CN101479009B

CN101479009B - There is the flavor oil of low sulfur content and the application in oral care composition thereof

Info

Publication number: CN101479009B
Application number: CN200780023728.4A
Authority: CN
Inventors: 罗伯特·莱斯利·Jr·斯温; 格哈德·诺贝特·泽恩保尔; 史蒂文·哈密尔顿·赫克·Ⅱ; 马尔克·阿兰·赫斯特; 尼兰詹·拉姆吉; 丹尼斯·马丽·迈克科莱森
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd
Priority date: 2006-07-07
Filing date: 2007-07-06
Publication date: 2016-06-01
Anticipated expiration: 2027-07-06
Also published as: CN101479371B; CN101479371A; CN101479009A

Abstract

The present invention relates to the flavor oil being specially treated substantially to remove low-molecular-weight sulphur compound, especially dimethyl sulfoxide (DMSO), described flavor oil comprises mint type, fruit type and spice type flavoring agent. It has been found that described sulphur compound is the main producers of odorant such as dimethyl sulphide and methanthiol. These odorants produce via redox reaction, and described reaction relates to this type of sulfur-containing compound contained in flavor oil. Preferred processing method is method for washing, described method for washing has advantage simple, inexpensive and easy to implement, simultaneously it is important which obviate the problem that typical method has, described problem removes required component with including non-selectivity, and makes flavor oil experience be likely to destroy other component and cause that the extreme condition of inadvisable change occurs for local flavor or odor property. Other processing method optionally removing non-required component includes (1) and distills to remove polarity low boiling component, (2) it is filtered by sulphur compound being had selective adsorbent, (3) counter-current extraction and (4) column chromatography. Described processing method optionally carries out the required component having removed or having changed during workflow reengineering processes with add-back subsequently. The flavor oil processed especially is used especially in oral care composition, and described oral care composition comprises the component such as stannous ion with chemical reducing capability, and described stannous ion can react with sulfur-containing compound and produce stench product.

Description

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

Technical field

The present invention relates to the oral care composition comprising flavor system, described flavor system comprises flavor oil, described flavor oil is stable, degraded can be resisted and prevent stench and abnormal flavour, and described stench and abnormal flavour are essentially from sulphur-containing substance, for instance mercaptan (thiols) or mercaptan (mercaptans). These odorants produce via redox reaction, and described reaction relates to other component in sulfur-containing compound contained in flavor oil and described compositions. Flavor oil processes to reduce the content of low-molecular-weight sulphur compound, especially dimethyl sulfoxide (DMSO) especially. It has been found that dimethyl sulfoxide is the main producers of odorant such as dimethyl sulphide and methanthiol. Therefore, the invention provides the method preparing flavor oil and oral care composition, described flavor oil includes being substantially free of DMSO and the mint type of other sulphur-containing substance, fruit type and spice type flavoring agent, described oral care composition mixed with this type of flavor oil processed especially to improve taste and the stability of abnormal smells from the patient characteristic aspect.

Background of invention

Oral care product such as dentifrice and collutory are by the daily part as they oral care hygiene regimens of consumer. Oral care product can provide treatment and cosmetic hygiene benefits this point well known for consumer. Treatment beneficial effect includes the prevention of dental caries, gingivitis prevention or hypersensitivity and controls, and the described prevention of dental caries realizes usually by the various fluoride salts of use; The prevention of described gingivitis realizes by using antimicrobial such as triclosan, stannous fluoride or quintessence oil; Described hypersensitivity controls by using the composition of such as strontium chloride or potassium nitrate to realize. The Cosmetic benefits provided by oral care article includes the formation controlling dental plaque and dental calculus, removes and prevention tooth stain, tooth-whitening, fresh breath and totally improve mouth feel impression, and it is broadly characterized in that mouth feel aesthetics. Dental calculus and dental plaque and behavior and environmental factors cause the formation of teeth stains, thus having had a strong impact on the aesthetic property of tooth. The behavior and the environmental factors that tend to growth-promoting tooth discoloration characteristic include regular coffee for drinking, tea, cola or tobacco products, and also include using some oral products, described oral products comprises the composition promoting tooth discoloration, such as cationic antimicrobial agent and slaine.

Therefore, family's common oral care needs the product containing Multiple components, described composition acts as providing complete treatment and beautification benefits scope with different mechanism, comprises preventing decayed tooth, antimicrobial, anti-gingivitis, antiplaque and anti-dental calculus and anti-abnormal flavour, oral cavity fresh and cool, mottle removal, mottle control and tooth whitening. In order to make oral care product used in everyday such as dentifrice and collutory can provide complete oral care efficacy, need active substance together with additive combination, many of which has the shortcoming that can cause negative aesthetic property during use, taste unpleasant specifically and sensation and growth-promoting mottle. Unpleasant taste has been described as having following one or more aspect with mouthfeel: bitterness, metal fishy smell, astringent taste, become taste, fiber crops taste, prickling sensation, burning sensation, sensation of pricking or even excitement. The typical composition for oral care utilities being attended by these negative aesthetic properties includes antimicrobial, for instance cetylpyridinium chloride, chlorhexidine, tin salt, mantoquita and zinc salt; Dental bleaching agent, for instance peroxide; Anticalculus agent, for instance pyrophosphate, tripolyphosphate and hexametaphosphate; And excipient, for instance sodium bicarbonate and surfactant. In order to alleviate the negative aesthetic property caused by these compositions, it is common to use flavoring agent and sweeting agent prepare oral care product so that taste is good as much as possible and can be esthetically acceptable to the consumers.

Due to many certified oral benefits, it is therefore desirable for stannous ion is incorporated in oral care composition. The stannous ion generally provided by the stannous fluoride in oral care composition can be used for providing beneficial effect, including antimicrobial, antiplaque, gingivitis and antiallergic beneficial effect, and can be used for anti-halitosis in advance. But it has proven convenient that owing to the known preparation comprising stannous ion is unsightly desirable, therefore challenging with stannous ion preparation. In addition it has been found that some flavor oil, especially mint type oil, can show unstability and produce stench when being used in combination with stannous ion.

After extracting natural flavour mountaineous oil from plant or plant material, its refine or process further is described in the art improving quality and stability. In general, these processing methods are intended to remove or reduce the constituent content in described oil, and described component is believed to be the reason causing unstability or inadvisable taste or odor property. Such as, undertaken flavor oil processing to remove or reduce the content of terpenes, menthofuran, pulegone and dimethyl sulphide. This type of processing method is described in such as 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 include distillation, nitrogen bubble and chemical treatment to aoxidize or to inactivate this type of inadvisable component.

Such as, retortable Oleum menthae is to remove or to reduce the content of the dimethyl sulphide according to reports with inadvisable greenweed taste. Have been carried out steam distillation or vacuum distilling takes refine Oleum menthae. But, this type of distillating method is not exclusively satisfactory. Typical steam distillation method not only eliminates dimethyl sulphide, but also eliminates other lower boiling constituent of peppermint oil. Therefore, when refine Oleum menthae, it is necessary to isolate required low boiling component from distillate, and they are added back in flavoring agent at least partly. Which increase cost and the time of still-process. Adjoint another problem of refine Oleum menthae most popular method is that they can make Oleum menthae experience extreme condition, for instance superheated. This can cause flavoring agent that worthless change occurs.

Continue to need to improve local flavor oil handling to provide best taste and odor property and stability, remove the component producing stench specifically, especially dimethyl sulfoxide, it has been found that dimethyl sulfoxide is the principal mode of malodor precursors sulfur material in flavor oil. Therefore, the present invention relates to from original flavor oil, remove this type of previously unrecognized inadvisable component forming inadvisable abnormal smells from the patient, obtain stable flavoring agent simultaneously, described flavoring agent be substantially free of can not taken amount this type of produce stench component, thus owing to reacting with the sub-stannum in reducing agent such as oral care composition, so also without producing stench or polluting the trend of local flavor.

Summary of the invention

In one aspect, the present invention relates to process or the refine further of flavor oil to reduce the content of sulfur-containing compound such as dimethyl sulfoxide. Preferred processing method is method for washing, it has advantage that is simple, inexpensive and that be easily achieved, simultaneously it is important which obviate the problem that typical method has, described problem removes required component with including non-selectivity, and makes flavor oil experience be likely to destroy other component and cause that the extreme condition of inadvisable change occurs for local flavor and odor property. Other selectivity removes the processing method of non-required component and includes (1) distillation to remove polarity low boiling component, (2) it is filtered by sulphur compound being had selective adsorbent, (3) counter-current extraction and (4) column chromatography. Described processing method optionally can carry out the required component having removed or having changed during workflow reengineering processes with add-back subsequently.

In yet another aspect, the invention provides oral care composition, described compositions comprises

A () has the oral cavity nursing agent of chemical reducing capability,

B () comprises the flavor system of flavor oil or extract, described flavor oil or extract are substantially free of sulphur-containing substance, obtained sulphur-containing substance includes dimethyl sulfoxide, dimethyl sulphide, dimethyl disulfide and dimethyl sulfone, they are the reasons causing and producing stench and abnormal flavour in described compositions, and

(c) oral area acceptable carrier.

Having the oral cavity nursing agent of chemical reducing capability selected from stannous ion source and phenols, described phenols is originated from such as tea, Pericarpium Citri tangerinae, Punica granatum L. and quercus. Described compositions has stablizes complete flavor characteristics, and taste is pleasant and pure and fresh, thus promoting the compliance of user and commonly used property.

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

Detailed Description Of The Invention

Although providing the claims particularly pointing out and being distinctly claimed the present invention after description, it is believed that be better understood the present invention by following explanation.

Except as otherwise noted, all percentage ratios hereafter used and ratio are all by the weighing scale of total composition. Except as otherwise noted, the percentage ratio of all each composition, ratio and the content that the present invention relates to are based on the actual content of composition, and are likely to the solvent, filler or other material that are combined with described composition not included in commercially available product.

Except as otherwise noted, all measurements mentioned above all carry out at 25 DEG C.

" comprise/include " herein and refer to and can add other step and composition not affecting final result. This term include term " by ... composition " and " substantially by ... form ".

As used herein, word " comprises/includes " and its variant is defined as nonrestrictive so that in list, the narration of entry is not excluded for other similar entry that to be likely in the material of the present invention, compositions, apparatus and method useful.

As used herein, word " preferably ", " preferably " and their variant refer to the embodiment of the present invention being provided that specific beneficial effect in certain circumstances. But, other embodiment can also be preferred under identical or other environment. Additionally, it is useless that the detailed description of one or more preferred embodiments is not representing other embodiment, and it is not intended to get rid of other embodiment from scope of the invention.

" oral care composition " refers to and is not deliberately swallowed the Formulations for systemic administration for particular therapeutic agent in generally using process, but can retain the sufficiently long time in the oral cavity substantially to contact all of dental surface and/or oral cavity tissue to obtain the product with orally active. Described oral care composition can be various ways, including toothpaste, dentifrice, gutta-percha, gums glue, collutory, mousse, foam, denture care products, mouth spraying agent, medicine caked sugar, chewable tablet or chewing gum. This oral care composition also can be incorporated on tooth joint strip or thin film directly to use or to adhere to oral surfaces.

Except as otherwise noted, the term " dentifrice " that the present invention uses refers to paste, gel or liquid preparation. Dentrifice composition both can be alternatively the combination of two or more independent Dentrifice compositions for single-phase composite. Dentrifice composition can be any desired form, as deep striped, shallow striped, multilamellar, have gel around paste or their combination in any. In the dentifrice including two or more independent Dentrifice compositions, every kind of Dentrifice composition can be loaded in physically separate distributor chambers, distributes side by side.

As used herein, term " allotter " refers to that any being suitable to distributes the pump of compositions (such as dentifrice), pipe or container.

