CN101479371B - Flavor oils with reduced sulfur content and use in oral care compositions - Google Patents

Abstract

The invention relates to flavor oils including mint-, fruit- and spice-type flavors that are specially processed to substantially eliminate low-molecular weight sulfur compounds, in particular dimethyl sulfoxide (DMSO), which has been found to be the main precursor of malodorous species such as dimethyl sulfide and methyl mercaptan. These malodorous species are produced via oxidation-reduction reactions involving such sulfur-containing compounds present in flavor oils. A preferred processing method is an aqueous-washing process, which has advantages of being simple, inexpensive and easy to implement while importantly avoiding the problems of typical processes including non-selective removal of desirable components and subjecting the flavor oils to extreme conditions that may destroy other components and result in undesirable changes in flavor or odor character. Other processing methods to selectively remove non-desired components include (1) distillation to remove polar low boiling point components, (2) filtration through adsorbents selective for sulfur compounds, (3) countercurrent extraction and (4) column chromatography. The processing methods may optionally be followed by reengineering to add back desired components that may have been removed or altered during the processing. The specially processed flavor oils are particularly useful in oral care compositions comprising components with chemical reducing capability such as stannous ions, which react with the sulfur-containing compounds to produce malodorous products.

Description

Have the flavor oil of low sulfur content and the application in oral care composition thereof

Technical field

The present invention relates to comprise the oral care composition of flavor system, described flavor system comprises flavor oil, described flavor oil is stable, degraded be can resist and stench and peculiar smell prevented, and described stench and peculiar smell be mainly from S-contained substance, for example mercaptan (thiols) or mercaptan (mercaptans).These repugnant substances produce via redox reaction, and described reaction relates to other component in sulfocompound contained in the flavor oil and the described composition.With the special content of processing with reduction lower molecular weight sulphur compound, especially dimethyl sulfoxide (DMSO) (DMSO) of flavor oil.Find that dimethyl sulfoxide (DMSO) is for example main precursor of dimethyl sulphide and thiomethyl alcohol of repugnant substance.Therefore, the invention provides the method for preparing flavor oil and oral care composition, described flavor oil comprises mint type, fruit type and the spices type flavour agent that is substantially free of DMSO and other S-contained substance, and described oral care composition is mixed with this type of flavor oil of processing especially to improve the stability of taste and smell characteristic aspect.

Background of invention

Dental care products for example dentifrice and collutory by the daily part as their mouth care sanitation programmes of human consumer.Dental care products can be the human consumer provide the treatment and cosmetic health beneficial effect this point well known.The treatment beneficial effect comprises the prevention of dental caries, gingivitis prevention or hypersensitivity control, and the described prevention of dental caries is usually by realizing with various fluoride salts; Described gingivitis prevention is by for example triclosan, tin protofluoride or essential oil are realized with biocide; The control of described hypersensitivity assigns to realize by the one-tenth that uses strontium chloride for example or saltpetre.The cosmetic beneficial effect that provides by the mouth care goods comprises the formation of control dental plaque and dental calculus, removes and prevention tooth stain, and tooth-whitening, fresh breath and totally improve the mouthfeel impression, it is characterised in that widely mouthfeel is attractive in appearance.Dental calculus and dental plaque and behavior and environmental factors cause the formation of teeth stains, thereby have had a strong impact on the attractive in appearance of tooth.The behavior and the environmental factors that are tending towards short odontiasis tooth color shifting properties comprise regular coffee for drinking, tea, cola or smoking tobaccos product, and comprising some oral products of use, described oral products comprises composition such as cationic antimicrobial agent and the metal-salt that promotes tooth discoloration.

Therefore, the daily mouth care of family need to contain the product of Multiple components, described composition works to provide complete treatment and beautifies the beneficial effect scope with different mechanism, comprises preventing decayed tooth, antimicrobial, anti-gingivitis, antiplaque and anti-dental calculus and anti-peculiar smell, oral cavity fresh and cool, color spot removal, color spot control and tooth whitening.For example dentifrice and collutory can provide complete oral care efficacy in order to make dental care products used in everyday, active substance and additive combination need to be in the same place, wherein many have a shortcoming that can cause during use negative aesthetic property, is taste and sensation and the short spot that adds lustre to that makes us unhappy specifically.Taste and the mouthfeel of making us unhappy have been described to have following one or more aspect: bitter taste, metal fishy smell, astringent taste, saline taste, numb flavor, prickling sensation, burning sensation, sensation of pricking or even excitement.The typical composition that is used for the mouth care purposes that is attended by these negative aesthetic properties comprises biocide, for example cetylpyridinium chloride, chlorhexidine, tin salt, mantoquita and zinc salt; Dental bleaching agent, for example superoxide; Anticalculus agent, for example pyrophosphate salt, tri-polyphosphate and hexametaphosphate; And vehicle, for example sodium bicarbonate and tensio-active agent.In order to alleviate the negative aesthetic property that is caused by these compositions, usually prepare dental care products with seasonings and sweeting agent so that taste is good as much as possible and can be accepted by the human consumer.

Because many certified oral cavities beneficial effect, therefore expectation is incorporated into stannous ion in the oral care composition.Usually the stannous ion that is provided by the tin protofluoride in the oral care composition can be used to provide beneficial effect, comprises antimicrobial, antiplaque, gingivitis and antianaphylaxis beneficial effect, and can be used for anti-halitosis in advance.Yet confirm, because the known preparation that comprises stannous ion is not attractive in appearance desirable, therefore challenging with the stannous ion preparation.Find that in addition some flavor oil, especially mint type oil can show unstable and produce stench when uniting use with stannous ion.

After from plant or plant material, extracting natural flavour mountaineous oil, with its refining or further process to improve quality and stability is described in the art.In general, these treatment processs are intended to remove or reduce component concentration in the described oil, and described component it is believed that it is the reason that causes unstable or inadvisable taste or odor property.For example, flavor oil is processed to remove or reduce the content of terpenes, menthofuran, pulegone and dimethyl sulphide.This type for the treatment of process is described in for example United States Patent (USP) 3,867,262,4,440,790,4,613,513,4,708,880,4,844,883,4,816,616,4,948,595,5,116,625,5,128,154,5,204,128,5,298,238,5,425, in 962 and 6,479,088, and comprise that distillation, nitrogen bubble and chemical treatment are with oxidation or this type of inadvisable component of inactivation.

For example, retortable spearmint oil is to remove or to reduce the content of the dimethyl sulphide that has according to reports inadvisable greenweed flavor.Implement vapor distillation or vacuum distilling and taken the refining spearmint oil.Yet this type of distillating method is not exclusively satisfactory.Typical vapor distillation method has not only been removed dimethyl sulphide, but also has removed other lower boiling constituent of peppermint oil.Therefore, when the refining spearmint oil, need to from distillate, isolate required low boiling component, and with they at least part of being added back in the flavour agent.This has increased cost and the time of still-process.Another problem that refining spearmint oil most popular method is followed is that they can make spearmint oil experience extreme condition, for example superheated.This can cause flavour agent that worthless variation occurs.

Continue to need improve the local flavor oil handling so that best taste and odor property and stability to be provided, remove specifically the component, the especially dimethyl sulfoxide (DMSO) that produce stench.Have now found that dimethyl sulfoxide (DMSO) is the principal mode of stench precursor sulfur material in the flavor oil.Therefore, the present invention relates to from original flavor oil, remove the inadvisable component of this type of before unrecognized inadvisable smell of formation, obtain simultaneously stable flavour agent, described flavour agent be substantially free of can not taken amount this type of produce the component of stench, thereby since with for example inferior tin reaction in the oral care composition of reductive agent, therefore do not produce stench yet or pollute the trend of local flavor.

Summary of the invention

In one aspect, the present invention relates to the further processing of flavor oil or refining to reduce for example content of dimethyl sulfoxide (DMSO) of sulfocompound.Preferred treatment process is method for washing, it has advantage simple, inexpensive and that be easy to realize, while is its problem of having avoided typical method to have importantly, remove required component with comprising non-selectivity, and make flavor oil experience may destroy other component and cause local flavor and the extreme condition of inadvisable variation occurs odor property.The treatment process that other selectivity is removed non-required component comprises (1) distillation to remove the depolarization low boiling component, and (2) sorbent material filters by having optionally to sulphur compound, (3) counter-current extraction and (4) column chromatography.Described treatment process can be chosen wantonly and carry out subsequently the required component of having removed or having changed during workflow reengineering is processed with add-back.

In one aspect of the method, the invention provides oral care composition, described composition comprises

(a) have the oral cavity nursing agent of chemical reduction ability,

(b) comprise the flavor system of flavor oil or extract, described flavor oil or extract are substantially free of S-contained substance, the S-contained substance that obtains comprises dimethyl sulfoxide (DMSO), dimethyl sulphide, dimethyl disulfide and dimethyl sulfone, they are to cause the reason that produces stench and peculiar smell in the described composition, and

(c) oral area acceptable carrier.

Oral cavity nursing agent with chemical reduction ability is selected from stannous ion source and phenols, and described phenols is from for example tea, cowberry, pomegranate and oak bark source.Described composition has stablizes complete flavor characteristics, and taste is pleasant and pure and fresh, thereby impels user's compliance and frequent usability.

For a person skilled in the art, by following detailed description, these and other feature, aspect and advantage of the present invention will become apparent.

Detailed Description Of The Invention

Particularly point out and claimed claims of the present invention clearly although after specification sheets, provide, should believe by following explanation and can understand better the present invention.

Except as otherwise noted, hereinafter used all per-cents and ratio all by the weighing scale of total composition.Except as otherwise noted, the per-cent of each composition of all that the present invention relates to, ratio and content is all based on the actual content of composition, and is not included in solvent, filler or other material that may be combined with described composition in the product of commercially available acquisition.

Except as otherwise noted, all measurements of mentioning of this paper are all carried out under 25 ℃.

" comprise/comprise " herein and refer to add other step and the composition that does not affect net result.This term comprise term " by ... form " and " basically by ... composition ".

As used herein, word " comprises/comprise " and its variant be defined as non-limiting so that the narration of tabulation discal patch purpose do not get rid of other also may be in material of the present invention, composition, apparatus and method useful similar clauses and subclauses.

As used herein, word " preferably ", " preferably " and their variant refer to can provide embodiment of the present invention of specific beneficial effect under specific environment.Yet other embodiment also can be preferred under identical or other environment.In addition, the detailed description of one or more preferred embodiments is not that other embodiment of expression is useless, and the non-embodiment that is intended to get rid of other from category of the present invention.

" oral care composition " refers to deliberately do not swallowed to be used for the whole body administration of particular therapeutic agent in the normal operation process, but can keep the sufficiently long time basically to contact all dental surfaces and/or oral cavity tissue to obtain having the product of orally active in the oral cavity.Described oral care composition can be various ways, comprises toothpaste, dentifrice, gutta-percha, gums glue, collutory, mousse, foam, artificial tooth care products, mouth spraying agent, medicine sugar, chewable tablet or chewing gum.This oral care composition also can be incorporated on strip or the film directly to use or to adhere to oral surfaces.

Except as otherwise noted, the term " dentifrice " of the present invention's use refers to paste, gel or liquid preparation.Dentrifice composition both can be the combination that single-phase composite also can be two or more independent Dentrifice compositions.Dentrifice composition can be any desired form, as gel arranged around dark striped, shallow striped, multilayer, the paste or their arbitrary combination.In comprising the dentifrice of two or more independent Dentrifice compositions, every kind of Dentrifice composition can be loaded into physically independently in the distributor chambers, distributes side by side.

Term as used herein " divider " refers to any pump, pipe or container that is suitable for assign group compound (such as dentifrice).

As used herein, term " tooth " refers to nature tooth and artificial teeth or artificial tooth.

