Flavor oils with reduced sulfur content and use in oral care compositions

Technical field

The present invention relates to oral hygiene compositions comprising a flavoring system that includes fragrance oils that do not degrade and do not produce an unpleasant odor or undesirable taste, mainly derived from sulfur-containing compounds such as thiols or mercaptans. These unpleasant odors are formed by oxidation / reduction reactions involving sulfur-containing compounds present in flavoring oils and other ingredients in the composition. Flavor oils are specially processed to reduce the content of low molecular weight sulfur compounds, in particular dimethyl sulfoxide (DMSO), which has been found to be the main precursor of odor compounds such as dimethyl sulfide and methyl mercaptan. The present invention therefore provides methods of producing flavor oils, including mint, fruit and spice flavors, which are essentially free of DMSO and other sulfur-containing compounds, as well as oral hygiene compositions containing such specially processed flavor oils that improve stability in terms of taste profile and fragrances.

Background of the invention

Oral hygiene products, such as dentifrice and mouthwash, are regularly used by consumers as part of their daily oral hygiene. It is well known that oral hygiene products can provide clients with both hygienic and therapeutic benefits. Therapeutic benefits include the prevention of tooth decay, which is usually achieved through the use of various fluoride salts, as well as the prevention of gingivitis through the use of an antimicrobial agent such as tricolsane, stannous fluoride or essential oils, or the control of tooth sensitivity through the use of ingredients such as strontium chloride or potassium nitrate. The cosmetic benefits provided by oral hygiene products include control over deposit formation

EP2 038 012 and tartar, removing and preventing hyperpigmentation, teeth whitening, breath freshening, and overall improvement in mouthfeel, which can be broadly characterized as a mouthfeel. Tartar and sediment along with behavioral and environmental factors lead to the formation of discoloration on the teeth, which significantly affect the aesthetic appearance of the teeth. Behavioral and environmental factors that contribute to hyperpigmentation include coffee, tea, coca cola and tobacco products, as well as the use of certain oral hygiene products that contain ingredients that promote discoloration such as cationic antimicrobials and metal salts.

That is why everyday home oral hygiene requires the use of products containing many components operating in accordance with various mechanisms to provide a full range of therapeutic and aesthetic benefits, including the prevention of caries, microbes, gingivitis, sediments, tartar as well as a refreshing mouth feel. removal of discolorations, control of discoloration and teeth whitening. In order for oral hygiene products for daily use, such as dentifrices and mouthwashes, to provide comprehensive oral hygiene, active agents and additives must be combined, many of which adversely cause negative aesthetic effects when used, in particular an unpleasant taste and feeling and contribute to the formation of discoloration. An unpleasant taste and mouthfeel have been described as having at least one of the following aspects: bitter, metallic, tart, salty, numbing, pinching, burning, stinging and even annoying. Typical ingredients for oral hygiene that are associated with negative aesthetic effects include antimicrobial agents such as cetyl pyridine chloride, chlorexidine, stannous, copper and zinc salts; teeth whitening agents such as peroxides; anticalculus agents such as pyrophosphate, tripolyphosphate and hexametaphosphate; and excipients such as baking soda and surfactants. To alleviate the negative aesthetic effects caused by these ingredients, hygiene products

EP2 038 012 of the mouth are usually formed with the addition of flavors and sweeteners to have a good taste and be accepted by the consumer.

Because of the many proven benefits for the oral cavity, it is desirable to add stannous ions to the oral cleaning composition. The stannous ions, usually supplied from stannous fluoride present in oral hygiene compositions, are used to provide antimicrobial and anti-sediment benefits, prevent gingivitis and reduce their sensitivity, as well as to prevent odor from the mouth. However, formulation using stannous ions has proved difficult because formulas containing stannous ions are unsightly. In addition, it has been found that some flavor oils, and especially mint type oils, used in combination with stannous ions may exhibit instability and cause an unpleasant odor.

Refining or further processing of natural flavoring oils after their extraction from plants or plant materials to improve quality and stability has been described in the art. Essentially, these treatment methods are intended to remove ingredients from oils that are believed to be responsible for, or limit, the instability or undesirable taste or smell properties. For example, flavoring oils were processed to remove or reduce the content of terpenes, mentofuran, pulegon and dimethyl sulfide. Such machining processes are described, for example, in US Patent Nos. 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; 5,425,962 and 6,479,088, and include distillation, nitrogen sputtering, and chemical treatment to oxidize or inactivate such undesirable components.

Peppermint oils can, for example, be distilled to remove or reduce the level of dimethyl sulfide, which according to information causes an undesirable green weed note. Steam or vacuum distillation is carried out to refine peppermint oil. However, such distillation processes are not satisfactory enough. A typical steam distillation process removes not only dimethyl sulfide, but also other peppermint oil components with a low boiling point. Therefore, when refining peppermint oil, you need to separate the ingredients

EP2 038 012 characterized by a low boiling point from the distillate and add them back at least partially to the flavoring agent. This increases the cost and time of the distillation process. An additional problem with most currently used methods of refining peppermint oil is the possibility of subjecting the oil to extreme conditions, such as excessive heat. This can cause unwanted changes in the flavoring agent.

There is still a need to improve the processing of flavoring oils to provide optimal flavor and fragrance properties, and in particular to remove odor generating components, specifically dimethyl sulfoxide, which has been found to be the major compound in flavoring oils that is a precursor to odor. Accordingly, the present invention contemplates the removal of such previously unrecognizable undesirable odor-producing ingredients from initial flavor oils in producing a stable taste that is substantially free of unwanted amounts of such unpleasant odors, thereby being free of unpleasant odors or tendency to contaminate the flavor. on reactions with reducing agents, such as stannous substances in oral care compositions.

Summary of the invention

In one aspect, the present invention is directed to further processing or refining flavoring oils to reduce the content of sulfur-containing components, such as dimethyl sulfoxide. The preferred method of processing is the water rinsing process, which has the advantage of simplicity, low cost and ease of use, with the important avoidance of problems associated with typical processes, including non-selective removal of desired ingredients and subjecting flavoring oils to extreme conditions that may destroy other ingredients and lead to undesirable changes in taste and aroma. Other processing methods for the selective removal of unwanted components include (1) distillation to remove polar components characterized by low boiling point, (2) filtration through selective adsorbents for sulfur compounds, (3) countercurrent extraction, and (4) column chromatography. After processing according to these methods can

EP2 038 012 optionally followed by re-engineering to add back desired components that may have been removed or changed during processing.

The present invention provides oral hygiene compositions consisting of:

(a) an oral hygiene product having the ability to chemically reduce, (b) a flavoring system containing flavoring oils or extracts, the level of sulfur-containing compounds, including dimethyl sulfoxide, dimethyl sulfide, dimethyl disulfide and dimethyl sulfate, responsible for the formation of unpleasant smell and undesirable taste in said compositions is less than 20 ppm by weight per volume of flavor oil or extract, and (c) an orally acceptable carrier.

The oral hygiene agent with chemical reduction capacity is selected from stannous ion sources and phenolic compounds from sources such as tea, cranberry, pomegranate and oak bark. The compositions have a constant, intense flavor profile and are tasty and refreshing, which makes users prone to their frequent use.

These and other features, aspects and advantages of the present invention will become apparent to those skilled in the art from reading the detailed description below.

Detailed description of the invention

Although the description ends with claims, in particular those indicating and expressly claiming the invention, it is believed that the present invention will be better understood with reference to the following description.

All percentages and ratios used herein are by weight based on the total composition, unless otherwise stated. All percentages, ratios and levels of ingredients referred to herein are based on the actual amount of the ingredient and do not include solvents, fillers and other substances with which the ingredient may be combined as a commercially available product, unless otherwise stated .

All measurements referred to herein have been performed at 25 ° C, unless otherwise stated.

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As used herein, the term "comprising" means that other steps and other ingredients that do not affect the final result may be added. The term includes "consisting of" and "consisting essentially of".

The word "include" as used herein and variations thereof are to be understood as non-limiting, so that enumeration of items in the list is not intended to exclude other similar items that may also be useful in the substances, compositions, devices and methods of the present invention.

As used herein, the words "preferred", "preferably", and variants refer to embodiments of the invention that offer certain benefits under certain circumstances. However, in the same or different circumstances, other embodiments may also be beneficial. Furthermore, the enumeration of one or more preferred embodiments does not mean that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

By "oral hygiene composition" is meant a product that, when normally used, is not intended to be swallowed for the purpose of systemically administering specific therapeutic agents, but rather can be kept in the mouth for a time sufficient to contact substantially all dental surfaces and / or oral tissues for the purpose of oral action. The oral hygiene composition can come in a variety of forms, including as toothpaste, dentifrice, tooth gel, mouthwash, mousse, foam, dental care product, mouth spray, lozenge, chewable tablet or chewing gum. The oral hygiene composition may be applied to strips or coatings for direct contact or adhesion to the surface of the oral cavity.

The term "dentifrice" as used herein means gel, liquid or paste formulas, unless otherwise stated. The dentifrice composition may be a single phase composition or may be a combination of two or more separate dentifrice compositions. The dentifrice composition may be in any desired form, such as deeply striated, surface striated, multi-layered, with a gel surrounding the paste, or in any combination thereof. Any composition for cleaning teeth inside

EP2 038 012 dentifrice containing two or more separate dentifrice compositions may be in a physically separated dispenser container and may be dispensed in parallel.

The term "dispenser" as used herein means any pump, tube or container capable of dispensing compositions, such as dentifrices.

The term "teeth" as used herein refers to natural teeth as well as to artificial teeth or dental prostheses.