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

Term " flavor oil " refers to the quintessence oil as flavoring agent, and it is the component of distillation or the ethereal oil extracted and these ethereal oils from plant. as used herein, when relating to Herba Menthae and mint type oil, term " flavor oil " includes the oil of various grade, it is initially natural or unprocessed (just mentioning out from plant source) that described oil typically refers to natural crude oil, and exquisite or rectification so that oil conformance with standard and remove unwanted local flavor/odor characteristics (such as passing through fractional distillation). rectification level is generally the class of trade being supplied to end user for use as flavoring agent and spice. typical quintessence oil and their key component are derived from following those, such as Herba thymi vulgaris (thymol, carvacrol), Adeps Bovis seu Bubali (carvacrol, terpenes), Fructus Citri Limoniae (limonene, terpinene, phellandrene, pinene, citral), lemonweed (citral, methyl heptenone, citronellal, geraniol), orange blossom (linalool, nopinene, limonene), orange (limonene, citral), Pimpinella anisum Linn. (anethole, safrole, 1-ally-3,4-methy-lene dioxy benzene), Flos Caryophylli (acetaminol, acetic acid clove tree ester, caryophyllene), Flos Rosae Rugosae (geraniol, citronellol), Herba Rosmarini Officinalis (Borneolum Syntheticum, norbornene ester, Camphora), Herba Erodii (geraniol, citronellol, linalool), Garden lavender (linalyl acetate, linalool), Herba Cymbopogonis Citrari (geraniol, citronellol, citronellal, camphene), Eucalyptus (cineole), Mentha arvensis L. syn.M.haplocalyxBrig (menthol, menthyl ester), spearmint (carvone, limonene, pinene), Herba pyrolae japonicae (methyl salicylate), Camphora (safrole, 1-ally-3,4-methy-lene dioxy benzene, acetaldehyde, Camphora), bay tree (acetaminol, myrcene, good taste alcohol), Cortex Cinnamomi (cinnamic aldehyde, cinnamyl acetate, acetaminol), Camellia sinensis (4-terpineol, eucalyptole) and Cacumen Platycladi (Cacumen Biotae) (��-keep ketone, ��-keep ketone, fenchone). quintessence oil, their compositions and preparation are described in greater detail in " EncyclopediaofChemicalTechnology " the 4th edition and " TheMerckIndex " the 13rd edition of Kirk-Othmer.

Term " oral area acceptable carrier " includes for the safely effectively material in oral care composition, excipient or additive, includes but not limited to fluoride sources, anti-dental calculus or anticalculus agent, buffer, grinding agent such as silicon dioxide, alkali metal hydrogencarbonate, thickening material, wetting agent, water, surfactant, titanium dioxide, flavoring agent, sweeting agent, xylitol, coloring agent and their mixture.

Can be used for the active component of the present invention and other composition can be classified according to effect or the operational mode of its beauty treatment and/or treatment beneficial effect or its supposition or describe. It should be appreciated, however, that in some cases, can be used for the active substance of the present invention and other composition can provide more than one beauty treatment and/or treat beneficial effect or effect, or worked by more than one model of action or run. Therefore, classification herein for convenience only, and is not intended to be limited in by composition in listed particularly point out a application or several application.

The terms " tartar " and " dental calculus " are used interchangeably, and refer to the dental plaque biofilm mineralized.

Solvent and the optional components of the present invention are described in paragraphs below.

Flavor system

The present invention comprises flavor system, described flavor system comprises flavor oil, and described flavor oil is stable, anti-degraded and prevent abnormal flavour and stench, described abnormal flavour and stench are essentially from sulphur-containing substance, for instance mercaptan (thiols) or mercaptan (mercaptans). These odorants produce via redox reaction, and described reaction relates to other component in flavor oil component and described compositions. More particularly, have been found that low-molecular-weight sulphur compound such as dimethyl sulfoxide (DMSO) is present in some natural flavour mountaineous oil, present in an amount at least sufficient to and there is the reagent reacting that namely quite strong reducing power is easily oxidised, causing generation odorant, including dimethyl sulphide and methanthiol. Therefore, the invention provides flavor oil and oral care composition, described flavor oil includes mint type, fruit type and spice type flavoring agent, it is specially treated to reduce DMSO and other sulphur-containing substance content, described oral care composition mixed with this type of flavor oil processed to improve taste and stability. The flavor oil processed is preferably substantially free from this type of worthless sulphur-containing substance, including being reduced into the dimethyl sulfoxide of odorant, dimethyl sulphide, dimethyl disulfide and dimethyl sulfone. Other sulfur-containing compound also is present in the oil processed, but these will not present the problem producing stench aspect. Substantially free refers to that flavor oil comprises less than the sulphur-containing substance for malodor precursors of about 20ppm herein. It has been found that can result in, together with the preparation of reagents of such as sub-stannum, the stench being described as " skunk taste " more than the flavor oil of this type of sulphur-containing substance of about 20ppm by comprising. Additionally, this type of redox reaction resulting in stench can adversely reduce the concentration of the sub-stannum of activity in described compositions, reduce effect thus potential. After process such as washing, in flavor oil, the content of sulfur-containing foul precursor substance, less than approximately 10ppm, is more preferably less than about 1ppm, and is even more preferably less than about 0.5ppm, or be entirely free of.

The present invention relates to following discovery, the main sulfur-containing foul precursor substance being present in flavor oil is DMSO, and the content that sample has is up to 300ppm or higher. Following table shows the content of DMSO and dimethyl sulphide (DMS) in Herba Menthae Rotundifoliae and Mentha arvensis L. syn.M.haplocalyxBrig sample. As follows, main matter is DMSO; DMS is notable in flavor oil to be existed with relatively low content.

Table 1: Mentha arvensis L. syn.M.haplocalyxBrig and the content of DMSO and DMS in 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
Herba Menthae Rotundifoliae (1% crop)	235	< 1

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

Report, nature exists DMSO. Such as, in selected water fruits and vegetables, corn and beverage, the amount of naturally occurring of DMSO is reported in " J.Agric.FoodChem. " (1981,29,1089-91). The most high-load reported is the 16ppm in black tea drink. In most of samples, the content found is higher less than 1ppm, concentration or the content found in process sample such as Fructus Lycopersici esculenti paste. The increase of DMSO content is considered as caused by the oxidation of commercial processes period two methyl sulfide (DMS). DMS is ubiquity in nature, and is the reason causing numerous food product characteristic odor. Also report DMSO is present in Oleum Menthae Rotundifoliae [" AnaisdeAcademiaBrasileiradeCiencias ", 1972,44 (Suppl.), 273-7] and Oleum menthae [" Agric.Biol.Chem. ", 1980,44 (7), 1535-43] in. The not report of found content in this paper Herba Menthae flavor oil.

Via Sample Dilution, liquid infusion to GC-MS system will can realize the mensuration of dimethyl sulfoxide in Oleum menthae (DMSO) and dimethyl sulphide (DMS) content subsequently. In brief, preparing calibration benchmark by being added to by DMSO and the DMS of known quantity in Oleum menthae, described Oleum menthae had previously been washed with water these components of removing, until lower than quantifying lower limit. Water-washing technique as described herein, and is described in greater detail in hereinafter. By with 800 �� L diluted ethyl acetate 200 �� L aliquots prepare for analyze every kind of standard sample and sample, described ethyl acetate comprise isotope-labeled DMSO (¹³C₂) and DMS (²H₆) stable internal standard substance. The standard sample and sample prepared is analyzed by 1 �� L aliquot being expelled in the shunting/nothing shunting entrance of Agilent6890GC. Being transferred to by effluent in the single quadrupole mass spectrometer of Agilent5973, described mass spectrograph is with Salbutamol Selected Ion Monitoring (SIM) mode operating. To each analyte, added analyte concentration is mapped by the peak area ratio (analyte/internal standard substance) of calibration benchmark. Based on its analyte measured and internal standard substance peak area ratio, by the concentration of each unknown sample of respective alignment curvilinear interpolation. Using these detection analysis conditions, the quantization nominal lower limit of DMSO and DMS is the quantization upper limit respectively 500 and 100ppm of 1ppm (w/v), DMSO and DMS.

The flavor oil of the present invention is generally used in oral care composition with the amount of about 0.001% to about 5% by weight of the composition. The content of flavor oil preferably about 0.01% to about 4%, more preferably from about 0.05% to about 3%, and most preferably from about 0.1% to about 2%. Described flavor oil can exist as the whole flavor composition in oral formulations, or combines with other selected flavor components. The flavor oil being preferred in oral care composition includes coming from those in Herba Menthae classification, for instance Mentha piperita (Mentha arvensis L. syn.M.haplocalyxBrig), Rhizoma Zingiberis Recens Herba Menthae (Herba Menthae), Mentha viridis L (U.S. this locality Herba Menthae Rotundifoliae), Herba Ziziphorae clinopodioidis (Scotland spearmint) and emerald green Herba Menthae (China's Herba Menthae Rotundifoliae kind). Expect that described oral care composition has mint flavored completely, because Herba Menthae is wherein topmost flavoring agent.

Except selectivity Herba Menthae flavor oil above, described flavor system also can comprise additional flavor components, described additional flavor components includes but not limited to wintergreen oil, clove bud oil, Cortex cinnamomi japonici (Ramulus Cinnamomi), Salvia japonica Thunb., parsley oil, origanum, Fructus Citri Limoniae, orange, cis-jasmone, 2, 5-dimethyl-4-hydroxyl-3 (2H)-furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone, vanillin, ethyl vanillin, anisaldehyde, 3, 4-methylenedioxy benzene formaldehyde, 3, 4-dimethoxy benzaldehyde, 4-hydroxy benzaldehyde, Benzaldehyde,2-methoxy, benzaldehyde, cinnamic aldehyde, jasminolene, ��-methylcinnamaldehyde, o-methoxy cinnamic aldehyde, jasminal acrylic guaethol, heliotropine, 4-cis-heptenal, diacetyl, the p-tert-butyl benzene yl acetate of methyl, menthol, methyl salicylate, ethyl salicylate, acetic acid 1-menthyl ester, alkanone, ��-ionone, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethyl n-butyrate., ethyl acetate, methyl 2-aminobenzoate, isoamyl acetate, isoamyl butyrate, allyl hexanoate, acetaminol, eucalyptole, thymol, cinnamyl alcohol, capryl alcohol, octanal, decanol, capraldehyde, phenethanol, benzylalcohol, ��-terpinol, linalool, alkene, citral, maltol, ethylmaltol, anethole, dihydroanethole, carvone, menthone, dorinone, ionone, ��-decalactone, nonyl lactone and peach aldehyde, and their mixture. in general, suitable flavor components is comprised architectural feature and functional group is less inclined to those of redox reaction. these include the derivant of flavor compounds that is saturated or that comprise stable aromatic ring or ester group. some oxidation or degradation reaction can be experienced without causing that the flavor compounds that flavoring agent characteristic or characteristic remarkable change also is suitable. single or pure compound form can provide flavor components, or provide in the form of compositions by adding natural oil or extract, described natural oil or extract preferably process or other refining treatment is to remove component through washing of the present invention, described component is more unstable, and degrading and change desired flavor characteristic, affecting the more unacceptable product of organ sensation's aspect thus obtaining.

Described flavor system also can comprise the protective agent component preventing producing stench and abnormal flavour in compositions, for instance those described in the common co-pending patent application submitted to that exercise question is " FLAVORSFORORALCOMPOSITIONS ". This type of protective agent includes carbonyl compound, for instance ascorbic acid; Cis-jasmone; 2,5-dimethyl-4-hydroxyl-3 (2H)-furanones; 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone; Vanillin; Ethyl vanillin; Anisaldehyde; 3,4-methylenedioxy benzene formaldehyde; Veratraldehyde; 4-hydroxy benzaldehyde; Benzaldehyde,2-methoxy; 4-methoxybenzaldehyde; Benzaldehyde; Cinnamic aldehyde; Jasminolene; ��-methylcinnamaldehyde; O-methoxy cinnamic aldehyde; Jasminal; And their combination. Having many in these protective agents is flavor components.