Term " flavor oil " refers to the essential oil as seasonings, and it is distillation from plant or the ethereal oil that extracts and the component of these ethereal oils.As used herein, when relating to peppermint and mint type oil, term " flavor oil " comprises the oil of various grades, described oil typically refers to natural crude oil initial natural or unprocessed (just mentioning out from plant-sourced), and exquisite or rectifying so that oily conformance with standard and remove unwanted local flavor/odor characteristics (for example by fractionation).The rectifying level is generally and offers the end user with the class of trade as seasonings and spices.Typical essential oil and their main ingredient are to derive from following those, for example Thymus vulgaris (thymol, isothymol), wild marjoram (isothymol, terpenes), lemon (limonene, terpinene, phellandrene, firpene, citral), lemonweed (citral, Sulcatone, geranial, Geraniol), flores aurantii (linalool, beta-pinene, limonene), orange (limonene, citral), anise (p-propenylanisole, safrole), cloves (oxymethoxyallylbenzene, acetic acid Syzygium aromaticum ester, caryophyllene), rose (Geraniol, geraniol), Rosmarinus officinalis (borneol, norbornene ester, camphor), Herba Erodii (Geraniol, geraniol, linalool), lavender (Linalyl acetate, linalool), lemongrass (Geraniol, geraniol, geranial, amphene), eucalyptus (eucalyptol); Mentha arvensis L. syn.M.haplocalyxBrig (menthol, menthyl ester), spearmint (Karvon, limonene, firpene); Wintergreen (wintergreen oil), camphor (safrole, acetaldehyde, camphor), Laurus nobilis (oxymethoxyallylbenzene, myrcene, good flavor alcohol), Chinese cassia tree (phenylacrolein, cinnamyl acetate, oxymethoxyallylbenzene), tea tree (4-terpineol, Terpane) and CedarLeaves (α-keep ketone, β-keep ketone, fenchone).Essential oil, their composition and preparation are described in greater detail in Kirk-Othmer's in " Encyclopedia of Chemical Technology " the 4th edition and " The Merck Index " the 13rd edition.

Term " oral area acceptable carrier " comprises for the safety of oral care composition and effective material, vehicle or additive, includes but not limited to fluoride sources, anti-dental calculus or anticalculus agent, damping fluid, abrasive for example silicon-dioxide, alkali metal hydrocarbonate, thickening material, wetting agent, water, tensio-active agent, titanium dioxide, flavour agent, sweeting agent, Xylitol, tinting material and their mixture.

Can be used for activeconstituents of the present invention and other composition can classify or describe according to the effect of its beauty treatment and/or treatment beneficial effect or its supposition or operational mode.Yet should be appreciated that in some cases can be used for active substance of the present invention and other composition can provide more than one beauty treatment and/or treatment beneficial effect or effect, or work or move by more than one mode.Therefore, the classification of this paper is for convenience's sake, but not is intended to composition is limited in the listed application that particularly points out or several application.

Term " tartar " and " dental calculus " are used interchangeably herein, and refer to the dental plaque biofilm that mineralizes.

Basal component of the present invention and optional components are described in the following paragraph.

Flavor system

The present invention comprises flavor system, described flavor system comprises flavor oil, and described flavor oil is stable, anti-degraded and prevent peculiar smell and stench, described peculiar smell and stench be mainly from S-contained substance, for example mercaptan (thiols) or mercaptan (mercaptans).These repugnant substances produce via redox reaction, and described reaction relates to other component in flavor oil component and the described composition.More particularly, found the lower molecular weight sulphur compound for example dimethyl sulfoxide (DMSO) (DMSO) be present in some natural flavour mountaineous oil, present in an amount at least sufficient to namely be easy to oxidized reagent react with having quite strong reducing power, cause the generation repugnant substance, comprise dimethyl sulphide and thiomethyl alcohol.Therefore, the invention provides flavor oil and oral care composition, described flavor oil comprises mint type, fruit type and spices type flavour agent, it is processed to reduce DMSO and other S-contained substance content by special, and described oral care composition is mixed with this type of flavor oil of processing to improve taste and stability.The flavor oil of processing preferably is substantially free of this type of worthless S-contained substance, comprises dimethyl sulfoxide (DMSO), dimethyl sulphide, dimethyl disulfide and the dimethyl sulfone that can be reduced into repugnant substance.Other sulfocompound also can be present in the oil of processing, yet these can not present the problem that produces the stench aspect." be substantially free of " herein and refer to that flavor oil comprises and be the S-contained substance of stench precursor less than about 20ppm.Find, will comprise greater than the flavor oil of about this type of S-contained substance of 20ppm and prepare the stench that can cause generation to be described to " skunk flavor " with the reagent of for example inferior tin.In addition, this type of redox reaction that causes producing stench can adversely reduce the concentration of active inferior tin in the described composition, thereby reduces potentially effect.Process after for example washing that the content of sulfur-containing foul precursor substance is more preferably less than about 1ppm less than about 10ppm in the flavor oil, and even be more preferably less than about 0.5ppm, or do not have at all.

The present invention relates to following discovery: the main sulfur-containing foul precursor substance that is present in the flavor oil is DMSO, and the content that sample has is up to 300ppm or higher.Following table has shown the content of DMSO and dimethyl sulphide (DMS) in spearmint and the Mentha arvensis L. syn.M.haplocalyxBrig sample.As follows, essential substance is DMSO; DMS significantly exists with lower content in flavor oil.

Table 1: the content of DMSO and DMS in Mentha arvensis L. syn.M.haplocalyxBrig and the Oleum Menthae Rotundifoliae feed

Sample	DMSO(ppm，w/v)	DMS(ppm，w/v)
			Mentha arvensis L. syn.M.haplocalyxBrig feed sample 1	318	10.3
Mentha arvensis L. syn.M.haplocalyxBrig feed sample 2	312	22.1
			Mentha arvensis L. syn.M.haplocalyxBrig feed sample 3	181	46.8
Spearmint (1% crop)	235	<1

Spearmint oil is provided by I.P.Callison, and Oleum Menthae Rotundifoliae is provided by Labbeemint

Report, have DMSO in the nature.For example, in selected fruit, vegetables, cereal and the beverage the natural amount of DMSO be reported in " J.Agric.Food Chem. " (1981,29,1089-91) in.The high-content of reporting is the 16ppm in the black tea drink.In most of samples, the content of finding is less than 1ppm, and is concentrated or to process the content that sample for example finds in the tomato paste higher.The increase of DMSO content is considered to because due to the oxidation of commercial processes period two dimethyl sulfide (DMS).DMS is at the occurring in nature ubiquity, and is the reason that causes the numerous food product characteristic odor.Also reporting DMSO is present in Oleum Menthae Rotundifoliae [" Anais de Academia Brasileira deCiencias ", 1972,44 (Suppl.), 273-7] and the spearmint oil [" Agric.Biol.Chem. ", 1980,44 (7), 1535-43].The report that does not have the content of finding in this paper peppermint flavor oil.

Via sample dilution, subsequently liquid infusion can be realized the mensuration of dimethyl sulfoxide (DMSO) in the spearmint oil (DMSO) and dimethyl sulphide (DMS) content in the GC-MS system.In brief, prepare calibration reference in the spearmint oil by the DMSO of known quantity and DMS are added to, described spearmint oil was before removed these components by washing, until be lower than the quantification lower limit.Water-washing technique and is described in greater detail in hereinafter as described herein.Prepare for every kind of standard analyzing and sample by dilute 200 μ L aliquots containigs with 800 μ L ethyl acetate, described ethyl acetate comprise isotope-labeled DMSO ( ¹³C ₂) and DMS ( ²H ₆) stable internal standard substance.Analyze standard and the sample prepared in shunting by 1 μ L aliquots containig being expelled to Agilent 6890 GC/nothing minute influx effluent is transferred in the single quadrupole mass spectrometer of Agilent5973, described mass spectrograph is to select ion monitoring (SIM) mode operating.To each analyte, the peak area ratio (analyte/internal standard substance) of calibration reference is mapped to add analysis substrate concentration.Based on its analyte of measuring and internal standard substance peak area ratio, by the concentration of each unknown sample of respective alignment curve interpolation.Use these to detect analysis condition, the quantification nominal lower limit of DMSO and DMS is 1ppm (w/v), and the quantification upper limit of DMSO and DMS is respectively 500 and 100ppm.

Flavor oil of the present invention generally is used for oral care composition with about 0.001% to about 5% amount by weight of the composition.The content of flavor oil is preferably about 0.01% to about 4%, and more preferably from about 0.05% to about 3%, and most preferably from about 0.1% to about 2%.Described flavor oil can be used as that whole flavor composition in the oral preparations exists or with other selected flavor compound combination.Be preferred for flavor oil in the oral care composition and comprise from the peppermint classification those, for example peppermint (Mentha arvensis L. syn.M.haplocalyxBrig), ginger peppermint (peppermint), Mentha viridis L (the local spearmint of the U.S.), Herba Ziziphorae clinopodioidis (Scotland spearmint) and emerald green peppermint (Chinese spearmint kind).Expect that described oral care composition has mint flavor fully, because peppermint is topmost flavour agent wherein.

Except selectivity peppermint flavor oil above, described flavor system also can comprise additional flavor compound, described additional flavor compound includes but not limited to wintergreen oil, clove bud oil, cassia bark, Salvia japonica Thunb., Parsley seed oil, origanum, lemon, orange, cis-jasmone, 2,5-dimethyl-4-hydroxyl-3 (2H)-furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone, Vanillin, vanillal, aubepine, 3,4-methylenedioxy benzene formaldehyde, Veratraldehyde, the 4-hydroxy benzaldehyde, Benzaldehyde,2-methoxy, phenyl aldehyde; Phenylacrolein, hexyl cinnamic aldehyde, α-methylcinnamaldehyde, o-methoxy cinnamic aldehyde, α-n-Amyl cinnamaldehyde 1-ethoxy-2-hydroxy-4-propenyl benzene (guaethol), heliotropine, the 4-cis-heptenal, biacetyl, p-tert.-butylbenzene methyl acetate, menthol, wintergreen oil, salicylic ether, 1-menthyl acetate oxane ketone, α-ionone, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethyl butyrate, ethyl acetate, methyl o-aminobenzoate, Isoamyl Acetate FCC, isoamyl butyrate, pineapple aldehyde, oxymethoxyallylbenzene, Terpane, thymol, styryl carbinol, octanol, octanal, decyl alcohol, capraldehyde, phenylethyl alcohol, benzylalcohol, α-terpinol, linalool limonene, citral, voitol, veltol plus, methyl allylphenol, dihydroanethole, Karvon, piperitone, dorinone, ionone, γ-decalactone, γ-nonyl lactone and peach aldehyde, and their mixture.In general, suitable flavor compound be comprise constitutional features and functional group and be not inclined to those of redox reaction.These comprise derivative saturated or that comprise the flavor compounds of stablizing aromatic ring or ester group.Can experience some oxidation or DeR but can not cause the flavor compounds of flavour agent characteristic or characteristic remarkable variation to suit yet.Can form single or pure compound provide flavor compound, perhaps provide with the form of composition by adding natural oil or extract, described natural oil or extract preferably through the present invention wash process or other refining treatment to remove component, described component is more unstable, and can degrade and change desired flavor characteristic, thereby obtain to affect the more unacceptable product in organ sensation aspect.

Described flavor system also can comprise the protective material component that prevents from the composition producing stench and peculiar smell, and for example exercise question is those described in the co-pending patent application of common submission of " FLAVORS FOR ORAL COMPOSITIONS ".This type of protective material comprises carbonyl compound, for example xitix; Cis-jasmone; 2,5-dimethyl-4-hydroxyl-3 (2H)-furanone; 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone; Vanillin; Vanillal; Aubepine; 3,4-methylenedioxy benzene formaldehyde; Veratraldehyde; The 4-hydroxy benzaldehyde; Benzaldehyde,2-methoxy; 4-methoxybenzaldehyde; Phenyl aldehyde; Phenylacrolein; Hexyl cinnamic aldehyde; α-methylcinnamaldehyde; O-methoxy cinnamic aldehyde; α-n-Amyl cinnamaldehyde; And their combination.Having many in these protective materials is flavor compound.

