CN101351243B - Dentifrices comprising biogenic silica materials - Google Patents

Abstract

Unique dentifrices comprising unique abrasive biogenic silica materials are provided. Such compositions exhibit excellent abrasive characteristics, either alone, or in combination with other types of abrasives. In such combinations (with precipitated silica materials, as one example), simultaneously high pellicle film cleaning properties and . moderate dentin abrasion levels are possible in order to accord the user a dentifrice that effectively cleans tooth surfaces without detrimentally abrading such surfaces, even at low levels of such biogenic silica additives. Such biogenic silica particles thus surprisingly accord beneficial properties within dentifrice compositions. Encompassed within this invention is the method of utilizing such biogenic silica products within dentifrices, either as the majority abrasive component, or in combination with any other type of commonly used abrasive material.

Description

The dentifrice that contains biogenic silica materials

Invention field

The present invention relates to contain unique dentifrice of unique abrasiveness biogenic silica materials.Single with or during with other type abrasiveness coupling, this compositions has good nonferromagnetic substance.This class combination (for example the earth silicon material with precipitation makes up) can realize efficient Mycoderma sanitary characteristics and medium dentin abrasion level simultaneously, give a kind of effective teeth surfaces of user but the dentifrice of dental surface that do not wear and tear nocuously, even contain low-level biogenic silica additive.Therefore, this class biogenic silica granule gives Dentrifice composition useful performance surprisingly.Method of the present invention is included in the dentifrice and adopts this class biogenic silica product, or as main abrasive component or with the method for the grinding-material coupling commonly used of any other type.

Background technology

Usually comprise grinding-material in the conventional dentifrice composition, in order to remove the various deposits on the dental surface, comprise Mycoderma.The Mycoderma adhesion firmly usually contains brown or yellow substance, and this makes tooth discoloration.Though cleaning teeth is very important, grinding can not be too violent and damage tooth.It is desirable to, the grinding-material that effectively cleans the teeth can at utmost be removed Mycoderma, and is minimum to wearing and tearing and the damage of hard dental tissue simultaneously.Therefore, the performance of dentifrice should be extremely sensitive to the degree of wear of grinding composition and causing.The grinding cleaning material of dry powder form of normally add flowing constitutes dentifrice composition, perhaps before the preparation dentifrice or during add the polishing agent of the dry powder form that flows and make it to disperse.And in recent years, this grinding agent serosity that provides is conducive to store, transport and join in the target dentifrice formulation.

Synthetic low structure silica is effective as grinding agent, has hypotoxicity feature and compatible with other dentifrice composition such as sodium fluoride, thereby this material has been used for this purpose.During the synthetic silica product of preparation, purpose is to obtain maximum cleaning performance is provided but to the hard minimum silica product of dental surface influence.Can the dentistry researcher give more sustained attention and identify the grinding-material that satisfies these purposes.

With regard to compatible with active component, these components must be the compositions that can be used as in the Dentrifice composition, the rheologic behavio(u)r (its function and aesthetic requirement being changed by user) that can change said preparation produces the dentifrice of dosage forms, and the amount of all components existence simultaneously should have cost benefit and enough grinding and clean-up performances.Dentifrice and other similar pastes must have suitable rheological properties, constitute (viscosity build), orthostatic (stand up), the sagging property (brush sag) of toothbrush etc. as viscosity, to improve control.In toothpaste preparation, for example, the stable paste that can satisfy many consumer demands need be provided, and these demands include but not limited to: as the paste of dimensional stability by pressure (being squeezing tube) from container (as flexible pipe), extrude remove recover behind the pressure before state ability, easily transfer to the ability that can not go out from the afterflow of flexible pipe relaying after shifting on the head toothbrushes, have the tendency of the dimensional stability kept and have (have at least and be beneficial to user) attractive in appearance suitable mouthfeel when target tooth is brushed teeth when being applied to for before brushing teeth.

Usually, dentifrice mainly is made up of one or more wetting agents (as Sorbitol, glycerol, Polyethylene Glycol etc.), in order to suspend suitably and the delivery of oral care product, suitable mechanical cleaning is with the grinding agent that polishes the object tooth (for example silicon dioxide that normally precipitates), water and other active component (if any the fluorochemical of dental caries performance) and provide other function as producing other component of foam and sensory appeal.By suitably selecting and utilizing thickening agent (as aquation silicon dioxide, hydrocolloid, natural gum etc.) suitable rheologic behavio(u)r can be given this dentifrice, suitably hold these important wetting agents, grinding agent and anti-dental caries composition to form the proper supporting network.

Dentifrice composition has adopted or has described many water-fast abrasiveness polishing agents.These grinding and polishing agent comprise natural and synthetic grinding particulate material.Usually the synthetic grinding and polishing agent known to comprises unbodied precipitated silica product and silica gel, and the calcium carbonate (PCC) of precipitation.Other grinding and polishing agent that can be used for dentifrice comprises Chalk, magnesium carbonate, calcium hydrogen phosphate and its dihydrate form, calcium pyrophosphate, Zirconium orthosilicate., potassium metaphosphate, magnesium orthophosphate, tricalcium phosphate, perlite etc.