Described flavor system also can comprise cool agent or coolant, for instance menthol, menthyl ester, carboxylic acid amides, ketal, glycol and their mixture. Coolant example suitable in the present composition is to Herba Menthae carboxylic acid amides reagent, for instance trade name is that the N-ethyl of " WS-3 " is to Herba Menthae-3-carboxylic acid amides; Trade name is the WS-23 of " WS-23 "; The p-benzene acetonitrile Herba Menthae carboxylic acid amides of N-; And other material in series, for instance WS-5, WS-11, WS-14 and WS-30. Other suitable coolant includes the 3-1-Herba Menthae oxygen base the third-1 being called TK-10 prepared by Takasago, 2-glycol; MGAMenthyl ester, for instance menthyl acetate, acetoacetic acid menthyl ester, menthyl lactate (Thered is provided by HaarmannandReimer) and monomenthyl succinate (being provided by V.Mane with trade name Physcool). Term menthol used herein and menthyl include the dextrorotation of these compounds and laevoisomer and their racemic mixture. TK-10 is described in the United States Patent (USP) 4,459,425 authorizing Amano et al. that on July 10th, 1984 announces. WS-3 and other reagent are described in the United States Patent (USP) 4,136,163 authorizing Watson et al. that on January 23rd, 1979 announces.

Described flavor system generally comprises sweeting agent. suitable sweeting agent include known in the art those, including natural and artificial sweeting agent. some suitable water-soluble sweetening agents include monosaccharide, disaccharide, polysaccharide and derivant, for instance xylose, ribose, glucose (dextrose), mannose, galactose, fructose (levulose), sucrose (Saccharum Sinensis Roxb.), maltose, Nulomoline (mixture derived from the fructose of sucrose and glucose), the starch of partial hydrolysis, corn-syrup solids, dihydrochalcone, monellin, stevioside, glycyrrhizin, xylitol and erithritol. suitable water-soluble artificial sweeting agent includes soluble saccharin salt, namely saccharin sodium or saccharin calcium salt, cyclamate, 3,4-dihydro-6-methyl isophthalic acid, 2,3-thiazine-4-ketone-2, the sodium salt of 2-dioxide, ammonium salt or calcium salt, 3,4-dihydro-6-methyl isophthalic acid, 2,3-thiazine-4-ketone-2, the potassium salt (acesulfame-K) of 2-dioxide, free acid form saccharin, etc. other suitable sweeting agent includes the sweeting agent based on dipeptides, the sweeting agent that such as L-Aspartic acid is derivative, such as L-aspartyl-L-phenyl methyl lactamine (aspartame) and U.S. Patent No. 3, 492, material described in 131, L-��-aspartyl-N-(2, 2, 4, 4-tetramethyl-3-vulcanizes trimethylene)-D-alanine amide hydrate, L-aspartyl-L-phenyl glycerol and L-aspartyl-L-2, 5-dihydro phenylglycine, L-aspartyl-2, 5-dihydro-L-phenylalanine, the methyl ester etc. of L-aspartyl-L-(1-cyclohexenyl group)-alanine. the water-soluble sweetening agent derived from naturally occurring water-soluble sweetening agent can be used, for instance the chlorinated derivatives (such as the product description to known sucralose) of common Saccharum Sinensis Roxb. (sucrose) and protein-based sweeteners such as West Africa arrowroot (Africa hesperidium element I and II). described compositions preferably comprises by weight about 0.1% to about 10%, it is preferable that the sweeting agent of about 0.1% to about 1%.

Additionally, described flavor system can comprise sialorrhea agent, heat agent and numb agent. These reagent are with by weight of the composition about 0.001% to about 10%, it is preferable that the content of about 0.1% to about 1% is present in compositions. Suitable sialorrhea agent includes being produced by TakasagoAgent example of heating is Fructus Capsici and nicotinate, such as benzyl nicotinate. Suitable numb agent includes benzocaine, lignocaine, clove bud oil and ethanol.

Chemical reducing agent

The flavor system comprising flavor oil that the present invention processed especially and extract is used especially in compositions, described compositions comprises the reagent with chemical reducing capability, in particular to becoming the stannous ion of preferred active substance in oral care composition because of its extensive beneficial effect range and from the phenols with available antimicrobial, antiinflammatory and antioxidant activity of plant source and derivant. In these phenols and derivant, have and many may also used as flavoring agent.

Stannous ion has great reduction characteristic, can be oxidized to tetravalent tin form with DMSO when reacting, and described DMSO is then reduced into odorant DMS and is reduced into methanthiol (CH further₃SH). The reaction of Ya Xi and reagent such as DMSO is not only due to produce odorant, but also owing to can reduce sub-Theil indices thus reducing compositions effect, is therefore worthless. Many phenols being used as active substance or flavoring agent in oral care composition are easily oxidized, namely have reduction characteristic, and mode that therefore can be identical with sub-stannum is reacted with DMSO.

The compositions of the present invention preferably comprises stannous ion source, including stannous fluoride and/or other tin salt. Have been found that stannous fluoride contributes to alleviating dental caries, gingivitis, dental plaque and sensitivity, and contribute to improving the beneficial effect breathed. Other tin salt includes two hydrated stannous chlorides, stannous acetate, gluconic acid Asia stannum, stannous oxalate, stannous sulfate, lactic acid Asia stannum and stannous tartrate. Preferred stannous ion source is stannous fluoride and two hydrated stannous chlorides. The content of tin salt is calculated as about 0.1% to about 11% by the weight of described total composition. The content of tin salt is preferably from about 0.4% to about 7% by the weighing scale of described total composition, more preferably about 0.45% to about 5%, and and most preferably about 0.45% to about 3%. The preparation with effect generally includes the sub-Theil indices provided by stannous fluoride and other tin salt. Stannous ion content in total composition is in the scope of about 3,000ppm to about 15,000ppm.

The dentifrice comprising tin salt, especially stannous fluoride and stannous chloride is described in the United States Patent (USP) 5,004,597 authorizing Majeti et al.. Other description of tin salt is found in the United States Patent (USP) 5,578,293 authorizing Prencipe et al. and the United States Patent (USP) 5,281,410 authorizing Lukacovic et al.. Except stannous ion source, also can comprise other composition needed for stable sub-stannum, for instance the Majeti et al. and Prencipe et al. composition described in patent.

From vegetative source such as tea, Pericarpium Citri tangerinae, Punica granatum L. and quercus phenols also can be incorporated in the present composition. This phenols includes catechin, nutgall catechin gallic acid ester, epicatechin (EC), epigallo catechin (EGC), epigallocatechin gallate (EGCG) (EGCG), L-Epicatechin gallate (ECG), theaflavin, thearubigins, anthocyanidin/procyanidin and anthocyanidin (such as cyanidin, delphinidin, pelargonidin, peonidin, enidin and morning glory pigment); Tannic acid; Gallic acid; Ellagic acid; Elladitannin; Curcumin. Described phenols can provide as pure compound or as plant extract. Can be used as in the U.S. Patent application 11/595,530 as US2007/0053849A1 announcement that the phenols of oral care active is disclosed in common transfer.

Except component described above, this compositions also can comprise additional optional components, is referred to as oral area acceptable carriers material, and it is described in paragraphs below.

Oral area acceptable carrier material

Described oral area acceptable carrier includes one or more and is suitable to the local compatible solid used of oral area or liquid excipient or diluent. As used herein, term " compatible " refers to that the component of compositions can mix but do not interact, and described interaction can significantly reduce stability and/or effect of compositions.

The carrier of the present invention or excipient include gel, collutory under dentifrice, non-ground agent gel, gum or wash the common and conventional constituents of saliva, mouth spraying agent, chewing gum, medicine caked sugar and breath mints, and they will be described in greater detail in the following.

Selecting of carrier to be used is substantially determine according to the method in compositions introducing oral cavity. Can be used for the carrier material of toothpaste, gutta-percha or similar products and include abrasive material, foaming agent, binding agent, wetting agent, flavoring agent and sweeting agent etc., as being disclosed in the United States Patent (USP) 3,988,433 authorizing Benedict. Carrier material for biphase dentifrice formulation is disclosed in the material in following document: the 5 of the United States Patent (USP) that on May 23rd, 1993 announces JIUYUE in 5,213,790,1992 announcement on the 8th, 5,281 announced on January 25th, 145,666 and 1994,410, above-mentioned patent all authorizes Lukacovic et al.; With the United States Patent (USP) 4,849,213 and 4,528,180 authorizing Schaeffer. Collutory, wash saliva or mouth spray carrier materials generally includes water, flavoring agent and sweeting agent etc., for instance authorize disclosed in the United States Patent (USP) 3,988,433 of Benedict. Medicine caked sugar carrier material typically comprises a kind of candy substrate; Chewing gum carrier materials includes a kind of gum base, flavoring agent and sweeting agent, and this is disclosed in the United States Patent (USP) 4,083,955 such as authorizing Grabenstetter et al.. Sachet carrier materials generally includes sachet, flavoring agent and sweeting agent. For for gel under the gum around delivery of active substances to periodontal pocket or periodontal pocket, by the United States Patent (USP) 5,198 that such as on March 30th, 1993 announces, the United States Patent (USP) 5 of 220 and 1993 on JIUYUE announcement in 7,242,910 select " under gum gel carrier ", and above-mentioned two patents all authorize Damani. The carrier being suitable to prepare the present composition is well known in this area. Their selection depends on hiding the secondary Considerations such as stability such as taste, cost and frame.

The compositions of the present invention can also be gel form under moisture or nonaqueous non-abrasive gel and gum. In yet another aspect, the present invention also provides for being marked with the toilet article of this compositions. Toilet article include for the utensil with the tooth in oral cavity and other contact tissue, and described utensil is filled with compositions described herein. Toilet article can be injected into fiber, and this fiber includes dental floss or dental tape, thin slice, strip, thin film and polymer fiber.

In one embodiment, the compositions of the subject innovation is dentifrice form, such as toothpaste, gutta-percha and dentifrice. The component of these toothpaste and gutta-percha generally includes one or more dental abrasive (about 6% to about 50%), surfactant (about 0.5% to about 10%), thickening agent (about 0.1% to about 5%), wetting agent (about 10% to about 55%), flavoring agent (about 0.04% to about 2%), sweeting agent (about 0.1% to about 3%), coloring agent (about 0.01% to about 0.5%) and water (about 2% to about 45%). This type of toothpaste or gutta-percha may also include 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, dentifrice comprises essentially all aneroid component.

Other embodiment of the subject innovation is fluid product, including collutory or collutory, mouth spraying agent, dental solutions and flush fluid. The component of these collutory and mouth spraying agent generally includes one or more water (about 45% to about 95%), ethanol (about 0% to about 25%), wetting agent (about 0% to about 50%), surfactant (about 0.01% to about 7%), flavoring agent (about 0.04% to about 2%), sweeting agent (about 0.1% to about 3%) and coloring agent (about 0.001% to about 0.5%). This type of collutory and mouth sprays may also include 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 solutions generally comprises one or more in water (about 90% to about 99%), preservative (about 0.01% to about 0.5%), thickening agent (0% to about 5%), flavoring agent (about 0.04% to about 2%), sweeting agent (about 0.1% to about 3%) and surfactant (0% to about 5%).

Type and the concrete limiting examples of involved oral area acceptable carrier in the present compositions or excipient will chapters and sections below can be discussed.