Described flavor system also can comprise cool agent or refrigerant, for example menthol, menthyl ester, carboxylic acid amides, ketal, glycol and their mixture.The refrigerant example that is applicable in the present composition is to peppermint carboxylic acid amides reagent, and for example the N-ethyl of commercial " WS-3 " by name is to peppermint-3-carboxylic acid amides; The WS-23 of commercial " WS-23 " by name; The p-benzyl cyanide peppermint of N-carboxylic acid amides; And other material in the series, for example WS-5, WS-11, WS-14 and WS-30.Other suitable refrigerant comprises the 3-1-peppermint oxygen base the third-1 that is called TK-10 by the Takasago preparation, 2-glycol; MGA (

MGA); Menthyl ester, for example menthyl acetate, etheric acid menthyl ester, p-Menthyl lactate ( ML is provided by Haarmannand Reimer) and mono succinate menthyl ester (Physcool is provided by V.Mane with trade(brand)name).As used herein, term menthol and menthyl comprise dextrorotation and levoisomer and their racemic mixture of these compounds.TK-10 is described in the United States Patent (USP) 4,459,425 of authorizing the people such as Amano of announcing on July 10th, 1984.WS-3 and other reagent are described in the United States Patent (USP) 4,136,163 of authorizing the people such as Watson of announcing on January 23rd, 1979.

Described flavor system comprises sweeting agent usually.Suitable sweeting agent comprise known in the art those, comprise natural and artificial sweeting agent.Some suitable water-soluble sweetening agents comprise monose, disaccharides, polysaccharide and derivative, for example starch, corn-syrup solids, dihydrochalcone, monellin, stevioside, Liquiritigenin, Xylitol and the tetrahydroxybutane of wood sugar, ribose, glucose (dextrose), seminose, semi-lactosi, fructose (sinistrose), sucrose (granulated sugar), maltose, Nulomoline (derived from the fructose of sucrose and the mixture of glucose), partial hydrolysis.Suitable water-soluble artificial sweeting agent comprises soluble saccharin salt, be soluble saccharin or asccharin calcium salt, cyclamate, 3,4-dihydro-6-methyl isophthalic acid, 2,3-dislikes thiazine-4-ketone-2, the sodium salt of 2-dioxide, ammonium salt or calcium salt, 3,4-dihydro-6-methyl isophthalic acid, 2,3-Evil thiazine-4-ketone-2, the sylvite of 2-dioxide (asccharin of Acesulfame-K), free acid form, etc.Other suitable sweeting agent comprises the sweeting agent based on dipeptides; the L-Aspartic acid sweeting agent of deriving for example; L-aspartyl-L-phenyl methyl lactamine (aspartame) and United States Patent (USP) 3 for example; 492; the material of describing in 131; L-α-aspartyl-N-(2; 2; 4; 4-tetramethyl--3-vulcanizes trimethylene)-D-alanine acid amides hydrate; L-aspartyl-L-phenyl glycerine and L-aspartyl-L-2,5-dihydro phenylglycocoll; L-aspartyl-2,5-dihydro-L-phenylalanine; the methyl esters of L-aspartyl-L-(1-cyclohexenyl)-L-Ala etc.Can use the water-soluble sweetening agent derived from naturally occurring water-soluble sweetening agent, for example the chlorinated derivatives of common granulated sugar (sucrose) product description of known Sucralose (for example to) and protein-based sweeting agent West Africa arrowroot (African hesperidium element I and II) for example.Described composition preferably comprises by weight about 0.1% to about 10%, preferred about 0.1% to about 1% sweeting agent.

In addition, described flavor system can comprise salivation agent, heat agent and numb agent.The content of these reagent in composition is take by weight of the composition as about 0.001% to about 10%, and preferred about 0.1% to about 1%.Suitable salivation agent comprises is produced by Takasago

The example of agent of heating is capsicum and nicotinate, such as benzyl nicotinate.Suitable numb agent comprises Benzocaine, lignocaine, clove bud oil and ethanol.

Chemical reducing agent

Comprising flavor oil that the present invention processed especially and the flavor system of extract especially can be used in the composition, described composition comprises the reagent with chemical reduction ability, in particular to the stannous ion that becomes in the oral care composition preferred active substance because of its extensive beneficial effect scope with from phenols and the derivative of available antimicrobial, the anti-inflammatory of having of plant-sourced and antioxidant activity.In these phenols and derivative, have manyly also can be used as seasonings.

Stannous ion has great reduction characteristic, can be oxidized to the tetravalent tin form when reacting with DMSO, and described DMSO then is reduced into repugnant substance DMS and further is reduced into thiomethyl alcohol (CH ₃SH).Ya Xi and reagent for example the reaction of DMSO not only owing to can produce repugnant substance, thereby but also reduce the composition effect owing to can reduce inferior tin content, be worthless therefore.Many phenols that are used as active substance or flavour agent in oral care composition are easily oxidized, namely have reduction characteristic, and mode that therefore can be identical with inferior tin is reacted with DMSO.

Composition of the present invention preferably comprises stannous ion source, comprises tin protofluoride and/or other tin salt.Have been found that tin protofluoride helps to alleviate carious tooth, gingivitis, dental plaque and susceptibility, and help to improve the beneficial effect of breathing.Other tin salt comprises two hydrated stannous chlorides, stannous acetate, the inferior tin of glyconic acid, stannous oxalate, stannous sulfate, the inferior tin of lactic acid and stannous tartrate.Preferred stannous ion source is tin protofluoride and two hydrated stannous chlorides.The content of tin salt counts about 0.1% to about 11% by the weight of described total composition.The content of tin salt is preferably about 0.4% to about 7% by the weighing scale of described total composition, and more preferably from about 0.45% to about 5%, and most preferably from about 0.45% to about 3%.The inferior tin content that is provided by tin protofluoride and other tin salt is provided preparation typical case with effect, and the content of stannous ion in total composition is about 3, and 000ppm is to about 15, in the scope of 000ppm.

The dentifrice that comprises tin salt, especially tin protofluoride and tin protochloride is described in the United States Patent (USP) 5,004,597 of authorizing the people such as Majeti.Other description of tin salt is found in the United States Patent (USP) 5,578,293 of authorizing the people such as Prencipe and authorizes in the people's such as Lukacovic the United States Patent (USP) 5,281,410.Except stannous ion source, also can comprise and stablize other required composition of inferior tin, such as the composition described in people's patents such as the people such as Majeti and Prencipe.

From plant-sourced for example tea, cowberry, pomegranate and oak bark phenols also can be incorporated in the composition of the present invention.This phenols comprises catechin, nutgall catechin gallic acid ester, l-Epicatechol (EC), epigallocatechin (EGC), NVP-XAA 723 (EGCG), L-Epicatechin gallate (ECG), theoflavin, thearubigins, cyanidin(e)/pycnogenols and anthocyanidin (for example Cyanidin, delphinidin, pelargonidin, peonidin, syringidin and morning glory pigment); Tannic acid; Gallic acid; Ellagic acid; Ellagitannins; Curcumine.Described phenols can be used as pure compound or provides as plant milk extract.The phenols that can be used as oral care active is disclosed in the U.S. Patent application 11/595,530 as US 2007/0053849A1 announcement of common transfer.

Except above-described component, this composition also can comprise additional optional components, is referred to as oral area and can accepts solid support material, and it is described in the following paragraph.

Oral area acceptable carrier material

Described oral area acceptable carrier comprises that one or more are suitable for compatible solid or liquid excipient or thinner that local oral area is used.As used herein, term " compatible " refers to that the component of composition can mix but do not interact, and described interaction meeting significantly reduces stability and/or the effect of composition.

Carrier of the present invention or vehicle comprise gel, collutory under dentifrice, non-abrasive gel, the gum or the common and conventional component of washing saliva, mouth spraying agent, chewing gum, medicine sugar and breath freshening peppermint, and they will be described in more detail hereinafter.

The selection of carrier to be used is to determine according to the method in composition introducing oral cavity basically.The solid support material that can be used for toothpaste, gutta-percha or analogous products comprises abrasive material, pore forming material, tackiness agent, wetting agent, flavour agent and sweeting agent etc., as is disclosed in the United States Patent (USP) 3,988,433 of authorizing Benedict.The solid support material that is used for the two-phase dentifrice formulation is disclosed in the material of following document: 5 of the United States Patent (USP) announcement on September 8th, 5,213,790,1992 of announcing on May 23rd, 1993,5,281 of announcement on January 25th, 145,666 and 1994,410, above-mentioned patent is all authorized the people such as Lukacovic; With the United States Patent (USP) 4,849,213 and 4,528 of authorizing Schaeffer, 180. collutoryes, wash saliva or the mouth spraying agent solid support material generally includes water, flavour agent and sweeting agent etc., for example authorize in the United States Patent (USP) 3,988,433 of Benedict disclosed.Medicine sugar solid support material typically comprises a kind of candy substrate; The chewing gum solid support material comprises a kind of gummy matrix, flavour agent and sweeting agent, and this is disclosed in such as in the United States Patent (USP) 4,083,955 of authorizing the people such as Grabenstetter.The pouch solid support material generally includes sachet, flavour agent and sweeting agent.For being used for gel under the gum of delivery of active substances around periodontal pocket or the periodontal pocket, by the United States Patent (USP) 5,198 of for example announcing on March 30th, 1993, the United States Patent (USP) 5 that on September 7th, 220 and 1993 announced, 242,910 select " gel carrier under the gum ", and above-mentioned two patents are all authorized Damani.The carrier that is suitable for preparing the present composition is well known in this area.Their selection is depended on such as less important Considerations such as taste, cost and frame Tibetan stability.

Composition of the present invention can also be gel form under moisture or nonaqueous non-abrasive property gel and the gum.In yet another aspect, the present invention also provides the toilet article that are marked with this composition.Toilet article comprise that described utensil has injected composition described herein for the utensil that contacts with other tissue with the oral cavity Tooth.Toilet article can be injected into fiber, and this fiber comprises dental floss or dental tape, thin slice, strip, film and polymer fiber.

In one embodiment, this theme inventive composition is the dentifrice form, such as toothpaste, gutta-percha and tooth powder.The component of these toothpaste and gutta-percha generally includes one or more dental abrasive (about 6% to about 50%), tensio-active agent (about 0.5% to about 10%), thickening material (about 0.1% to about 5%), wetting agent (about 10% to about 55%), seasonings (about 0.04% to about 2%), sweeting agent (about 0.1% to about 3%), tinting material (about 0.01% to about 0.5%) and water (about 2% to about 45%).This type of toothpaste or gutta-percha also can comprise one or more caries preventive agents (about 0.05% to about 0.3% as fluorion) and anti-calculus agent (about 0.1% to about 13%).Certainly, tooth powder comprises basically all aneroid components.

Other embodiment of this theme invention is liquid product, comprises collutory or collutory, mouth spraying agent, dental solution and flush fluid.The component of these mouth wash shuies and mouth spraying agent typically comprises one or more water (about 45% to about 95%), ethanol (about 0% to about 25%), wetting agent (about 0% to about 50%), tensio-active agent (about 0.01% to about 7%), seasonings (about 0.04% to about 2%), sweeting agent (about 0.1% to about 3%) and tinting material (about 0.001% to about 0.5%).This type of collutory and mouth sprays also can comprise one or more caries preventive agents (about 0.05% to about 0.3% as fluorion) and anti-calculus agent (about 0.1% to about 3%).The component of dental solution generally comprises one or more in water (about 90% to about 99%), sanitas (about 0.01% to about 0.5%), thickening material (0% to about 5%), seasonings (about 0.04% to about 2%), sweeting agent (about 0.1% to about 3%) and the tensio-active agent (0% to about 5%).

Can be comprised in oral area acceptable carrier in the composition of the present invention or the type of vehicle, in company with concrete limiting examples, will discuss in the chapters and sections below.

The tooth affinity agent

The present invention can comprise the tooth affinity agent, polymeric surfactant (PMSA) for example, and this polymeric surfactant is polymer electrolyte, more particularly is anionic polymer.Described polymeric surfactant comprises anionic group, and for example therefore phosphate radical, phosphonate radical, carboxylate radical or their mixture have and positively charged ion or the interactional ability of positively charged entity." mineral substance " descriptor is intended to show the surfactivity of polymkeric substance or affinity for mineral surfaces, for example calcium phosphate mineral or tooth.

Polymeric surfactant can be used in the composition of the present invention owing to having anti-color spot beneficial effect.It is believed that, described polymeric surfactant can provide anti-color spot beneficial effect, this is because they have reactivity or affinity to mineral surfaces, cause not expecting the film protein portion desorb that is adsorbed, be specifically with in conjunction with the color body that stains tooth, dental calculus development and attract that inadvisable little living bacterial classification accompanies those.The confining force of these polymeric surfactants on tooth can prevent that also color spot from producing, and this is due to the destruction of color body binding site on dental surface.