Specifically and since the low structure silica product of the synthetic precipitation that produces have cleaning capacity, comparatively safe and with the compatibility of commonly used clean the teeth composition such as wetting agent, thickening agent, flavoring agent, anti-caries agent etc., used as the abrasive component in the dentifrice formulation.As everyone knows, synthetic precipitated silica produces usually by the following method: tending to interosculate in the initial primary particles that forms forms a plurality of aggregations (being the discreteness bunch collection of primary particles) but is not gathered under the condition of three dimensional gel structure by adding mineral acid and/or sour gas, makes amorphous silica in the solubility alkalescence silicate go stable and is precipitated out from solution.Aqueous components by filtration, washing and drying steps and reactant mixture is separated and obtains precipitation, and then, this dry products of mechanical lapping provides granularity and the suitable product of particle size distribution.

Usually can adopt methods such as spray drying, nozzle drying (as water tower or fountain), wheeled drying (wheeldrying), rapid draing, the wheeled drying of rotation (rotary wheel drying), baking oven/fluid bed drying to finish the silicon dioxide dry run.

Because to a certain extent, some conventional grinding-material is subjected at utmost cleaning the restriction relevant with at utmost reducing dentin abrasion, rather than whole production technology, comprises with the raw material transportation, buys and the finally restriction of modification relevant issues.This class raw material comprises silica sand and mineral acid (as sulphuric acid), and the transportation of himself, use, purification, storage and final Waste disposal are had any problem.Though these abrasive product finished products have good dental treatment effect, need to develop for making and/or be incorporated into the novel dental grinding agent that complexity is lower in the final preparation (with its dentifrice) always.

And the ability that tooth grinding and sanitary characteristics were optimized is only limited to usually controls improvement to the structure of the various precipitated silica components that are used for this purpose.This area to the improvement example that cleans the teeth the precipitated silica structure used referring to the U.S. Patent number 3,967,563,3,988 below with reference to document: Wason, 162,4,420,312 and 4, the U.S. Patent number 4,992 of 122,161, Aldcroft etc., 251 and the U.S. Patent number 5 of 5,035,879, Newton etc., 098,695 and the U.S. Patent number 5,891 of McGill etc., 421 and 5,419,888.U.S. Patent number 5,647,903, the DeWoIf of the improvement of silica gel: McGill etc. have also been described, the U.S. Patent number 3,538,230 of the U.S. Patent number 4,303,641 of II etc., the U.S. Patent number 4,153,680 of Seybert and Pader etc. in the following document.These disclosures have been described, and the improvement of these earth silicon materials has been improved the Mycoderma cleaning capacity of dentifrice and reduced dentifrice to Dentinal wear levels.Yet these general improvement can not produce the delivery performance of good level, need the not commensurability independent material of dentifrice manufacturer adding and other similar components to obtain cleaning and the abrasive characteristic of varying level.In order to compensate this limitation, can combination that attempt various silicon dioxide reach varying level.This silicon dioxide combination comprises the combination of different grain size and particular table area (silica dioxide granule), U.S. Patent number 3,577,521 referring to Karlheinz Scheller etc., the U.S. Patent number 4 of Macyarea etc., the U.S. Patent number 5 of 618,488, Muhlemann, 124,143 and the U.S. Patent number 4,632,826 of Ploger etc.Yet these dentifrice that obtain can not provide grinding and the efficient Mycoderma cleaning capacity of desired level simultaneously.

Carried out another time and attempted providing precipitated silica with some structure and the physical mixture of silica gel, specifically referring to the United States Patent (USP) 5,658,553 of Rice.Usually the viewpoint of accepting is: silica gel particle has the edge, therefore in theory, compares with precipitated silica (even low structure type), and silica gel can be with surface abrasion to darker degree.Therefore, this mixtures of material that the present invention provides together can be improved the wearing and tearing of controlling this moment, but wear levels is higher, thereby its Mycoderma cleaning capacity is higher than and singly uses precipitated silica.In this disclosure, proved that the silica gel that mixes and the precipitated silica that produce respectively can improve PCR and RDA level, but the silicon dioxide that provides in the past obviously is provided the control to low abrasive characteristic, and the silicon dioxide that provided in the past has very high PCR effect.Unfortunately, a though step in these results' the correct developing direction really, but still be starved of the silicon dioxide that has sufficiently high Mycoderma clean-up performance, has low radial (radioactive) dentin abrasion feature simultaneously grinding agent that cleans the teeth is provided, to go under the Dentinal situation except Mycoderma not destroying.In fact, need PCR level and RDA level to be significantly higher than the grinding agent that the silicon dioxide industry that cleans the teeth provided in the past but the product that wearing and tearing reduce.Also have, the patent of Rice just has the initial step of required abrasive characteristic product to exploitation.A kind of mode is to utilize the combination advantage of multi-form physical mixed silicon dioxide, but the Mycoderma clean level is very high and the dentin abrasion degree is low to moderate medium form, and this is that present toothpaste industry does not still have.Therefore, require the lower dentifrice of production complexity can adopt abrasive silica now, can be used as the adding component (drop-in component) in the dentifrice that has measurable rheologic behavio(u)r and/or improve performance, this abrasive silica compatible with other standard dentifrice components (the tooth Grinding Quality is outstanding), may reduce industrial manufacturing cost and improve the Mycoderma cleaning capacity, abrasive levels with customization may be the industrial useful especially improvement of dentifrice.Yet point out that up to now and again this improvement does not occur.

Advantage of the present invention and general introduction

Find at present, add some biogenic silica in the dentifrice, namely derived from the silicon dioxide of rice husk, as wherein independent abrasive component or as with the auxiliary additive of other grinding-material coupling, efficient tooth grinding effect can be provided.Special advantage is, with regard to the overall Grinding Quality (requirement) of polishing compounds, can be by the auxiliary combination of adding polishing compounds of concrete selection and they with respect to the derive ratio of dioxide-containing silica of rice husk in the target dentifrice, can customize the dentifrice with required Mycoderma clean-up performance (PCR) and ratio of radial dentin abrasion (RDA).

