CN104703575A - Oral care composition - Google Patents
Oral care composition Download PDFInfo
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- CN104703575A CN104703575A CN201380053017.7A CN201380053017A CN104703575A CN 104703575 A CN104703575 A CN 104703575A CN 201380053017 A CN201380053017 A CN 201380053017A CN 104703575 A CN104703575 A CN 104703575A
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- CN
- China
- Prior art keywords
- calcium
- silicate hydrate
- oral care
- calcium silicate
- care composition
- Prior art date
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; 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
Abstract
An oral care composition is disclosed comprising calcium silicate hydrate comprising from 20 to 70% SiO2 by weight of the calcium silicate hydrate; and physiologically acceptable carrier comprising humectant, surfactant, thickener or a mixture thereof.
Description
the technical field of invention
The present invention relates to oral care composition, such as toothpaste, natural gum, collutory etc.Particularly, the present invention relates to the oral care composition comprising calcium silicate hydrate.The invention still further relates to such composition for by the mineralising again of individual tooth and/or the purposes brightened and the method for the preparation of said composition.
background of invention
Unfortunately, the product that we like as consumer has negative effect to our tooth usually.Acidic beverages and sweets, such as, can cause decayed tooth by invasion and attack are coated with enamel that is that take care of one's teeth.In addition, therefore tobacco-based product and beverage such as coffee & tea leaf also can cause usual unengaging smile by stain teeth.
Except we consume, constantly change from the balance of nature between the tooth hydroxyapatite (HAP) of the dental enamel dissolution of tooth and the HAP that on tooth or in tooth, spontaneous material is formed from saliva.This type of change can produce the unappealing tooth with raw dental caries condition.But developed the product about decayed tooth and/or teeth whitening, it comprises the product using calcium salt for the mineralising again of tooth.
WO 2008/068149 A (Unilever) discloses a kind of oral care product, it comprise the insoluble calcium phosphate comprising not synthos the first compositions, comprise phosphate ion sources the second separate composition and for sending the instrument of each compositions to dental surface.Preferred insoluble calcium phosphate is calcium silicates.
WO 2008/015117 A (Unilever) discloses the calcia-silica composite biological material of amorphous state or crystalline state, it has the average pore size of 0.8 to 4 nm as BET method mensuration, the calcia-silica content of wherein said biomaterial is at least 80 wt%, surplus is one or more optional other materials, and wherein the mol ratio of calcium oxide and silicon dioxide is at least 0.1.
We find at present to provide the calcium silicates of hydrate forms to improve its performance providing in oral care benefits unexpectedly.Particularly, find that the calcium silicate hydrate from oral care composition effectively deposits on tooth surfaces, even also like this in the substantially not phosphatic situation of such composition.In addition, find that calcium silicate hydrate provides oral care benefits, and unnecessary there is ad hoc structure (such as many mesopores), therefore allow to manufacture more easily.
Test and definition
dentifrice
" dentifrice " for the object of the invention refers to for the cream on the tooth in cleaning oral cavity or other surfaces, powder, liquid, glue or other preparations.
toothpaste
" toothpaste " for the object of the invention refers to the cream or gel dentifrice that adopt toothbrush application.Particularly preferably be and be applicable to by scrubbing the toothpaste that about 2 minutes carry out cleaning teeth.
collutory
The liquid teeth cleaning agent that " collutory " for the object of the invention uses when referring to and rinse oral cavity.Particularly preferably be the applicable collutory being rinsed oral cavity by about half a minute of blurting out before expectoration expectorant and/or gargle.
granularity
Granularity used herein refers to particle diameter, except as otherwise noted.Diameter to refer to when not forming the spheroid of stricti jurise maximum detection span on granule from meansigma methods.For polydispersion sample, diameter refers to and such as uses dynamic light scattering (see international standard ISO 13321) and instrument such as Zetasizer Nano
tMthe z-particle mean size that (Malvern Instruments Ltd, UK) measures.
pH
PH refers to the value at the temperature of atmospheric pressure and 25 DEG C.When relating to the pH of oral care composition, refer to when compositions described in 1 weight portion at 25 DEG C dispersed and/or be dissolved in the pure water of 20 weight portions time the pH that measures.Particularly, can by artificial mixing 1 g oral care composition and 20 ml water 30 s, then the pH measured by pH measured immediately by employing reagent paper or pH meter.
dissolubility
" solubility " used herein and " insoluble " refer to the dissolubility of source (such as calcium salt) under 25 DEG C and atmospheric pressure in water." solubility " refers to and is dissolved in water to provide concentration to be the source of the solution of at least 0.1 mol/L." insoluble " refers to and is dissolved in water to provide concentration to be the source of the solution being less than 0.001 mol/L.Therefore, " microsolubility " is defined as and refers to and be dissolved in water to provide concentration to be greater than 0.001 mol/L and to be less than the source of the solution of 0.1 mol/L.
hydrate water
" hydrate water " used herein refers to that the mode chemical bonding that removes is to the water of this material with the chemical composition only substantially can not changed material by heating.Particularly, removing when this water only can heat at higher than 200 DEG C.Use and adopt the thermogravimetry (TGA) of Netzsch TG instrument to measure fluid loss.At N
2in 30 to 900 DEG C, 10 are adopted under atmosphere
othe rate of heat addition of/min carries out TGA.