It is believed that polymeric surfactant in conjunction with in the dental care products short add lustre to the spot composition for example the ability of stannous ion and cationic antimicrobial agent also be useful.Described PMSA also can provide the dental surface conditioning effect, and its effects on surface thermodynamic property and surface film character produce suitable impact, this gargle wash or scrub during and the most important thing is gargling the clean feel aesthetic property of giving improvement after washing or scrubbing.In the time of in being applied to oral compositions, many these polymeric reagents also known or expectation can provide the beneficial effect of control tartar, thereby provide improvement in tooth outward appearance and they aspect human consumer's sense of touch.

Suitable surface effect comprises: produce immediately the wetting ability dental surface after 1) processing; With 2) product is long-term after using keeps surface conditioning effects and to the control of film, comprise scrub or gargle wash after and longer whole during.Cause beneficial effect that surface hydrophilicity increases can by water contact angle relatively reduce record.Importantly, after using product, water-wetted surface keeps on dental surface for a long time.

Polymer-mineral matter tensio-active agent comprises that dental surface is had strong avidity, is deposited as polymer layer or tectum and produces any reagent of required surface modification effect at dental surface.The suitable example of this base polymer is polymer electrolyte, for example polycondensation phosphorylation polymkeric substance, polyphosphonates, phosphorous acid group-or the monomer of phosphonic acid ester or the multipolymer of polymkeric substance and following material: ethylenically unsaturated monomers and amino acid or other polymkeric substance, for example protein, polypeptide, polysaccharide, polyacrylic ester, polyacrylamide, polymethacrylate, poly-ethyl propylene acid esters, the polymethyl acrylic acid hydroxyalkyl acrylate, polyvinyl alcohol, polymaleic anhydride, the polymaleic acid ester, polymeric amide, polyvinylamine, polyoxyethylene glycol, polypropylene glycol, polyvinyl acetate and polyvinyl benzyl chloride, the polymkeric substance of polycarboxylate and carboxyl substituted and their mixture.Suitable polymer-mineral matter tensio-active agent comprises the United States Patent (USP) 5,292,501,5 of all authorizing the people such as Degenhardt, 213,789,5,093,170,5,009,882 and 4,939, the alkoxide polymer of the carboxyl substituted described in 284 and authorize the people's such as Benedict United States Patent (USP) 5, the polymkeric substance that bisphosphonates described in 011,913 is derived; Synthetic anionic polymer comprises the multipolymer (such as Gantrez) of polyacrylic ester and maleic anhydride or toxilic acid and methylvinylether, as authorizes described in the people's such as Gaffar the United States Patent (USP) 4,627,977.Preferred polymkeric substance is the polyacrylic acid of bisphosphonates modification.The activated polymkeric substance of tool has enough surface adhesion characteristics so that the desorb of film protein and maintenance are invested on the enamel surface.For dental surface, the polymkeric substance with end or side chain phosphoric acid salt or phosphonic acid ester functional group is preferred, can prove validity yet have mineral substance according to absorption avidity in conjunction with other polymkeric substance of activity.

Suitable other example that contains phosphonic acid ester polymer-mineral matter tensio-active agent comprises the US4 that authorizes the people such as Degenhardt, disclosed bisphosphonate ester polymer as anti-calculus agent in 877,603; Authorize the people's such as Dursch US4,749,758 and GB1, the disclosed multipolymer that contains phosphonate groups in 290,724 (all the transferring Hoechst), it is applicable in washing composition and the cleaning compositions; With the US5 that authorizes Zakikhani and equal, disclosed multipolymer and the cotelomer that can be used for comprising in the application that suppresses tartar and burn into coating, joint compound and ion exchange resin in 980,776 and authorize the people's such as Davis US6,071,434.Other polymkeric substance comprises GB1,290, the water solubility copolymer of disclosed vinyl phosphoric acid and vinylformic acid and salt thereof in 724, wherein said multipolymer comprises by weight about 10% to about 90% vinyl phosphoric acid and about 90% to about 10% vinylformic acid by weight, more particularly, the vinyl phosphoric acid that has of wherein said multipolymer and acrylic acid weight ratio are 70% vinyl phosphoric acid than 30% vinylformic acid; 50% vinyl phosphoric acid is than 50% vinylformic acid; Or 30% vinyl phosphoric acid is than 70% vinylformic acid.Other suitable polymkeric substance comprises by Zakikhani and the disclosed water-soluble polymers of Davis, its by bisphosphonates or polyphosphonates monomer and at least a other compound with unsaturated C=C key (as, acrylate and methacrylate monomer) copolymerization make, described polyphosphonates monomer have one or more undersaturated C=C keys (as, vinylidene-1,1-di 2 ethylhexyl phosphonic acid and 2-(hydroxyl oxygen phosphino-) ethylidene-1, the 1-di 2 ethylhexyl phosphonic acid), described polymkeric substance for example has those of following structure:

1. the vinylformic acid and 2-(hydroxyl oxygen phosphino-) ethylidene-1 that have following structure, the cotelomer of 1-di 2 ethylhexyl phosphonic acid:

2. have the vinylformic acid of following structure and the multipolymer of vinyl di 2 ethylhexyl phosphonic acid:

Suitable polymkeric substance comprises bisphosphonates/acrylic ester polymer, and it is provided take trade(brand)name ITC 1087 (molecular-weight average as 3000 to 60,000) and Polymer 1154 (molecular-weight average is 6000 to 55,000) by Rhodia.

Preferred polymeric surfactant other component in oral care composition for example fluorion and metal ion in the presence of be stable.Also preferably in the high preparation of water-content, have the polymkeric substance of limited hydrolysis degree, thereby might obtain simple single phase dentifrice or collutory preparation.If polymeric surfactant does not have these stabilising characteristics, a kind of selection is dual phase formulation, and polymer-mineral matter tensio-active agent and fluorochemical or other inconsistent component are separated.The another kind of selection is that non-aqueous, substantially non-aqueous or the composition with limited water gaging of preparation is to minimize the reaction between PMSA and other component.

Preferred polymeric surfactant is polyphosphate.Although there are some cyclic polyphosphoric acid salt derivatives, it has been generally acknowledged that poly-phosphate is comprised of two or more phosphate molecules of mainly arranging with linear configuration.Although pyrophosphate salt (n=2) says polyphosphate technically, but required polyphosphate be have a three or more approximately phosphate groups those so that the surface adsorption of effective concentration can produce enough non-binding phosphate radicals functional group, this has strengthened surperficial anion form surface charge and water-wet behavior.In all phosphoric acid salt, the inorganic phosphate of expectation comprises tri-polyphosphate, four poly-phosphate and hexametaphosphate.The poly-phosphate larger than four poly-phosphate occurs with the amorphous glass material usually.The straight chain polyphosphate that preferably has in the present invention following formula:

XO(XPO ₃) _nX

Wherein X is sodium, potassium or ammonium, and n mean value is about 3 to about 125.Preferred polyphosphate is that n mean value is those of about 6 to about 21, for example by FMC Corporation and Astaris produce with commercially available those of trade(brand)name Sodaphos (n ≈ 6), Hexaphos (n ≈ 13) and GlassH (n ≈ 21).These polyphosphate may be used singly or in combin.Polyphosphate when especially being lower than pH5, is easy to be hydrolyzed in the high preparation of water-content under acid pH.Therefore, preferably using the long-chain polyphosphate, is that mean chain length is about 21 Glass H specifically.It is believed that this type of long-chain polyphosphate can produce the short chain polyphosphate when the experience hydrolysis, it still can effectively be deposited on the tooth and anti-color spot beneficial effect is provided.

Substituting except polyphosphate or as polyphosphate, can use the compound of other Tripyrophosphoric acid, specifically Tripyrophosphoric acid inositol compound, for example phytic acid, inositol five (dihydrogen phosphoric acid ester), inositol four (dihydrogen phosphoric acid ester), inositol three (dihydrogen phosphoric acid ester) and their an alkali metal salt, alkaline earth salt or ammonium salt.This paper is phytic acid and its an alkali metal salt, alkaline earth salt or ammonium salt preferably, and phytic acid also is called as inositol 1,2,3,4,5,6-six (dihydrogen phosphoric acid ester) or phytinic acid.Term " phytinic acid " comprises phytic acid and its salt and other Tripyrophosphoric acid inositol compound herein.

The amount of tooth affinity agent is generally about 0.1% to about 35% by the weighing scale of described total oral compositions.In dentifrice formulation, described amount is preferably about 2% to about 30%, and more preferably from about 5% to about 25%, and most preferably from about 6% to about 20%.In the collutory composition, it is about 0.1% to 5% that the amount of tooth affinity agent is preferably, and more preferably from about 0.5% to about 3%.

Except producing surface modification effect, the tooth affinity agent also can be used for stablizing undissolved salt.For example, found the insoluble tin salt of Glass H polyphosphate solubilized.Therefore, in the composition that for example comprises tin salt, Glass H helps to reduce the color spot growgh promoting effects of inferior tin.

Fluoride source

Usually has the water soluble fluoridized compounds of capacity in dentifrice and other oral cavity composition in order to provide fluorinion concentration for composition, and/or when described fluoride compound take by weight for about 0.0025% to about 5.0%, can provide anti-caries effect during preferred about 0.005% to about 2.0% concentration use.The material of multiple generation fluorion can be used as soluble fluoride source suitable in the present composition.The suitable example that produces the fluorion material is disclosed in the United States Patent (USP) 3,535,421 of authorizing the people such as Briner on October 20th, 1970 and authorized on July 18th, 1972 in the people's such as Widder the United States Patent (USP) 3,678,154.Representational fluoride sources comprises: tin protofluoride, Sodium Fluoride, Potassium monofluoride, sodium monoflurophosphate, indium and other multiple source.Tin protofluoride and Sodium Fluoride and their mixture are preferred.

Abrasive

The dental abrasive that can be used in this theme invention composition comprises many different materials.Selected material must be with composition in relevant substances compatible and can the excessive wear dentine.Suitable abrasive comprises, for example comprise the silicon-dioxide of gel and precipitation, undissolved Sodium polymetaphosphate, hydrated aluminum oxide, calcium carbonate, Bibasic Calcium Phosphate dihydrate, Calcium Pyrophosphate, tricalcium phosphate, poly-calcium metaphosphate and resin ground material, such as the particle condensation product of urea and formaldehyde.

The another kind of abrasive that is used for this composition is the particulate state thermosetting polymer resin, is described in the United States Patent (USP) 3,070,510 of authorizing Cooley and Grabenstetter on December 25th, 1962.Suitable resin comprises for example trimeric cyanamide, phenol, urea, trimeric cyanamide-urea, carbamide, melocol, trimeric cyanamide-melocol, cross-linked epoxy compound and cross-linked polyester.

Preferred polytype silica dental abrasives makes the special cleaning of tooth but unique beneficial effect of the polished performance of not overwear vt. tooth glaze or dentine because they have.The median size of abrasive silica polishing material of the present invention and other abrasive is usually at about 0.1 to about 30 microns, and preferred about 5 to about 15 microns scope.Described abrasive can be precipitated silica or silica gel, as being published in the United States Patent (USP) 3,538,230 of authorizing the people such as Pader on March 2nd, 1970 and being published in the United States Patent (USP) 3 of authorizing DiGiulio on January 21st, 1975, silica xerogel described in 862,307.Example comprises W.R.Grace ﹠amp; The silica xerogel that Company, DavisonChemical Division sell take " Syloid " as trade(brand)name and for example J.M.Huber Corporation with trade(brand)name

The precipitated silica of selling especially has

119, 118,

109 Hes

The silicon-dioxide of 129 names.This class silica dental abrasives that can be used in the toothpaste of the present invention is described in greater detail in the United States Patent (USP) 4,340,583 of authorizing Wason July 29 nineteen eighty-two; The United States Patent (USP) that is published on February 18th, 1,997 5,603,920 with common transfer; Be published in the United States Patent (USP) 5,589,160 on December 31st, 1996; Be published in the United States Patent (USP) 5,658,553 on August 19th, 1997; Be published in the United States Patent (USP) 5,651,958 and the United States Patent (USP) 6,740,311 that is published on May 25th, 2004 on July 29th, 1997.