The term "flavoring oils" refers to the essential oils used as flavorings that are volatile distilled or pressed oils of plant origin, and the components of these volatile oils. The term "flavoring oils" used in this description for peppermint or peppermint type oils includes various types of oil, which is usually referred to as primary natural or developed (freshly pressed from plant sources) and refined or rectified to standardize the oil and remove unwanted odor / fragrance (e.g. by fractional distillation). The rectified grade is usually a commercial grade delivered to end users for use as a flavoring or perfume. Typical essential oils and their main components can be obtained, for example, from thyme (thymol, carvacrol), oregano (carvacrol, terpen), lemon (limonene, terpinene, felandren, pinene, citral), lemongrass (citral, methylheptanone, citronelal, geraniol) ), orange flower (linalool, β-pinene, limonene), orange (limonene, citral), anise (anethole, safrol), carnation (eugenol, eugenol acetate, caryophyllene), rose (geraniol, citronellol), rosemary (borneol, esters bornyl, camphor), geranium (geraniol, citronellol, linalool), lavender (linalyl acetate, linalool), citronella (geraniol, citronelol, citronelal, camphene), eucalyptus (eucalyptol), peppermint (menthol, menthyl esters), garden mint (carvone, limonene, pinene ), wintergreen (methyl salicylate), camphor (safrol, acetaldehyde, camphor), broad beans (euganol, myrcene, chavikol), cinnamon (cinnamaldehyde, cinnamyl acetate, eugenol), tea tree (terpinen-4-ol, cyneol) and cedar leaves (alpha-thujone, beta-thujon, fenchon). Essential oils, their compositions and manufacturing methods are described in detail in Kirk-Othmer, Encyclopedia of Chemical Technology, Fourth Edition and The Merck Index, Thirteenth Edition.

The term "orally acceptable carrier" includes safe and effective substances and conventional additives such as

EP2 038 012 used in oral care compositions, including, but not limited to, fluoride ion sources, anticalculus or sediment agents, buffers, abrasive materials such as silica, alkali metal bicarbonate salts, thickeners, humectants, water, agents surfactants, titanium dioxide, flavors, sweeteners, xylitol, coloring agents and mixtures thereof.

Active and other ingredients useful herein may be classified or described herein based on their cosmetic and / or therapeutic benefit or their intended mode of action or function. It should be understood, however, that active and other ingredients useful herein may, in some cases, provide more than one cosmetic and / or therapeutic benefit or function, or have more than one mode of action. Accordingly, the classifications in this specification are only practical and are not intended to limit the ingredient to the particular use or uses specifically mentioned.

In the present specification, the terms "plaque" and "tartar" are used interchangeably and refer to mineralized plaque deposits.

The essential and optional ingredients of the present compositions are described in the following paragraphs.

Flavor system

The present compositions contain a flavoring system that includes fragrance oils that do not degrade and do not produce an unpleasant odor or undesirable taste, mainly derived from sulfur-containing compounds such as thiols or mercaptans. These unpleasant odors are formed by oxidation / reduction reactions involving flavor oils and other ingredients in the composition. More specifically, it has been discovered that low molecular weight sulfur compounds, such as dimethyl sulfoxide (DMSO), are present in certain natural flavor oils in amounts suitable to react with agents with fairly strong reducing properties, i.e. they can be easily oxidized, resulting in compounds with bad smell, including dimethyl sulfide and methyl mercaptan. The present invention uses flavored oils, including mint, fruit and spice oils, which are specially processed to reduce the content of DMSO and other sulfur-containing compounds, and

EP2 038 012 provides oral hygiene compositions containing such specially processed flavor oils for improved taste and stability. Preferably, the processed flavor oils are substantially free of such unwanted sulfur-containing compounds, including dimethyl sulfoxide, dimethyl sulfide, dimethyl disulfide, and dimethyl sulfate, which could be reduced to odorless compounds. Other sulfur-containing compounds may still be present in the processed oil, but these compounds do not appear to create problems in terms of odor formation. The term "substantially free of" as used herein means that the flavor oil contains less than 20 ppm of sulfur-containing compounds that are precursors of an unpleasant odor. It has been discovered that the combination of flavoring oils containing more than 20 ppm of such sulfur-containing compounds with agents such as stannous substances can lead to the formation of an unpleasant odor, which is referred to as "skunks."

In addition, such redox reactions leading to the formation of an unpleasant odor are disadvantageous in that they reduce the concentration of the active stannous substance in the composition, thus potentially reducing its effectiveness. Preferably, the level of sulfur-containing compounds precursor of unpleasant odor in flavored oils after processing by aqueous scrubbing is less than about 10 ppm, more preferably less than about 1 ppm, and even more preferably less than about 0.5 ppm, or these compounds are not present at all.

The present invention includes the discovery that the main sulfur-containing compounds that are the precursors of unpleasant odors present in flavor oils are DMSO, with samples of up to 300 ppm and more in samples. The table below shows DMSO and dimethyl sulfide (DMS) levels in garden mint and peppermint samples. As outlined below, the main compound is DMSO; significantly lower amounts of DMS were found in flavored oils.

Table 1. DMSO and DMS levels in the raw material, which is peppermint oil and spearmint oil

EP2 038 012

<td>A sample</td><td>DMSO (ppm, mass volume)</td><td>DMS (ppm, mass volume)</td>

<td>Peppermint sample 1</td><td> 318</td><td> 10,3</td>

<td>Peppermint sample 2</td><td> 312</td><td> 22,1</td>

<td>Peppermint sample 3</td><td> 181</td><td> 46,8</td>

<td>Garden mint (1% heads)</td><td> 235</td><td> &lt; 1</td>

Peppermint oils provided by IP Callison, peppermint oils provided by Labbeemint

DMSO has been reported in nature. For example, naturally occurring DMSO levels in selected fruits, vegetables, cereals, and beverages are reported in J. Agric. Food Chem. 1981, 29, pp. 1089-91.

The highest level of 16 ppm was recorded in a drink prepared on the basis of black tea. In most samples, the level found did not exceed 1 ppm, and the highest levels were found in concentrated or processed samples, such as tomato concentrate. It was thought that the increase in DMSO levels may be due to oxidation of dimethyl sulfide (DMS) during commercial processing. DMS can be found in large quantities in nature and is responsible for the characteristic odor of many food products. DMSO has also been reported in peppermint oil [Anais de

Academia Brasileira de Centaas, 1972, 44 (Suppl.), 273-7] and in peppermint oil [Agric. Biol. Chem., 1980, 44 (7), 1535-43]. In this description, no record of levels detected in peppermint oils has been made.

Dimethyl sulfoxide (DMSO) and dimethyl sulfide (DMS) levels in mint oils were determined by diluting the sample followed by liquid injection into the GC-MS system. Briefly, calibration standards were prepared by increasing the concentration of known amounts of DMSO and DMS in peppermint oil that had previously been rinsed with water to remove these ingredients to go below the lower quantification limit. The water scrubbing technique is in accordance with the present invention and is described in detail below. Each standard and sample was prepared for analysis by diluting a 200 μΐ aliquot with 800 μl ethyl acetate containing the labeled internal stable isotope standards for DMSO (¹³C2) and DMS (²H6). Prepared standards and samples were analyzed by injecting a 1 μl portion into the multi-part / inseparable inlet of an Agilent 6890 GC chromatograph. The waste water column has been moved

EP2 038 012 to a single Agilent 5973 quadruple mass spectrometer that operated in selective ion monitoring (SIM) mode. Peak area ratios (analyte / internal norm) for calibration norms were plotted for each analyte, taking into account increased analyte concentrations. Each unknown sample concentration was inserted from the appropriate calibration curve based on its measured analyte relative to the internal standard peak area. Using these assay conditions, the nominal lower quantification limit for both DMSO and DMS was 1 ppm (weight / volume) with upper quantification limits of 500 ppm for DMS and 100 ppm for DMS, respectively.

Flavor oils are typically used in oral hygiene compositions in amounts from about 0.001% to about 5% by weight of the composition. Preferably, flavor oil may be present in an amount of from 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%. The flavor oil may be present in the entire flavor composition of the oral formulation or may be combined with other selected flavor ingredients. Flavor oils preferred for use in oral hygiene compositions include oils derived from Mentha species, such as M. piperita (peppermint), M. arvensis (field mint), M. spicata (garden mint), M. cardiaca (ginger mint) ) and M. viridis Crispa (mint green from China).

It is desirable for the oral hygiene composition to have a general mint flavor, which means that mint is the predominant flavor in this composition.

In addition to the peppermint flavor oils selected above, the flavor system may contain additional flavor ingredients, such as, among others, virgin oil, clove oil, Chinese cinnamon oil, sage, parsley oil, marjoram oil, lemon, orange, cis-jasmon, 2 , 5-dimethyl-4-hydroxy-3 (2H) -furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H) -furanone, vanillin, ethyl vanillin, anisaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 430 hydroxybenzaldehyde, 2-methoxybenzaldehyde, benzaldehyde, cinnamaldehyde, hexyl cinnamaldehyde, alpha-methyl cinnamaldehyde, ortho-methoxy cinnamaldehyde, alpha-amyl cinnamaldehyde, propenylguuaetol, heliotropin, cis-4-heptenal, diacetyl, methyl butyl phenyl acetate, menthol, methyl salicylate, 1-menthyl acetate, oxanone, alpha-izonone,

EP2 038 012 ethyl cinnamate, butyl cinnamate, ethyl butyrate, ethyl acetate, methyl anthranilate, isoamyl acetate, isoamyl butyrate, allyl capronate, eugenol, eucalyptol, thymol, cinnamyl alcohol, octanol, octal, decanol, decanal, phenylethyl alcohol, phenylethyl alcohol, alpha-terpineol, linalool, limonene, citral, maltol, maltol ethyl, anethole, dihydroanetol, carvone, mentone, beta-damaskenone, ionone, gamma decalactone, gamma nonalactone, gamma undecalactone and mixtures of these compounds. Substantially preferred flavor components are those that contain structural properties and functional groups that are less susceptible to oxidation-reduction reactions. These include derivatives of chemical flavors that are saturated or contain aromatic rings or ester groups. It is also suitable to use chemical flavors that may undergo some oxidation or degradation without causing a significant change in the nature of the taste or its profile. Flavor ingredients may be provided to the composition individually or as purified chemical compounds, or by the addition of natural oils or extracts, which have preferably been subjected to this treatment by water scrubbing or other refining to remove ingredients that are relatively unstable and may reduce or alter the desired taste profile - fragrance, which results in a less satisfactory product from an organoleptic point of view.