be substantially free of
" being substantially free of " used herein refers to based on described oral care composition gross weight, by weight, lower than 1.5%, preferably lower than 1.0%, more preferably less than 0.75%, also more preferably less than 0.5%, even more preferably less than 0.1% and most preferably 0.0 to 0.01%, comprise the four corner wherein contained.
viscosity
The viscosity of toothpaste is the value of the tachometric survey adopting Brookfield viscometer No. 4 axles and 5 rpm under room temperature (25 DEG C).Be worth in centipoise (cP=mPa.s), unless otherwise noted.
again mineralising
" again mineralising " used herein refers to that original position (namely in the oral cavity) generation calcium phosphate (is included in 10 nm to 20 μm on tooth on tooth, preferably 75 nm to 10 μm, most preferably 150 nm to 5 μm of thick layers, comprise the four corner wherein contained) to reduce the probability of tooth sensitivity, decayed tooth, regenerate enamel and/or improve teeth appearance by brightening by means of this type of new calcium phosphate of generation.
miscellaneous
Except in an embodiment, or otherwise clearly indicate, in description, mention the material of reaction or the amount of condition, the amount of the physical property of material and/or use optionally can be interpreted as and to be modified by word " about ".
All amounts with the weighing scale of final oral care composition, unless otherwise.
It should be noted that, in the scope of any value of regulation, any concrete higher limit can be associated with any concrete lower limit.
In order to avoid query, word " comprise " be intended to " comprising " but not necessarily refer to " by ... composition " or " by ... form ".In other words, the step enumerated or selection do not need exhaustive.
The disclosure of the present invention existed herein is considered to cover the whole embodiments as existed in multinomial dependent claims each other, does not consider the fact that claim can exist when not multinomial subordinate or redundancy.
Feature about of the present invention concrete in (such as compositions of the present invention) disclosed situation, this type of is open is also considered to be applied to any other aspect of the present invention (such as method of the present invention), adds necessary change.
summary of the invention
In first aspect, the present invention relates to a kind of oral care composition, it comprises:
A) calcium silicate hydrate, its comprise account for this calcium silicate hydrate 20 to 70% SiO
2; With
B) physiologically acceptable carrier, it comprises wetting agent, surfactant, thickening agent or its mixture.
In second aspect, the present invention relates to tooth mineralising and/or the method that brightens again making individual, it comprises the step of oral care composition to one or more teeth of individual of any embodiment applying first aspect.
In the third aspect, the present invention relates to the method preparing oral care composition, it comprises the steps:
I) silicate ion source is made to contact with calcium ion source with forming reactions mixture in an aqueous medium;
Ii) calcium silicate hydrate is reclaimed from reactant mixture;
Iii) described calcium silicate hydrate and physiologically acceptable carrier is made to merge.
The method of the third aspect is particularly suitable for the compositions preparing first aspect.Therefore, the present invention is also provided and to be obtained by the method for a third aspect of the present invention and/or the oral care composition of obtainable first aspect.Every other aspect of the present invention can more easily become obvious after the detailed description considered hereinafter and embodiment.
accompanying drawing briefly describes
Fig. 1 illustrates the XRD figure of the calcium silicate hydrate powder being suitable for embodiment of the present invention.
Fig. 2 illustrates the low-angle XRD figure of the material of Fig. 1.
Fig. 3 illustrates the TGA result of the material of Fig. 1.
specifically describe
At least calcium oxide (CaO), silicon dioxide (SiO is comprised for calcium silicate hydrate of the present invention
2) and water.
The present inventor has been found that the ability adopting the silicon dioxide content of recruitment to improve calcium silicate hydrate mineralising dental tissue again.Therefore, described calcium silicate hydrate comprises and accounts at least 20% of this calcium silicate hydrate weight, and preferably at least 30%, more preferably at least 40%, the most preferably silicon dioxide of at least 55%.
The present inventor also has been found that, compared with the calcium silicates of the non-hydrated of some routines, calcium silicate hydrate illustrates the deposition improved on dental tissue.Therefore, in order to allow to exist water and calcium oxide (with other component, if necessary), the dioxide-containing silica of calcium silicate hydrate be this calcium silicate hydrate be not more than 70 % by weight, be preferably not more than 65 % by weight, be most preferably not more than 60 % by weight.
Described calcium silicate hydrate preferably comprises and accounts at least 5% of this calcium silicate hydrate weight, and more preferably at least 10%, also more preferably at least 15%, the even more preferably hydrate water of amount of at least 20% and most preferably at least 25%.Water content be generally account for described calcium silicate hydrate weight be not more than 50%, more preferably no more than 40%, be even most preferably not more than 30% more preferably no more than 35%.
In order to provide the calcium again needed for mineralising, described calcium silicate hydrate preferably comprises and accounts at least 5% of this calcium silicate hydrate weight, and more preferably at least 7%, also more preferably at least 10%, the even more preferably calcium oxide of amount of at least 12% and most preferably at least 15%.CaO content be generally account for described calcium silicate hydrate weight be not more than 50%, more preferably no more than 40%, be even most preferably not more than 25% more preferably no more than 30%.