Tooth affinity agent

The present invention can include tooth affinity agent, for instance polymeric surfactant (PMSA), and this polymeric surfactant is polyelectrolyte, more particularly anionic polymer. Described polymeric surfactant comprises anionic group, for instance phosphate radical, phosphonate radical, carboxylate radical or their mixture, therefore has the ability interacted with cation or positively charged entity. " mineral " descriptor is intended to indicate that the surface activity of polymer or affinity are for mineral surfaces, for instance calcium phosphate mineral or tooth.

Polymeric surfactant can be used in the compositions of the present invention owing to having anti-mottle beneficial effect. It is believed that, described polymeric surfactant can provide anti-mottle beneficial effect, this is because mineral surfaces is had reactivity or affinity by them, thus causing the membrane proteins part desorbing being undesirably adsorbed, staining the color body of tooth, dental calculus development with combining and attracting inadvisable micro-raw strain together those specifically. These polymeric surfactants retentivity on tooth still prevents mottle and produces, and this is destruction to color body binding site on tooth surfaces due to.

It is believed that polymeric surfactant is also useful in conjunction with the ability of growth-promoting mottle composition such as stannous ion and cationic antimicrobial agent in oral care product. Described PMSA may also provide dental surface conditioning effect, and thermodynamic properties of some typical surfaces and surface film character are produced suitable impact by it, and this is in rinse or scrubs period and the most important thing is at rinse or the clean feel aesthetic property giving improvement after scrubbing. When being applied in oral compositions, these polymeric reagents many it is known that or expect to provide the beneficial effect controlling tartar, thus teeth appearance and they give the sense of touch of consumer in provide and improve.

Suitable surface effect includes: produce hydrophilic dental surface immediately after 1) processing; With 2) product is long-term after using keeps surface conditioning effects and the control to thin film, including scrubbing or after rinse and longer whole period. Cause the beneficial effect that surface hydrophilicity increases can pass through the relatively reduced of water contact angle to record. It is essential that after using product, water-wetted surface keeps on tooth surfaces for a long time.

Polymer-mineral matter surfactant includes that dental surface has strong affinity, any reagent of surface modification effect needed for dental surface deposits into polymeric layer or cover layer and produces. the suitable example of this base polymer is polyelectrolyte, such as polycondensation phosphorylated polymer, polyphosphonates, the copolymer of the monomer of phosphorous acid group-or phosphonate ester or polymer and following material: ethylenically unsaturated monomers and aminoacid or other polymer, such as protein, polypeptide, polysaccharide, polyacrylate, polyacrylamide, polymethacrylates, poly-ethyl propylene acid esters, polymethylacrylic acid hydroxyalkyl acrylate, polyvinyl alcohol, polymaleic anhydride, poly ester, polyamide, polyvinylamine, Polyethylene Glycol, polypropylene glycol, polyvinyl acetate and polyvinylbenzylchloride, the polymer of polycarboxylate and carboxyl replacement and their mixture. suitable polymer-mineral matter surfactant includes the United States Patent (USP) 5,292,501,5 all authorizing Degenhardt et al., 213,789,5,093,170,5,009,882 and 4,939, the alkoxide polymer that carboxyl described in 284 replaces, the polymer derivative with the bisphosphonates authorized described in the United States Patent (USP) 5,011,913 of Benedict et al., synthetic anionic polymer, including the copolymer (such as Gantrez) of polyacrylate and maleic anhydride or maleic acid and methyl vinyl ether, as authorized described in the United States Patent (USP) 4,627,977 of Gaffar et al.. preferred polymer is diphosphonate modified polyacrylic acid. active polymer has enough surface binding propensity membrane proteins desorbing maintenance to be invested on enamel surface. for dental surface, the polymer with end or side chain phosphate or phosphonate function is preferred, but other polymer with mineral combination activity can prove effectiveness according to absorption affinity.

Suitable other example containing phosphonate ester polymer-mineral matter surfactant includes the bisphosphonate ester polymer as anti-calculus agent authorized disclosed in the US4,877,603 of Degenhardt et al.; Authorizing the copolymer containing phosphonate groups disclosed in US4,749,758 and GB1,290,724 (all the transferring Hoechst) of Dursch et al., it is suitable in detergent and Cleasing compositions; With authorize the Zakikhani US5,980,776 being equal to and authorize can be used for disclosed in the US6,071,434 of Davis et al. and include suppressing the copolymer in the application of tartar and burn into coating, cement and ion exchange resin and cotelomer. Other polymer includes GB1,290, vinyl phosphoric acid disclosed in 724 and the water solubility copolymer of acrylic acid and salt thereof, wherein said copolymer comprises the vinyl phosphoric acid by weight about 10% to about 90% and the acrylic acid by weight about 90% to about 10%, more particularly, the vinyl phosphoric acid that wherein said copolymer has and the vinyl phosphoric acid that acrylic acid weight rate is 70% acrylic acid than 30%; The vinyl phosphoric acid of 50% acrylic acid than 50%; Or the acrylic acid that the vinyl phosphoric acid of 30% is than 70%. Other suitable polymer includes water-soluble polymer disclosed in Zakikhani and Davis, its other compound that there is unsaturated C=C key with at least one by bisphosphonates or polyphosphonates monomer (as, acrylate and methacrylate monomer) copolymerization prepare, described polyphosphonates monomer have one or more undersaturated C=C key (as, ethenylidene-1,1-di 2 ethylhexyl phosphonic acid and 2-(hydroxyphosphinyl) ethylidene-1,1-di 2 ethylhexyl phosphonic acid), described polymer be such as structured with those:

1. there is acrylic acid and 2-(hydroxyphosphinyl) ethylidene-1 of following structure, the cotelomer of 1-di 2 ethylhexyl phosphonic acid:

2. there is the acrylic acid of following structure and the copolymer of vinyl di 2 ethylhexyl phosphonic acid:

Suitable polymer includes bisphosphonates/acrylate polymer, and it is provided with trade name ITC1087 (mean molecule quantity for 3000 to 60,000) and Polymer1154 (mean molecule quantity is 6000 to 55,000) by Rhodia.

It is stable under the existence of the preferred polymeric surfactant other component such as fluorion and metal ion in oral care composition. It is also preferred that have the polymer of limited hydrolysis degree in the preparation that water content is high, it is possible to obtain simple single phase dentifrice or mouthwash formulations. If polymeric surfactant does not have these stability characteristic (quality)s, a kind of selection is dual phase formulation, wherein makes polymer-mineral matter surfactant separate with fluoride or other inconsistent component. Alternatively prepare non-aqueous, substantially non-aqueous or that there is limited water compositions the reaction between PMSA and other component to be minimized.

Preferred polymeric surfactant is polyphosphate. Despite the presence of some cyclic polyphosphoric acid salt derivatives, but it has been generally acknowledged that Quadrafos is made up of main two or more phosphate molecules with linear configuration arrangement. Although pyrophosphate (n=2) is polyphosphate technically, but required polyphosphate is have those of an about three or more phosphate groups so that the surface adsorption of valid density can produce enough non-binding phosphonate functional group, which enhances anion form surface charge and the water-wet behavior on surface. In all phosphate, it is desirable to inorganic phosphate include tripolyphosphate, four Quadrafos and hexametaphosphate. The Quadrafos bigger than four Quadrafos generally occurs with amorphous glass material. Preferably there is the linear polyphosphate of following formula in the present invention:

XO(XPO₃)_nX

Wherein X is sodium, potassium or ammonium, and n meansigma methods is about 3 to about 125. Preferred polyphosphate is n meansigma methods is those of about 6 to about 21, for instance by FMCCorporation and Astaris produce with commercially available those of trade name Sodaphos (n �� 6), Hexaphos (n �� 13) and GlassH (n �� 21). These polyphosphate may be used singly or in combin. Polyphosphate at acidic, when being especially less than pH5, it is easy in the preparation that water content is high be hydrolyzed. It is therefore preferable that use long chain polyphosphates, average chain length is the GlassH of about 21 specifically. It is believed that this type of long chain polyphosphates can produce short chain polyphosphate, and it still can effectively be deposited on tooth and provide antiplaque beneficial effect when experience hydrolysis.

Except polyphosphate or as the replacement of polyphosphate, the compound of other polyphosphoric acid can be used, polyphosphoric acid cyclohexanehexol compound specifically, for instance phytic acid, inositol five (dihydrogen phosphoric acid ester), inositol four (dihydrogen phosphoric acid ester), inositol three (dihydrogen phosphoric acid ester) and their alkali metal salt, alkali salt or ammonium salt. Preferably phytic acid and its alkali metal salt, alkali salt or ammonium salt herein, phytic acid is also referred to as inositol 1,2,3,4,5,6-six (dihydrogen phosphoric acid ester) or phytic acid. The terms " phytic acid " includes phytic acid and its salt and other polyphosphoric acid cyclohexanehexol compound.

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

Except producing surface modification effect, tooth affinity agent can be additionally used in stablizes undissolved salt. For instance, it has been found that the insoluble tin salt of GlassH polyphosphate solubilized. Therefore, in the compositions such as comprising tin salt, GlassH contributes to reducing the mottle growgh promoting effects of sub-stannum.

Fluoride source

Dentifrice and other oral cavity composition are generally of enough water soluble fluoridized compounds to provide fluorinion concentration for compositions, and/or when described fluoride compound is with by weight for about 0.0025% to about 5.0%, it is preferable that the concentration of about 0.005% to about 2.0% can provide anti-caries effect when using. The material of multiple generation fluorion is used as soluble fluoride source suitable in the present composition. It is suitable for producing the example of fluorion material and is disclosed in the United States Patent (USP) 3,535,421 authorizing Briner et al. on October 20th, 1970 and on July 18th, 1972 authorizes in the United States Patent (USP) 3,678,154 of Widder et al.. Representational fluoride sources includes: stannous fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate, indium and other multiple source. Stannous fluoride and sodium fluoride and their mixture are preferred.

Grinding agent

Can be used for the dental abrasive in the subject innovation compositions and include many different materials. Selected material must be the substances compatible relevant to compositions and will not excessive wear dentine. Suitable grinding agent includes the silicon dioxide of such as gel and precipitation, undissolved sodium hexametaphosphate, hydrated alumina, calcium carbonate, Bibasic Calcium Phosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate and resinous abrasive materials, such as the particulate condensation products of carbamide and formaldehyde.

Being particulate thermosetting polymer resin for the another kind of grinding agent in this compositions, it is described in December in 1962 and within 25th, authorizes in the United States Patent (USP) 3,070,510 of Cooley and Grabenstetter. Suitable resin includes such as tripolycyanamide, phenol, urea, tripolycyanamide-urea, carbamide, melocol, melamine urea formaldehyde, cross-linked epoxides and cross-linked polyester.

Preferred polytype silica dental abrasives, because they have the unique benefits of the polished performance making tooth clean especially but unduly wearing and tearing dentium nitor or dentine. The abrasive silica polishing material of the present invention and the mean diameter of other grinding agent are generally at about 0.1 to about 30 micron, and preferably in the scope of about 5 to about 15 microns. Described grinding agent can be precipitated silica or silica gel, as being published in the United States Patent (USP) 3,538,230 authorizing Pader et al. on March 2nd, 1970 and being published in and authorize the United States Patent (USP) 3 of DiGiulio on January 21st, 1975, silica xerogel described in 862,307. Example include silica xerogel that W.R.Grace&Company, DavisonChemicalDivision sell with " Syloid " for trade name and such as J.M.HuberCorporation with trade nameThe precipitated silica sold, especially has119��118��109 HesThe silicon dioxide of 129 names. Can be used for this kind of silica dental abrasives in toothpaste of the present invention to be described in greater detail in and authorize the United States Patent (USP) 4,340,583 of Wason July 29 nineteen eighty-two; With the common United States Patent (USP) 5,603,920 being published on February 18th, 1997 transferred the possession of; It is published in December, 1996 United States Patent (USP) of 31 days 5,589,160; It is published in the United States Patent (USP) 5,658,553 on August 19th, 1997; It is published in the United States Patent (USP) 5,651,958 on July 29th, 1997 and is published in the United States Patent (USP) 6,740,311 on May 25th, 2004.