Specifically; except a series of in demand low radial dentin abrasion effects are provided; as if the combination of the silicon dioxide that rice husk is derived and other dental abrasive (as the silicon dioxide of precipitation, calcium carbonate etc.) may provide high-caliber Mycoderma clean-up performance; and the optimization cleaning effectiveness provides bigger grinding protection border for the end user simultaneously.

Recognize, use this rice husk silica product of deriving that surprising effective nonferromagnetic substance can be provided in the dentifrice.During with other known dental abrasive coupling, the result is unexpected, because this coupling can effectively be cleaned Mycoderma when realizing low-level (but still effectively) wearing and tearing.Find that total result is that the overall grinding agent of this class may have (hone) Mycoderma cleaning and radial dentin abrasion performance.This ability has satisfied some demand in the dentifrice industry, because might find Mycoderma cleaning (PCR) performance height, radial dentin abrasion (RDA) is lower simultaneously grinding agent or grinding agent combination long after.As if along with certain abrasive component in the dentifrice increases to about 20 weight % (all grinding agents), the raising of these features can reach platform (PCR: RDA ratio is increased to very near 1.0 and is astonishing).Yet when surpassing this content, this ratio may significantly reduce, and when certain abrasive component proportion surpasses 20 weight % in the dentifrice, as if in most of the cases this ratio is reduced to and is lower than 0.80.And when the silicon dioxide of deriving when rice husk was the grinding agent of unique existence, this ratio reduced lowlyer, is lower than 0.71.Yet in every kind, as if this PCR: RDA ratio also depends on cleaning and the abrasive levels of other wherein contained grinding agent.

All umbers used herein, percent and ratio all represent with weight, except as otherwise noted.It is for referencial use that all lists of references that this paper is quoted are included this paper in.

Therefore, an advantage of the invention is and provide the silicon dioxide of deriving with rice husk as the equal very easy dental abrasive of unique grinding-material thereby preparation and production.Another advantage of the present invention is to be set to desired level according to the addition of rice husk silicon dioxide and other grinding agent PCR and the RDA ratio of simultaneous selected amount, to be fit to specific end user's needs.Advantage of the present invention also has, and provides contain rice husk and derive silicon dioxide as the dentifrice of grinding-material a kind of comprising, and the PCR that this dentifrice has: the RDA ratio range depends on the content of this type abrasive material.

Therefore, the present invention includes and contain the derive dentifrice of silicon dioxide grinding-material of rice husk, this dentifrice is optional to comprise other tooth abrasive component, the PCR of described dentifrice: RDA ratio great majority are 0.70; Perhaps, this ratio is 0.70-0.80; Perhaps, this ratio surpasses 0.80.

Usually, in order to the synthetic precipitated silica of below method preparation: the alkali metal silicate solutions with dilution under the condition that can not be gathered into colloidal sol and gel mixes with water-soluble inorganic strong acid, stirs, and leaches the silicon dioxide of precipitation then.Wash the precipitation that obtains then, the dry desired particle size that also is ground to.An example can be referring to the U.S. Patent number 5,891,421 of McGill etc.

Preferred biogenic silica materials is derived from rice husk, and as United States Patent (USP) 6,406,678 is described.The production technology of this class silica product has fully been described in this patent (it is for referencial use to include this paper in).Therefore, the description of this class production technology is referring to this list of references, and is as described below:

Though because growth geographic area and rice strain is different, the dioxide-containing silica of rice husk may be different, the dioxide-containing silica of rice husk is generally the 13-15% of dry weight.To go up substantially all be in demand amorphous form to contained silicon dioxide in most of biogenetic derivation materials such as the rice husk, but in biogenetic derivation substrate, find to have many other impurity, particularly generate longer-chain hydrocarbons such as lignin and cellulose (containing many inorganic salts such as calcium salt, magnesium salt etc.) and their chemical compound.Other impurity (mainly being hydro carbons) of finding in silicon dioxide and the biogenetic derivation material must be separated during preparation rice husk silicon dioxide.After removing hydrocarbons, the remaining small amounts of inorganic salt of being not difficult to remove substantially.End product is the high-purity amorphous silica white powder that grinds.

First optional step that produces rice husk silicon dioxide can be the cleaning rice husk.This step generally comprises the screening rice husk and removes stem, soil block, leaf and other parts, and water then namely contains the solution washing rice husk of surfactant, to improve the soakage of rice husk.Phase credit aqueous surfactant solution washing rice husk can accelerate the absorption of next step oxidizing solution, believes by the meticulous process that grinds rice husk of pulverizing, grating or other conventional method also can reach this purpose.Therefore, in this production decision, the screening rice husk with surfactant solution washing, meticulously grinds to accelerate this process.Yet it should be noted that these steps are optional, can directly from rice husk, extract high-purity amorphous silica without these steps, but following steps may increase process time.

After randomly cleaning and grinding rice husk, an optional step is that their are immersed in the water that improves temperature.Rice husk immersed in the water preferably at high temperature carry out, thereby remove various soluble impurities, and increase hole (they are easier to by the infiltration of the oxidizing solution of next step) in the rice husk, also can make the contained lignin of rice husk and cellulose that some beneficially alterings take place.Observe, with steeping rice husk 12 hours or can accelerate subsequent step for more time near the water logging of boiling point, be about to rice husk and immerse in the aqueous oxidizing to reduce organic step in the rice husk.