In calcium silicate hydrate calcium oxide and silicon dioxide relative scale measure as calcium (Ca) easily: the atomic ratio of silicon (Si).As mentioned above, the present inventor has been found that the ability adopting the silicon dioxide content of recruitment to improve calcium silicate hydrate mineralising dental tissue again.Therefore, described calcium silicate hydrate is preferably with lower than 1:1, and more preferably less than 1:1.2, also more preferably 1:1.5 to 1:4, most preferably the atomic ratio (Ca:Si) of 1:1.7 to 1:3 comprises Ca and Si.
Described calcium silicate hydrate can be amorphous.But even if the present inventor is surprisingly found out that described calcium silicates is at least part of crystallization, it still may play the effect of effectively mineralising dental tissue again.Therefore, preferably, described calcium silicate hydrate is at least part of crystallization.Such as can there is degree of crystallinity by X-ray diffraction qualification.
Described calcium silicate hydrate can be many mesopores.Such as people such as J. Wu. " Hierachically Nanostructured Mesoporous Spheres of Calcium Silicate Hydrate:Surfactant-Free Son DEG C of hemical Synthesis and Drug-Delivery System with Ultrahigh Drug-Loading Capacity ", Advanced Materials, 2010,22, record many mesopores calcium silicate hydrate in 749-753 page.But the present inventor has been found that even do not exist under many mesopores, calcium silicate hydrate still can be effectively deposited on dental tissue and mineralising dental tissue again.When being not wishing to be bound by theory, the present inventor believes this is because exist and make calcium silicates have more reactive hydrate water.Therefore, described calcium silicate hydrate is not preferably many mesopores.Such as can use small angle x-ray diffraction (SAXD) and/or nitrogen absorption-desorbing qualification presence or absence mesopore.
Described calcium silicate hydrate is preferably microgranular, because this makes maximum surface area contact with dental tissue.Therefore, described compositions preferably comprises granule, and it comprises described calcium silicate hydrate.More preferably, the average particle size of described granule is five (5) μm or less, comprise even more preferably 10 to 100 % by weight of the granule of the calcium silicate hydrate used in the present invention, especially 25 to 100 % by weight, the granule of 70 to 100 % by weight has the granularity of 0.1 to 1.5 μm the most especially.
Except calcium oxide, silicon dioxide and water, the granule comprising calcium silicate hydrate can comprise other components, such as metal cation, anion (such as phosphate radical) etc.But preferably described granule is with at least 70% of described particle weight, more preferably at least 80%, also more preferably at least 90%, even more preferably the amount of at least 95% comprises CaO, SiO
2and water.Most preferably, described granule is by CaO, SiO
2form with water (or at least substantially by CaO, SiO
2form with water).
Usually, oral care composition of the present invention accounts for 0.1 to 60% of described calcium silicate hydrate weight, and more preferably 0.2 to 50%.
Even more preferably, described compositions is with at least 0.3 % by weight, and also more preferably the amount of at least 0.5 % by weight or even at least 1 % by weight comprises calcium silicate hydrate.In the most preferred embodiment, described compositions is to account at least 5 % by weight of described oral care composition, and the amount of 10 to 40 % by weight comprises described calcium silicate hydrate best.
When described compositions be toothpaste or dentifrice, the calcium silicate hydrate of preferred higher amount.This is because usual each use consumer only applies toothpaste with small size (such as about 2 ml).In addition, toothpaste is generally opaque, therefore allows the calcium silicate hydrate introducing high-load, and does not affect the outward appearance of consumer anticipation.Therefore, in one embodiment, described compositions is toothpaste or dentifrice, and with at least 2 % by weight, more preferably at least 5 % by weight, and most preferably the amount of 7 to 40 % by weight comprises calcium silicate hydrate.
When described compositions is collutory, the calcium silicate hydrate of preferred relatively low amount.This is because every non-toothpaste uses consumer usually to use collutory with larger volume (such as about 20 ml).In addition, collutory is generally transparent, therefore introduces the outward appearance of the calcium silicate hydrate possibility negative effect consumer anticipation of high-load.Therefore, in one embodiment, described compositions is collutory, and with at least 0.2 % by weight, more preferably at least 0.5 % by weight, and most preferably the amount of 1 to 10 % by weight comprises calcium silicate hydrate.
Find that compositions of the present invention can original position mineralising tooth and do not comprise phosphate source in compositions itself again.When being not wishing to be bound by theory, the present inventor believes that this may react in saliva because of the calcium source in compositions of the present invention and phosphate anion, and/or Si-OH group can have the affinity to Ca ion in tooth.
Therefore, in one embodiment, described compositions can be substantially free of phosphate source.When described compositions be single phase aqueous composition (namely comprise account for said composition weight be greater than 1.5% water, be preferably greater than the water of 5%, the water more preferably greater than 10% and most preferably 20 to 90% water) time, this is especially preferred.In phase aqueous preparation, there is calcium silicate hydrate and phosphate source can cause calcium and phosphatic premature reaction and product unstability.
For some compositions, particularly anhydrous composition (being namely substantially free of the compositions of water) or two-phase Aquo-composition, be preferably mixed into phosphate source in the composition to help in-situ preparation calcium phosphate.
Operable phosphate source is only constrained to it to a certain extent and may be used for being applicable in the compositions that uses in the oral cavity in the present invention.The illustrative examples being suitable for phosphate source type of the present invention comprises tertiary sodium phosphate, biphosphate list sodium, sodium hydrogen phosphate, tetrasodium pyrophosphate, tetrasodium pyrophosphate, sodium hexameta phosphate, tripotassium phosphate, biphosphate list potassium, dipotassium hydrogen phosphate, its mixture etc.Described phosphate source is preferably water miscible that.