Applicable grinding agent mixture is as above-mentioned in being listed inDifferent grades of silica abrasive. In the Dentrifice composition of the subject innovation, the total amount of grinding agent is by weight generally in the scope of about 6% to about 70%. Toothpaste preferably comprises the grinding agent of about 10% to about 50% by weight of the composition. The Dental solution of the subject innovation, mouth sprays, collutory and non-abrasive gel combination generally seldom contain grinding agent or are entirely free of grinding agent.

Anti-calculus agent

This compositions optionally includes the anti-calculus agent added, as can as the pyrophosphate of pyrophosphate ion source. The pyrophosphate used in the present composition includes pyrophosphoric acid two alkali metal salt, pyrophosphoric acid four alkali metal salt and their mixture. Sodium Acid Pyrophosphate (Na₂H₂P₂O₇), tetrasodium pyrophosphate (Na₄P₂O₇) and tetrapotassium pyrophosphate (K₄P₂O₇) non-hydrated form and hydrated form be preferred material. In the present compositions, pyrophosphate can exist in one of three manners: solution substantially solubilized, essentially insoluble, or the mixture of dissolving and undissolved pyrophosphate.

Compositions including substantially solubilized pyrophosphate refers to that at least one of which pyrophosphate ion source has enough amounts to provide the compositions of at least about 1.0% free pyrophosphate ion. 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. The difference of the pH value according to compositions, free pyrophosphate ions can exist by various protonation states.

Referring to including the compositions of the pyrophosphate of essentially insoluble solution comprises lower than about 20%, it is preferable that the total pyrophosphate less than approximately 10% is dissolved in the compositions in compositions. In these compositionss, tetrasodium pyrophosphate is preferred pyrophosphate. In Dentrifice composition, tetrasodium pyrophosphate can be anhydrous form or decahydrate form, or any other stabilizes to 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 preferably sufficiently small with aesthetically acceptable and in use soluble. The pyrophosphate amount used in preparing these compositionss is any amount that can effectively control dental calculus, and this amount is typically about 1.5% to about 15% by the weighing scale of described Dentrifice composition, it is preferable that about 2% to about 10%, and most preferably from about 3% to about 8%.

Compositions also can comprise the mixture dissolved with undissolved pyrophosphate. The above-mentioned any pyrophosphate mentioned can be used.

" EncyclopediaofChemicalTechnology " the 3rd edition the 17th volume (Wiley-IntersciencePublishers, 1982) of Kirk&Othmer describe in further detail pyrophosphate.

The optional reagent that can substitute for or can use with pyrophosphate combination includes known substance, the anionic polymer such as synthesized, copolymer (such as Gantrez) including polyacrylate and maleic anhydride or maleic acid and methyl vinyl ether, such as authorizing the United States Patent (USP) 4 of Gaffer et al., described in 627,977; And such as poly-aminopropanesulfonic acid (AMPS), diphosphate (such as EHDP; AHP), polypeptide (such as poly-aspartate and polyglutamic acid) and their mixture.

Chelating agen

Another kind of optional reagent is chelating agen, also referred to as sequestering agent, such as gluconic acid, tartaric acid, citric acid and its pharmaceutically useful salt. Chelating agen energy complexation is present in the calcium in bacteria cell wall. Chelating agen destroys dental plaque also by removing calcium from calcium bridge, and it is complete that described calcium bridge helps to maintain biomass. It is not intended, however, that use the chelating agen that calcium had high-affinity, because this can cause teeth demineralization, this deviates from mutually with the purpose of the present invention and intention. The common calcium-binding constant of suitable chelating agen is about 10¹To 10⁵To provide the improvement cleaning action forming dental plaque and the calculus reduced. Chelating agen also has and the ability of metal ion compound, hence helps to prevention product adverse effect in stability or outward appearance. The ion of chelating such as ferrum or copper contributes to postponing the oxidation deterioration of finished product.

Suitable chelating agen example is gluconic acid sodium salt or potassium and sodium citrate or potassium, citric acid/alkali-metal citrate combination; Disodium tartrate, di-potassium tartrate, sodium potassium tartrate tetrahydrate, sodium bitartrate, potassium hydrogen tartrate, sodium polyphosphate, potassium or ammonium and and their mixture. Suitable in the present invention, the amount of chelating agen is about 0.1% to about 2.5%, it is preferred to about 0.5% to about 2.5%, and even more preferably about 1.0% to about 2.5%.

Other chelating agen applying also for the present invention is the polycarboxylate of anionic polymerisation. These materials are well-known in the art, and they are with the form application of its free acid or part or water-soluble alkali (such as potassium, and the preferred sodium) salt preferably completely neutralized or ammonium salt. Example is maleic anhydride or 1: 4 to 4: 1 copolymer of acid and the polymerisable ethylenically unsaturated monomers of another kind, described monomer preferably has about 30, the methyl vinyl ether (methoxy-ethylene) of 000 to about 1,000,000 molecular weight (M.W.). These copolymers such as obtain with the trade name GantrezAN139 (M.W.500,000) of GAFChemicalsCorporation, AN119 (M.W.250,000) and S-97 pharmaceutical grade (M.W.70,000).

Other effective polymeric polycarboxylate includes 1: 1 copolymer of maleic anhydride and ethyl acrylate, hydroxyethyl methylacrylate, NVP or ethylene, the latter can trade name such as MonsantoEMANo.1103, MW10,000 and EMAGrade61 obtain, and 1: 1 copolymer of acrylic acid and methyl methacrylate or hydroxyethyl methylacrylate, acrylic acid methyl ester. or ethyl acrylate, IVE or NVP.

Additional effective polymeric polyphosphate is disclosed in authorizes the United States Patent (USP) 4 of Gaffar on February 6th, 1979, on January 15th, 138,477 and 1980 authorizes the United States Patent (USP) 4,183 of Gaffar et al., 914, and include the copolymer of maleic anhydride and styrene, isobutene. or ethyl vinyl ether; Polyacrylic acid, polyitaconic acid and poly; Low with the molecular weight of commodity UniroyalND-2 by name to 1,000 sulfo group acrylic acid oligomer.

Other activating agent

The present invention optionally includes other reagent, such as antimicrobial. Including being water-insoluble based non-cationic antimicrobial agent such as halogenated diphenyl ethers, oxybenzene compound in this reagent, described compound includes phenol and homologue, an alkyl and many alkyl and the halogenated phenol of aromatics, resorcinol and derivant, bisphenol compound and halogenated salicylanilides, benzoin ester and Halogenated carbanilides. Water soluble antimicrobials includes quaternary ammonium salt and double; two-two guanidinesalts and triclosan monophosphate. Quaternary agent includes the carbon chain lengths (being generally alkyl) of one or two substituent group on wherein quaternary nitrogen and is about 8 to about 20, is typically about 10 to 18 carbon atoms, remain substituent group (being generally alkyl or benzyl) simultaneously and there is less carbon number 1 to about 7 carbon atom according to appointment, be generally methyl or ethyl those. Typical quaternary ammonium antibacterial agents embodiment has Dodecyl trimethyl ammonium chloride, TPC, brominated phenododecinium bromide, chlorination N-myristyl-4-ethylpyridine, dodecyl dimethyl (2-benzene oxygen ethyl) ammonium bromide, benzyl dimethoylstearyl ammonium chloride, cetylpyridinium chloride, quaternised 5-amino-1, double; two (2-the ethylhexyl)-5-methyl hexahydropyrimidine of 3-, alkyl benzyl dimethyl ammonium chloride, benzethonium chloride and methyl benzethonium chloride. Other compound is double; two [4-(R-the amino)-1-pyridinium alkanes being disclosed in the United States Patent (USP) 4,206,215 authorizing Bailey announced on June 3rd, 1980. May also comprise other antimicrobial such as mantoquita, zinc salt and tin salt. Also usefully enzyme, including endo-glycosidase, papain, glucanase, glucosan allosteric hydrolytic enzyme (mutanase) and their mixture. Mentioned reagent is disclosed in the United States Patent (USP) 2,946,725 authorizing Norris et al. July 26 nineteen sixty and JIUYUE in 1977 is authorized in the United States Patent (USP) 4,051,234 of Gieske et al. on the 27th. In. Preferred antimicrobial includes zinc salt, tin salt, cetylpyridinium chloride, chlorhexidine, triclosan, triclosan monophosphate and flavor oil such as thymol. Triclosan and this type of other reagent are disclosed in the United States Patent (USP) 5,015,466 of Parran, the Jr. of announcement on May 14th, 1991 et al. and are disclosed in the United States Patent (USP) 4,894,220 authorizing Nabi et al. announced January 16 nineteen ninety. These reagent can provide anti-plaque benefits, and the content of these reagent is typically about 0.01% to about 5.0% by weight of the composition.

It is the dentin desensitizer controlling hypersensitivity that another kind can join the optional activating agent in the present composition, the such as salt of potassium, calcium, strontium and stannum, including nitrate, chloride, fluoride, phosphate, pyrophosphate, polyphosphate, citrate, oxalates and sulfate.

Peroxide source

The compositions of the present invention can comprise peroxide source, because oral cavity is had numerous beneficial effect by it. It has long been known that hydrogen peroxide and other comprise peroxide reagent can to after dental caries, dental plaque, gingivitis, periodontitis, halitosis, teeth stains, recurrent oral ulceration, artificial tooth induced pain, appliance damage, exodontia and after periodontal surgery, traumatic oral damage and the effectively treating property such as mucosal infections, viral stomatitis and/or prophylactic treatment. The reagent comprising peroxide applies chemical machinery effect in the oral cavity, generate by with histaminase and ptyalin reciprocal action and the thousands of small oxygen bubbles that produces. Collutory gargle action with this intrinsic chemical machinery effect can be strengthened. It has been recommended that other reagent is delivered in infected gingival sulcus with this type of effect. Peroxide collutory can prevent the known anaerobic bacteria relevant with periodontal disease surely grow and breed.

Peroxide source includes peroxide, perborate, percarbonate, peroxy acid, persulfate and their combination. Suitable peroxide includes hydrogen peroxide, urea peroxide, calper calcium peroxide, sodium peroxide, zinc peroxide and their mixture. Preferred percarbonate is SODIUM PERCARBONATE. Preferred persulfate is potassium hydrogen persulfate. The peroxide source being preferred in dentifrice formulation includes calper calcium peroxide and urea peroxide. Hydrogen peroxide and urea peroxide are preferred in mouthwash formulations. Following amount represents the amount of peroxide raw material, although peroxide source also can comprise the composition outside peroxide raw material. The compositions of the present invention can comprise by weight of the composition about 0.01% to about 30%, it is preferable that about 0.1% to about 10%, and the peroxide source of more preferably from about 0.5% to about 5%.

Surfactant

This compositions may also include surfactant, is also commonly referred to as foaming agent. Suitable surfactant is that those have the material of appropriate stability and foam in whole wide pH value range. Surfactant can be anion, non-ionic, both sexes, zwitterionic, cationic or their mixture.