First of this rice husk silicon dioxide production decision must step be that rice husk is immersed in the aqueous solution that contains the oxidisability solute to reduce the Organic substance in the rice husk.The present invention considers that the material of any number finishes this step, these materials comprise many chlorates, perchlorate, nitrate, permanganate and some peroxide (as Fenton reagent (Fenton ' s reagent)), but they are not preferred.Peracetic acid is preferred oxidisability solute, because its residue is easy to remove in the last optional step of this technology.Yet hydrogen peroxide is most preferred oxidant, because it only produces water after consuming.If the process of processing rice husk does not have full consumption to fall peroxide, as the normal conditions finding, for guaranteeing to have subdued the Organic substance in the rice husk fully, remaining oxygen spontaneity at short notice overflows, and can accelerate this process by heating, mechanical oscillation, electrolysis or various other any means known.Therefore, technology described herein is the technology very friendly to environment.

The predose of the hydrogen peroxide of the preferred embodiment for the present invention (contained in the aqueous solution) is: every kilogram of about 0.1 mole of hydrogen peroxide of rice husk (about 3.4 gram hydrogen peroxide).The temperature that it should be noted that this solution of raising can be accelerated it to the effect of rice husk.Discovery is in full force and effect at 90-100 ℃ of scope 6-8 hour with the temperature maintenance of described solution.Use and need the working pressure container when surpassing 100 ℃ temperature.Though can or more reduce under the low temperature in room temperature at least, should notice that the temperature reduction can increase index and reduce the required time.Therefore, though considered that this situation is not preferred.The predose of hydrogen peroxide can significantly reduce, and just has to monitor to guarantee that at least some unreacted hydrogen peroxide are retained in the enough time in the solution during reducing, in order to reduce the Organic substance in the rice husk as required.

After above-mentioned minimizing step, water thoroughly washs rice husk, and preferred dry rice husk to water content is 10 weight % or lower then.Application of pure water wash rice husk (if doing like this), as with ferrum or the low-down deionized water of content of beary metal or distilled water, drip washing water itself can not mix in the silicon dioxide objectionable at least like this.

Can finish drying by any conventional means, but preferably use hot-air dry, because method as herein described obtains origin of heat easily.After reducing the Organic substance in the rice husk, preferably drip washing and drying, " burnings " rice husk (in the presence of oxygen, heating to burn or oxidation) then as mentioned above.The preferred range of burning rice husk is about 500-950 ℃.Be starkly lower than under the temperature of this scope, expending the carbon-containing impurities complete oxidation in chien shih rice husk when too much, some temperature may not be finished oxidation.Be much higher than under the temperature of this scope, progressively increasing because impurity, particularly carbon-containing impurities selective oxidation heat release produce the risk of focus, beginning to change some silicon dioxide into undesired crystal form by amorphous form.

As mentioned above, high-temperature oxydation rice husk in the presence of oxygen-containing gas.In order to guarantee all rice husks of abundant oxidation, generally place them in the thin bed top ventilating air.Under about 600 ℃, the quick oxidation of rice husk when reaching temperature set-point to rice husk, is completely oxidized to meticulous white amorphous silica in air, and it is residual that do not observe carbon this moment.

Because silicon dioxide is stable, porous and insoluble in water and acid (except fluohydric acid gas), further use various acid and other solution washing, drip washing, flushing, with residual particles impurity after the removal oxidation, as calcium compounds.

The silicon dioxide abrasive composition that rice husk of the present invention is derived is the oral cleaning composition goods, as the instant additive in dentifrice, the toothpaste etc., is especially suitable for use as the raw material of toothpaste production technology.If with other grinding agent (as J.M. Huber Corp. (J.M.Huber Corporation) with trade name ZEODENT

Any product that provides) coupling, can add this grinding agent of any amount, but usually for higher PCR: RDA ratio (surpassing 0.80), addition is at most 20% of grinding agent gross weight, and for lower ratio (0.70-0.80), addition can surpass 20%, at the most 50 weight %, ratio was less than 0.70 o'clock, and rice husk is derived silica volume above 50 weight %.

The silicon dioxide abrasiveness compositions that rice husk of the present invention is derived the detergent components that provides in the dentifrice composition of the present invention is provided uses separately, but at least for the material of abrasive power type, some consumers contour RDA level in may not accepting.Therefore, may preferred composition material of the present invention in the suitable dentifrice formulation and the combination of other grinding agent physical mixed, with acquisition target dentifrice performance, and reach the grinding effect of required protection level.The grinding agent additive that therefore, can have any amount of other general type in the dentifrice of the present invention.Other this abrasive grains comprises such as but not limited to the calcium carbonate of precipitation (PCC), the calcium carbonate (GCC) that grinds, dicalcium phosphate or its dihydrate, silica gel (itself and any structure), amorphous sediment silicon dioxide (itself and any structure), perlite, titanium dioxide, calcium pyrophosphate, hydrated alumina, the calcine aluminium oxide, insoluble Polymeric sodium metaphosphate., insoluble potassium metaphosphate, insoluble magnesium carbonate, Zirconium orthosilicate., aluminium silicate etc., if desired, they can be added in the required abrasive composition polishing feature with customization target formulation (as dentifrice etc.).