Usually, described phosphate source forms 0.5 to 15 % by weight, and more preferably 2 to 12 % by weight, the most preferably oral care composition of 4 to 9 % by weight, based on described composition total weight meter, comprises the four corner wherein contained.In the most preferred embodiment, the phosphate source used is tertiary sodium phosphate and biphosphate list sodium, and wherein the weight ratio of tertiary sodium phosphate and biphosphate list sodium is 1:4 to 4:1, preferred 1:3 to 3:1, most preferably 1:2 to 2:1, comprises the whole ratios wherein contained.
Described oral care composition preferably has the pH being greater than 5.0.If the pH of described compositions is too low, then it can reduce the pH in oral cavity, thus hinders the in-situ preparation of calcium phosphate.Therefore, preferably the pH of oral care composition is 5.5 to 11.0, more preferably 6.0 to 10.5, most preferably 7.0 to 10.0.
Compositions of the present invention is oral care composition, therefore comprises physiologically acceptable carrier.Described carrier comprises at least surfactant, thickening agent, wetting agent or its combination.
Preferably, described oral care composition comprises surfactant.Preferably, described compositions comprises and accounts at least 0.01% of described composition weight, and more preferably at least 0.1%, the most preferably surfactant of 0.5 to 7%.Suitable surfactant comprises anionic surfactant, such as C
8to C
18the sodium of alkyl sulfate, magnesium, ammonium or ethanolamine salt (such as sodium lauryl sulfate), C
8to C
18the sodium of alkyl sulfosuccinates, magnesium, ammonium or ethanolamine salt (such as dioctyl sodium sulfosuccinates acid esters sodium), C
8to C
18the sodium of salts of alkyl sulfoacetates ester, magnesium, ammonium or ethanolamine salt (such as lauryl sulfoacetate ester sodium), the sodium of C8 to C18 alkylsarcosines, magnesium, ammonium or ethanolamine salt (such as sodium lauryl sarcosinate), C
8to C
18the sodium of the sodium of alkyl phosphate, magnesium, ammonium or ethanolamine salt (it optionally can comprise maximum 10 oxirane and/or propylene oxide units) and sulfated monoglycerides, magnesium, ammonium or ethanolamine salt.Other suitable surfactants comprise non-ionic surface active agent, the ethoxylate of the sorbitan fatty esters of such as optional polyethoxylated, the fatty acid of ethoxylation, macrogol ester, fatty mono glyceride and dialycerides and ethylene oxide/propylene oxide block polymer.Other suitable surfactants comprise amphoteric surfactant, such as betaines or sulfobetaines bases.Also the mixture of any above-mentioned material can be used.More preferably, described surfactant comprises or is anion surfactant.Preferred anion surfactant is sodium lauryl sulfate and/or dodecylbenzene sodium sulfonate.Most preferably, described surfactant is sodium lauryl sulfate.
Also can use thickening agent in the present invention and only be constrained to it to a certain extent and can add in the compositions be suitable for use in oral cavity.The illustrative examples of the thickener types that can use in the present invention comprises sodium carboxymethyl cellulose (SCMC), hydroxyethyl-cellulose, methylcellulose, ethyl cellulose, Tragacanth, Radix Acaciae senegalis, POLY-karaya, sodium alginate, carrageenin, Guar beans, xanthan gum, Irish moss, starch, modified starch, silicon-dioxide-substrate thickening agent comprise aerosil, aluminium-magnesium silicate (such as Veegum), carbomer (cross linked acrylic) and its mixture.
Usually, preferably sodium carboxymethyl cellulose and/or carbomer, most preferably sodium carboxymethyl cellulose.
When use carbomer time, expect weight average molecular weight be at least 700,000 those, preferred desired molecular weight be at least 1,200,000 those, most preferably desired molecular weight is at least about 2,500,000 those.Also the mixture of carbomer can be used herein.
In particularly preferred embodiments, carbomer is Synthalen PNC, Synthalen KP or its mixture.Be recited as high molecular and cross linked polyacrylate and identified by CAS 9063-87-0.The material of these types can from supplier as Sigma be purchased.
In another particularly preferred embodiment, the sodium carboxymethyl cellulose (SCMC) used is SCMC 9H.Be recited as the sodium salt of the cellulose derivative of the carboxymethyl with the hydroxyl being bonded to Glucopyranose. backbone monomer and identified by CAS 9004-32-4.It can obtain from supplier such as Alfa Chem.
Usually, described thickening agent forms 0.01 to about 10 % by weight, and more preferably 0.1 to 9 % by weight, the most preferably oral care composition of 1.5 to 8 % by weight, based on described composition total weight meter, comprises the four corner wherein contained.
When oral care composition of the present invention be toothpaste or gel time, its common viscosity is about 30,000 to 180,000 centipoise, preferably 60,000 to 170,000 centipoise, most preferably 65,000 to 165,000 centipoise.
In oral care composition of the present invention, preferably use suitable wetting agent, they comprise such as glycerol, Sorbitol, propylene glycol, dipropylene glycol, diglycerol, glyceryl triacetate, mineral oil, Polyethylene Glycol (preferred PEG-400), alkane glycol as butanediol and hexanediol, ethanol, pentanediol or its mixture.Preferred wetting agent is glycerol, Polyethylene Glycol, Sorbitol or its mixture.