Can be used for the anion surfactant of the present invention to include containing 8 water soluble salts to the alkylsurfuric acid of 20 carbon atoms (such as alkyl sodium sulfate) in alkyl, and the water soluble salt of the sulfonate monoglycerides of the fatty acid containing 8 to 20 carbon atoms. The example of this analog anion surfactants is sodium lauryl sulfate (SLS) and coco group monoglyceride sulfonates. Other suitable anion surfactants are sarcosinate such as sodium lauroyl sarcosine, taurate, lauryl sulfoacetate sodium, lauroyl sodium isethionate, laureth carboxylic acid sodium and dodecylbenzene sodium sulfonate. It is used as the mixture of anion surfactant. Many suitable anion surfactants are disclosed in be authorized in the United States Patent (USP) 3,959,458 of Agricola et al. on May 25th, 1976. In this compositions, the typical content of anion surfactant ranges for about 0.025% to about 9%, is about 0.05% to about 5% in some embodiments, is about 0.1% to about 1% in other embodiments.

Another kind of suitable surfactant is chosen from the group being made up of sarcosinate surfactant, isethionate surfactant and taurate surfactant. What may be preferably used for this paper is alkali metal or the ammonium salt of these surfactants, such as following sodium salt and potassium salt: Hamposyl L salt, Hamposyl M salt, palmitoyl sarcosine salt, Hamposyl S salt and oleoyl sarcosinates. Described sarcosinate surfactant about 0.1% can be present in the present composition to about 2.5% by the weighing scale of described total composition, it is preferable that about 0.5% to about 2.0%.

Cationic surfactant for the present invention includes the derivant (described compound has a chain alkyl chain comprising about 8 to 18 carbon atoms) of fatty quaternary ammonium compounds such as lauryl trimethyl ammonium chloride; Cetylpyridinium chloride; Cetyl trimethylammonium bromide; Diisobutyl benzene oxygen ethyl dimethyl benzyl ammonium chloride; Coconut alkyl trimethyl ammonium nilrite; Cetyl pyridinium fluoride etc. Preferred compound is quaternary ammonium fluoride, and in the United States Patent (USP) 3,535,421 of its Briner being described in announcement on October 20th, 1970 et al., wherein said quaternary ammonium fluoride has detergent property. In compositions disclosed by the invention, some cationic surfactant also is used as antibacterial. Although cationic surfactant such as chlorhexidine is also applied for the present invention, but owing to they can stain oral hard tissue, is therefore not preferred. It will be apparent to one skilled in the art that this probability, and when mixing cationic surfactant it must be appreciated that this restricted.

Can be used for the compound that the nonionic surfactant in the present composition includes to be produced for organic hydrophobic compound condensation of aliphatic series or alkyl aromatic with itself by alkylene oxides group (itself is hydrophilic). The embodiment of suitable nonionic surfactant include polypropylene glycol and the addition polymers (polyethers) of oxirane, alkyl phenol polyethylene oxide condensation compound, derived from the mixture of oxirane with propylene oxide and the product of condensation of product of 1��2-diaminoethane, the ethylene oxide condensate of aliphatic alcohol, long chain tertiary amine oxides, long chain tertiary phosphine oxide, long chain dialkyl sulfoxides and these materials.

The derivant of aliphatic quaternary ammonium and sulfonium compound is included for the amphion synthetic surfactant of the present invention, wherein this aliphatic group can be straight or branched, and one of them aliphatic series substituent group comprises about 8 to 18 carbon atoms, and an aliphatic substituent group comprises anionic water solubilizing group, for instance carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.

Suitable beet alkali surface activator is disclosed in be authorized in the United States Patent (USP) 5,180,577 of Polefka et al. on January 19th, 1993. Typical alkyl dimethyl betaine includes decyl betaine or 2-(N-decyl-N, N-dimethyl amine) acetas, coco betaine or 2-(N-cocoyl-N, N-dimethyl amine) acetas, myristyl betaine, palmityl betaine, lauryl betaine, cetyl betaine, stearyl betaine etc. The example of amido betaines has cocoamidoethyl betaine, cocoamidopropyl, lauramido propyl betaine etc. Selected glycine betaine includes cocoamidopropyl, and lauramido propyl betaine is preferred.

Thickening agent

When preparing toothpaste or gel, thickening agent can be added to provide required compositions denseness, active release characteristics required in use, frame to hide the stability etc. of stability and compositions. Suitable thickening agent includes the combination of or carboxy vinyl polymer, carrageenin, hydroxyethyl cellulose (HEC), the water soluble salt such as sodium carboxymethyl cellulose (CMC) of natural and synthesis of clay (i.e. veegum and LAPONITE) and cellulose ether and carboxymethyl hydroxyethyl cellulose sodium. It is used as natural gum, for instance karaya, xanthan gum, Radix Acaciae senegalis and Tragacanth. The silicon dioxide of colloidal magnesium aluminum silicate or segmentation can be used as part thickening agent to improve texture further.

Can be used as the suitable carboxy vinyl polymer of thickening agent or gellant and include carbomer, it is a class homopolymer of acrylic acid and pentaerythritol alkyl ether or the crosslinking of sucrose alkyl ether. Carbomer is passableSeries is commercially available from B.F.Goodrich, including Carbopol934, and 940,941,956 and their mixture.

Thickening agent can by described total toothpaste or gel combination weighing scale normally about 0.1% to about 15%, it is preferable that about 2% to about 10%, and more preferably from about the amount of 4% to about 8% uses. Higher concentration can be used for chewing gum, lozenges and breath mint, sachet, non-abrasive gel and subgingival gel.

Wetting agent

In this compositions, another kind of optional carrier material is wetting agent. Wetting agent is used for preventing dentifrice composition from hardening occurring after ingress of air and makes compositions give oral cavity damp, and for specific wetting agent, wetting agent can be additionally used in the imparting desirable sweet taste of dentifrice composition. Based on pure wetting agent, the content of this wetting agent is typically about 0% to about 70% by the weighing scale of the present composition, it is preferable that about 5% to about 25%. Applicable wetting agent for the subject innovation compositions includes edible polyhydric alcohol, such as glycerol, sorbitol, xylitol, butanediol, Polyethylene Glycol, propylene glycol and trimethyl glycine.

Miscellaneous Carriers material

The water used when preparing commercial suitable oral cavity composition should be preferably the water of low ion concentration and without organic impurities. The content of water is up to about 99% by the weighing scale of Aquo-composition described herein. The amount of these water includes the free water added and the water brought into by other materials (as by sorbitol).

The present invention may also comprise alkali metal hydrogencarbonate, and it can provide many functions, including grinding, deodorization, buffering and adjustment pH value. Alkali metal hydrogencarbonate is water miscible, unless stabilized, it is prone to release carbon dioxide in Aquo System. Sodium bicarbonate (also referred to as yeast powder) is conventional alkali metal hydrogencarbonate. This compositions can include about 0.5% to about 30%, preferably about 0.5% to the alkali metal hydrogencarbonate of about 15%, most preferably from about 0.5% to about 5%.

Buffer agent can be used to regulate the pH value of this compositions. As used herein, buffer agent relates to regulate the reagent of Aquo-composition such as collutory and dental solutions pH. In view of peroxide stability, it is preferable that by the scope of pH regulator to about pH4.0 to about pH6.0. Buffer agent includes sodium bicarbonate, monosodium phosphate, tertiary sodium phosphate, sodium hydroxide, sodium carbonate, sodium pyrophosphate, citric acid and sodium citrate. The typical amounts of buffer agent is calculated as about 0.5% to about 10% by the weight of this compositions.

Poloxamer can be used in this compositions. Poloxamer belongs to nonionic surfactant also can be divided into emulsifying agent, binding agent, stabilizer and other relevant function by function. Poloxamer is end is di-functional block's polymer of primary hydroxyl, and molecular weight is from 1,000 to more than 15,000. Poloxamer is sold with trade name Pluronics and Pluraflo by BASF. The poloxamer that the present invention is suitable is Poloxamer407 and PlurafloL4370.

Other emulsifying agent that can be used in this compositions includes polymer emulsifier, as purchased from B.F.goodrichSeries, and it is mainly the acrylic acid polymer of high molecular, as the emulsifying agent of lyophobic dust.

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

Other optional reagent that can be used for this compositions includes the dimethicone copolyol being selected from alkyl dimethicone polyol and alkyloxydimethicone polyol, such as C12-C20 alkyl dimethicone polyol and their mixture. It is highly preferred that the cetyl dimethicone polyol of trade name AbilM90. Generally, the content of dimethicone copolyol is about 0.01% to about 25% by weight, it is preferable that about 0.1% to about 5%, more preferably from about 0.5% to about 1.5%. This dimethicone copolyol auxiliary provides positive tooth feel benefits.

Flavor oil produces the removal of malodor components

Another aspect of the present invention be refine or purification process to remove or to significantly reduce the content of inadvisable sulphur-containing substance in flavor oil and extract, thus preparing herein referred " selectivity " flavor oil.

Method for washing

Preferred purification process is method for washing, and it is simple, inexpensive and is prone to extensive enforcement. Water-bearing media can be all the mixture of water or water and solvent, and wherein the content of solvent is about 20% or lower. The method removing inadvisable component relates generally to be extracted in aqueous phase them from flavor oil. DMSO and dimethyl sulfone are high-polarity, and can freely be dissolved in water or other solvent such as alcohol. It is prone to, by tasteless water or water-alcohol mixture, be extracted from oil by these compounds. The use of cosolvent such as alcohol can improve the removal of polarity relatively low material such as DMS. Described cosolvent can be any food stage water miscible solvent, for instance ethanol, isopropanol, glycerol and propylene glycol, and it will extract worthless material such as DMS from oil, without significantly extracting required component. The pH of water-bearing media is typically in about 3 to about 12, it is preferable that about 7 to neutral scope. Definite pH preferred value depends on the pH stability of handled flavor oil. Described water-bearing media optionally comprises salt, and it can help to make major part flavor components " saltout out " from aqueous phase, and they is remained in flavor oil self. With about 90: 10 to about 10: 90, it is preferable that the water of about 70: 30 to about 30: 70 scopes and the volume ratio of oil, flavor oil sample and water-bearing media are mixed. Generally, water is more many, and the speed removing DMSO is more fast. But, too much water can cause emulsifying, and causes oil phase to be finally difficult to aqueous phase separate. Conventional water can be used, it is preferable that USP level water. Described method is generally implemented at ambient temperature. Equally, the temperature stability of flavor oil is depended in the selection of temperature conditions.

Make aqueous phase stand stirring with oil phase or be vigorously mixed situation so that water better contacts with oil, produce muddy mixture. Oil phase and aqueous phase are continued to mix about 30 minutes to maximum 3 hours or longer. According to mixing condition and batch sizes, completing purification or extraction fully in about 30 minutes, the content of sulphur compounds being about to residue in oil is reduced to target content. Mixing makes respectively to be separated, then by oil phase and aqueous phase separation after stopping. Then isolated oil phase is stood extra washing and/or is filtered to eliminate the muddiness of any remnants in described oil by hydrophilic/hydrophobic sorbent material by each fresh water. Institute's washing oil is also subject to centrifugal or cools down to reach the purpose that the water in institute's washing oil will be stayed to separate. At regular intervals, in quantitative analysis oil phase the content of DMSO and other sulfur-containing compound to determine the need for extra stirring/mixing or washing step.