(they are combinations of independent rice husk silicon dioxide or rice husk silicon dioxide and other grinding-material to grinding agent, when as mentioned above) mixing dentifrice composition, the level of its existence is about 5-50 weight %, is more preferably 10-35 weight %, especially when dentifrice is toothpaste.The whole dentifrice or the oral cavity cleaning preparation that mix abrasive composition of the present invention can comprise following possible composition easily, and its relative quantity is (all amounts all are weight %) as follows:

The dentifrice prescription

Component content

Liquid-carrier:

Wetting agent (total amount) 5-70

Deionized water 5-70

Binding agent 0.5-2.0

Anti-caries agent 0.1-2.0

Chelating agen 0.4-10

Silicon dioxide thickening agents ^*3-15

Surfactant 0.5-2.5

Grinding agent 10-50

Sweeting agent＜1.0

Coloring agent＜1.0

Flavoring agent＜5.0

Antiseptic＜0.5

In addition, as mentioned above, grinding agent of the present invention can with other grinding-material coupling, other grinding-material for example comprises: other suitable grinding-material that the calcium carbonate of the silicon dioxide of precipitation, silica gel, dicalcium phosphate, Tri-Compress, calcium metasilicate, calcium pyrophosphate, aluminium oxide, calcine aluminium oxide, aluminium silicate, precipitation and grinding, Chalk, bentonite, graininess thermosetting resin and those of ordinary skills are known.

Except described abrasive component, dentifrice also can contain one or more sense organ reinforcing agents (organoleptic enhancing agent).The sense organ reinforcing agent comprises wetting agent, sweeting agent, surfactant, flavoring agent, coloring agent and thickening agent (being also referred to as binding agent, natural gum or stabilizing agent sometimes).

Be dentifrice adding machine somesthesia or " mouthfeel quality " and prevent the dentifrice drying with wetting agent.Suitable wetting agent comprises Polyethylene Glycol (various different molecular weight), propylene glycol, glycerol, erithritol, xylitol, Sorbitol, mannitol, lactose and hydrogenated starch hydrolysate, and the mixture of these chemical compounds.The general content of wetting agent is about the 20-30 weight % of dentifrice composition.

Sweeting agent can be added dentifrice composition, so that product has pleasant taste.Suitable sweeting agent comprises glucide (saccharin sodium, potassium saccharin or Calcium o-benzolsulfimide), cyclamate (sodium salt, potassium salt or calcium salt), acesulfame potassium, thaumatin, neohesperidin dihydrochalcone (neohisperidin dihydrochalcone), the glycyrrhizin of ammonification, dextrose, levulose, sucrose, mannose, and glucose.

Said composition adopts surfactant in the present composition, so that more can be accepted in beauty treatment.Surfactant is preferably and makes said composition have the cleaning material of cleaning and foam performance.Suitable surfactant is the anion of safe and effective amount; cation; nonionic; amphion; both sexes and beet alkali surface activator; as sodium lauryl sulphate; dodecylbenzene sodium sulfonate; Hamposyl L; Hamposyl M; palmitoyl sarcosine; the alkali metal salts or ammonium salt of hard ester acylsarcosine and N-Oleoylsarcosine; polyoxyethylene sorbitan monostearate; isostearate and laurate; dodecylthiopropionic acid sodium; the N-Hamposyl L; the N-lauroyl; the sodium salt of N-nutmeg acyl or N-palmitoyl sarcosine; potassium salt and ethanolamine salt; the polyethylene oxide condensation compound of alkylphenol; cocamidopropyl betaine; lauroyl amido CAB, palmityl betanin etc.Sodium lauryl sulphate is preferred surfactants.The content of surfactant generally is about 0.1-15 weight % in the oral care composition of the present invention, preferably is about 0.3-5 weight %, according to appointment 0.3-2 weight %.

Randomly, flavoring agent can be added dentifrice composition.Suitable flavoring agent includes but not limited to: this flavoring agent chemical compound of other of wintergreen oil, Oleum menthae, Oleum Menthae Rotundifoliae, Sassafras oil and Oleum Caryophylli, Cortex cinnamomi japonici (Ramulus Cinnamomi), trans-anethole, menthol, thymol, eugenol, eucalyptole, Fructus Citri Limoniae, Fructus Citri junoris and interpolation fruity, spice flavor.From chemically, these flavoring agents are made up of aldehyde, ketone, ester, phenol, acid and aliphatic alcohol, aromatic alcohol and other pure mixture.

Can add coloring agent to improve the aesthetic appearance of product.Suitable coloring agent is selected from the coloring agent that corresponding management authorities such as FDA and European food and medicine instruct authorities' approval listed in the catalogue, comprises pigment such as TiO ₂And coloring agent such as FD﹠amp; C and D﹠amp; The C dyestuff.

Thickening agent can be used for dentifrice composition of the present invention provides and stablizes toothpaste and prevent the gel-like structure that is separated.Suitable thickening comprises: silicon dioxide thickening agents; Starch; The glycerin of starch; Natural gum is as karaya (karaya), gum tragacanth, Radix Acaciae senegalis, Ficus elastica, Radix Acaciae senegalis, xanthan gum, guar gum and cellulose gum; Aluminium-magnesium silicate (Veegum); Carageen polysaccharide; Sodium alginate; Agar-agar; Pectin; Gelatin; Cellulosic cpd such as cellulose, carboxymethyl cellulose, hydroxyethyl-cellulose, hydroxypropyl cellulose, hydroxy methocel, hydroxymethyl carboxypropyl cellulose, methylcellulose, ethyl cellulose and sulfate cellulose; Natural and synthetic clay such as Strese Hofmann's hectorite. (hectorite) clay; And the mixture of these chemical compounds.The general content of thickening agent or binding agent is about the 0-15 weight % of dentifrice composition.