Described wetting agent can described oral care composition weight 10 to 90% exist.More preferably, described carrier wetting agent forms 25 to 80 % by weight of described compositions, and most preferably 45 to 70%, based on described composition total weight meter, comprise the four corner wherein contained.
Oral care composition as herein described can comprise optional member conventional in this area.These compositions comprise antimicrobial, antiinflammatory, caries preventive agent, speckle buffer agent, fluorine source, vitamin, plant extract, desensitizer, antilithic, biomolecule, spice, protein material, antiseptic, opacifier (especially titanium dioxide), coloring agent, pH adjusting agent, sweeting agent, particulate abrasive, polymer, buffer agent and in order to the pH of buffer compositions and the salt of ionic strength and its mixture.Specific examples of such components usually and overall form described compositions be less than 20 % by weight, 0.0 to 15 % by weight of preferred described compositions, most preferably 0.01 to 12 % by weight, comprise the four corner wherein contained.
Oral care composition of the present invention can use in mineralising and/or the method that brightens again at the individual tooth that makes comprising the step that contacts with described oral care composition of one or more tooth that makes individual.
Described compositions is normally packed.With toothpaste or gel form, described compositions can be packaged in common plastics laminate, metal tube or single compartment allotter.Can dental surface be applied to by any physical means such as toothbrush, finger tip or be directly applied to sensitizing range by applicator.With liquid mouthwash form, described compositions can be packaged in bottle, pouch or other are easily in container.
Described compositions even also can be effective when oral hygiene routine every day for individual.Such as, described compositions can be brushed on tooth and/or in individual human mouth inner circumferential and enclose flushing.Described compositions can such as with the teeth contact time period of 1 second to 20 hours.More preferably, 10 seconds to 10 hours, also more preferably 30 seconds to 1 hour, most preferably 1 minute to 5 minutes.Described compositions can use every day, such as, used once, twice or three times every day by individual.
In preferred embodiments, described oral care composition be applied to tooth and do not apply phosphate to tooth (and non-natural is present in the phosphate in oral cavity).
The oral care composition comprising calcium silicate hydrate can by the manufacture of any method easily, but in preferred embodiments, the method manufacture of described oral care composition by comprising the steps:
I) silicate ion source is made to contact with calcium ion source with forming reactions mixture in an aqueous medium;
Ii) calcium silicate hydrate is reclaimed from reactant mixture;
Iii) described calcium silicate hydrate and physiologically acceptable carrier is made to merge.
In described reactant mixture, the amount of calcium source and silicate source can change to control CaO and SiO in final calcium silicate hydrate
2amount.Described reactant mixture is preferably with lower than 1:1, and more preferably less than 1:1.2, also more preferably 1:1.5 to 1:4, most preferably the atomic ratio (Ca:Si) of 1:1.7 to 1:3 comprises Ca and Si.
Silicate source is preferably water-soluble silicate, such as ammonium silicate, alkali silicate or its combination.More preferably, described silicate source is alkali silicate, such as sodium silicate, potassium silicate or its combination.
Calcium source can be such as soluble calcium salt, such as calcium halide, lime nitrate etc.But the present inventor finds to use insoluble or microsolubility calcium source to produce a kind of calcium silicate hydrate unexpectedly, it is easier than the calcium silicate hydrate being derived from solubility calcium source disperses.Therefore, preferably calcium ion source is selected from insoluble calcium source, microsolubility calcium source or its mixture.The example of microsolubility or insoluble calcium phosphate comprises calcium salt or its mixture of such as calcium hydroxide, calcium oxide, calcium acetate, calcium lactate, calcium gluconate, calcium carbonate, calcium sulfate, carboxymethylcellulose calcium, calcium alginate, citric acid.Most preferably, described calcium source is microsolubility calcium salt, particularly calcium hydroxide, calcium oxide or its mixture.
The pH of described reactant mixture preferably higher than pH 6.0 to guarantee that therefore solid silicic acid hydrate of calcium makes easy separation from described reactant mixture precipitation.The present inventor also has been found that the pH of described reactant mixture can affect the ability of calcium silicate hydrate mineralising dental tissue again.Therefore, preferably the pH of described reactant mixture is 8.0 to 12.5, more preferably 8.5 to 12.0.
The temperature of described reactant mixture can react for calcium source and silicate source any suitable temperature forming calcium silicate hydrate.But the present inventor has been found that if temperature controls in particular range, then can provide the calcium silicate hydrate be more easily dispersed in mouth care preparation.Preferably, the temperature of described reactant mixture is at least 10 DEG C, more preferably at least 15 DEG C, most preferably at least 20 DEG C.Have been found that described reaction temperature does not need height to obtaining calcium silicate hydrate.Usually, the reaction temperature of described reactant mixture not higher than 70 DEG C, more preferably no higher than 40 DEG C, even more preferably no higher than 35 DEG C, most preferably not higher than 30 DEG C.
Preferably, the described response time is at least 1 hour, more preferably at least 2 hours, most preferably 3 to 10 hours.