High-shear mixer can be used to reach the mixing of flavor oil and water and the improvement that the contact removal to realize DMSO within a short period of time. Available agitator includes high-shear mixer, for instance for the Ross agitator of batch-mixed or on-line mixing. High-speed dispersion mixer that the example of suitable batch agitator includes being made up of vertical axis and high shear disc type blade (be generally used for 1 gallon to 1000 gallon batch). Described blade rotates with the speed of at most about 10,000RPM, and produces flow pattern in fixing mixing container. Described blade produces vortex, and container contents is pulled to blade sharp edges place by it. Then described blade is by oil phase mechanically breaking up, and distributes it in aqueous phase. Another kind of batch agitator model is the design of high shear rotor-stator stirrer, and it is made up of single stage rotor with high speed rotating in fixed stator. When the blade rotated is by stator, they mechanical shearing water-oil phase. Laboratory scale portable agitator has the mixing rate of 500 to 10,000RPM (for 0.3 to 15L liquid capacity). Commercial-scale large stirrer has the speed of 3600-1200RPM (being the rotor of 64mm to 330mm for diameter), for 15L-22,710L liquid capacity. The example of the online agitator of ultra-high shear is Ross model, and it has level Four or more stages rotor, and it rotates with the speed of 15000 foot per minute in fixed stator. When the blade rotated is by stator, they mechanical shearing contents.

In an example, 250mL Oleum menthae is joined in 2L glass beaker. It is added thereto to 150mLUSP level water, and is stirred vigorously with magnetic stirring apparatus, until oil and water form the mixture of muddiness. It is continuously stirred at room temperature. At about 0.5 hour, 1 hour and 2 h apart places, stop stirring so that being respectively separated. Within a few minutes, respectively it is separated and takes out 1mL oil sample originally for analysis. After stirring 2 hours, make respectively to be separated, and decantation goes out upper strata oil, and make it stand 24 to 48 hours in vial to make a small amount of dregs clarification remaining in oil further. Then make oil be filtered through 0.45um hydrophilic PVDF filter (Millipore) so that breakdown of oil, and be stored in glass jar, until using.

Unprocessed Oleum menthae feed (being provided by I.P.Callison) is implemented said method, and in oil phase, the content of DMSO is shown below. GC-MSD is used to carry out quantitative DMSO. As shown in structure, washing about after half an hour, the DMSO more than 95% is removed from the oil, and after 2 hours, residual quantity is less than 1ppm.

Sample	DMSO (ppm, w/v)
		Oleum menthae feed #1	307
Wash the feed of 35 minutes	12.7
		Wash the feed of 60 minutes	16.5
Wash the feed of 2 hours	< 1

Except DMSO, washing processes and also removes other water soluble compound in oil, for instance low-molecular-weight alcohols and aldehydes and the poor compound such as dimethyl sulphide (DMS) of water solublity. But, compared with DMSO, the removal of DMS carries out with slower speed. It is believed that aqueous phase polarity dies down when aqueous phase dissolved DMSO and other organic compound, form the medium that DMS is had with other compound with similar polarity and dissolubility property better removal effect.

In another example, the compound removed from sample Oleum menthae experiencing water-washing process of the present invention is measured. Make the rectification Oleum menthae sample provided by I.P.Callison stand washing in 5 hours, then experience the step washed with fresh water again 7 hours. Each washing step is all for the mixture enforcement of the water of 1: 1 with oil, gentle agitation simultaneously. Via SPMEGC-MS, the Oleum menthae before and after this washing step is analyzed, and assesses about minimizing amount of every kind of component by comparing gained chromatograph. In table 2 below, it is provided that the part of compounds list that its concentration reduces via washing step. Between removed compound percentage ratio and LogP (Octanol/water Partition Coefficients), there is goodish dependency. When considering the molecular weight of every kind of compound, described dependency is even better. It is essential that the key component concentration of relative non-polarity does not significantly change because of water-washing step in Oleum menthae. These key components include menthol, menthone, ��-and nopinene, limonene etc.

Table 2: the compound removed by washing Oleum menthae

Compound number	The compound reduced	Approximate minimizing percentage ratio (%)
			1	Methanol	95
2	Methyl formate	95
			3	Ethanol	95
4	Acetone	65
			5	Furan	90
6	Ethyl formate	90
			7	Methyl acetate	85
8	Dimethyl sulphide	99⁺
			9	Carbon bisulfide	90
10	2 methyl propanal	60
			11	Acetic acid	70
12	2-butanone	70
			13	2-methylfuran	70
14	3-methylfuran	70
			15	2-methyl isophthalic acid-propanol	40
16	Crotonic aldehyde	60

17	3-methylbutyraldehyd	50
			18	2 methyl butyraldehyde	50
19	2 pentanone	35
			20	Cyclopentanol	35
21	2-ethyl furan	20
			22	2-methyl-1-butene alcohol	15
23	2 methyl crotonaldehyde	30
			24	Dimethyl disulfide	40
25	3-guaiacene	30
			26	Hexanal	15
27	Dimethyl sulfoxide	99⁺
			28	Furfural	35
29	2-hexenoic aldehyde	15
			30	2,5-diethyl THF	5

In odor property, washed or selectivity Oleum menthae are compared with tradition rectification oil. By experienced seasoning panel of expert, washed Oleum menthae and unwashed rectification Oleum menthae being evaluated, adopt 0 to 100 grade, wherein 0 is difference wet goods level, and 100 is the oil that quality is fabulous. The average rank not washing oil is 33, and the average rank of washed oil is 67, and this shows that washed oil is better than unwashed rectification oil.

By identical seasoning panel of expert, adopt identical grade, the typical Mentha arvensis L. syn.M.haplocalyxBrig for dentifrice is accounted for leading finished product flavor oil and evaluates. Described finished product flavor oil comprises the rectification Oleum menthae of 62% or washed Oleum menthae. The average rank not washing rectification 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% stannous fluoride and the dentifrice with rectification Oleum menthae or washed Oleum menthae seasoning. Dentifrice is stored 3 months at 40 DEG C. During this period, the dentifrice containing washed oil does not produce any abnormal flavour, and not washed rectification oil creates abnormal flavour really. By experienced seasoning expert, the existence of stench during storing and intensity are implemented evaluation, adopt 0 (free from extraneous odour) to 10 (strong abnormal flavour) grade. The evaluation mark of dentifrice sample is as follows. This shows that reducing agent such as sub-stannum exists the stability of lower washing oil.

This series of experiments shows, method for washing can be used for stable rectification flavor oil and do not experience the natural crude oil of refine or rectification process or rough flavor oil. Advantageously, described method for washing is simple, effective and economical, and avoids the improper of flavor oil is executed heat. Described method is enough to prepare business level flavor oil, without more 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 sulphur compound is had selective material and carries out by employing. This type of filtering material includes the commercially available material that can be used as adsorbent and molecular sieve. Example includes the following material provided by EngelhardCorporation and JohnsonMattheyCatalysts.

A) compositions of SELEXSORBCDX-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 7x14 order.

B) compositions of SELEXSORBCOS-hydrated alumina (88-99%w/w%) and alkali metal oxide (1-5%w/w%), density-49.8 cubic feet, surface area is 255 meters squared per gram, is of a size of 7x14 order.

C) nickel/nickel oxide on catalyst CP367-inert carrier

D) mixture of catalyst CP366-basic copper carbonate, basic zinc carbonate and aluminium oxide.

In an example, use above-mentioned material as adsorbent, make the rectification Oleum menthae experience provided by I.PCallison filter. Sorbent material (60g) is contained in the stainless steel column (deriving from Millipore, 3.5cm diameter x30cm length) that post bottom is equipped with filter plate (deriving from the microporous filter membrane of Millipore, 2umTTTP filter). 150mL Oleum menthae is poured on post bed top, and by the oil of post under bottom collection gravity feed. First collect 75mL oil (being appointed as the 1st to cut), then collect second 75mL ((being appointed as the 2nd to cut). Use preceding method, the oil filtered is carried out DMSO analysis. Result is summarized in hereinafter.

Table 3: remove DMSO from Oleum menthae by filtering

	Sample	DMSO (ppm, w/v)	Remove percentage ratio (%)
				1	The Oleum menthae of rectification	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	CP366 the 1st cuts	173	12
				7	CP366 the 2nd cuts	138	30

8	CP367 the 1st cuts	142	28
				9	CP367 the 2nd cuts	130	34

Counter-current extraction (CCE)

Counter-current extraction (CCE) technology can also be used for removing non-required component from flavor oil. This technology has been used in flavoring agent industry to prepare de-terpenes oil. In former patented method, by dual solvent extraction method and use polarity and non-polar solven to make quintessence oil take off terpenes. Described quintessence oil passes through mixing chamber, and stirs with two kinds of solvent counter current, causes 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 taken out with pump in the opposite direction and distribute tangerine oil. Terpenes is extracted by water-alcohol solvent from tangerine oil. Similarly, using water as extractant, CCE technology can be used for extracting DMSO and other sulphur compound. CCE technicism is set forth in " FlavoringAgents " (" FoodAdditiveToxicology ", 1995, Maga&Tu (editors)) of R.L.Swaine.

Distillation

It is also possible to use standard distillation and/or extractive technique by flavor oil fractional distillation to remove unwanted component. This can such as use vacuum distillation plant or rotary column sheet-pile to implement by standard distilation steps. By selecting required component and combining described component and again process or prepare finished product flavor oil. Such as in Oleum menthae, especially from those such as Oleum menthae that Herba Menthae or pennyroyal are originated, up to the present identify more than 225 kinds of volatile compounds. But it is also determined that, in numerous volatile components, only product entirety abnormal smells from the patient is produced actual influence by pole finite quantity really. Separate accordingly, it would be desirable to great majority are affected the compound of abnormal smells from the patient by effective screening technique from showing in a large number extremely weak or scentless volatile compound. Preferably include as far as possible many components being typically found in natural menthence with complete balanced minty taste is provided and without any abnormal flavour or stench. If Oleum menthae carries out low selectivity fractional distillation or refine, and more will remove and not have add-back by multicomponent, then gained Oleum menthae flavor composition is probably unacceptable. Accordingly, it would be desirable to optionally fractional distillation Oleum menthae is to provide the most aesthetically pleasing Herba Menthae flavoring agent.

Can pass through to distill (Oleum menthae is included commonly known those, such as Mentha arvensis L. syn.M.haplocalyxBrig, Herba Menthae Rotundifoliae and MIenlha spicata) fractional distillation removes worthless volatility (relatively low boiling) polar compound, DMSO and other sulfur-containing compound specifically, for instance sulfide and disulphide. Polarity, more lower boiling component can have less than approximately 120 DEG C, less than approximately 140 DEG C, less than approximately 160 DEG C, or are even less than the boiling point of about 180 DEG C. Described distillating method also will remove other low molecular weight compound, for instance C3-C9 aldehyde and alcohol.

Fractional distillation or selectivity Oleum menthae be substantially free of the low boiling-point and polarity compound including DMSO and dimethyl sulphide. other component being removed or substantially reducing includes branched paraffin aldehyde, for instance 2 methyl propanal, 2 methyl butyraldehyde and 3-methylbutyraldehyd, branched alkanols, for instance 2-methylpropanol, 2-methyl butanol and 3-methyl butanol, alkenols, for instance Z-3-hexenol, chain olefine aldehydr, for instance E-2-hexenoic aldehyde, other aldehyde, alcohol and ketone, for instance 3-methyl cyclohexanone, benzaldehyde, 1-OCOL, 3-octanone and 2,3-dehydrogenation-1,8-eucalyptole. the concrete component that selectivity Oleum menthae is likely to comprise is australene, nopinene, sabinene, myrcene, ��-phellandrene, ��-terpinene, limonene, cis-Ocimene, cineole, trans-ocimene, ��-terpinene, 3-capryl alcohol, terpinolene, sabinene hydrate, linalool, menthofuran, isopulegol, menthone, neomenthol, terpinen-4-ols, isomenthone, menthol, neoisomenthol, isomenthol, ��-terpinol, pulegone, menthyl acetate, carvone, the strange menthyl ester of acetic acid, menthone, b-bourbonene, ��-caryophyllene, thymol, trans-��-farnesene, ��-humulene, big root leaf alkene B, elemol, viridiflorol, cineole, ��-terpinene, 1-capryl alcohol, isovaleric acid n-pentyl ester, 1-methyl-4-(1-Methylethyl)-trans-2-cyclohexene-1-alcohol, 1-terpinol, ��-terpinol, 4,7-dimethyl benzofurans, citronellol, the new menthyl ester of acetic acid, acetaminol, ylangene, ��-copaene, longifolene, ��-gurjunene, caryophyllene, (+)-Biao dicyclo sesquiphellandrene, trans-��-farnesene, ��-caryophyllene, alloaromadendrene, ��-Cananga odorata oil alkene, big root leaf alkene D, big leaf alkene of dicyclo, 8-cadinene and terpinolene.