Applicable abrasive mixture is above-mentioned as listing in

The silica abrasive of different grades.The total amount of abrasive is generally about 6% by weight to about 70% scope in the Dentrifice composition of this theme invention; Toothpaste preferably comprises about 10% to about 50% abrasive by weight of the composition.Tooth solution, mouth sprays, collutory and the non-abrasive property gelatinous composition of the invention of this theme typically seldom contain or do not contain abrasive.

Anti-calculus agent

This composition optionally comprises additional anti-calculus agent, as can be used as the pyrophosphate salt of pyrophosphate ion source.The pyrophosphate salt that uses in the present composition comprises tetra-sodium two an alkali metal salts, tetra-sodium four an alkali metal salts and their mixture.Sodium Acid Pyrophosphate (Na ₂H ₂P ₂O ₇), tetrasodium pyrophosphate (Na ₄P ₂O ₇) and tetrapotassium pyrophosphate (K ₄P ₂O ₇) not hydration and hydrated form be preferred substance.In composition of the present invention, pyrophosphate salt can be with a kind of existence the in three kinds of modes: basically dissolving, basically do not dissolve, or the mixture of dissolving and undissolved pyrophosphate salt.

Comprise that the composition of the pyrophosphate salt of dissolving refers to that wherein at least a pyrophosphate ion source has enough amounts so that the composition at least about 1.0% free pyrophosphate ion to be provided basically.The content of free pyrophosphate ions can be about 1% to about 15%, is about 1.5% to about 10% in one embodiment, is about 2% to about 6% in another embodiment.According to the difference of composition pH value, free pyrophosphate ions can exist by various protonation states.

Comprising basically that the composition of undissolved pyrophosphate salt refers to comprise is lower than approximately 20%, preferably is dissolved in composition in the composition less than total pyrophosphate salt of about 10%.In these compositions, tetrasodium pyrophosphate is preferred pyrophosphate salt.In Dentrifice composition, tetrasodium pyrophosphate can be anhydrous form or decahydrate form, or any other is stable at the kind of solid form.Salt is its solid particulate form, and this form can be its crystallization and/or amorphous state.The particle diameter of salt is preferred enough little of can accept with in use soluble on attractive in appearance.The pyrophosphate salt amount of using in these compositions in preparation is any amount that can effectively control dental calculus, and this amount is generally about 1.5% to about 15% by the weighing scale of described Dentrifice composition, and preferably about 2% to about 10%, and most preferably from about 3% to about 8%.

Composition also can comprise the mixture of dissolving and undissolved pyrophosphate salt.Can use above-mentioned any pyrophosphate salt of mentioning.

At Kirk ﹠amp; In the 3rd edition the 17th volume (Wiley-Interscience Publishers, 1982) of " the Encyclopedia of Chemical Technology " of Othmer pyrophosphate salt has been described in more detail.

Can replace or can comprise known substance with the optional reagent that pyrophosphate salt is used in combination, the anionic polymer that for example synthesizes, the multipolymer (for example Gantrez) that comprises polyacrylic ester and maleic anhydride or toxilic acid and methylvinylether, such as at the United States Patent (USP) 4 of authorizing the people such as Gaffer, described in 627,977; And poly-aminopropanesulfonic acid (AMPS), diphosphonate (EHDP for example for example; AHP), polypeptide (for example poly aspartic acid and polyglutamic acid) and their mixture.

Sequestrant

Another optional reagent is sequestrant, also claims sequestering agent, such as glyconic acid, tartrate, citric acid and its pharmaceutically useful salt.The complexing of sequestrant energy is present in the calcium in the bacteria cell wall.Sequestrant also can destroy dental plaque by remove calcium from the calcium bridge, and described calcium bridge helps to keep biomass intact.Yet, do not wish to use the sequestrant that calcium was had high-affinity, because this can cause the tooth demineralize, this deviates from mutually with purpose of the present invention and intention.The common calcium binding constant of suitable sequestrant is about 10 ¹To 10 ⁵So that the cleaning action that improves of the dental plaque that form to reduce and calculus to be provided.Sequestrant also has the ability compound with metal ion, therefore helps to prevent the disadvantageous effect of product aspect stability or outward appearance.The chelating for example ion of iron or copper helps to postpone the deterioration by oxidation of finished product.

Suitable sequestrant example is gluconic acid sodium salt or potassium and Trisodium Citrate or potassium, citric acid/alkali metal citrate combination; Disodium tartrate, di-potassium tartrate, Seignette salt, sodium hydrotartrate, tartarus, sodium polyphosphate, potassium or ammonium and and their mixture.The amount that is applicable to sequestrant among the present invention is about 0.1% to about 2.5%, is preferably about 0.5% to about 2.5%, and more preferably about 1.0% to about 2.5%.

The polycarboxylate that also to be applicable to other sequestrant of the present invention be anionoid polymerization.These materials are well-known in the art, and they are used with the form of its free acid or part or the preferred fully water-soluble alkali of neutralization (for example potassium, and preferred sodium) salt or ammonium salt.Example is 1:4 to the 4:1 multipolymer of maleic anhydride or acid and another kind of polymerisable ethylenically unsaturated monomers, and described monomer preferably has about 30,000 methylvinylethers (methoxy-ethylene) to about 1,000,000 molecular weight (M.W.).These multipolymers for example obtain with trade(brand)name GantrezAN 139 (M.W.500,000), AN119 (M.W.250,000) and the S-97 pharmaceutical grade (M.W.70,000) of GAF Chemicals Corporation.

Other effective polymeric polycarboxylate comprises the 1:1 multipolymer of maleic anhydride and ethyl propenoate, hydroxyethyl methylacrylate, NVP or ethene, the latter can trade(brand)name Monsanto EMA No.1103 for example, MW10,000 and EMA Grade 61 obtain and the 1:1 multipolymer of vinylformic acid and methyl methacrylate or hydroxyethyl methylacrylate, methyl acrylate or ethyl propenoate, IVE or NVP.

Additional effective polymerization polyphosphate is disclosed in the United States Patent (USP) 4 of authorizing Gaffar on February 6th, 1979, authorized the people's such as Gaffar United States Patent (USP) 4,183 on January 15th, 138,477 and 1980,914, and comprise the multipolymer of maleic anhydride and vinylbenzene, iso-butylene or ethyl vinyl ether; Polyacrylic acid, polymethylene Succinic Acid and polymaleic acid; Low to 1,000 sulfo group acrylic acid oligomer with the molecular weight of commodity Uniroyal ND-2 by name.

Other promoting agent

The present invention optionally comprises other reagent, such as biocide.Being included in this reagent is water-insoluble non-cationic biocide such as halogenated diphenyl ethers, oxybenzene compound, and described compound comprises halogenated phenol, Resorcinol and derivative thereof, bisphenol cpd and halo salicylamide, benzoin ester and the halo carbanilide of phenol and homologue, an alkyl and many alkyl and aromatics.Water soluble antimicrobials comprises quaternary ammonium salt and two-two guanidinesalts and triclosan monophosphate.Quaternary ammonium reagent comprise on the quaternary nitrogen wherein one or two substituent carbon chain lengths (being generally alkyl) for about 8 to about 20, be generally about 10 to 18 carbon atoms, remain simultaneously substituting group (being generally alkyl or benzyl) and have lower carbonatoms according to appointment 1 to about 7 carbon atoms, be generally those of methyl or ethyl.Typical quaternary ammonium antiseptic-germicide embodiment has Trimethyllaurylammonium bromide, TPC, brominated phenododecinium bromide, chlorination N-tetradecyl-4-ethylpyridine, dodecyl dimethyl (2-benzene oxygen ethyl) brometo de amonio, benzyl dimethyl stearyl chlorination ammonium, cetylpyridinium chloride, quaternised 5-amino-1, two (2-the ethylhexyl)-5-methyl hexahydropyrimidines of 3-, alkyl benzyl dimethyl ammonium chloride, benzethonium chloride and methyl benzethonium chloride.Other compound is the two [4-(R-is amino)-1-pyridine alkane that are disclosed in the United States Patent (USP) of authorizing Bailey 4,206,215 of announcing on June 3rd, 1980.Also can comprise other biocide such as mantoquita, zinc salt and tin salt.Also enzyme usefully comprises endo-glycosidase, papoid, dextranase, dextran allosteric lytic enzyme (mutanase) and their mixture.Mentioned reagent is disclosed in the United States Patent (USP) 2,946,725 of authorizing the people such as Norris July 26 nineteen sixty and authorized on September 27th, 1977 in the people's such as Gieske the United States Patent (USP) 4,051,234.Preferred biocide comprises for example thymol of zinc salt, tin salt, cetylpyridinium chloride, chlorhexidine, triclosan, triclosan monophosphate and flavor oil.Triclosan and this type of other reagent are disclosed in the Parran that announced on May 14th, 1991, and the people's such as Jr. United States Patent (USP) 5,015,466 and being disclosed in is announced January 16 nineteen ninety authorizes the people's such as Nabi United States Patent (USP) 4,894,220.These reagent can provide the antiplaque beneficial effect, and the content of these reagent is generally about 0.01% to about 5.0% by weight of the composition.

The another kind of optional promoting agent that can join in the present composition is the dentin desensitizer of control hypersensitivity, for example the salt of potassium, calcium, strontium and tin comprises nitrate, muriate, fluorochemical, phosphoric acid salt, pyrophosphate salt, polyphosphate, Citrate trianion, oxalate and vitriol.

Peroxide source

Composition of the present invention can comprise peroxide source, because it has numerous beneficial effects to the oral cavity.People early have recognized that, hydrogen peroxide and other comprise peroxide reagent can for after carious tooth, dental plaque, gingivitis, periodontitis, halitosis, teeth stains, recurrent oral ulcer, artificial tooth induced pain, appliance damage, the exodontia and behind the periodontal surgery, traumatic oral damage and mucosal infections, viral stomatitis etc. carry out effectively therapeutic and/or prophylactic treatment.The reagent that comprises superoxide applies the chemical machinery effect in the oral cavity, generate the thousands of small oxygen bubbles by producing with histaminase and ptyalin interaction.Gargling of collutory moved with strengthening this intrinsic chemical machinery effect.Recommended to be used for other reagent is delivered in the infected gums crack with this type of.The superoxide collutory can prevent the known anaerobic bacterium relevant with periodontopathy surely to grow and breed.

Peroxide source comprises superoxide, perborate, percarbonate, peroxy acid, persulphate and their combination.Suitable superoxide comprises hydrogen peroxide, urea peroxide, calcium peroxide, sodium peroxide, zinc peroxide and their mixture.Preferred percarbonate is SPC-D.Preferred persulphate is potassium hydrogen persulfate.The peroxide source that is preferred in the dentifrice formulation comprises calcium peroxide and urea peroxide.Hydrogen peroxide and urea peroxide are preferred in the collutory preparation.Following amount represents the amount of superoxide raw material, although peroxide source also can comprise the composition outside the superoxide raw material.Composition of the present invention can comprise by weight of the composition about 0.01% to about 30%, preferred about 0.1% to about 10%, and 0.5% to about 5% peroxide source more preferably from about.

Tensio-active agent

This composition also can comprise tensio-active agent, and it is also referred to as pore forming material usually.Suitable tensio-active agent has the material of appropriateness stability and foam for those in whole wide pH value scope.Tensio-active agent can be negatively charged ion, non-ionic, both sexes, zwitterionic, cationic or their mixture.

Can be used for anion surfactant of the present invention comprises and contains 8 water-soluble salts to the alkylsurfuric acid of 20 carbon atoms (such as sodium alkyl sulfate) in the alkyl and contain 8 to the water-soluble salt of the sulfonation monoglyceride of the lipid acid of 20 carbon atoms.The example of this analog anion surfactants is Sodium Lauryl Sulphate BP/USP (SLS) and coco group monoglyceride sulfonates.Other suitable anion surfactant is sarcosinate such as sodium lauroyl sareosine, taurate, lauryl sulfoacetate sodium, lauroyl sodium isethionate, laureth carboxylic acid sodium and Sodium dodecylbenzene sulfonate.Also can use the mixture of anion surfactant.Many suitable anion surfactants are disclosed in the United States Patent (USP) 3,959,458 of authorizing the people such as Agricola on May 25th, 1976.The typical content scope of anion surfactant is about 0.025% to about 9% in this composition, is about 0.05% to about 5% in some embodiments, is about 0.1% to about 1% in other embodiments.