Step (ii) generally includes solid-liquid separation step.Such as, can by be selected from centrifugal, sedimentation, filtration, drying or its combination method be separated described calcium silicate hydrate from described reactant mixture.Then the solid silicic acid hydrate of calcium reclaimed from described reactant mixture can adopt solvent, particularly polar organic solvent (such as C
1-C
4alcohol) or aqueous solvent, more preferably aqueous solvent, most preferably water washing.
When making the calcium silicate hydrate experience drying steps of recovery, preferably baking temperature is not too high, because this can cause hydrate water to lose from this material.Therefore, the calcium silicate hydrate of preferably described recovery is not heated above the temperature of 400 DEG C, is not more preferably heated above the temperature of 300 DEG C, is not also more preferably heated above the temperature of 200 DEG C, is not most preferably heated above the temperature of 150 DEG C.
Step (iii) is usually directed to normal compound and blending constituent to prepare mouth care preparation, and wherein these class methods are that those skilled in the art know.
There is provided following examples to help to understand the present invention.There is provided embodiment and the scope of unrestricted claim.
Embodiment
embodiment 1
This embodiment is demonstrated compared to the deposition of the improvement of calcium silicate hydrate on dental tissue being purchased calcium silicates.
the preparation of calcium silicate hydrate powder
Calcium hydroxide and sodium silicate mixture is in deionized water used to prepare calcium silicate hydrate (CSH).Form initial Ca:Si than the mixture for 1:2.Mixture described in continuous stirring, remains on the temperature of 45 DEG C simultaneously.Hydrochloric acid is used to regulate the pH of described reactant mixture and be maintained at about 11.After stirring 5 hours, filter described reactant mixture and adopted water washing filter cake three times before again filtering.At 80 DEG C in stove dry cake 12 hours to obtain final CSH powder.
the sign of calcium silicate hydrate powder
The granularity using laser diffraction (Malvern Mastersizer 2000 & Malvern ZetaSizer Nano series) to measure CSH powder also finds the particle mean size with 355 nm.
Powder X-ray diffraction (XRD) figure of described material shown in Fig. 1.Peak is in the figure of semi-crystal be obvious at the described material of expression.
The low-angle XRD figure of described material shown in Fig. 2.Do not exist in the figure of mesopore in expression and there is no obvious peak.
Use thermogravimetry (TGA) the measurement quality loss adopting Netzsch TG instrument.At N
2in 30 to 900 DEG C, 10 are adopted under atmosphere
othe rate of heat addition of/min carries out TGA.Result is shown in Figure 3.These results show that described material comprises the about 19 wt% hydrate waters water of only removing at higher than 200 DEG C (namely can) and about 8 wt% physical bond water (water namely removed at 200 DEG C).
deposition and mineralising evaluation again
In order to evaluate the deposition on dental surface, with 1.0 g powder to the ratio mixed C SH powder of 10 ml water and water to prepare slurry.That is supplied by P.Q. company (Microcal ET) is purchased calcium silicates (CaSiO
3, CS) and as tester.
The Tooth-brushing device (Lion, Japan) being equipped with soft toothbrush is used to adopt fresh CSH-water slurry or CS-water slurry to scrub cattle enamel block.The load of toothbrush is 170 g +/-5 g, starts automatic brushing with the speed of 150 rpm.After scrubbing 1 minute and hatching again 1 minute in the slurry, by distilled water wash block teeth twice (2 × 20 ml).But, in the mouth cavity fluid (SOF) of simulation, soak block teeth under the condition of shaking in a water bath at 37 DEG C.Process described block teeth 14 times to brush teeth with twice simulation every day and carry out one week.
After process in a week, the SEM image on shooting enamel block surface.From SEM image clearly CSH provide than being purchased CS on tooth surfaces better and finer and close deposition.From corresponding cross-sectional SEM image, find out that the sample being purchased CS process does not have the layer formed over their surface, and the sample of CSH process illustrates the evidence forming new layer from the teeth outwards.Use the analysis of EDX (energy dissipation X-ray spectrum) to identify Si, Ca in new layer and P element, show that CSH deposition on tooth surfaces and induce biomineralization.Therefore, compared to being purchased CS, CSH improves deposition and remineralization efficacy again.
embodiment 2
This embodiment demonstration CaO and SiO
2relative quantity on the impact of calcium silicate hydrate properties.
Adopt the initial Ca:Si ratio that 2:1,1:1 are different with 1:2, use the method identical with embodiment 1 to prepare calcium silicate hydrate.
Mix with water separately with the calcium silicate hydrate with different initial Ca:Si ratios of the ratio of 1.0 g/10 ml by preparation.Adopt the single treatment of CSH-water slurry under brushing program in the same manner as in Example 1 after, the CSH with different initial Ca:Si ratios causes similar good and fine and close deposition on tooth surfaces, and the sem analysis as the enamel block by scrubbing represents.