Using method

The present invention also relates to cleaning of teeth and the method preventing tedious oral condition, described oral condition includes dental caries, microorganism infection, dental plaque, dental calculus, mottle and oral malodor and tooth erosion.

The using method of the present invention includes contacting the enamel surface of experimenter with the oral cavity composition of the present invention with oral mucosa. Using method can be scrub with dentifrice, rinse or chewing gum product with dentifrice slurry or collutory. Other method includes contacting topical oral gel, mouth spraying agent or other form with tooth and the oral mucosa of patient. Experimenter can be any human or animal of oral compositions described in its tooth surface contact. " animal " is intended to include house pet or other domestic animal or the animal encaged.

Such as, processing method can include someone and uses a kind of Dentrifice composition to scrub the tooth of Canis familiaris L.. Another example includes, with oral cavity composition, the mouth of cat is rinsed the long enough time to see beneficial effect. The pet care product such as chaw and toy that comprise this oral cavity composition can be prepared. Described compositions is included in flexible relative but in robust material, such as rawhide, the rope being made up of naturally occurring or synthetic fiber and the polymer product be made up of nylon, polyester or thermoplastic polyurethane. When animal chew, lick or bite the said goods time, contained active component is released in the salivary medium in the oral cavity of animal, and this is equivalent to effectively scrub or rinse.

Embodiment

The following example further describes and demonstrates the embodiment in the scope of the invention. These given embodiments are only used to illustrate, being not considered as limitation of the present invention, because without departing substantially from the spirit and scope of the invention when, it is carried out many changes is possible.

Key component in selectivity Oleum menthae of the present invention is shown in hereinafter.

Embodiment I

Component	%	%
			Australene	0.63	0.19
Nopinene	0.90	0.23
			Sabinene	0.03	0.01
Myrcene	0.03	0.01
			��-terpinene	0.01	0.01
Limonene	0.50	0.05
			Cis-Ocimene	0.01	0.01
Cineole	2.64	4.71
			Trans-ocimene	0.01	0.01
��-terpinene	0.01	0.01
			3-capryl alcohol	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
Isopulegol	0.02	0.02
			Menthone	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

��-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
Menthone	0.06	1.35
			The other alkene of beta waves	0.02
��-caryophyllene	0.11	3.12
			Thymol	0.03	0.02
Trans-��-farnesene	0.08	0.01
			��-humulene	0.02	0.24
Big root leaf alkene D	0.32	0.05
			Glycerol triacetate		0.17
Big root leaf alkene B		0.08
			Elemol		0.89
Viridiflorol	0.03	0.03
			Menthalactone		0.17

It is shown in hereinafter according to the flavor composition comprising selectivity Oleum menthae that the present invention processes. Selectivity Oleum menthae is substantially free of DMSO and other malodor precursors sulphur compound. In affecting organ sensation's test, the flavor composition comprising Oleum menthae of the present invention is accredited as aesthetically pleasing and can be incorporated in the oral care composition comprising reducing agent such as Ya Xi and tea polyphenols without producing stench or abnormal flavour.

Embodiment II

Composition	%
		Selectivity Oleum menthae	60%
Anethole	10%
		Menthol	25%
Cineole	5%

Embodiment III

Composition	%
		Selectivity Oleum menthae	42%
Selectivity Oleum Menthae Rotundifoliae	5%
		WS-3 coolant	10%
Anethole	7%
		Menthol	35%
Aloe	1%

The oral compositions comprising the selectivity Oleum menthae in stannous ion, flavor composition and oral area acceptable carriers is shown in hereinafter, and wherein component amount represents with percentage by weight (%). These compositionss can use conventional method to prepare. Embodiment IV illustrates biphase Dentrifice composition; First-phase and second-phase can be packaged in the allotter compartment of physical separation, and generally distribute side by side with the ratio of 50: 50. Embodiment V illustrates single phase dentifrice compositions.

Embodiment IV

Embodiment V

1 zinc carbonate AC, is supplied by BruggemannChemical:NewtownSquare, PA, USA

Dimension disclosed herein and value are not intended to be understood to be limited strictly to described exact value. On the contrary, except as otherwise noted, each such dimension refers to cited numerical value and the functionally equivalent scope around this numerical value. Such as, the dimension being disclosed as " 40mm " is intended to indicate that " about 40mm ".

The All Files quoted in detailed Description Of The Invention is all incorporated herein by reference in relevant portion. Quoting of any file is not construed as admitting that it is prior art for the present invention. When any implication of term or definition and any implication of term in the file that is incorporated by reference or definition contradiction in the present invention, it should obedience gives implication or the definition of this term in the present invention.

Although having illustrate and described specific embodiments of the present invention, change and modification it should be apparent to those skilled in the art that multiple other can be made when without departing substantially from spirit and scope of the present invention. Therefore, claims are intended to cover in all such change in the scope of the invention and modification.

Claims

1. the flavor composition being used in oral care product, described flavor composition comprises one or more flavor oil being substantially free of sulphur-containing substance or extracts, described sulphur-containing substance can react with the sub-stannum in described oral care product and produce stench and abnormal flavour, the content of wherein said sulphur-containing substance reduce by washing and by weight per unit volume flavor oil or extract less than 1ppm, the medium of wherein said washing is selected from the mixture being all water or water and solvent, the content of described solvent is 20% or lower, and selected from ethanol, isopropanol, glycerol and propylene glycol, described flavor oil or extract derive from Mentha arvensis L. syn.M.haplocalyxBrig, MIenlha spicata or Herba Menthae Rotundifoliae, and the malodor precursors of described sulphur-containing substance includes dimethyl sulfoxide, dimethyl sulphide, dimethyl disulfide or dimethyl sulfone.

2. flavor composition as claimed in claim 1, described compositions comprises the flavoring agent that one or more are additional, described flavoring agent selected from wintergreen oil, clove bud oil, Cortex cinnamomi japonici (Ramulus Cinnamomi), Salvia japonica Thunb., parsley oil, origanum, Fructus Citri Limoniae, orange, cis-jasmone, 2,5-dimethyl-4-hydroxyl-3 (2H)-furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone, vanillin, ethyl vanillin, anisaldehyde, 3,4-methylenedioxy benzene formaldehyde, Veratraldehyde, 4-hydroxy benzaldehyde, Benzaldehyde,2-methoxy, benzaldehyde, cinnamic aldehyde, jasminolene, ��-methylcinnamaldehyde, o-methoxy cinnamic aldehyde, jasminal 1-ethoxy-2-hydroxy-4-propenyl benzene, heliotropine, 4-cis-heptenal, diacetyl, the p-tert-butyl benzene yl acetate of methyl, menthol, methyl salicylate, ethyl salicylate, acetic acid 1-menthyl ester, alkanone, ��-ionone, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethyl n-butyrate., ethyl acetate, methyl 2-aminobenzoate, isoamyl acetate, isoamyl butyrate, allyl hexanoate, acetaminol, eucalyptole, thymol, cinnamyl alcohol, capryl alcohol, octanal, decanol, capraldehyde, phenethanol, benzylalcohol, ��-terpinol, linalool, alkene, citral, maltol, ethylmaltol, anethole, dihydroanethole, carvone, menthone, dorinone, ionone, ��-decalactone, nonyl lactone and peach aldehyde.

3. flavor composition as claimed in claim 1, it is used for oral care product, and the form of described product gel, collutory, mouth spraying agent, mousse, foam, denture care products, medicine caked sugar, chewable tablet, chewing gum and the tooth for being adhered directly on tooth under dentifrice, gutta-percha, gum paste.

4. flavor composition as claimed in claim 3, it is for comprising the dentifrice of one or more carrier materials, and described carrier material is selected from fluorine ion source, anti-calculus agent, grinding agent, desensitizer, tooth affinity agent and additional flavoring agent.

5. flavor composition as claimed in claim 4, wherein said tooth affinity agent is 3 or longer polyphosphate and phytic acid selected from average chain length.

6. an oral care product, described oral care product comprises

(a) stannous ion source,

(b) flavor composition, described flavor composition comprises one or more flavor oil being substantially free of sulphur-containing substance or extracts, described sulphur-containing substance can react with sub-stannum and produce stench and abnormal flavour, the content of wherein said sulphur-containing substance reduce by washing and by weight per unit volume flavor oil or extract less than 1ppm, the medium of wherein said washing is selected from the mixture being all water or water and solvent, the content of described solvent is 20% or lower, and selected from ethanol, isopropanol, glycerol and propylene glycol, described flavor oil or extract derive from Mentha arvensis L. syn.M.haplocalyxBrig, MIenlha spicata or Herba Menthae Rotundifoliae, and the malodor precursors of described sulphur-containing substance includes dimethyl sulfoxide, dimethyl sulphide, dimethyl disulfide or dimethyl sulfone, with

(c) oral area acceptable carrier.

7. oral care product as claimed in claim 6, wherein said stannous ion source includes the mixture of a kind of tin salt or tin salt, and described tin salt is selected from stannous fluoride, stannous chloride, two hydrated stannous chlorides, stannous acetate, gluconic acid Asia stannum, stannous oxalate, stannous sulfate, lactic acid Asia stannum and stannous tartrate.

8. oral care product as claimed in claim 6, described product comprises one or more carrier materials, and described carrier material is selected from fluorine ion source, antimicrobial, anti-calculus agent, grinding agent, desensitizer, tooth affinity agent and additional flavoring agent.

9. oral care product as claimed in claim 8, wherein said tooth affinity agent is 3 or longer polyphosphate and phytic acid selected from average chain length.

10. oral care product as claimed in claim 8, wherein said additional flavoring agent includes one or more selected from following additional flavoring agent: wintergreen oil, clove bud oil, Cortex cinnamomi japonici (Ramulus Cinnamomi), Salvia japonica Thunb., parsley oil, origanum, Fructus Citri Limoniae, orange, cis-jasmone, 2, 5-dimethyl-4-hydroxyl-3 (2H)-furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H)-furanone, vanillin, ethyl vanillin, anisaldehyde, 3, 4-methylenedioxy benzene formaldehyde, 3, 4-dimethoxy benzaldehyde, 4-hydroxy benzaldehyde, Benzaldehyde,2-methoxy, benzaldehyde, cinnamic aldehyde, jasminolene, ��-methylcinnamaldehyde, o-methoxy cinnamic aldehyde, jasminal 1-ethoxy-2-hydroxy-4-propenyl benzene, heliotropine, 4-cis-heptenal, diacetyl, the p-tert-butyl benzene yl acetate of methyl, menthol, methyl salicylate, ethyl salicylate, acetic acid 1-menthyl ester, alkanone, ��-ionone, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethyl n-butyrate., ethyl acetate, methyl 2-aminobenzoate, isoamyl acetate, isoamyl butyrate, allyl hexanoate, acetaminol, eucalyptole, thymol, cinnamyl alcohol, capryl alcohol, octanal, decanol, capraldehyde, phenethanol, benzylalcohol, ��-terpinol, linalool, alkene, citral, maltol, ethylmaltol, anethole, dihydroanethole, carvone, menthone, dorinone, ionone, ��-decalactone, nonyl lactone and peach aldehyde.