The flavor system may also include a protective component that prevents the formation of an undesirable odor and taste of the composition, as described in the joint and pending application entitled FLAVORS FOR ORAL

COMPOSITIONS. FLAVORS FOR ORAL HYGIENE COMPOSITIONS. Such protective agents include carbonyl compounds such as ascorbic acid, cis-jasmon, 2,5-dimethyl-4-hydroxy-3 (2H) -furanone, 5-ethyl-3-hydroxy-4-methyl-2 (5H) -furanone, ethyl vanillin, vanillin, anisaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde,

2-methoxybenzaldehyde, 4-methoxybenzaldehyde, benzaldehyde, cinnamaldehyde, hexyl cinnamaldehyde, alpha-methyl cinnamaldehyde, ortho-methoxy cinnamaldehyde, alpha-amyl cinnamaldehyde and combinations thereof. Many of these protective agents are flavoring ingredients.

EP2 038 012

The flavor system may further consist of cooling agents or cooling agents such as menthol, menthyl esters, carboxamides, ketals, diols and mixtures thereof. Examples of suitable cooling agents useful for the present compositions include paramentan carboxamide agents, such as N-ethyl-p-menthane-3-carboxamide, known under the trade name as "WS-3", N, 2,3-trimethyl-2-isopropylbutanamide , known as "WS-23", Np-benzeneacetonitrile-methane carboxamide, and others, such as the WS-5, WS-11, WS-14 and WS-30 series. Additional preferred cooling agents include 3-1-menthoxypropane-1,2-diol, known as TK-10 and manufactured by the company

Takasago; Mentalone Acetal Glycerol (Frescolat® MGA); menthyl esters such as menthyl acetate, menthyl acetyl acetate, menthyl lactate (Frescolat® ML supplied by Haarmann and Reimer), and monomenthyl succinate (under the trade name Physcool®, supplied by V. Mane). The terms menthol and menthyl as used herein include dextrorotatory and levorotatory isomers of these compounds and racemic mixtures thereof. TK-10 described in U.S. Patent No. 4,459,425 Amano et al., Published July 10, 1984. WS-3 and other agents described in U.S. Patent No. 4,136,163 Watson et al., Published January 23, 1979.

The flavor system will typically contain a sweetener. Preferred sweeteners include those well known in the art, including both natural and artificial sweeteners. Some preferred water-soluble sweeteners include monosaccharides, disaccharides, polysaccharides and their derivatives such as xylose, ribose, glucose (dextrose), mannose, galactose, fructose (levulose), sucrose (sugar), maltose, invert sugar (mixture fructose and glucose derived from sucrose), partially hydrolyzed starch, solids from corn syrup, dihydrochalkones, monellin, steviosides, glycyrrhizin, xylitol and erythrol. Preferred water-soluble sweeteners include soluble saccharin salts, i.e. sodium or calcium saccharin salts, cyclamate salts, sodium, ammonium or calcium salts 3,4-dihydro-6-methyl, 1,2,3-oxathiazine-4-on- 2,2-dioxide, potassium salt 3,4-dihydro-6-methyl-1,2,3-oxathiazine-4-one-2,2-dioxide (acesulfame-K), the free acid form of saccharin. Other suitable sweeteners include dipeptide based sweeteners, such as sweetener derived from Lasparaginic acid, such as L-aspartyl-L-phenylalanine methyl ester (aspartame)

EP2 038 012 and materials described in US Patent No. 3,492,131, L-alphaaspartyl-N- (2,2,4,4-tetramethyl-3-thiethanyl) -D-alaninamide hydrate, Laspartyl-L-phenylglycerol methyl and L-aspartyl methyl esters -L-2,5-dihydrophenyl-glycine, L-aspartyl-2,5-dihydro-L-phenylalanine, L-aspartyl-L- (1-cyclohexene) -alanine. Water-soluble sweeteners derived from naturally occurring water-soluble sweeteners such as the chlorinated derivative of ordinary sugar (sucrose), known for example as sucralose, as well as protein-based sweeteners such as thaumatococus danielli (Taumatin) can be used I and II). The composition preferably contains from about 0.1% to about 10% sweetener, more preferably from about 0.1% to about 1% by weight.

In addition, the flavor system may contain saliva stimulants, warming agents and anesthetics. These agents are present in the compositions in an amount of from about 0.001% to about 10%, preferably from about 0.1% to about 1% by weight of the composition. Beneficial saliva stimulants include Jambu® produced by Takasago. Examples of warming agents are paprika and nicotinate esters such as benzyl nicotinate. Preferred anesthetics include benzocaine, lidocaine, clove bud oil and ethanol.

Chemical reducing agents

The flavor system containing the present specially processed flavor oils and extracts are particularly useful in compositions containing agents that have the ability to chemically reduce, in particular stannous ions, which as described above are the preferred active agents in oral hygiene compositions due to the many benefits as well as phenolic compounds and their derivatives derived from plant sources with the potential to act as antimicrobials, anti-inflammatory agents and antioxidants. Many of these phenolic compounds and their derivatives are also useful as flavoring agents.

The stannous ions have quite strong reducing properties and are oxidized to the tin form during reaction with DMSO, after which it is reduced to a DMS compound with an unpleasant odor, and then to methyl mercaptan (CH3SH). The reaction of stannous substances with agents such as DMSO is undesirable not only because of the formation of unpleasant compounds

EP2 038 012 smell, but also due to a decrease in the level of stannous substances, and thus the effectiveness of the composition. Many of the phenolic compounds used in oral care compositions as active agents or flavoring agents are susceptible to oxidation, i.e. they have reducing abilities, so they can react with DMSO in the same way as stannous substances.

The present compositions preferably include a stannous ion source, including stannous fluoride and / or stannous salts. Stannous fluoride helps to prevent tooth decay, gingivitis, deposits, and also to refresh the breath and reduce the sensitivity of the sensation. Other stannous salts include stannous chloride dihydrate, stannous acetate, stannous gluconate, stannous oxalate, stannous sulfate, stannous lactate, and stannous tartrate. The preferred stannous salts are stannous fluoride and stannous chloride dihydrate. The stannous salts will be present in an amount of from about 0.1% to about 11% by weight of the total composition. Preferably the stannous salts may be present in an amount from about 0.4% to about 7%, more preferably from about 0.45% to about 5%, and most preferably from about 0.45% to about 3% by weight of the total composition. Formulas that provide efficacy typically contain stannous substances in the form of stannous fluorides and other stannous salts, ranging from about 3,000 ppm to about 15,000 ppm stannous ions by weight of the total composition.

Dentifrices containing stannous salts, in particular stannous fluoride and stannous chloride, are described in US Patent No. 5,004,597 to Majeti et al. Other descriptions of stannous salts can be found in US Patent No. 5,578,293 published to Prencipe et al. and U.S. Patent No. 5,281,410 published to Lukacovic et al. In addition to the stannous ion source, other ingredients needed to stabilize stannous substances may be added, such as those described in the patents of Majeti et al. and Prencipe et al.

Phenolic compounds from plant sources such as tea, cranberry, pomegranate and oak bark can also be added to the present compositions. Such flavor compounds include catechin, galocatechin gallate, epicatechin (EC), epigallocatechin (EGC), epigallocatechin gallate (EGCG), epicatechin gallate (ECG), theaflavin, tearubigins, anthocyanidins / proanthocyanidins, and anthocyanins (e.g. cyanidine, dolphinidine, pelargonidine, peonidine, malvidine and petunidin); tannic acid; gallic acid; ellagic acid; elagitaninę; curcumin.

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Phenolic compounds can be provided as purified compounds or plant extracts. Phenolic compounds that can be used as active oral hygiene agents are disclosed in commonly cited US Patent Application No. 11 / 595,530 published under US 2007 / 0053849A1.

In addition to the ingredients described above, the present compositions may further consist of optional ingredients which together are called orally acceptable carriers.

Carriers acceptable for oral use

An orally acceptable carrier consists of at least one compatible solid or liquid excipient or diluent that is suitable for external oral administration. The term "compatible" as used in this specification means that the components of the composition can be mixed without interacting in a manner that would significantly reduce the stability and / or the effectiveness of the composition.

Carriers and excipients in accordance with the present invention may include the conventional and conventional components of dentifrices, non-abrasive gels, subgingival gels, mouthwashes, mouth sprays, chewing gums, lozenges and peppermints for breath freshening as described more precisely in this document.