Another kind of suitable tensio-active agent is to be selected from the group that is comprised of sarcosinate surfactant, hydroxyethylsulfonic acid salt surfactant and taurate tensio-active agent.What preferably can be used for this paper is basic metal or the ammonium salt of these tensio-active agents, such as following sodium salt and sylvite: Sarkosyl L salt, Hamposyl M salt, palmitoyl sarcosine salt, Hamposyl S salt and oleoyl sarcosinates.Described sarcosinate surfactant can be by the weighing scale of described total composition about 0.1% to about 2.5%,, preferred about 0.5% to about 2.0% amount is present in the present composition.

Be used for cats product of the present invention and comprise that the derivative (described compound has a chain alkyl chain that comprises about 8 to 18 carbon atoms) of aliphatic quaternary ammonium compound is such as lauryl trimethyl ammonium chloride; Cetylpyridinium chloride; Cetyl trimethylammonium bromide; Diisobutyl benzene oxygen ethyl dimethyl benzyl ammonium chloride; Coco group alkyl trimethyl ammonium nitrite; Fluoridize hexadecyl pyridine etc.Preferred compound is quaternary ammonium fluoride, and it is described in the people's such as Briner that announced on October 20th, 1970 the United States Patent (USP) 3,535,421, and wherein said quaternary ammonium fluoride has detergent property.In composition disclosed by the invention, some cats product also can be used as sterilant.Although cats product such as chlorhexidine also are applicable to the present invention, because they can stain oral hard tissue, be not preferred therefore.Skilled in the art will recognize that this possibility, and when mixing cats product, must know this restricted.

The ionic surfactant pack that can be used in the present composition is drawn together the compound that is produced with the organic hydrophobic compound condensation that itself can be aliphatic series or alkyl aromatic by alkylidene oxide group (itself is hydrophilic).The embodiment of suitable nonionogenic tenside comprises the polyethylene oxide condensation compound of addition polymer (polyethers), the alkylphenol of polypropylene glycol and oxyethane, derived from the mixture of ethylene oxide condensate, long chain tertiary amine oxide compound, long chain tertiary phosphine oxide, long-chain dialkyl sulphoxide and these materials of the product of the condensation of the reaction product of oxyethane and propylene oxide and 1，2-diaminoethane, fatty alcohol.

Be used for the derivative that zwitter-ion synthetic surfactant of the present invention comprises aliphatic quaternary ammonium, Phosphonium and sulfonium compound, wherein this aliphatic group can be straight or branched, and one of them aliphatic substituting group comprises about 8 to 18 carbon atoms, and an aliphatic substituting group comprises the anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.

Suitable beet alkali surface activator is disclosed in the United States Patent (USP) 5,180,577 of authorizing the people such as Polefka on January 19th, 1993.Typical alkyl dimethyl betaine comprises decyl betaine or 2-(N-decyl-N, the N-dimethyl amine) acetic ester, coco betaine or 2-(N-cocoyl-N, N-dimethyl amine) acetic ester, tetradecyl trimethyl-glycine, palmityl betaine, lauryl betaine, cetyl betaine, stearyl betaine etc.The example of amido betaines has cocoamidoethyl trimethyl-glycine, cocoamidopropyl, lauramido propyl betaine etc.Selected trimethyl-glycine comprises cocoamidopropyl, and preferred lauramido propyl betaine.

Thickening material

When preparation toothpaste or gel, add thickening material so that required composition denseness, in use required active substance release characteristics, the stability that frame is hidden stability and composition etc. to be provided.Suitable thickening material comprises one or carboxy vinyl polymer, carrageenin, Natvosol (HEC), natural and the water-soluble salt of synthesis of clay (being veegum and LAPONITE) and ether of cellulose such as the combination of Xylo-Mucine (CMC) and carboxymethyl hydroxyethyl cellulose sodium.Also can use natural gum such as kuteera gum, xanthan gum, Sudan Gum-arabic and tragacanth gum.The silicon-dioxide of colloidal magnesium aluminum silicate or segmentation can be used as the part thickening material with the further texture that improves.

The suitable carboxy vinyl polymer that can be used as thickening material or jelling agent comprises carbomer, and it is the crosslinked class homopolymer of vinylformic acid and pentaerythritol alkyl ether or sucrose alkyl oxide.Carbomer can

Series is commercially available from B.F.Goodrich, comprises Carbopol 934,940, and 941,956 and their mixture.

Thickening material can by described total toothpaste or gelatinous composition usually about 0.1% to about 15%, preferred about 2% to about 10%, more preferably from about 4% to about 8% amount is used.Higher concentration can be used for gel under chewing gum, medicinal sugar and breath freshening mint, sachet, non-abrasive property gel and the gum.

Wetting agent

Another kind of optional solid support material is wetting agent in this composition.Wetting agent is used for preventing that dentifrice composition from hardening behind ingress of air, and makes composition give the oral cavity with damp, and for specific wetting agent, wetting agent also can be used for giving dentifrice composition with desirable sweet taste.Take pure wetting agent as the basis, the content of this wetting agent is generally about 0% to about 70%, preferred about 5% to about 25% by the weighing scale of the present composition.The suitable wetting agent that is used for this theme invention composition comprises edible polyvalent alcohol, such as glycerine, sorbyl alcohol, Xylitol, butyleneglycol, polyoxyethylene glycol, propylene glycol and Trimethyl glycine.

Mix solid support material

That the water that uses when the commercial suitable oral cavity composition of preparation should preferably hang down ion content and do not contain organic impurity.The content of water mostly is about 99% most by the weighing scale of aqueous composition described herein.The amount of these water comprises the free-water of adding and the water of being brought into by other materials (as by sorbyl alcohol).

The present invention also can comprise alkali metal hydrocarbonate, and it can provide many functional packet spotting-in mills, deodorizing, buffering and adjusting pH value.Alkali metal hydrocarbonate is water miscible, unless stabilized, it is easy to release of carbon dioxide in Aquo System.Sodium bicarbonate (being also referred to as saleratus) is the alkali metal hydrocarbonate of commonly using.This composition can comprise about 0.5% to about 30%, and preferred about 0.5% to about 15%, most preferably from about 0.5% to about 5% alkali metal hydrocarbonate.

By using the pH value of buffer reagent adjustable composition.As used herein, buffer reagent relates to for regulating for example reagent of collutory and dental pH value of solution of aqueous composition.In view of peroxide stability, preferably pH regulator is arrived about pH4.0 to the scope of about pH6.0.Buffer reagent comprises sodium bicarbonate, monosodium phosphate, tertiary sodium phosphate, sodium hydroxide, yellow soda ash, trisodium phosphate, citric acid and Trisodium Citrate.The typical amounts of buffer reagent counts about 0.5% to about 10% by the weight of this composition.

Poloxamer can be used in this composition.Poloxamer belongs to nonionogenic tenside, also can be divided into emulsifying agent, tackiness agent, function that stablizer is relevant with other by function.Poloxamer is the terminal difunctionality block polymer of primary hydroxyl that is, molecular weight is from 1,000 to surpassing 15,000.Poloxamer is sold with trade(brand)name Pluronics and Pluraflo by BASF.The suitable poloxamer of the present invention is Poloxamer 407 and Pluraflo L4370.

Can be used for other emulsifying agent in this composition and comprise that polymer emulsifier is as available from B.F.goodrich

Series, and it mainly is the acrylic acid polymer of high molecular, as the emulsifying agent of lyophobic dust.

Titanium dioxide also can be added in this composition.Titanium dioxide is the white powder that opacity can be provided to composition.The content of titanium dioxide is generally about 0.25% to about 5% by the weighing scale of described Dentrifice composition.

Other optional reagent that can be used for this composition comprises the dimethicone copolyol that is selected from alkyl dimethicone copolyol and alkoxyl group dimethicone copolyol, such as C12-C20 alkyl dimethicone copolyol and their mixture.It is highly preferred that the hexadecyl dimethione polyol of trade(brand)name Abil M90.Usually, the content of dimethicone copolyol is about 0.01% to about 25% by weight, and preferred about 0.1% to about 5%, more preferably from about 0.5% to about 1.5%.This dimethicone copolyol assisted Extraction is for positive tooth feel beneficial effect.

Produce the removal of malodor components in the flavor oil

Another aspect of the present invention be refining or purification process to remove or significantly to reduce the content of inadvisable S-contained substance in flavor oil and the extract, prepare alleged " selectivity " flavor oil of this paper.

Method for washing

Preferred purification process is method for washing, and it is simple, inexpensive, and is easy to extensive enforcement.Water-bearing media can be the mixture of water or water and solvent entirely, and wherein solvent is about 20% or lower.The method of removing inadvisable component relates generally to they are extracted into from flavor oil and contains aqueous phase.DMSO and dimethyl sulfone are height polarity, and can freely be dissolved in water or other solvent for example in the alcohol.Be easy to the mixture with tasteless water or water and alcohol, these compounds are extracted from oil.The cosolvent for example use of alcohol can improve the low for example removal of DMS of material of polarity.Described cosolvent can be any food grade water miscible solvent, for example ethanol, Virahol, glycerine and propylene glycol, and it will extract for example DMS of worthless material from oil, and can significantly not extract required component.The pH of water-bearing media is generally about 3 to about 12, and preferred about 7 to the scope of neutrality.Definite pH preferred value depends on the pH stability of the flavor oil of processing.Described water-bearing media is optional to comprise salt, and it can help to make most of flavor components " to saltout out " from containing aqueous phase, and they are remained in the flavor oil self.With about 90:10 to about 10:90, preferred about 70:30 water of about 30:70 scope extremely: the oil volume ratio, with flavor oil sample and water-bearing media mixing.Usually, water is more, and the speed of removing DMSO is faster.Yet too much water can cause emulsification, and causes oil phase and water finally to be difficult to separate.Can use conventional water, preferred USP level water.Described method is implemented usually at ambient temperature.Equally, the temperature stability of flavor oil is depended in the selection of temperature condition.

Make water and oil phase stand to stir or violent troubled water so that water and oil better contact the mixture of generation muddiness.Oil phase and water are continued to mix about 30 minutes to maximum 3 hours or longer.According to mixing condition and batch sizes, in about 30 minutes, finish fully purifying or extraction, the content of sulphur compounds that is about to residue in the oil is reduced to target content.After mixing stops, making respectively to be separated, then with oil phase and aqueous phase separation.Then with fresh water isolated oil phase is stood the extra muddiness of washing and/or filtering to eliminate any remnants in the described oil by the hydrophilic/hydrophobic sorbing material at every turn.Institute's washing oil also stands centrifugal or cooling and will stay moisture in institute's washing oil from out purpose to reach.At regular intervals in the quantitative analysis oil phase content of DMSO and other sulfocompound need to determine whether extra stirring/mixing or washing step.

Useful high-shear mixer reaches flavor oil and mixes with the improvement that contacts to realize the removal of DMSO within a short period of time with water.Available agitator comprises high-shear mixer, for example is used for the Ross agitator of batch-mixed or on-line mixing.The example of suitable batch agitator comprises the high-speed dispersion mixer (being generally used for 1 gallon to 1000 gallon batch) that is comprised of Z-axis and high-shear disc type blade.Described blade is with at most about 10, the speed rotation of 000RPM and produce flow pattern in fixing mixing vessel.Described blade produces vortex, and it is pulled to blade sharp edges place with container contents.Then described blade is distributed to aqueous phase with the oil phase mechanically breaking up and with it.Another kind of batch agitator model is high-shear rotor-stator agitator design, and it is comprised of the single-stage rotor with high speed rotating in fixed stator.When the blade of rotation passes through stator, their mechanical shearing profit two-phases.Laboratory scale portable agitato has the mixing rate of 500 to 10,000RPM (being used for 0.3 to 15L liquid capacity).The speed of (be the rotor of 64mm to 330mm for diameter) that commercial-scale large stirrer has 3600 to 1200RPM is used for 15L-22, the 710L liquid capacity.The example of the online agitator of ultra-high shear is the Ross model, and it has level Four or multi-stage rotor more, its in fixed stator with speed rotation of 15000 feet per minutes.When the blade of rotation passes through stator, their mechanical shearing contents.