Randomly, therapeutic agent can be used for the present composition, with prevention and treatment dental caries, periodontal disease and temperature sensitivity.The example of therapeutic agent is (but being not limited to) fluorine source chemical compound, as sodium fluoride, sodium monofluorophosphate, single fluorophosphoric acid potassium, stannous fluoride, potassium fluoride, prodan, ammonium fluosilicate etc.; Condensed phosphate is as tetrasodium pyrophosphate, tetrapotassium pyrophosphate, Sodium Acid Pyrophosphate, pyrophosphoric acid one hydrogen trisodium; Tripolyphosphate, hexametaphosphate, trimetaphosphate and pyrophosphate; Antimicrobial is as triclosan, biguanide such as Win-21904, chlorhexidine and gluconic acid chlorhexidine; Enzyme is as papain, bromelain, glucoamylase, amylase, dextran enzyme, mutant enzyme, lipase, pectase, tannase and protease; Quaternary ammonium compound is as benzalkonium chloride (BZK), benzethonium chloride (BZT), cetylpyridinium chloride (CPC) and domiphen bromide; Slaine is as zinc citrate, zinc chloride and stannous fluoride; Sanguinaria canadensis extract and Sanguinarine; Ethereal oil is as eucalyptole, menthol, thymol and cresotic acid; Amine fluoride; Peroxide etc.In the treatment therapeutic agent of safety and effect level can be separately be used for dentifrice formulation or with other material coupling.

Randomly, also antiseptic can be added the present composition to prevent bacterial growth.The suitable antiseptic that the approval that can add safe and effective amount is used for oral cavity composition for example has methyl parahydroxybenzoate, propyl p-hydroxybenzoate and sodium benzoate, or their combination.

Dentifrice described herein also can comprise various other compositions, as desensitizer, consolidant, other caries preventive agent, chelating agen, vitamin, aminoacid, protein, other antiplaque/antilithic, opacifiers, antibiotic, antienzyme, enzyme, pH controlling agent, oxidant, antioxidant etc.

Except described additive, water provides the balance of described compositions.Water is preferably deionization, water free from foreign meter.Dentifrice contains the 0-60 weight % water of having an appointment usually, the water content scope of some product narrower (all sources), and for example about 5-35% also has the scope of some narrower as 20-35 weight %.

The useful silicon dioxide thickening agents that is used for these toothpaste preparations includes but not limited to: amorphous sediment silicon dioxide such as ZEODENT 165 silicon dioxide.Other preferred (but being not limited to) silicon dioxide thickening agents is ZEODENT

163 and/or 167 and ZEOFREE

153,177 and/or 265 silicon dioxide, they can be available from J.M.Huber Corporation, Havre de Grace Md., U.S.A.

For the object of the invention, the definition of " dentifrice " is as including this paper " dental health product and put into practice " (Oral Hygiene Products and Practice) for referencial use in, Morton Pader, " article of everyday use science and technology series " (Consumer Science and Technology Series), the 6th volume, MarcelDekker, 1988, the 200 pages of NY are described.That is, " dentifrice " be " ... make the material of the accessible surface of cleaning teeth with toothbrush.Dentifrice mainly is made up of main components such as water, detergent, wetting agent, binding agent, flavoring agent and fine-powdered grinding agents ... think that dentifrice is the dosage form that contains grinding agent, is used for anti-caries agent is delivered to tooth." dentifrice formulation contains the composition (for example, anti-caries agent such as sodium fluoride, sodium phosphate, flavoring agent such as glucide) that must dissolve before mixing dentifrice formulation.

Measure the performance of various silicon dioxide described herein and toothpaste (dentifrice) as follows, except as otherwise noted.

Use good sharp target instrument company (Horiba Instruments, Boothwyn, LA-300 type laser light scattering measuring apparatus median grain diameter Pennsylvania) available from Pennsylvania Bu Siwen.

In order to measure brightness, will segment material and be pressed into ganoid agglomerate, treat that with safe section grace luminance meter (Technidyne Brightmeter) S-5/BC estimates its brightness.This instrument is equipped with the two-beam optical system, with 45 irradiation sample, observes reflected light at 0 °.It meets tappi test method T452 and T646, and ASTM standard D985.With enough pressure dusty material is pressed into the thick agglomerate of about 1cm, the agglomerate smooth surface of generation is smooth, does not have loose granule or gloss.

Include this paper U.S. Patent number for referencial use 6 in, 616,916 describe the hardness of measuring the precipitated silica/silica gel of the application's report with Brass Einlehner (BE) grinding test in detail, this method comprises Einlehner AT-1000 dismembyator, common using method is as follows: (1 takes by weighing the weight of Fourdrinier brass wire mesh, makes it contact for 10% silicon dioxide aqueous suspensions set time; (2) the pyrite milligram number that loses according to Fourdrinier silk screen after every rotation 100,000 times is then measured wear extent.The result who measures with milligram loss unit can be expressed as 10% pyrite Einlehner (BE) attrition value.

According to Hefferen, Journal of Dental Res., in July, 1976-August, 55 (4), 563-573 page or leaf and Wason U.S. Patent number 4,340,583,4,420,312 and 4,421,527 described methods are measured radial dentin abrasion (RDA) value of the dentifrice that contains the used silicon dioxide compositions of the present invention, and this delivers document and patent, and to include this paper in for referencial use.