Under the condition of shaking in a water bath, at 37 DEG C, the obtained calcium silicate hydrate powder with different initial Ca:Si ratios is immersed in SOF.After immersion 24 hours, powder for drying is characterized to detect the change of any composition by XRD.The XRD figure with the sample of the initial Ca:Si ratio of 2:1 and 1:1 illustrates the characteristic peak of calcium carbonate.For the figure of sample of initial Ca:Si ratio with 1:2, these illustrate the characteristic peak of hydroxyapatite, show that calcium silicate hydrate is under such conditions bioactive in SOF, and original position likely can be induced to form hydroxyapatite.
embodiment 3
This embodiment confirms that calcium Source Type is on the impact of calcium silicate hydrate properties.
originate in the preparation of the calcium silicate hydrate powder of lime nitrate
Lime nitrate and sodium silicate mixture is in deionized water used to prepare calcium silicate hydrate (CSH).Formed and there is initial Ca:Si than the mixture for 1:2.Mixture described in continuous stirring, under remaining on the temperature of 45 DEG C simultaneously.Hydrochloric acid is used to regulate the pH of described reactant mixture and be maintained at about 11.After stirring 5 hours, filter described reactant mixture, with washing with alcohol once, wash twice with water, then finally filter.At 80 DEG C in stove dry cake 12 hours to obtain final CSH powder.
originate in the preparation of the calcium silicate hydrate powder of calcium hydroxide
Prepare described CSH powder as described in example 1 above.
performance comparision
XRD result illustrates that the product being derived from lime nitrate is not pure CSH; And the product being derived from calcium hydroxide is substantially pure CSH really.In addition, powder size 417 nm being derived from lime nitrate after water and washing with alcohol process is still greater than powder size 355 nm being derived from calcium hydroxide only adopting water washing.Prepare CSH from lime nitrate and substitute water washing (as what complete for the powder being derived from calcium hydroxide) by washing with alcohol and cause even larger granule.
embodiment 4
PH is on the impact of calcium silicate hydrate properties in this embodiment demonstration reaction.
The method identical with embodiment 1 is used to prepare described calcium silicate hydrate, except pH remains on the value of 9.5,11.7 or 13.1.
Under the ratio of 1.0 g/10 ml, the CSH obtained under different pH is mixed with water.Adopt the single treatment of CSH-water slurry under brushing program in the same manner as in Example 1 after, the CSH obtained under different pH causes similar good and fine and close deposition on tooth surfaces, as confirmed by SEM.
Under the condition of shaking in a water bath, at 37 DEG C, obtained calcium silicate hydrate powder is immersed in SOF under different pH.After immersion 24 hours, powder for drying is characterized to test composition change by XRD.The sample prepared under the pH of 9.5 and 11.7 illustrates the trend changing into hydroxyapatite, shows that calcium silicate hydrate is with this understanding bioactive in SOF, and original position likely can be induced to form hydroxyapatite.For the sample prepared under the pH of about 13.1, calcium silicate hydrate does not change into hydroxyapatite in SOF, and the CSH showing to be derived from relatively high pH has biological activity lower in SOF.
embodiment 5
This embodiment demonstration response time and temperature are on the impact of calcium silicate hydrate properties.
Use method similar to Example 1 to prepare calcium silicate hydrate, except reaction temperature is room temperature (25 DEG C) but not 45 DEG C, the response time is 2 hours and 5 hours.Find that the CSH powder obtained at different temperatures has similar deposition well on tooth surfaces.But the powder obtained under the condition that room temperature and 2 hours are stirred is not pure CSH, also has other phases such as calcium carbonate.The powder obtained under room temperature (25 DEG C) or 45 DEG C and the stirring condition of 5 hours is pure, and causes the CSH of the independent feature obtained by XRD analysis to scheme.Therefore, the increase in response time improves the purity of CSH powder.
embodiment 6
This embodiment demonstration phosphate is on the impact of the deposition of calcium silicate hydrate.
The method identical with embodiment 1 is used to prepare calcium silicate hydrate.In order to evaluate the impact that phosphatic existence deposits on tooth surfaces on CSH, prepare CSH-phosphate slurry and CSH-water slurry respectively.By with the ratio rapid mixing 1M K of 1.5:10:1 (ml:ml:g)
2hPO
4, water and CSH prepare described CSH-phosphate slurry.By preparing described CSH-water slurry with the ratio mixed C SH of 1.0g/10ml and water.Fresh slurry process block teeth are adopted under the program identical with embodiment 1.Process described block teeth 14 times to brush teeth with twice simulation every day and carry out one week.Use is purchased CS thing in contrast.By mixing 1M K with the ratio of 1.5:10:1 (ml:ml:g)
2hPO
4, water and CS prepare described CS-phosphate slurry.
After process in a week, have phosphate or do not have phosphatic CSH to provide than being purchased CS deposition better and finer and close on tooth surfaces, the SEM image as block teeth surface confirms.Si, Ca in the layer that EDX analysis and characterization is newly formed and P element.Therefore, and be purchased compared with CS, CSH has deposition and the remineralization efficacy again of raising, there is phosphate and has little impact on CSH deposition effect on tooth surfaces.
embodiment 7
This embodiment demonstrates according to toothpaste preparation of the present invention.
Anhydrous and moisture phase dentifrice preparation can as shown in table 1ly be prepared.
Table 1
| Component (%w/w) | Anhydrous toothpaste | Aqueous dentifrice |
| Glycerol | To 100 | --- |
| PEG 400 | 10.50 | --- |
| Spice | 1.20 | 1.00 |
| Tertiary sodium phosphate | 3.80 | --- |
| Calcium silicate hydrate * | 15.00 | 30.00 |
| Sodium monofluorophosphate | 1.11 | 1.11 |
| Sweeting agent | 0.20 | 0.20 |
| Biphosphate list sodium | 3.20 | --- |
| PEG 3000 | 1.75 | --- |
| Pigment | 0.05 | --- |
| Abrasive silica | 7.00 | --- |
| Sodium lauryl sulfate | 2.00 | 2.20 |
| Sorbitol (70%) | --- | 20.0 |
| Water | --- | To 100 |
| Benz. alcohol | --- | 0.50 |
| Potassium nitrate | --- | 0.50 |
| Thickening silica | --- | 1.00 |
| SCMC | --- | 0.30 |
* from the * CSH powder of embodiment 1.