In an example, the 250mL spearmint oil is joined in the 2L glass beaker.To wherein adding 150mLUSP level water, and use the magnetic stirring apparatus vigorous stirring, until oil and water form the mixture of muddiness.At room temperature continue to stir.At about 0.5 hour, 1 hour and 2 hours intervals, stop to stir so that respectively be separated.In several minutes, respectively be separated and take out the 1mL oil sample this for analysis.Stir after 2 hours, make respectively to be separated, and decantation goes out upper strata oil, and make it in vial, leave standstill 24 to 48 hours further to make a small amount of dregs clarification remaining in the oil.Oil is filtered by 0.45um hydrophilic PVDF strainer (Millipore) so that breaking of oil, and be stored in the glass jar, until use.

Unprocessed spearmint oil feed (being provided by I.P.Callison) is implemented aforesaid method, and the content of DMSO illustrates hereinafter in the oil phase.Come quantitative DMSO with GC-MSD.Shown in structure, after washing about half an hour, the DMSO greater than 95% removes from oil, and residual quantity is less than 1ppm after 2 hours.

Sample	DMSO(ppm，w/v)
		Spearmint oil feed #1	307
Wash 35 minutes feed	12.7
		Wash 60 minutes feed	16.5
2hr. wash 2 hours feed	<1

Except DMSO, washing is processed and also have been removed other water-soluble cpds in the oil, for example the pure and mild aldehyde of lower molecular weight and water-soluble relatively poor compound dimethyl sulphide (DMS) for example.Yet, to compare with DMSO, the removal of DMS is carried out with slower speed.It is believed that water polarity dies down when aqueous phase dissolved DMSO and other organic compound, form DMS and have the medium that other compound of similar polarity and dissolubility property has better removal effect.

In another example, the compound that experience water washing process of the present invention is removed from the sample spearmint oil is measured.Make the rectifying spearmint oil sample that is provided by I.P.Callison stand washing in 5 hours, then experience is again with 7 hours step of fresh water washing.Each washing step is all implemented for water and the oil mixt of 1:1, simultaneously mild stirring.Via SPME GC-MS, the spearmint oil before and after this washing step is analyzed, and by comparing the gained chromatogram, assessed about reduction of every kind of component.In following table 2, the part of compounds tabulation that provides its concentration to reduce via washing step.Between removal compound per-cent and Log P (Octanol/water Partition Coefficients), there is goodish dependency.When considering the molecular weight of every kind of compound, described dependency even better.Importantly, in the spearmint oil there be not because of the water-washing step noticeable change relatively nonpolar main ingredient concentration.These main ingredients comprise menthol, piperitone, α-and beta-pinene, limonene etc.

Table 2: the compound of removing by washing spearmint oil

Compound number	The compound that reduces	The approximate per-cent (%) that reduces
			1	Methyl alcohol	95
2	Methyl-formiate	95
			3	Ethanol	95
4	Acetone	65
			5	Furans	90
6	Ethyl formate	90
			7	Methyl acetate	85
8	Dimethyl sulphide	99 +
			9	Dithiocarbonic anhydride	90
10	2 methyl propanal	60
			11	Acetic acid	70
12	2-butanone	70
			13	The 2-methyl furan	70
14	The 3-methyl furan	70
			15	2-methyl isophthalic acid-propyl alcohol	40
16	Crotonic aldehyde	60
			17	3-methyl butyraldehyde	50
18	2 methyl butyraldehyde	50
			19	2 pentanone	35
20	Cyclopentanol	35
			21	The 2-ethyl furan	20
22	2-methyl-1-butene alcohol	15
			23	2 methyl crotonaldehyde	30
24	Dimethyl disulfide	40
			25	The 3-guaiacene	30
26	Hexanal	15
			27	Dimethyl sulfoxide (DMSO)	99 +
28	Furfural	35
			29	The 2-hexenoic aldehyde	15
30	2,5-diethyl THF	5

Aspect odor property, washed or selectivity spearmint oil and traditional rectifying oil are compared.By experienced seasoning panel of experts washed spearmint oil and unwashed rectifying spearmint oil are evaluated, adopted 0 to 100 grade, wherein 0 is poor wet goods level, and 100 be the fabulous oil of quality.The average rank of washing oil is not 33, and the average rank of washed oil is 67, and this shows that washed oil is better than unwashed rectifying oil.

By identical seasoning panel of experts, adopt identical grade, the typical Mentha arvensis L. syn.M.haplocalyxBrig that is used for dentifrice is accounted for leading finished product flavor oil evaluate, described finished product flavor oil comprises 62% rectifying spearmint oil or washed spearmint oil.The average rank of not washing rectifying oil is 58, and the average rank of washed oil is 75, and this shows that washed oil has better quality.

Preparation comprises 0.454% tin protofluoride and with the dentifrice of rectifying spearmint oil or washed spearmint oil seasoning.Dentifrice is stored 3 months under 40 ℃.During this period, contain the excessively oily dentifrice of washing and do not produce any peculiar smell, and not washed rectifying oil has produced peculiar smell really.By experienced seasoning expert existence and the intensity of stench between the shelf lives are implemented evaluation, adopt 0 (free from extraneous odour) to 10 (strong peculiar smell) grade.The evaluation mark of dentifrice sample is as follows.This shows for example stability of the lower washing oil of inferior tin existence of reductive agent.

This series of experiments shows that method for washing can be used for stablizing the rectifying flavor oil and do not experience refining or the natural crude oil of rectification process or rough flavor oil.Advantageously, described method for washing is simple, effective and economical, and has avoided the improper heat of executing to flavor oil.Described method is enough to prepare the business level flavor oil, and need not complicated rectificating method.

Filter method

The another kind of technology that can be used for removing DMSO and other sulphur compound from flavor oil is to filter, and adopts to have optionally to sulphur compound that material carries out.This type of filtering material comprises the material that can be used as sorbent material and molecular sieve of commercially available acquisition.The following material that is provided by Engelhard Corporation and Johnson Matthey Catalysts is provided example.

A) composition of SELEXSORB CDX-hydrated alumina (60-85%w/w%) and aluminosilicate (15-40%w/w), density-42.2 cubic feet, surface-area is 431 meters squared per gram, is of a size of 7 x, 14 orders.

B) composition of SELEXSORB COS-hydrated alumina (88-99%w/w%) and alkalimetal oxide (1-5%w/w%), density-49.8 cubic feet, surface-area is 255 meters squared per gram, is of a size of 7 x, 14 orders.

C) nickel/nickel oxide on the catalyzer CP367-inert support

D) mixture of catalyzer CP366-ventilation breather, zinc subcarbonate and aluminum oxide.

In an example, use above-mentioned materials as sorbent material, the rectifying spearmint oil experience that is provided by I.P Callison is filtered.Sorbing material (60g) is contained in the stainless steel column (deriving from Millipore, 3.5cm diameter x 30cm length) of post bottom outfit filter plate (deriving from the millipore filtration of Millipore, 2um TTTP strainer).The 150mL spearmint oil is poured on post bed top, and collects under the gravity feed oil by post in the bottom.At first collect 75mL oil (being appointed as the 1st cuts), then collect second 75mL ((being appointed as the 2nd cuts).Use preceding method, the oil that filters is carried out DMSO analyze.The results are summarized in hereinafter.

Table 3: from spearmint oil, remove DMSO by filtering

	Sample	DMSO(ppm，w/v)	Remove per-cent (%)
				1	The spearmint oil of rectifying	197	-
2	Selexsorb COS the 1st cuts	173	12
				3	Selexsorb COS the 2nd cuts	130	34
4	Selexsorb CDX the 1st cuts	66	66
				5	Selexsorb CDX the 2nd cuts	7.4	96
6	CP 366 the 1st cuts	173	12
				7	CP 366 the 2nd cuts	138	30
8	CP 367 the 1st cuts	142	28
				9	CP 367 the 2nd cuts	130	34

Counter-current extraction (CCE)

Counter-current extraction (CCE) technology also can be used for removing non-required component from flavor oil.This technology has been used to take off terpenes oil with preparation in the flavour agent industry.In former patented method, by dual solvent extraction method, make essential oil take off terpenes with polarity and non-polar solvent.Described essential oil passes through mixing section, and stirs with two kinds of solvent adverse currents, causes the terpenes continuous extraction in polar solvent.In the modification of former CCE method, take out tangerine oil by the water-alcohol solvent stream contrary pump of taking out with pump in the opposite direction, distribute tangerine oil.Water-alcohol solvent extracts terpenes from tangerine oil.Similarly, make water as extraction agent, the CCE technology can be used for extracting DMSO and other sulphur compound.The CCE technicism is set forth in R.L.Swaine's " Flavoring Agents " (" Food AdditiveToxicology ", 1995, Maga ﹠amp; Tu (editor)) in.

Distillation

But also Application standard distillation and/or extractive technique with the flavor oil fractionation to remove unwanted component.This can implement by the standard distilation steps, for example uses vacuum distillation plant or rotary column sheet-pile.By selecting needed component and making up described component and again process or prepare the finished product flavor oil.For example, in spearmint oil, especially from those of peppermint or pennyroyal source for example in the spearmint oil, up to the present identified and surpassed 225 kinds of volatile compounds.Yet what also determine is that in numerous volatile constituents, only utmost point finite quantity produces actual influence to the whole smell of product really.Therefore, the compound that needs effective screening method great majority to be affected smell is separated from show in a large number extremely weak or scentless volatile compound.Many usually be present in component in the natural menthence so that the peppermint taste of complete equilibrium to be provided preferred comprising as far as possible, and without any peculiar smell or stench.If to spearmint oil hang down selectivity fractionation or refining and more polycomponent remove and do not have add-back, then gained spearmint oil flavor composition may be unacceptable.Therefore, need optionally the fractionation spearmint oil so that desirable peppermint flavour agent the most attractive in appearance to be provided.

By distillation spearmint oil (is comprised usually known those, such as Mentha arvensis L. syn.M.haplocalyxBrig, spearmint and peppermint) fractionation to be to remove worthless volatility (than lower boiling) polar compound, in particular to DMSO and other sulfocompound, for example sulfide and disulphide.Polarity, more lower boiling component can have less than about 120 ℃, less than about 140 ℃, and less than about 160 ℃, or even less than about 180 ℃ boiling point.Described distillating method also will remove other low-molecular weight compound, for example C3-C9 aldehyde and alcohol.

Fractionation or the selectivity spearmint oil be substantially free of the low boiling-point and polarity compound that comprises DMSO and dimethyl sulphide.Other is removed or the component of significantly minimizing comprises the side chain alkanal, for example 2 methyl propanal, 2 methyl butyraldehyde and 3-methyl butyraldehyde; Side chain alkanol, for example 2-methylpropanol, 2-methyl butanol and 3-methyl butanol; Alkenols, for example Z-3-hexenol; Chain olefine aldehydr, for example E-2-hexenoic aldehyde; Other aldehyde, pure and mild ketone, for example 3-methylcyclohexanone, phenyl aldehyde, 1-OCOL, 3-octanone and 2,3-dehydrogenation-1,8-Terpane.The concrete component that the selectivity spearmint oil may comprise is α-pinene, beta-pinene, sabinene, myrcene, α-phellandrene, α-terpinene, limonene, cis-ocimene, eucalyptol, trans-ocimene, γ-terpinene, the 3-octanol, terpinolene, sabinene hydrate, linalool, menthofuran, l-Isopulegol, piperitone, neomenthol, terpinen-4-ols, isomenthone, menthol, neoisomenthol, isomenthol, α-terpinol, pulegone, menthyl acetate, Karvon, the strange menthyl ester of acetic acid, piperitone, the b-bourbonene, β-caryophyllene, thymol, trans-β-farnesene, α-humulone, large root leaf alkene B, elemol, viridiflorol, eucalyptol, γ-terpinene, the 1-octanol, the isovaleric acid n-pentyl ester, 1-methyl-4-(1-methylethyl)-trans-2-tetrahydrobenzene-1-alcohol, the 1-terpinol, α-terpinol, 4,7-dimethyl benzofuran, geraniol, the new menthyl ester of acetic acid, oxymethoxyallylbenzene, ylangene, α-copaene, longifolene, α-gurjunene, caryophyllene, (+)-Biao dicyclo sesquiphellandrene, trans-β-farnesene, β-caryophyllene, alloaromadendrene, γ-cananga oil alkene, large root leaf alkene D, large leaf alkene of dicyclo, 8-cadinene and terpinolene.