The choice of carrier to be used is essentially determined by how the composition will be introduced into the mouth. Carrier materials for toothpaste, tooth gel and similar agents include abrasives, foaming agents, binders, humectants, flavors and sweeteners, etc., as disclosed in, e.g., US Patent No. 3,988,433 to Benedict . Carrier materials for two-phase dentifrice formulations are disclosed in US Patent Nos. 5,213,790 published May 23, 1993; 5,145,666 published on August 8, 1992 and 5,281,410 published on January 25, 1994, all for Lukacovic et al. and US Patent Nos. 4,849,213 and 4,528,180 to

Schaeffer. Carrier materials for mouthwashes, rinses, or mouth sprays typically include water, flavors and sweeteners, etc., as disclosed in, e.g., US Patent No. 3,988,433 to Benedict. Lozenge carrier materials typically include a candy base; chewing gum carrier materials include a gum base, flavors, and

EP2 038 012 sweeteners as described in US Patent No. 4,083,955 to Grabenstetter et al. The sachet carrier materials include the sachet bag, flavors and sweeteners. For subgingival gels used to deliver active substances to or near periodontal pockets, the "subgingival gel carrier" is selected, as disclosed in US Patent Nos. 5,198,220 and 5,242,910 published March 30, 1993 and September 7, 1993, respectively Damani. Carriers suitable for preparing compositions according to the present invention are well known in the art. Their selection will depend on secondary factors such as taste, cost and storage stability.

The compositions of the present invention may also be in the form of non-abrasive gels and subgingival gels, which may be aqueous or non-aqueous. In yet another aspect, the invention provides a dental implement impregnated with the composition of the present invention. The dental implement includes an appliance in contact with teeth and other oral tissues, said appliance being impregnated with the composition of the present invention. The dental fixture may be impregnated with fibers, including dental floss or tape, flakes, strips, membranes and polymeric fibers.

In one embodiment, the compositions of the invention are in the form of dentifrices such as toothpastes, tooth gels and tooth powders. The components of such toothpastes and tooth gels generally include one or more tooth abrasives (from about 6% to about 50%), a surfactant (from about 0.5% to about 10%), a thickener (from 0.1% to about 5%), humectant (from about 10% to about 55%), flavor (from about 0.04% to about 2%), sweetener (from about 0.1 % to about 3%), coloring agent (from about 0.01% to about 0.5%) and water (from about 2% to about 45%). Such toothpaste or tooth gel may also contain one or more anti-caries agents (from about 0.05% to about 0.3% as fluoride ion) and anti-calculus agents (from about 0.1% to about 13% ). In principle, all components of tooth powders are obviously non-aqueous.

Other embodiments of the invention are liquid products, including mouthwash or rinses, lip sprays,

EP2 038 012 dental solutions and irrigation fluids. The components of such mouthwashes and mouth sprays typically include one or more of water (from about 45% to about 95%), ethanol (from about 0% to about 25%), humectant (from about 0% up to about 50%), surfactant (from about 0.01% to about 7%), flavor (from about 0.04% to about 2%), sweetener (from about 0.1% to about 3% ) and coloring agent (from about 0.001% to about 0.5%). Such mouthwashes and mouth sprays may also contain one or more anti-caries agents (from about 0.05% to about 0.3% as fluoride ion) and tartar agents (from about 0.1% to about 3 %). The components of dental solutions generally include one or more of water (from about 90% to about 99%), a preservative (from about 0.01% to about 0.5%), a thickener (from about 0% to about 5%) %), flavor (from about 0.04% to about 2%), sweetener (from about 0.1% to about 3%) and surfactant (from about 0% to about 5%).

The types of orally acceptable carriers or excipients which may be added to the compositions of the present invention, together with specific non-limiting examples, are described in the following paragraphs.

Basic tooth protection

An oral care product according to the present invention may include an agent having affinity for tooth surfaces, such as polymeric surfactants (PMSA), which are polyelectrolytes, polymers, and more particularly anionic polymers. PMSA agents contain anionic groups, e.g., phosphate, phosphonate, carboxyl group or mixtures of these compounds, and therefore have the ability to react with cationic or positively charged entities. The "mineral" descriptor is intended for transferring the surface or material activity of the polymer towards mineral surfaces, such as calcium phosphate minerals or teeth.

PMSA agents are useful in the present compositions because of their anti-discoloration property. PMSA agents are thought to provide prevention of discoloration due to their chemical activity or the protection of mineral surfaces, allowing desorption of unwanted parts

EP2 038 012 absorbed sheath proteins, especially those that are responsible for the adhesion of tooth staining substances, the growth of tartar and the attraction of undesirable species of microorganisms. Retaining such PMSA agents on teeth can also prevent accumulation of discoloration due to the non-sticking of substances discoloring tooth surfaces.

The ability of PMSA agents to bind discoloration transfer components used in oral hygiene products, such as stannous ions and cationic antimicrobials, was also found helpful. Means

PMSA also provide nutrition for the surface of the teeth, which results in the desired effects on the thermodynamic properties of the surface and the surface film, which in turn improves the feeling of aesthetics and cleanliness, both when brushing teeth and, more importantly, after rinsing or brushing. Many of these polymeric agents are believed and expected to have advantages in combating deposits when used in oral care compositions, and thus provide improved dental appearance that makes a tangible impression on consumers.

Desirable surface effects include: 1) creating a hydrophilic surface on the teeth immediately after cleaning them; and 2) maintaining the surface nourishing effect and controlling the acquired casing for long periods after using the product, including brushing and rinsing, and for even longer periods. The effect of creating a more hydrophilic surface can be measured in terms of the relative reduction of contact angles in water. Importantly, the hydrophilic surface is kept on the tooth surface for a longer period after using the product.

Polymer mineral surfactants contain a component that has the ability to strongly adhere to the surface of the teeth, ensure the application of a polymer film or coating on the surface of the teeth and allow the formation of desired effects of surface appearance modification. Suitable examples of such polymers are polyelectrolytes, such as condensed phosphorylated polymers; polyphosphonates; copolymers of phosphate or phosphonate, containing monomers or polymers with other monomers, such as ethylenically unsaturated monomers and ammonos or with other polymers,

EP2 038 012 such as proteins, polypeptides, polysaccharins, (poly) acrylate, (poly) acrylamide, (poly) methacrylate, (poly) ethacrylate, (poly) hydroxyalkyl methacrylate, (poly) vinyl alcohol, (poly) maleic anhydride, (poly ) maleate, (poly) amide, (poly) ethyleneamine, (poly) ethylene glycol, (poly) propylene glycol, (poly) vinyl acetate and vinyl (poly) benzyl chloride; polycarboxylates and polymers with a carboxy substituent; and mixtures thereof. Suitable polymeric mineral active surface agents include alcohol polymers with carboxy substituents described in US Patent Nos. 5,292,501; 5,213,789, 5,093,170; 5,009,882; and 4,939,284; all belonging to Degenhardt et al. and diphosphonate polymers derivatized in US Patent No. 5,011,913, Benedict et al .; synthetic anionic polymers, including polyacrylates and copolymers of anhydride or maleic acid and methyl vinyl ether (e.g. Gantrez), as described, for example, in US Patent No. 4,627,977, Gaffar et al. A preferred polymer is diphosphonate-modified polyacrylic acid. Active polymers must have a sufficient surface with a tendency to bind to desorb the cover film proteins and to remain on the tooth enamel surfaces. It is preferable to use polymers with phosphates or phosphonates having end or side chain functionalities to interact with tooth surfaces, although other polymers with mineral binding activity may also be effective, depending on their similarity in adsorption.

Additional examples of suitable phosphonates containing polymeric mineral surfactants include geminal diphosphonate polymers disclosed as anticalculus agents in US Patent No. 4,877,603, Degenhardt et al .; a phosphonate group containing copolymers is disclosed in US Patent No. 4,749,758, Dursch et al .; and British Patent No. 1,290,724 (both to Hoechst) suitable for use in washing and cleaning compositions; and copolymers and cotelomers disclosed as useful for applications such as inhibition of the scale and size of corrosion, coatings, cements and ion exchange resins in US Patent No. 5,980,776, Zakikhani et al. and No. 6,071,434, Davis et al. Additional polymers include water-soluble copolymers of vinyl phosphonic acid and acrylic acid and its salts disclosed in British Patent No. 1,290,724,

EP2 038 012 wherein the copolymer contains from about 10% to about 90% by weight of vinylphosphonic acid and from about 90% to about 10% by weight of acrylic acid, more specifically the copolymers have a weight ratio of vinylphosphonic acid to acrylic acid of 70% vinylphosphonic acid to 30% acid acrylic; 5 50% vinylphosphonic acid to 50% acrylic acid; or 30% vinylphosphonic acid to 70% acrylic acid. Other suitable polymers include the water-soluble polymers disclosed by Zakikhani and Davis, and prepared by copolymerization of diphosphonate or polyphosphonate monomers having one or more unsaturated C = C bonds (e.g., vinylidene-1,110 diphosphonic acid and 2- (hydroxyphosphinyl) ethylidene-1 acid , 1-diphosphonic), with at least one further compound having C = C unsaturation (e.g. acrylate and methacrylate monomers) such as those with the structure below:

1. Cotelomer of acrylic acid and 2 (hydroxyphosphinyl) ethylidene-1,1-diphosphonic acid with the structure:

COO^- COO^- COO^-_ABOUT

<img file="PL2038012T3_D0001.tif" />

CH₂CH _ABOUTAFTER₃^-2

<img file="PL2038012T3_D0002.tif" />

2. Copolymer of acrylic acid and vinyl diphosphonic acid with the structure:

<img file="PL2038012T3_D0003.tif" />

n.

Preferred polymers include diphosphonate / acrylate polymers supplied by Rhodia under the designation ITC 1087 (average molecular weight 3000-60,000) and Polymer 1154 (average molecular weight 600055.000).

