rheological equationm of state, good quality, pleasant and usually greater than the proportion of water, preferably about 1-1.5 grams per milliliter, more preferably from about 1.1-1.3g/ml.Dentifrice with above-mentioned viscosity and proportion can be accepted by consumer usually.
Hereinafter having listed embodiments of the invention in order to illustrate, is not in order to limit the present invention by any way.
Embodiment 1-2
According to method for preparing following dentifrice composition
Composition | Comparative Example A An | Embodiment 1 | Embodiment 2 |
Sodium fluoride, USP | 0.25 | 0.25 | 0.25 |
Silicon dioxide, sedimentary (Zeodent119) | 20 | 20 | 20 |
Sorbitol | 30.4 | 21 | 14 |
Pure water * | 29.4 | 53.85 | 60.8 |
Triclosan, USP | 0.05 | - | 0.05 |
Carbopol 956 | 0.2 | 0.3 | 0.3 |
Sodium carboxymethyl cellulose | 0.85 | 1 | 1 |
Saccharin sodium, USP | 0.15 | 0.25 | 0.25 |
Ten phosphate dihydrate trisodiums | 1.3 | 0.5 | 0.5 |
Sodium alkyl sulfonate | 2.1 | 1.8 | 1.8 |
The flavoring agent system | 0.8 | 0.8 | 0.8 |
Titanium dioxide, USP (Rutile) | 0.5 | 0.25 | 0.25 |
Glycerol | 10 | -- | -- |
Polyethylene Glycol | 4 | -- | -- |
Amount to | 100 | 100 | 100 |
Brookfield viscosity (BKU) (after 10 minutes) | 13-37 | 18 | 15 |
pH | 6.8-7.4 | 6.8 | 6.8 |
Soluble fluoride content (pure water: 3: 1 serosity of dentifrice composition) | 265-315ppm | 268ppm | 268ppm |
Proportion (g/ml) | 1.32-1.38 | 1.2 | 1.2 |
*Comprise water from sorbitol solution, surfactant solution etc.
Embodiment 1 and 2 has described the non-limitative example of dentifrice composition of the present invention, and Comparative Example A An also is provided.All three kinds of preparations provide the surprising good rheological equationm of state and stability; Yet the unit formulation cost of Comparative Example A An is than the preparation cost high about 50% of embodiment 1 and 2.In addition, embodiment 1 and 2 has remarkable stability, though they contain the water more than 50%.In addition, embodiment 1 provides the fragrance of improvement to discharge (being the susceptibility of fragrance) under the flavouring system level identical with Comparative Example A An with B.Surprising is that the growth of microorganism of embodiment 1 and Comparative Example A An are suitable with embodiment 2 after 1 month, although embodiment 1 does not contain triclosan.
Embodiment 3-4
According to method for preparing following dentifrice composition
Composition | Embodiment 3 | Embodiment 4 |
Sodium fluoride, USP | 0.243 | 0.243 |
Silicon dioxide, sedimentary (Zeodent119) | 22 | 21 |
Sorbitol | 30 | 30 |
Pure water * | 32.657 | 38.057 |
Carbopol 956 | 0.3 | 0.3 |
Sodium carboxymethyl cellulose | 1 | 1.1 |
Saccharin sodium, USP | 0.25 | 0.25 |
Ten phosphate dihydrate trisodiums | 3 | 0.5 |
Sodium dihydrogen phosphate | 2 | -- |
Sodium alkyl sulfonate | 7.5 | 7.5 |
The flavoring agent system | 0.8 | 0.8 |
Titanium dioxide, USP (Rutile) | 0.25 | 0.25 |
Amount to | 100 | 100 |
Brookfield viscosity (BKU) (after 10 minutes) | 21 | 18 |
pH | 6.8 | 6.8 |
Soluble fluoride content (pure water: 3: 1 serosity of dentifrice composition) | 268ppm | 268ppm |
Proportion (g/ml) | 1.29 | 1.22 |
*Comprise water from sorbitol solution, surfactant solution etc.
Claims (8)
1. a dentifrice composition is characterized in that, this dentifrice composition comprises:
A.6%-70% abrasive polishing materials;
B.0.5%-4.5% thickening agent;
C.0.5%-45% six hydroxyl wetting agents;
D.0.05%-2.5% anti-decayed tooth agent; With
E. at least 30% water,
Wherein compositions does not contain binary and trihydroxylic alcohol, and the viscosity of said composition is 8-100BKU.
2. dentifrice composition as claimed in claim 1 is characterized in that described thickening agent is selected from carboxymethyl cellulose, carbomer, xanthan gum and composition thereof.
3. dentifrice composition as claimed in claim 1 is characterized in that said composition contains at least 40% water.
4. dentifrice composition as claimed in claim 1 is characterized in that, described six hydroxyl wetting agents are selected from Sorbitol, xylitol, glucose and composition thereof.
5. dentifrice composition as claimed in claim 1 is characterized in that the viscosity of said composition is 15-80BKU.
6. dentifrice composition as claimed in claim 1, it is characterized in that, said composition also contains auxiliary compounds, is selected from peroxide source, alkali metal hydrogencarbonate source, anticalculus agent, surfactant, titanium dioxide, antioxidant, coloring agent, flavouring system, sweeting agent, herbal medicinal product, antimicrobial and composition thereof.
7. a method that cleans human or animal's dental surface is characterized in that the method comprising the steps of: with the described dentifrice composition contact of claim 1 dental surface.