Generally represent the clean-up performance of dentifrice composition with the Mycoderma cleaning than (" PCR ") value.The PCR test can detect at dentifrice composition under the fixing condition of brushing teeth and remove the ability of Mycoderma on the tooth.PCR test is referring to " with dentifrice at external removal stain " (In Vitro Removal of Stain WithDentifrice) G.K.Stookey etc., J.Dental Res., 61,1236-9,1982.The character that the effect of PCR and RDA is looked each component of dentifrice composition is with concentration and different.The value of PCR and RDA does not have unit.

The preferred embodiment for the present invention

Biogenic silica is used as the grinding agent that cleans the teeth

Embodiment 1-4

In these embodiments, detect several STRATOSIL derived from rice husk according to the method described above ^TMThe various performances of S-100 silica sample the results are shown in Table 1.

Table 1

Embodiment	1	2	3	4
					MPS，μm	48	18.52	5.65	4.0
Brightness		78.4	89.1	90.7
					The Einlehner attrition value, the milligram loss	20.41	40.5	25.14	20.29
The %325 residue	-	-	-	0
					The BET surface area, m 2/g	-	-	-	297
Ctab surface is long-pending, m 2/g	-	-	-	123
					Oil absorbs	-	-	-	77
5％pH	-	-	-	4.3
					The hole total measurement (volume), ml/g	-	-	-	1.28

STRATOSIL ^TMS-100 silicon dioxide is derived from rice husk, available from the international silicon dioxide technology company limited of Texas Wood orchid (International Silica Technologies, LLC, TheWoodlands, Texas).Embodiment 1 be do not grind, spray-dired STRATOSIL S-100 sample, show that its granularity is big.Embodiment 2-4 is the STRATOSIL S-100 sample that grinds.With the Einlehner attrition value generally the silica abrasive of the precipitation of about 3-8 milligram loss compare, the Einlehner attrition value of the sample that granularity is very little is very high, is about the loss of 20-25 milligram.

Toothpaste preparation with the several example preparations among the above-mentioned silicon dioxide embodiment has shown optimum cleaning of teeth benefit.

In order to prepare dentifrice, glycerol, sodium carboxymethyl cellulose, Polyethylene Glycol and Sorbitol are mixed, stir up to these composition dissolvings and form first mixture.Also deionized water, sodium fluoride, tetrasodium pyrophosphate and saccharin sodium are mixed, stir up to these composition dissolvings and form second mixture.Mix this two kinds of mixture then while stirring.Then under agitation add optional color and obtain " pre-composition ".This pre-composition is placed in the Ross blender (130LDM type) antivacuum mixed silica thickening agent, abrasive silica of the present invention and titanium dioxide down.Take out about 15 minutes of the mixture that 30 inches vacuum stirring obtain.At last, add sodium lauryl sulphate and flavoring agent, stirred this mixture about 5 minutes with the mixing velocity that reduces.The dentifrice that obtains is transferred in the plastic lamination dentifrice tube, stored the detection that is used for future.Following table 2 has provided the prescription of this dentifrice.In order to measure PCR and the RDA that the present invention cleans grinding agent, think that used dentifrice prescription is suitable test dentifrice prescription.

Table 2 dentifrice prescription

1 2 3 4 5

Glycerol, 99.5%, g 0000 11.000

Sorbitol, 70%, g 58.467 58.467 58.467 58.467 40.007

Deionized water, g 12.715 12.715 12.715 12.715 20.000

600，g 5.000 5.000 5.000 5.000 3.000

2000CMC，g 0.500 0.500 0.500 0.500 1.200

Sodium benzoate, g 0.500 0.500 0.500 0.500 0

Tetrasodium pyrophosphate, g 0000 0.500

Saccharin sodium, g 0.200 0.200 0.200 0.200 0.200

Sodium fluoride, g 0.243 0.243 0.243 0.243 0.243

Silicon dioxide thickening agents

165, g 8.500 13.500 8.500 8.500 1.500

The silicon dioxide of embodiment 1, g 10 0000

The silicon dioxide of embodiment 2, g 0 5.0 000

The silicon dioxide of embodiment 3, g 00 10 00

The silicon dioxide of embodiment 4, g 000 10 20

TiO ₂，g 0.500 0.500 0.500 0.500 0.500

Sodium lauryl sulphate, g 1.875 1.875 1.875 1.875 1.200

Spice, g 1.500 1.500 1.500 1.500 0.650

ZEODENT The 165th, amorphous, the precipitation high structural silica dioxide thickening agent, can be available from J.M. Huber Corp. of Maryland State Havre de Grace; CARBOWAX

The 600th, available from DOW Chemical product company (Dow Chemical Company, Midland, Polyethylene Glycol Michigan) of available; CEKOL

The 2000th, available from the CMC of the Noah group company (Noviant Group, Arnhem, the Netherlands) of Arnhem, netherlands.

Estimate PCR and the RDA performance of prepared dentifrice formulation according to the method described above; The measured value of each dentifrice formulation sees the following form 3.

Table 3

Preparation RDA PCR PCR/RDA

1 133 66 0.50

2 125 75 0.60

3 125 89 0.71

4 138 91 0.66

5 136 107 0.79

Surprisingly, the RDA value does not rely on the silicon dioxide granularity, and the RDA value is basic identical between the granule of 48 μ m-4 μ m.The STRATOSIL silica granules hardness that the Einlehner attrition value is represented is also irrelevant with the RDA of toothpaste, and RDA does not rely on the loading level of silicon dioxide in the toothpaste.Yet PCR value and PCR/RDA ratio tend to increase along with the increase of the reduction of silicon dioxide granularity and this rice husk silicon dioxide derived material addition.