EP2 038 012

Preferred PMSA agents will be stable with other ingredients of the oral care composition such as ion fluoride and metal ions. Polymers that have limited hydrolysis in formulas with a high water content are also preferred, which allows the creation of simple single-phase formulas for oral hygiene or rinsing compositions. If the PMSA agent does not have such stabilization properties, then one option may be a biphasic formula with a polymer mineral surfactant separated from fluoride or another incompatible component. Another option is to create an anhydrous, essentially anhydrous, or limited water composition to minimize reactions between PMSA agents and other components.

The preferred PMSA is polyphosphate. It is commonly believed that polyphosphate has two or more particles located substantially in a linear configuration, although some cyclic derivatives may be present. Although pyrophosphates (n = 2) are technically polyphosphates, desirable polyphosphates are those having an average of three or more phosphate groups, so that surface adsorption at effective concentrations produces sufficiently unbound phosphate functional groups that increase anionic surface charge, such as and the hydrophilic nature of the surface. Desirable inorganic polyphosphate salts for use include, but are not limited to, tripolyphosphate, tetrapolyphosphate, and hexametaphosphate. Polyphosphates larger than tetraphosphates are usually in the form of glassy amorphous materials. Preferred in the present invention are linear polyphosphates with the formula:

XO (XPO3) nX where X is sodium, potassium or ammonium, an is equal on average from about 3 to about 125. Preferred polyphosphates have an average number n in the range of from about 6 to about 21; these include compounds known commercially under the names Sodaphos (n «6), Hexaphos (n« 13) and Glass H (n «21) manufactured by FMC Corporation and Astaris. Such polyphosphates can be used individually or in combinations. Polyphosphates are susceptible to hydrolysis in formulas with a high water content at an acid pH value, especially below a pH of 5. Therefore, it is preferable to use

EP2 038 012 long chain polyphosphates, especially the Glass H product with an average chain length of about 21. It was recognized that during hydrolysis such long chain polyphosphates form short chain polyphosphates, still effective in deposition on teeth and preventing discoloration.

Other polyphosphorylated compounds may be used in addition or instead of polyphosphate, in particular polyphosphorylated inositol compounds such as phytic acid, myo-inositol pentakis (dihydrogen phosphate); myo-inositol tetrakis (dihydrogen phosphate) myo-inositol trikis (dihydrogen phosphate) and alkali metal salts, basic beryllium or ammonium salts. Phytic acid, also known as myo-inositol 1,2,3,4,5,6-hexakis (dihydrogenorthophosphate) or inositol hexaphosphoric acid and its alkali metals, alkaline earth metal or ammonium salts, is preferred here. The term "phytate" as used herein includes phytic acid and its salts as well as other polyphosphorylated inositol compounds.

The content of the dentifrice is typically from about 0.1% to about 35% by weight of the composition. In dentifrice formulations, the contents are preferably from about 2% to about 30%, more preferably from about 5% to about 25%, and most preferably from about 6% to about 20%. In mouthwash compositions, the amount of dentifrice is preferably from about 0.1% to about 5%, and more preferably from about 0.5% to about 3%.

In addition to creating surface-modifying effects, an agent having affinity for tooth surfaces can also dissolve insoluble salts. For example, Glass H has been found to dissolve insoluble tin (II) salts. Therefore, in compositions containing, for example, stannous salts, Glass H helps to reduce the effect of stannous substances that promote discoloration.

Fluoride source

Often, a sufficient amount of water soluble fluoride compound is present in dentifrices and other oral compositions to provide a concentration of fluoride ions in the composition, and / or when used, it is present in an amount from about 0.0025% to about 5.0% by weight, preferably from about 0.005% to about 2.0% by weight, to provide anti-caries effect. A wide variety of materials can be used as sources of soluble fluoride included in the present composition

EP2 038 012 ensuring the yield of fluoride ion. Examples of preferred fluoride-releasing materials are found in US Patent No. 3,535,421 published October 20, 1970 to Briner et al. and in US Patent No. 3,678,154 published July 18, 1972 to

Widder et al. Representative sources of fluoride ions include: stannous fluoride, sodium fluoride, potassium fluoride, sodium monofluorophosphate, indium fluoride and many other compounds. Stannous fluoride and sodium fluoride are preferred, as are mixtures thereof.

Abrasive materials

Dental abrasives useful in the compositions of the invention include a wide variety of materials. The material chosen must be one that is compatible with the composition and does not excessively rub off the dentin. Preferred abrasives include, for example, silicas, including gels and precipitated products, insoluble sodium polymetaphosphate, hydrated alumina, calcium carbonate, dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate, and resinous abrasives, such as condensation products urea and formaldehyde in the form of solid particles.

Another class of abrasives for use in the compositions of the invention is a polymerized thermosetting resin in the form of particulates, as described in US Patent No. 3,070,510 published December 25, 1962 to Cooley and Grabenstetter. Preferred resins include, for example, melamine, phenol, urea, melamine urea, melamine formaldehyde, urea formaldehyde, melamine urea formaldehyde, crosslinked epoxy and crosslinked polyester resins.

Different types of silica dental abrasives are preferred because of the unique benefits associated with exceptional tooth cleaning and polishing without excessive abrasion of tooth enamel or dentin. The silica abrasive polishing materials discussed herein, as well as other abrasives, generally have an average particle size of from about 0.1 to about 30 microns, and preferably from about 5 to about 15 microns. The abrasive may be precipitated silica or silica gels, such as silica xerogels described in US Patent No. 3,538,230 published March 2, 1970 (Pader et al) and US Patent No. 3,862,307 published January 21, 1975 (DiGiulio). Examples

EP2 038 012 include xerogels of silica commercially available under the trade name "Syloid" manufactured by WR Grace &amp; Company, Davison Chemical Division and precipitated silica materials, such as those marketed by JM Huber Corporation under the trade name Zeodent®, in particular silicas designated as Zeodent® 119, Zeodent® 118, Zeodent® 109 and Zeodent® 129. Types of silica dental abrasives useful in toothpastes in accordance with the present invention are described in more detail in U.S. Patent No. 4,340,583 (Wason) published June 29, 1982 and in U.S. Patent Nos. 5,603,920 published February 18, 1997, 5,589,160 published December 31, 1996 , 5,658,553 published on August 19, 1997, 5,651,958 published July 29, 1997 and 6,740,311 published May 25, 2004.

Mixtures of abrasives, such as mixtures of the different types of Zeodent® silica abrasives listed above can be used. The total amount of abrasive in dentifrice compositions of the invention typically ranges from about 6% to about 70% by weight; toothpastes preferably contain from about 10% to about 50% abrasives by weight of the composition.

The dental solution, mouth spray, mouthwash and non-abrasive gel compositions of the invention typically contain little or no abrasive.

Anti-calculus agent

The compositions of the invention may optionally contain an additional anticalculus agent, such as a pyrophosphate salt, as a source of pyrophosphate ion. Pyrophosphate salts useful in the present compositions include di- and tetrametallic pyrophosphate salts and mixtures thereof. Preferred compounds are disodium dihydrogen pyrophosphate (Na2H2P2O7), tetrasodium pyrophosphate (Na4P2O7) and tetrapotassium pyrophosphate (K4P2O7) in anhydrous and hydrated forms. In the compositions of the present invention, the pyrophosphate salt may be present in one of three forms: substantially dissolved, substantially undissolved, or a mixture of dissolved and undissolved pyrophosphate.

EP2 038 012

Compositions containing essentially dissolved pyrophosphate refers to compositions in which at least one source of pyrophosphate ions is in an amount sufficient to provide at least about 1.0% free pyrophosphate ions. The amount of free pyrophosphate ions can be from about 1% to about 15%, from about 1.5% to about 10%, in one embodiment, and from about 2% to about 6% in another embodiment. Free pyrophosphate ions can be present in various protonated states depending on the pH of the composition.

Compositions containing predominantly undissolved pyrophosphate refer to compositions not containing more than about 20% of the total amount of pyrophosphate salt dissolved in the composition, preferably less than about 10% of the total amount of pyrophosphate dissolved in the composition. The tetrasodium pyrophosphate salt is the preferred pyrophosphate salt in these compositions. Tetrasodium pyrophosphate may be in the form of anhydrous salt or in the form of 10-hydrate, or in the form of any other stable solid compounds in dentifrice compositions. The salt is in the form of solid particles, which may be in a crystalline and / or amorphous state, preferably with a sufficiently small salt particle size to be acceptable for aesthetic reasons and easily soluble in use. The amount of pyrophosphate salt useful for preparing these compositions corresponds to any amount effective to control tartar, generally from about 1.5% to about 15%, preferably from about 2% to about 10%, and most preferably from about 3% to about 8% by weight dentifrice compositions.

The compositions may also contain a mixture of dissolved and undissolved pyrophosphate salts. Any of the above-mentioned pyrophosphate salts can be used.

Pyrophosphate salts are described in more detail in Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 17, WileyInterscience Publishers (1982).

Optional anticalculus agents to be used instead of or in conjunction with the pyrophosphate salt include materials such as synthetic anionic polymers, i.e. polyacrylates and copolymers of maleic anhydride or methyl vinyl acid and ether (e.g., Gantrez), as described, for example, in US Patent No. 4,627,977 to Gaffar et al., as well as e.g. acid

EP2 038 012 polyaminopropanesulfonic (AMPS), diphosphonates (e.g., EHDP, AHP), polypeptides (such as poly aspartic acid and poly glutamic acid) and mixtures thereof.