Using method

The present invention also relates to the method for cleaning of teeth and the tedious oral condition of prevention, described oral condition comprises carious tooth, infected by microbes, dental plaque, dental calculus, color spot and oral malodor and tooth erosion.

Using method of the present invention comprises that the enamel surface with the trier contacts with oral cavity composition of the present invention with oral mucosa.Using method can for scrub with dentifrice, with dentifrice slurry or mouth wash shua rinsing or chew gum product.Other method comprises the part is contacted with oral mucosa with patient's tooth with buccal cavity gel, mouth spraying agent or other form.The experimenter can be any human or animal that its dental surface contacts described oral compositions." animal " is intended to comprise household pet or other domestic animal, or the animal that encages.

For example, treatment process can comprise that the someone scrubs the tooth of dog with a kind of Dentrifice composition.Another example comprise with oral cavity composition with mouth rinsing sufficiently long time of cat to see beneficial effect.Can prepare the pet care product such as chaw and the toy that comprise this oral cavity composition.Be included in described composition relatively soft but in the robust material, such as rawhide, by natural or the rope that synthon are made and the polymer product of being made by nylon, polyester or thermoplastic polyurethane.When animal chew, lick or when biting the said products, contained active ingredient is released in the saliva matrix in the oral cavity of animal, this is equivalent to effectively scrub or rinsing.

Embodiment

The following example has further described and has proved the embodiment in the scope of the invention.These given embodiment only are in order to illustrate, should not to be considered to limitation of the present invention, because under the condition that does not deviate from the spirit and scope of the invention, it is carried out many changes is possible.

Main ingredient in the selectivity spearmint oil of the present invention is shown in hereinafter.

Example I

Component

％

％

[0171]

α-pinene	0.63	0.19
			Beta-pinene	0.90	0.23
Sabinene	0.03	0.01
			Myrcene	0.03	0.01
α-terpinene	0.01	0.01
			Limonene	0.50	0.05
Cis-ocimene	0.01	0.01
			Eucalyptol	2.64	4.71
Trans-ocimene	0.01	0.01
			γ-terpinene	0.01	0.01
The 3-octanol	0.05	0.05
			Terpinolene	0.01	0.00
Sabinene hydrate	0.04	0.34
			Linalool	0.07	0.59
Menthofuran	0.14	2.16
			L-Isopulegol	0.02	0.02
Piperitone	16.89	2.27
			Neomenthol	2.22	0.86
Terpinen-4-ols	0.03	0.04
			Isomenthone	3.56	0.40
Menthol	66.42	73.87
			Isomenthol	0.04	0.14
α-terpinol	0.35	0.58
			Pulegone	0.14	0.04
Menthyl acetate	3.53	5.95
			The strange menthyl ester of acetic acid	0.01	0.00
Piperitone	0.06	1.35
			The other alkene of beta waves	0.02
β-caryophyllene	0.11	3.12
			Thymol	0.03	0.02
Trans-β-farnesene	0.08	0.01
			α-humulone	0.02	0.24
Large root leaf alkene D	0.32	0.05
			Triacetin		0.17
Large root leaf alkene B		0.08
			Elemol		0.89
Viridiflorol	0.03	0.03
			The peppermint lactone		0.17

The flavor composition that comprises the selectivity spearmint oil of processing according to the present invention is shown in hereinafter.The selectivity spearmint oil is substantially free of DMSO and other stench precursor sulphur compound.In affecting organ sensation test, the flavor composition that comprises spearmint oil of the present invention is accredited as attractive in appearance desirable and can be incorporated in the oral care composition that comprises reductive agent such as Ya Xi and tea-polyphenol and can not produce stench or peculiar smell.

Example II

Composition	％
		The selectivity spearmint oil	60％
The p-propenylanisole	10％
		Menthol	25％
Eucalyptol	5％

EXAMPLE III

Composition	％
		The selectivity spearmint oil	42％
The selectivity Oleum Menthae Rotundifoliae	5％
		The WS-3 refrigerant	10％
The p-propenylanisole	7％
		Menthol	35％
Aloe	1％

Comprise the oral compositions that selectivity spearmint oil in stannous ion, the flavor composition and oral area can accept carrier and be shown in hereinafter, wherein become component to represent with weight percent (%).These compositions can use ordinary method to make.EXAMPLE IV shows the two-phase Dentrifice composition; First-phase and second-phase can be packaged in the divider compartment of physical separation, and usually distribute side by side with the 50:50 ratio.EXAMPLE V shows the single phase dentifrice composition.

EXAMPLE IV

The first Dentrifice composition The second Dentrifice composition

Composition % by weight Composition % by weight

Carboxymethyl cellulose 0.500 sodium hydroxide ( ^B)1.000

Water 2.768 colors 0.300

Flavour agent 1.000 water 21.840

Glycerine 36.432 flavour agents 1.000

Polyoxyethylene glycol 1.500 glycerine 28.992

Propylene glycol 8.000 Sunmorl N 60Ss 4.160

Sodium Lauryl Sulphate BP/USP ^(a)4.000 tin protochloride 3.000

Silicon-dioxide 28.000 silicon-dioxide 23.000

Phenylformic acid 0.600 soluble saccharin 0.300

Sodium Benzoate 0.600 poloxamer 15.500

Soluble saccharin 0.300 tin protofluoride 0.908

Titanium dioxide 1.000

Xanthan gum 0.300

Glass H poly-phosphate15.000

^(a)27.9%solution ^(b)50% solution

EXAMPLE V

Composition	IVA	IVB	IVC	IVD	IVE	IVF	IVG
								Phytic acid (20% solution)	4.000	2.000			10.000
Sodium phytate (20% solution)			10.000	4.000
								Zinc carbonate 1	2.000	1.000		2.000
Zinc oxide			5.000
								Zinc pyrophosphate					8.000
Zinc lactate						2.500
								Sodium polyphosphate						13.000
Tin protofluoride	0.454	0.454		0.454		0.454	0.454
								Sodium Fluoride			0.243		0.243
Tin protochloride			1.500		1.000		1.500
								Tea extract				2.000
EGCG						1.000	1.000
								Sunmorl N 60S	0.672	0.600	0.672	0.600	0.672	0.652	2.100
Sorbitol Solution USP	34.275	35.785	34.275	35.785	34.275		37.496
								Glycerine						38.519	14.425
HEC	0.300	0.300	0.300	0.300	0.300
								Na CMC	1.200	1.300	1.200	1.300	1.200		0.600
Carrageenin	0.500	0.500	0.500	0.500	0.500	0.600
								Xanthan gum						0.350	0.700
PEG						7.000
								Propylene glycol						7.000
Silica abrasive	20.000	16.000	20.000	16.000	20.000	25.000	20.000
								TiO 2(anatase octahedrite)	0.525	0.525	0.525	0.525	0.525		0.525
SLS (28% solution)	4.000	7.500	4.000	7.500	4.000	2.500	5.000
								Soluble saccharin	0.250	0.250	0.250	0.250	0.250	0.500	0.300
Flavour agent	0.950	0.950	0.950	0.950	0.950	0.800	1.000
								NaOH	0.006	0.122	0.006	0.122	0.006		0.600

[0198]

Tertiary sodium phosphate

1.100

Water and minor component, i.e. colored solutions

In right amount

In right amount

In right amount

In right amount

In right amount

In right amount

In right amount

¹Zinc carbonate AC, by Bruggemann Chemical:Newtown Square, PA, USA supply

Dimension disclosed herein and value are not intended to be understood to strictly be limited to described exact value.On the contrary, except as otherwise noted, each such dimension refers to the numerical value of quoting and centers on the scope that is equal on the function of this numerical value.For example, the dimension that is disclosed as " 40mm " is intended to expression " about 40mm ".

The All Files of quoting in detailed Description Of The Invention is all incorporated herein by reference in relevant portion.Should not be interpreted as admitting that for quoting of any file it is relevant prior art of the present invention.When any implication of term in any implication of term among the present invention or definition and the file of incorporating into way of reference or when defining contradiction, should obey implication or the definition of giving in the present invention this term.

Although illustrated and described specific embodiments of the present invention, it will be apparent to one skilled in the art that and in the situation that does not deviate from essence of the present invention and scope, can make a plurality of other changes and modification.Therefore, claims all such changes and modification of being intended to be included in the scope of the present invention.

Claims (11)

1. process flavor oil basically to remove the method for S-contained substance for one kind, described S-contained substance is the reason that causes stench and peculiar smell to produce, and described method comprises

(a) make described local flavor oil phase and contain water and mix, the described water that contains comprises and is no more than 20% solvent, and described solvent is selected from ethanol, Virahol, glycerine and propylene glycol, and has 7 or neutral pH,

(b) described water and the oil phase of containing placed under the troubled water 30 minutes at least,

(c) make and describedly respectively be separated, and

(d) collect washed oil phase,

Wherein washed oil comprises the stench precursor substance that per unit volume oil by weight is no more than 20ppm, and described stench precursor substance comprises dimethyl sulfoxide (DMSO), dimethyl sulphide, dimethyl disulfide and dimethyl sulfone.

2. the method for claim 1, described method also comprise via filtering by the hydrophilic/hydrophobic sorbing material, via centrifugal or via cooling, make described washed breaking of oil so that in the described washed oil residual water realize separating.

3. the method for claim 1 is wherein implemented described oil phase and the mixing that contains water 30 minutes to 6 hours.

4. the method for claim 1, the wherein said water that contains is water entirely.

5. the method for claim 1, wherein said each under high-shear, mix.

6. the method for claim 1, wherein said flavor oil derives from peppermint or spearmint.

7. the method for claim 1, wherein said flavor oil derives from Mentha arvensis L. syn.M.haplocalyxBrig.

8. flavor composition that is used for dental care products, described composition comprises one or more flavor oils that is substantially free of S-contained substance, described S-contained substance is the precursor that produces stench or peculiar smell in described composition or the product, wherein make described one or more flavor oils stand water washing process, described process comprises

(a) make described local flavor oil phase and contain water and mix, the described water that contains comprises and is no more than 20% solvent, and described solvent is selected from ethanol, Virahol, glycerine and propylene glycol, and has 7 or neutral pH,

(b) described water and the oil phase of containing placed under the troubled water 30 minutes at least,

(c) make and describedly respectively be separated, and

(d) collect washed oil phase,

Wherein washed flavor oil comprises the stench precursor substance that per unit volume oil by weight is no more than 20ppm, and described stench precursor substance comprises dimethyl sulfoxide (DMSO), dimethyl sulphide, dimethyl disulfide and dimethyl sulfone.

9. flavor composition as claimed in claim 8, wherein be the stench precursor S-contained substance content by weight the per unit volume flavor oil less than 10ppm.

10. flavor composition as claimed in claim 8, wherein be the stench precursor S-contained substance content by weight the per unit volume flavor oil less than 1ppm.

11. flavor composition as claimed in claim 8, described composition comprises one or more additional flavor compound, described flavor compound is selected from wintergreen oil, clove bud oil, cassia bark, Salvia japonica Thunb., Parsley seed oil, origanum, lemon, orange, cis-jasmone, 2,5-dimethyl-4-hydroxyl-3 (2H)-furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone, Vanillin, vanillal, aubepine, 3,4-methylenedioxy benzene formaldehyde, Veratraldehyde, the 4-hydroxy benzaldehyde, Benzaldehyde,2-methoxy, phenyl aldehyde; Phenylacrolein, hexyl cinnamic aldehyde, α-methylcinnamaldehyde, o-methoxy cinnamic aldehyde, the α-n-Amyl cinnamaldehyde 1-ethoxy-2-hydroxy-4-propenyl benzene, heliotropine, the 4-cis-heptenal, biacetyl, p-tert.-butylbenzene methyl acetate, menthol, wintergreen oil, salicylic ether, 1-menthyl acetate oxane ketone, α-ionone, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethyl butyrate, ethyl acetate, methyl o-aminobenzoate, Isoamyl Acetate FCC, isoamyl butyrate, pineapple aldehyde, oxymethoxyallylbenzene, Terpane, thymol, styryl carbinol, octanol, octanal, decyl alcohol, capraldehyde, phenylethyl alcohol, benzylalcohol, α-terpinol, linalool limonene, citral, voitol, veltol plus, methyl allylphenol, dihydroanethole, Karvon, piperitone, dorinone, ionone, γ-decalactone, γ-nonyl lactone and peach aldehyde.