8. dentifrice composition is characterized in that said composition comprises:
A.6%-70% silicon dioxide abrasive polishing materials;
B.0.5%-4.5% thickening agent is selected from carboxymethyl cellulose, carbomer, xanthan gum and composition thereof;
C.5%-30% six hydroxyl wetting agents are selected from Sorbitol, xylitol, glucose and composition thereof;
D.0.1%-1% sodium fluoride; With
E. at least 30% water,
Wherein compositions does not contain binary and trihydroxylic alcohol, and the viscosity of said composition is 15-50BKU.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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USPCT/US00/01866 | 2000-01-27 | ||
US0001866 | 2000-01-27 | ||
WOPCT/US00/01866 | 2000-01-27 |
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CN1424902A CN1424902A (en) | 2003-06-18 |
CN1201721C true CN1201721C (en) | 2005-05-18 |
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CNB008185727A Expired - Fee Related CN1201721C (en) | 2000-01-27 | 2000-07-18 | Improved low-cost dentifrice composition |
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EP (1) | EP1255526A1 (en) |
JP (1) | JP2004500377A (en) |
CN (1) | CN1201721C (en) |
AU (1) | AU783178B2 (en) |
CA (1) | CA2399362C (en) |
MX (1) | MXPA02007346A (en) |
PL (1) | PL202563B1 (en) |
RU (1) | RU2233651C2 (en) |
WO (1) | WO2001054657A1 (en) |
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WO2005049050A1 (en) * | 2003-11-19 | 2005-06-02 | Meiji Seika Kaisha, Ltd. | Sialagogue and, containing the same, oral composition and food composition |
EP1669056A3 (en) * | 2004-08-12 | 2007-05-30 | The Procter and Gamble Company | Oral compositions and systems |
WO2006081912A1 (en) * | 2005-02-04 | 2006-08-10 | Unilever N.V. | Multiphase toothpaste composition |
MX2007009242A (en) * | 2005-02-04 | 2007-09-19 | Unilever Nv | Multiphase toothpaste composition. |
US8900558B2 (en) | 2006-06-30 | 2014-12-02 | Colgate-Palmolive Company | High fluoride ion oral care composition and method for maintaining anticaries activity |
EA011286B1 (en) * | 2007-08-29 | 2009-02-27 | Общество С Ограниченной Ответственностью "Вдс" | Tablet for prophylaxis and treatment of teeth diseases and parodentium |
AR070356A1 (en) * | 2008-02-08 | 2010-03-31 | Colgate Palmolive Co | PRODUCT FOR ORAL CARE AND METHODS OF USE OF THE SAME |
US9022959B2 (en) * | 2009-07-30 | 2015-05-05 | Mcneil-Ppc, Inc. | Oral care systems |
CN105250149A (en) * | 2009-12-23 | 2016-01-20 | 高露洁-棕榄公司 | Oral care compositions |
WO2014124904A1 (en) * | 2013-02-14 | 2014-08-21 | Unilever Plc | Non-aqueous oral care compositions |
CN105307624B (en) | 2013-06-18 | 2019-12-31 | 株式会社Lg生活健康 | Oral composition |
WO2015106915A1 (en) * | 2014-01-14 | 2015-07-23 | Unilever Plc | Oral care compositions |
EP3180092A1 (en) * | 2014-08-15 | 2017-06-21 | The Procter and Gamble Company | Dentifrice with incremental chemistries |
CN109316378B (en) * | 2017-07-31 | 2021-09-28 | 好维股份有限公司 | Gel-forming composition for oral care products and oral care products comprising the same |
WO2022059642A1 (en) * | 2020-09-17 | 2022-03-24 | ライオン株式会社 | Dentifrice composition |
Family Cites Families (6)
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US4421527A (en) * | 1977-12-20 | 1983-12-20 | J. M. Huber Corporation | High fluoride compatibility dentifrice abrasives and compositions |
GB8804817D0 (en) * | 1988-03-01 | 1988-03-30 | Unilever Plc | Anticalculas oral compositions |
US5089255A (en) * | 1989-06-26 | 1992-02-18 | Colgate-Palmolive Company | Dental remineralization |
US5320830A (en) * | 1992-12-30 | 1994-06-14 | The Procter & Gamble Company | Oral compositions |
GB9812818D0 (en) * | 1998-06-12 | 1998-08-12 | Procter & Gamble | Dentfrice compositions |
US6045780A (en) * | 1998-06-22 | 2000-04-04 | Shemberg Marketing Corporation | Toothpaste composition |
-
2000
- 2000-07-18 AU AU62208/00A patent/AU783178B2/en not_active Ceased
- 2000-07-18 CA CA002399362A patent/CA2399362C/en not_active Expired - Fee Related
- 2000-07-18 CN CNB008185727A patent/CN1201721C/en not_active Expired - Fee Related
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- 2000-07-18 JP JP2001555636A patent/JP2004500377A/en active Pending
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CN1424902A (en) | 2003-06-18 |
AU783178B2 (en) | 2005-09-29 |
WO2001054657A1 (en) | 2001-08-02 |
MXPA02007346A (en) | 2002-12-09 |
AU6220800A (en) | 2001-08-07 |
JP2004500377A (en) | 2004-01-08 |
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EP1255526A1 (en) | 2002-11-13 |
CA2399362C (en) | 2006-11-07 |
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