Chelating agents

Another optional agent is a chelating agent, also called a sequestrant, such as gluconic acid, tartaric acid, citric acid and their pharmaceutically acceptable salts. Chelating agents are capable of complexing calcium found in bacterial cell walls. Chelating agents can also prevent the formation of deposits by removing calcium from calcium bridges, which helps to keep the biomass intact. However, it is undesirable to use a chelating agent that has too much affinity for calcium, as this can lead to demineralisation of the teeth, which is contrary to the aims and intentions of the invention. Preferred chelating agents will generally have a stable calcium binding of from about 10¹ up to 10⁵to provide better cleaning with reduced tendency to build-up and tartar. Chelating agents also have the ability to form compounds with metal ions, thus preventing adverse effects on the stability or appearance of products. Chelation of ions, such as iron or copper, helps to slow the gradual deterioration of final products due to oxidation.

Examples of suitable chelating agents are sodium or potassium gluconate and citrate, a combination of citric acid / alkali metal citrate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, sodium hydrogen tartrate, potassium hydrogen tartrate, sodium, potassium or ammonium polyphosphates, and mixtures thereof. Suitable amounts of chelating agent for use in the present invention are from about 0.1% to about 2.5%, preferably from about 0.5% to about 2.5%, and more preferably from about 1.0% to about 2.5% .

Still other chelating agents useful in the context of the present invention are anionic polymeric polycarboxylates. Such materials are well known in the art and used in the form of their free acids or partially or completely water-soluble alkali metals (e.g. potassium and preferably sodium) or ammonium salts. Examples may be 1: 4 to 4: 1 copolymers of maleic anhydride or acid with another polymerized ethylenically unsaturated monomer, preferably methyl vinyl ether (methoxyethylene) with a molecular weight (MW) of about

EP2 038 012

000 about 1,000,000. These copolymers are available, for example, as Gantrez AN 139 (MW 500,000), AN 119 (MW 250,000) and S-97 Pharmaceutical Grade (MW 70,000), from GAF Chemicals Corporation.

Other active polymeric polycarboxylates include 1: 1 copolymers of maleic anhydride with ethyl acrylate, hydroxyethyl methacrylate, N-vinyl-2-pyrrolidone or ethylene, the latter being available, for example, under the name Monsanto EMA No. 1103, MW 10,000 and EMA Grade 61, and also 1: 1 copolymers of acrylic acid with methyl or hydroxyethyl methacrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone.

Additional active polymeric polycarboxylates are disclosed in US Patent Nos. 4,138,477 of February 6, 1979 (Gaffar), No. 4,183,914 of January 15, 1980 (Gaffar et al.), And include copolymers of maleic anhydride with styrene, isobutylene or ethyl ether; polyacrylic acid, poly itaconic acid and maleic acid; and sulfoacrylic oligomers with a molecular weight as low as 1000 available as Uniroyal ND-2.

Other active measures

An oral hygiene product in accordance with the present invention may optionally include other agents such as antimicrobials. Such agents include water insoluble non-cationic antimicrobials such as halogenated diphenyl ethers, phenolic compounds, including phenol and its homologues, mono and polyalkyl, and aromatic halophenols, resorcinol and its derivatives, bisphenolic compounds and halogenated salicylanilides, and chloroated esters, benzoates . Water-soluble antimicrobials include quaternary ammonium and bis-biguanide salts, as well as triclosan monophosphate. Quaternary ammonium agents include those in which one or two of the substituents on the quaternary nitrogen atom have a carbon chain length (usually an alkyl group) from about 8 to about 20, usually from about 10 to about 18 carbon atoms, while the other substituents (usually a group alkyl or benzyl) have a lower number of carbon atoms, such as from about 1 to about 7 carbon atoms, usually methyl or ethyl groups. Dodecyltrimethylammonium bromide, tetradecylpyridinium chloride, domifene bromide, N-tetradecyl-4-ethyl pyridinium chloride, dodecyldimethyl (2-phenoxyethyl) ammonium bromide, benzyldimethyl stearylammonium chloride, cetylpyridinium chloride, quaterylpyridinium chloride

EP2 038 012 amino-1,3-bis (2-ethylhexyl) -5-methylhexahydropyrimidine, benzalkonium chloride, benzethonium chloride and methylbenzethonium chloride are examples of typical quaternary ammonium antibacterial agents. Other compounds are bis [4- (R-amino) -1-pyridinium] alkanes disclosed in US Patent No. 4,206,215 published June 3, 1980 to Bailey. Other antimicrobial agents such as copper salts, zinc salts and stannous salts may be added. Enzymes, including endoglycosidase, papain, dextranase, mutanase, and mixtures thereof are also useful agents. Such measures are disclosed in U.S. Patent No. 2,946,725 published on July 26, 1960 to

Norris et al. and in US Patent No. 4,051,234 published on September 27, 1977 to Gieske et al. Preferred antimicrobials include zinc salts, stannous salts, cetyl pyridine chloride, chlororexidine, triclosan, triclosan monophosphate and flavoring oils such as thymol. Triclosan and other such agents are disclosed in US Patent No. 5,015,466 published May 14, 1991 to Parran, Jr. et al. and US Patent 4,894,220 published January 16, 1990 to Nabi et al. These agents provide anti-sludge benefits and are usually present in amounts from about 0.01% to about 5.0% by weight of the composition.

Another optional active agent that can be added to the composition of the invention is a dentin desensitizing agent to combat hypersensitivity, such as potassium, calcium, strontium and tin salts, including nitrate, chloride, fluoride, phosphates, pyrophosphate, polyphosphate, citrate, oxalate and sulfate.

Peroxide source

The present compositions may contain a peroxide source due to its beneficial effect on the oral cavity. It has long been known that hydrogen peroxide and other peroxide-containing agents are effective in therapeutic and / or prophylactic treatments for dental caries, dental plaque, gingivitis, periodontitis, bad mouth odor, tooth discoloration, recurrent aphthous ulcers caused by dental prostheses, pathological changes caused by orthodontic appliances, post-extraction and post-periodontic surgery, post-traumatic oral damage and mucosal infections, herpetic stomatitis and the like. Oral peroxide containing agents exert a chemomechanical effect

EP2 038 012 production of thousands of tiny oxygen bubbles produced as a result of their interaction with tissue and salivary enzymes. The rinsing effect of the mouthwash enhances this internal chemo-mechanical effect. This is recommended for delivering other agents to infected gingival fissures. Peroxide mouthwash prevents colonization and multiplication of anaerobic bacteria that are known to be associated with periodontal disease.

Peroxide sources include peroxide compounds, perborates, percarbonates, peroxyacids, persulfates, and combinations thereof. Preferred peroxide compounds include hydrogen peroxide, urea peroxide, calcium peroxide, sodium peroxide, zinc peroxide, and mixtures thereof. The preferred percarbonate is sodium percarbonate. Oxons are preferred persulfates. Preferred peroxide sources for use in dentifrice preparations include calcium peroxide and urea peroxide. Hydrogen peroxide and urea peroxide are preferred for use in mouthwash. The following amounts indicate the amount of peroxide feed, although the peroxide source may contain components other than the peroxide feed. The composition of the invention may contain from about 0.01% to about 30%, preferably from about 0.1% to about 10%, and more preferably from about 0.5% to about 5%, peroxide source, by weight of the composition.

Surfactants

The present compositions may also contain surfactants, also commonly referred to as foaming agents. Useful surfactants are relatively stable and foam in a wide pH range. Anionic, nonionic, amphoteric, zwitterionic, cationic surfactants or mixtures thereof can be used.

Anionic surfactants useful in the present invention include water-soluble salts of alkyl sulfates having from 8 to 20 carbon atoms in the alkyl radical (e.g., sodium alkyl sulfate), and water-soluble salts of sulfonated fatty acid monoglycerides having from 8 to 20 carbon atoms. Examples of this type of anionic surfactant are sodium lauryl sulfate (SLS) and sodium coconut monoglyceride sulfonates. Other preferred anionic surfactants are sarcosinates, such as sodium lauroyl sarcosinate, taurates, sodium lauryl sulfoacetate, sodium lauroyl isethionate, sodium lauretharboxylate,

EP2 038 012 and sodium dodecylbenzene sulfonate. Mixtures of anionic surfactants can also be used. A number of suitable anionic surfactants are disclosed in US Patent No. 3,959,458, issued May 25, 1976 (Agricola et al.). The present composition typically contains anionic surfactant in an amount of from about 0.025% to about 9%, from about 0.05% to about 5% in some embodiments, and from about 0.1% to about 1% in other embodiments .

Another useful surfactant is selected from the group consisting of sarcosinate, isethionate and taurate surfactants. The alkali or ammonium salts of these surfactants, such as the sodium and potassium salts of the following compounds, are preferred for use: sodium lauroyl sarcosinate, sodium myristoyl sarcosinate, sodium palmitoyl sarcosinate, sodium stearoyl sarcosinate, and sodium oleoyl sarcosinate. The sarcosinate surfactant may be present in the compositions of this invention in an amount from about 0.1% to about 2.5%, more preferably from about 0.5% to about 2.0% by weight of the composition.

The cationic surfactants used in the present invention include derivatives of aliphatic quaternary ammonium compounds having one long alkyl chain containing from about 8 to 18 carbon atoms, such as lauryl trimethylammonium chloride; cetyl pyridinium chloride; cetyl bromide; di-isobutylphenoxyethyl-dimethylbenzylammonium chloride; coconut alkyltrimethylammonium nitrite; cetyl pyridinium fluoride; e.t.c. Preferred compounds are quaternary ammonium fluorides, described in US Patent No. 3,535,421, October 20, 1970 Briner et al. Wherein said quaternary ammonium fluorides have detergent properties. In the compositions discussed herein, some cationic surfactants also act as bactericides. Cationic surfactants such as chlorexidine, although suitable for use in this invention, are not preferred because of their ability to cause discoloration of hard tissues in the oral cavity. Those skilled in the art are aware of this possibility and should add cationic surfactants given this limitation.