Claims (17)
1. an oral care composition, it comprises:
A) calcium silicate hydrate, its comprise account for this calcium silicate hydrate weight 20 to 70% SiO
2; With
B) physiologically acceptable carrier, it comprises wetting agent, surfactant, thickening agent or its mixture.
2. oral care composition as claimed in claim 1, wherein said calcium silicate hydrate is microgranular.
3. oral care composition as claimed in claim 1 or claim 2, wherein said calcium silicate hydrate comprise account for described calcium silicate hydrate weight 5 to 40% the hydrate water of amount.
4. oral care composition as claimed in aforementioned any one of claim, wherein said calcium silicate hydrate comprise account for described calcium silicate hydrate weight 5 to 40% CaO.
5., as oral care composition claimed in aforementioned any one of claim, wherein said calcium silicate hydrate is not many mesopores.
6. as oral care composition claimed in aforementioned any one of claim, wherein said calcium silicate hydrate is at least part of crystallization.
7., as oral care composition claimed in aforementioned any one of claim, wherein said compositions is dentifrice, preferred toothpaste or collutory.
8., as oral care composition claimed in aforementioned any one of claim, wherein said calcium silicate hydrate comprises Ca and Si of the atomic ratio of 1:1.5 to 1:3.
9., as oral care composition claimed in aforementioned any one of claim, wherein said oral care composition is single-phase composite and is substantially free of phosphate.
10. make tooth mineralising and/or the method that brightens again of individual, it comprises and applies the step of the claimed oral care composition of any one of claim 1 to 9 to one or more teeth of individual.
11. methods as claimed in claim 10, are wherein applied to tooth to when tooth by oral care composition when not applying phosphate.
12. 1 kinds of methods preparing oral care composition, it comprises the steps:
I) silicate ion source is made to contact with calcium ion source with forming reactions mixture in an aqueous medium;
Ii) calcium silicate hydrate is reclaimed from reactant mixture;
Iii) described calcium silicate hydrate and physiologically acceptable carrier is made to merge.
13. methods as claimed in claim 12, wherein forming Ca:Si atomic ratio is the reactant mixture of 1:1.5 to 1:3.
14. as claim 12 or the claimed method of claim 13, and wherein silicate ion source is water-soluble silicate, preferred as alkali silicate.
15. methods as claimed in any one of claim 12 to 14, wherein said calcium ion source is selected from insoluble calcium phosphate, microsolubility calcium salt or its mixture.
16. methods as claimed in claim 15, wherein said calcium ion source is calcium hydroxide and/or calcium oxide.
17. methods as claimed in any one of claim 12 to 16, wherein said reactant mixture has the pH of 8.0 to 12.5.
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| CN2012082837 | 2012-10-12 | ||
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| EP12193013.5 | 2012-11-16 | ||
| PCT/EP2013/069714 WO2014056713A2 (en) | 2012-10-12 | 2013-09-23 | Oral care composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110465260A (en) * | 2019-07-12 | 2019-11-19 | 北京工业大学 | A kind of hydrated calcium silicate and preparation method thereof removing Cu in waste water ion |
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| US4486404A (en) * | 1982-11-06 | 1984-12-04 | Blendax-Werke R. Schneider Gmbh & Co. | Tooth and mouth care agents |
| CN1377252A (en) * | 1999-08-05 | 2002-10-30 | 布洛克医药公司 | Composition for restoring defects in calcified tissues |
| US20060110306A1 (en) * | 2004-04-06 | 2006-05-25 | American Dental Association Foundation | Nanostructured bioactive materials prepared by dual nozzle spray drying techniques |
| CN101600442A (en) * | 2006-12-05 | 2009-12-09 | 荷兰联合利华有限公司 | Oral care product |
| US20120141588A1 (en) * | 2010-12-07 | 2012-06-07 | Colgate-Palmolive Company | Dentifrice compositions containing calcium silicate and a basic amino acid |
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| US4486404A (en) * | 1982-11-06 | 1984-12-04 | Blendax-Werke R. Schneider Gmbh & Co. | Tooth and mouth care agents |
| CN1377252A (en) * | 1999-08-05 | 2002-10-30 | 布洛克医药公司 | Composition for restoring defects in calcified tissues |
| US20060110306A1 (en) * | 2004-04-06 | 2006-05-25 | American Dental Association Foundation | Nanostructured bioactive materials prepared by dual nozzle spray drying techniques |
| CN101600442A (en) * | 2006-12-05 | 2009-12-09 | 荷兰联合利华有限公司 | Oral care product |
| US20120141588A1 (en) * | 2010-12-07 | 2012-06-07 | Colgate-Palmolive Company | Dentifrice compositions containing calcium silicate and a basic amino acid |
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| CN110465260A (en) * | 2019-07-12 | 2019-11-19 | 北京工业大学 | A kind of hydrated calcium silicate and preparation method thereof removing Cu in waste water ion |
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