The silicon dioxide that rice husk is derived and other dental abrasive unite use

Embodiment 5-12

The several embodiment that prepare the mixture of unbodied precipitated silica and embodiment 4 rice husk silicon dioxide by the following method: the amount that takes by weighing listed each component of table 4 is packed in the plastic sample bag, put upside down this sealed sample bag and for several times silicon dioxide is mixed, up to mix homogeneously.The silicon dioxide coupling that two kinds of commercially available precipitated silica outturn samples and above-mentioned rice husk are derived.These products have following feature:

Table 5

Commercially available precipitated silica sample	A	B
			MPS，μm	12	11
Brightness	97	97
			Einlehner grinding value, the milligram loss	2.5	5.5
The %325 residue	0.75	0.75
			％H 2O	8	6
％Na 2SO 4(with conductance measurement)	1	1
			Oil absorbs	100	88
5％pH	7.3	7.7

Table 4

Embodiment	Embodiment 4 grams	Commercially available prod B gram	Commercially available prod A gram
				5	225	75	0
6	150	150	0
				7	75	225	0
8	225	0	75
				9	150	0	150
10	75	0	225
				11	75	0	225
12	30	0	270

According to embodiment 1 described method above-mentioned silica mixture sample is mixed in the dentifrice prescription.This dentifrice prescription sees the following form 5.

Table 5

The dentifrice prescription

Assess PCR and the RDA performance of the dentifrice formulation for preparing above according to the method described above; The measured value of each dentifrice formulation sees the following form 6.

Table 6

The preparation numbering	RDA	PCR	PCR/RDA
				6	136	100	0.74
7	132	100	0.76
				8	126	97	0.77
9	132	101	0.77
				10	128	99	0.77
11	112	96	0.86
				12	114	96	0.84
13	96	91	0.95

The Einlehner value shows that ZEODENT 114 is the silicon dioxide that nonferromagnetic substance is lower than ZEODENT 119 silicon dioxide.Toothpaste preparation 6-8 contains the mixture of STRATOSIL rice husk silicon dioxide and ZEODENT 119 silicon dioxide, and the ratio of the two is identical with the toothpaste preparation 9-11 that contains rice husk silicon dioxide and ZEODENT 114 silicon dioxide.For the precipitated silica of higher mixed proportion and rice husk silicon dioxide (preparation 11 and preparation 8), can obtain higher PCR/RDA ratio when adopting the lower ZEODENT 114 of nonferromagnetic substance.By changing the ratio of STRATOSIL silicon dioxide and conventional silicon dioxide, can obtain PCR/RDA ratio near 1 toothpaste, seen in preparation 13.The suitable nonferromagnetic substance of the conventional silicon dioxide that mixes with rice husk silicon dioxide provides PCR/RDA ratio higher dentifrice.

Though describe and disclose the present invention with reference to some preferred implementation and practice, but should not be considered as the present invention and only limit to these specific embodiment, the present invention should be contained equivalent structure, equivalent structures and all alternative embodiment and modification, only is subjected to the restriction of appended claims and the described scope of its equivalent.

Claims (7)

1. dentifrice, it contains the silica abrasive that rice husk is derived, optional other tooth abrasive component that comprises, the Mycoderma clean-up performance of wherein said dentifrice and radial dentin abrasion ratio are greater than 0.80, the silica abrasive that described rice husk is derived is the white powder of high-purity amorphous silica of grinding, its granularity is the 4-48 micron, and the combination of the independent rice husk silica abrasive of deriving or the rice husk silica abrasive of deriving and other tooth abrasive component accounts for the 5-50 weight % of dentifrice;

The silicon dioxide that described rice husk is derived is to be made by the method that contains the following step:

(a) rice husk is immersed in the aqueous solution that contains the oxidisability solute to reduce Organic substance in the rice husk; With

(b) under 500-950 ℃ temperature, burn this rice husk.

2. dentifrice as claimed in claim 1 is characterized in that, has another kind of tooth abrasive component.

3. dentifrice as claimed in claim 2, it is characterized in that described other tooth abrasive component is selected from the calcium carbonate of precipitated silica product, silica gel, precipitation, calcium carbonate, Chalk, magnesium carbonate, dicalcium phosphate and its dihydrate, calcium pyrophosphate, Zirconium orthosilicate., potassium metaphosphate, magnesium orthophosphate, tricalcium phosphate, perlite and their mixture of grinding.

4. dentifrice as claimed in claim 3 is characterized in that, described other tooth abrasive component is the precipitated silica product.

5. dentifrice as claimed in claim 2 is characterized in that, the total content of grinding agent is 30 weight % at the most in the described dentifrice, and the content of the silicon dioxide that wherein said rice husk is derived is at most 25 weight %.

6. dentifrice as claimed in claim 3 is characterized in that, the total content of grinding agent is 30 weight % at the most in the described dentifrice, and the content of the silicon dioxide that wherein said rice husk is derived is at most 25 weight %.

7. dentifrice as claimed in claim 4 is characterized in that, the total content of grinding agent is 30 weight % at the most in the described dentifrice, and the content of the silicon dioxide that wherein said rice husk is derived is at most 25 weight %.