Nonionic surfactants that can be used in the compositions of the present invention, compounds formed by the condensation of alkylene oxide groups (of a water-absorbing nature) with a hydrophobic organic

EP2 038 012 a compound which may be an aliphatic or alkylaromatic material. Examples of preferred nonionic surfactants include Pluronics, polyethylene oxide condensation products with alkylphenols, ethylene oxide condensation products with the reaction product of propylene oxide and ethylenediamine, ethylene oxide condensation products with aliphatic alcohols, long chain tertiary amine oxides, long-chain tertiary phosphine oxides chain, long chain dialkyl sulfoxides and mixtures of such substances.

Bisected ionic synthetic surfactants useful in the present invention include derivatives of aliphatic quaternary ammonium, phosphonium and sulfone compounds whose aliphatic radicals may have a linear or branched chain and one of the aliphatic substituents contains from 8 to 18 carbon atoms, while the other contains anionic water solubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate or phosphonate groups.

Suitable betaine surfactants are disclosed in US Patent No. 5,180,577 (Polefka et al.) Issued January 19, 1993. Typical alkyldimethyl betaines include decyl betaine or 2- (Ndecyl-N, N-dimethylammonio) acetate, cocobetaine or 2- (N - coco-N, N20 dimethyl ammonium) acetate, myristyl betaine, palmitic betaine, lauryl betaine, cetyl betaine, stearyl betaine, etc. Amidobetaines include cocoamidoethyl, cocamidopropyl betaine, lauramidopropyl betaine and the like. The betaines selected include amidopropyl betaines, and more preferably lauramidopropyl betaine.

Thickening substances

When preparing toothpaste or gels, thickeners are added to provide the desired consistency of the composition, desired active release properties during use, storage stability and stability of the composition, etc. Suitable thickeners include carboxyvinyl polymers, carrageenan, hydroxyethyl cellulose (HEC), natural and synthetic clays (e.g. Veegum and Laponite) and the water-soluble salts of cellulose ethers such as sodium carboxymethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose and combinations thereof. You can also use natural rubbers, such as karaja,

EP2 038 012 xanthan, acacia and tragacanth. To further improve the texture, colloidal magnesium aluminum silica or finely divided silica can be used as part of the thickener.

Suitable carboxyvinyl polymers used as thickening or gelling agents include carbomers which are homopolymers of acrylic acid crosslinked together with pentaerythritol alkyl ether or sucrose alkyl ether. Carbomers are commercially available from BF Goodrich as a series of Carbopol® products, including Carbopol 934, 940, 941, 956 and mixtures thereof.

Thickening agents are usually present in an amount of from about 0.1% to about 15%, preferably from about 2% to about 10%, and more preferably from about 4% to about 8% by weight of the total toothpaste or gel composition. Higher concentrations can be used in gums, lozenges and peppermints for breath freshening, sachets, non-abrasive gels and subgingival gels.

Moisturizing substances

Another optional carrier material in the present compositions is a moisturizer. The moisturizer is intended to keep the toothpaste composition from hardening as a result of contact with air, to give the composition a moist mouthfeel, and some moisturizers may also give the desired sweet taste to the toothpaste compositions. The moisturizing agent, based on a pure moisturizing agent, generally constitutes from about 0% to 70%, preferably from about 5% to 25% by weight of the present composition. Moisturizing agents suitable for use in the present invention's compositions are edible polyhydric alcohols such as glycerin, sorbitol, xylitol, butylene glycol, polyethylene glycol, propylene glycol and trimethyl glycine.

Various carrier materials

Water used in preparing commercially advantageous oral compositions should preferably be low in ion and contain no organic impurities. Water may constitute up to about 99% by weight of the aqueous compositions herein. This amount of water includes unbound water that is added and water introduced with other materials such as sorbitol.

An oral hygiene product in accordance with the present invention may also include an alkali metal bicarbonate salt that can perform many functions, including abrasive, drainage, buffering, and pH adjusting. salts

The alkali metal bicarbonate salts are water-soluble and, if not stabilized, tend to release carbon dioxide in the aqueous system. Sodium bicarbonate, also known as baking soda, is a commonly used alkali metal bicarbonate salt. The present composition may contain from about 0.5% to about 30%, preferably from about 0.5% to about 15%, and most preferably from about 0.5% to about 5% of the alkali metal bicarbonate salt.

The pH of the composition according to the invention can be adjusted by the use of buffering agents. Buffering agents as used herein refer to agents that can be used to adjust the pH of aqueous compositions, such as mouthwash and dental solutions, preferably in the range of from about pH 4.0 to about pH 6.0 for stability Peroxide. Buffering agents include sodium bicarbonate, sodium monophosphate, sodium triphosphate, sodium hydroxide, sodium carbonate, sodium acid pyrophosphate, citric acid and sodium citrate. Buffering agents are typically used in an amount of from about 0.5% to about 10% by weight of the present composition.

Poloxamers can be used in the compositions of the invention. Poloxamer is classified as a non-ionic surfactant and can also act as an emulsifying agent, stabilizing agent, binder and other similar functions. Poloxamers are block polymers containing two functional groups, terminated with primary hydroxyl groups, with a molecular weight from 1000 to over 15,000. Poloxamers are sold under the trade names Pluronics and Pluraflo by BASF. Poloxamers suitable for use in this invention are Poloxamer 407 and Pluraflo L4370.

Other emulsifiers that can be used in the present compositions include polymeric emulsifiers, such as the BF Goodrich Pemulen® series, and which are mainly high molecular weight polyacrylic acid polymers useful as emulsifiers for hydrophobic substances.

Titanium dioxide may also be added to the composition. Titanium dioxide is a white powder opacifying the composition. Titanium dioxide typically constitutes from about 0.25% to about 5% by weight of the dentifrice composition.

EP2 038 012

Other optional agents that can be used in the compositions of the present invention include dimethicone copolyols selected from alkyl and alkoxydimethicone copolyols such as C12 to C20alkyl dimethicone copolyols and mixtures thereof. Cetyl dimethicone copolyol marketed under the trade name Abil EM90 is highly preferred. Dimethicone copolyol is usually present in an amount of from about 0.01% to about 25%, more preferably from about 0.1% to about 5%, and more preferably from about 0.5% to about 1.5% by weight. Dimethicone copolyols help to ensure a positive tooth sensation.

io Removal of unpleasant ingredients from flavoring oils

Another aspect of the present invention relates to refining or purifying to remove undesirable compounds from flavor oils and extracts, or to limit their amount to prepare flavor oils referred to herein as "selected."

Water rinsing process

The preferred purification treatment is a water scrubbing process that is simple, inexpensive and easy to use on a large scale. The aqueous medium can only be water or a mixture of water and solvent in which the solvent constitutes no more than about 20%. The method of elimination of unwanted ingredients usually involves their extraction from the flavor oil to the aqueous phase. DMSO and dimethyl sulfide are highly polar and dissolve freely in water and other solvents such as alcohol. These compounds can easily be extracted from the oil with pure water or a mixture of water and alcohol. The use of a cosolvent such as alcohol can improve the removal of less polar compounds such as DMS. The co-solvent may be any food solvent capable of dissolving in water, such as ethanol, isopropanol, glycerin and propylene glycol, which will extract unwanted compounds such as

DMS from essential oil without significantly extracting the desired ingredients. The pH level in the aqueous environment may generally be in the range of from about 3 to about 12, preferably about 7 or the pH may be neutral. The exact pH preferences will depend on the pH stability of the flavored oil being processed. The aqueous environment may optionally contain salts that may

EP2 038 012 help in "salting out" most of the flavor ingredients from the water phase and keeping them in the flavor oil itself. The flavor oil samples are mixed with the aqueous medium in a water to oil volume ratio of from about 90:10 to about 10:90, more preferably from about 70:30 to about

30:70. Typically, the more water, the faster DMSO is removed; however, too much water can lead to the formation of an emulsion and impede the final separation of the oil phase from the aqueous phase. You can use regular water; USP grade water is preferred. The process is usually carried out at room temperature. Again, the choice of temperature conditions depends on the temperature stability of the flavor oil.

The water and oil phases are subjected to mixing or vigorous mixing to ensure better contact of water and oil, resulting in a turbid mixture. Mixing the oil phase with the aqueous phase lasts from about 30 minutes to about 3 hours, and even longer. Depending on the mixing conditions and the size of the charge, proper purification or extraction can be achieved after about 30 minutes, i.e. the amount of sulfur compounds remaining in the oil is reduced to the target level. After mixing, the phases can separate, after which the oil phase is separated from the aqueous phase. The separated oil phase can then be subjected to additional water rinsing with fresh water each time and / or filtration through a hydrophilic / hydrophobic adsorbing material to remove any remaining turbidity from the oil. The washed oil can also be subjected to fractional centrifugation or cooling to achieve separation of the water remaining in the washed oil. The amount of DMSO and other sulfur-containing compounds in the oil phase is calculated at certain intervals to determine if additional mixing / stirring or rinsing is needed.

Better mixing and contact of the flavor oil with water can be achieved by using high shear mixers to remove DMSO in less time. Mixers that can be used are high shear mixers, such as Ross mixers for batch mixing or on-the-fly mixing. Examples of suitable batch mixers include fast dispensers (typically used for batches between 4 and 3785 liters (1 to 1000 gallons)), having a shaft and a high shear disk blade.

EP2 038 012

The blade rotates at approximately 10,000 rpm and forms a flow pattern in a stationary mixing vessel. The blade creates a vortex that draws the contents of the vessel to the sharp edges of the blade. The blade then mechanically breaks the oil phase and disperses it into the water phase. Another batch mixer model is a high shear rotor / stator mixer having a single phase rotor that rotates quickly in a stationary stator. When the rotating blades pass through the stator, they mechanically cut the oil-water phase. Small laboratory mixers have a mixing speed of 500 to 10,000 rpm (with a capacity of 0.3 to 15 liters). Larger commercial mixers have a mixing speed of 3,600 to 12,000 rpm (with rotor diameter from 64 mm to 330 mm) with a capacity of 15 to 22,710 liters of liquid. An example of an on-going ultra-high shear mixing mixer is the Ross s model, which has four phases or larger rotors that rotate at 4 572 meters per minute (15,000 feet per minute) in a stationary stator. When the rotating blades pass through the stator, they mechanically cut the contents.

For example, 250 ml peppermint oil was introduced into a 2-liter glass beaker. Then 150 ml of USP grade water was added and vigorously mixed with a magnetic stirrer until the oil and water formed a turbid mixture. Stirring was continued at room temperature. After about half an hour, an hour and two hours, mixing was stopped to allow the phases to separate. After a few minutes, the phases separated and 1 ml oil sample was taken for analysis. After two hours of stirring, the phases were allowed to separate and the top layer of oil was decanted and allowed to remain in the glass bottle for 24-48 hours to further clarify the small amount of turbidity remaining in the oil. The oil was then filtered through a 0.45 um hydrophilic PVDF filter (Millipore) to purify the oil, and was then stored in a glass jar until use.

The above procedure was used for the developed raw peppermint oil (supplied by IP Callison), and the amounts of DMSO in the oil phase are given below. The amount of DMSO was calculated using the GC-MSD system. As the results show, after approx

EP2 038 012 half an hour of aqueous rinsing, more than 95% DMSO was removed from the oil, and after two hours no more than 1 ppm remained in the oil.

<td>A sample</td><td>DMSO (ppm, mass-volume)</td>

<td>Raw peppermint oil # 1</td><td> 307</td>

<td>Raw material washed for 35 min</td><td> 12,7</td>

<td>Raw material washed for 60 min</td><td> 16,5</td>

<td>Raw material washed for 2 hours</td><td> &lt;1</td>

In addition to DMSO, water rinsing removes other water-soluble compounds, such as low molecular weight alcohols and aldehydes, as well as less water-soluble compounds such as dimethyl sulfide (DMS) from the oil. However, DMS removal is slower compared to DMSO removal. It is believed that as the aqueous phase dissolves DMSO and other organic compounds, it becomes less polar, creating a better environment for removing DMS and other compounds with similar polarity and solubility.

In another example, compounds removed from a peppermint oil sample subjected to this water rinse process were determined. A sample of rectified peppermint oil provided by IP Callison was subjected to a 5-hour water rinse followed by an additional 7-hour rinse with fresh water. Each rinse was carried out with a water-to-oil ratio of 1: 1 with gentle mixing. Peppermint oil before and after the rinsing procedure was analyzed by the GC-MS system for micro phase extraction into the solid phase, and the approximate reduction of each component was estimated by comparing the resulting chromatograms. A partial list of compounds whose concentration has been reduced by scrubbing is shown in Table 2 below. There is a relatively good correlation between the compound percent removed and the P logo (octanol / water partition coefficient). The correlation is even greater when considering the molecular weights of each compound. Importantly, the concentrations of the relatively non-polar main components of peppermint oil do not change under the influence of the rinsing procedure. These main ingredients include menthol, menton, alpha and beta pinene, limonene.

EP2 038 012

Table 2. Compounds removed from peppermint oil during water flushing

<td>Relationship Number</td><td>Reducing the content of the compound</td><td>~% reduction in content</td>

<td> 1</td><td>methanol</td><td> 95</td>

<td> 2</td><td>Methyl formate</td><td> 95</td>

<td> 3</td><td>Ethanol</td><td> 95</td>

<td> 4</td><td>Acetone</td><td> 65</td>

<td> 5</td><td>furan</td><td> 90</td>

<td> 6</td><td>Formic acid ethyl ester</td><td> 90</td>

<td> 7</td><td>Acetic acid methyl ester</td><td> 85</td>

<td> 8</td><td>Dimethyl sulfide</td><td> 99+</td>

<td> 9</td><td>Carbon disulphide</td><td> 90</td>

<td> 10</td><td>2-methylpropanal</td><td> 60</td>

<td> 11</td><td>Acetic acid</td><td> 70</td>

<td> 12</td><td>2-butanone</td><td> 70</td>

<td> 13</td><td>2-methylfuran</td><td> 70</td>

<td> 14</td><td>3-methylfuran</td><td> 70</td>

<td> 15</td><td>2-methyl-1-propanol</td><td> 40</td>

<td> 16</td><td>Crotonaldehyde</td><td> 60</td>

<td> 17</td><td>3-methylbutanal</td><td> 50</td>

<td> 18</td><td>2-methylbutanal</td><td> 50</td>

<td> 19</td><td>2-pentanone</td><td> 35</td>

<td> 20</td><td>cyclopentanol</td><td> 35</td>

<td> 21</td><td>2-ethylfuran</td><td> 20</td>

<td> 22</td><td>2-methyl-1-butanol</td><td> 15</td>

<td> 23</td><td>2-methyl crotonaldehyde</td><td> 30</td>

<td> 24</td><td>Dimethyl disulphide</td><td> 40</td>

<td> 25</td><td>3-methyl crotonaldehyde</td><td> 30</td>

<td> 26</td><td>hexanal</td><td> 15</td>

<td> 27</td><td>dimethyl sulfoxide</td><td> 99+</td>

<td> 28</td><td>furfural</td><td> 35</td>

<td> 29</td><td>2-hexanal</td><td> 15</td>

<td> 30</td><td>2,5-diethyl THF</td><td> 5</td>

EP2 038 012

Washed or selected peppermint oil was compared to traditional rectified oil in terms of fragrance properties. Washed peppermint oil and unwashed rectified peppermint oils were compared for their fragrance by a panel of trained taste evaluators according to the 0-100 scale, where 0 means the worst oil quality and 100 means excellent oil quality. The average rating was 33 for unwashed oil and 67 for washed oil, indicating that the oil being washed is better than the unwashed oil rectified.

The typical final peppermint flavor oil for dentifrice, containing 62% rectified peppermint oil or rinsed peppermint oil, was evaluated by the same panel of flavor evaluation experts using the same scale. The average rating for unwashed rectified oil was 58 and for the washed oil 75, which indicates that the washed oil is of better quality.

A dentifrice containing 0.454% stannous fluoride was prepared and flavored with rectified peppermint oil or rinsed peppermint oil. Dentifrices were stored at 40 ° C for 3 months. During this period, the rinse aid dentifrice did not produce any unwanted odor, unlike the unwashed rectified oil. Assessments were carried out by trained taste evaluators using a scale from 0 (no undesirable odor) to 10 (intense undesirable odor) to determine the presence and intensity of the unpleasant odor during storage. The following are the ratings assigned to samples of dentifrices. These assessments show the stability of oils washed out with water in the presence of a reducing agent such as stannous.

Storage months 1 2 3

A dentifrice with unwashed 3 7 7 rectified oil

A dentifrice with rinsed oil 0 0 0

EP2 038 012

This series of experiments demonstrates that the water rinsing process can be used to stabilize rectified flavor oils as well as first-class natural or raw flavor oils that have not undergone the refining and purification process. Preferably, the water rinsing process is simple, effective and economical, and avoids excessive thermal processing of the flavor oil. The process may be sufficient to prepare flavoring oils on a commercial scale without the need for more sophisticated rectification processes.

Filtration process

Another technique that can be used to remove DMSO and other sulfur compounds from flavored oils is filtration that uses selective materials for sulfur compounds. Such filter materials include commercially available materials used as adsorbents and molecular sieves. Examples include the following materials provided by Engelhard Corporation and Johnson Matthey Catalysts.

a) SELEXSORB CDX - a mixture of hydrate of alumina (60-85% by weight) and aluminosilicate (15-40% by weight), density - 1195 l (42.2 cubic feet), area 431 m²/ g, 7x14 grid size.

b) SELEXSORB COS - a mixture of hydrate of alumina (88-99% by weight) and alkali metal oxide (1-5% by weight), density - 1410 l (49.8 cubic feet), area 255 m²/ g, 7x14 grid size.

c) Catalyst CP367 - nickel / nickel oxide on an inert basis

d) Catalyst CP366 - a mixture of copper (II) carbonate, basic zinc carbonate and alumina.

For example, rectified peppermint oil supplied by IP Callison was subjected to filtration using the above materials as adsorbing agents. The adsorbent material (60 g) was packed into a stainless steel column (production of Millipore films, diameter

3.5 cm x 30 cm long) equipped on the bottom with a filter insert (Izipore filter membrane from Millipore, TTTP filter 2 μm). 150 ml peppermint oil was poured from above on the bed and the oil that passed through the column under the influence of gravity gathered at its bottom The first 75 ml of oil was collected (and marked as the first fraction), then the second 75 ml (and marked as the 2nd faction). The filtered oil has been analyzed for

EP2 038 012 DMSO content according to the method described earlier. The results are summarized below.

Table 3 Removal of DMSO by filtering peppermint oil

<td></td><td>A sample</td><td>DMSO (ppm, mass volume)</td><td>% removed</td>

<td> 1</td><td>Rectified peppermint oil</td><td> 197</td><td> -</td>

<td> 2</td><td>1st fraction Selexsorb COS</td><td> 173</td><td> 12</td>

<td> 3</td><td>2nd Selexsorb COS fraction</td><td> 130</td><td> 34</td>

<td> 4</td><td>1st fraction Selexsorb CDX</td><td> 66</td><td> 66</td>

<td> 5</td><td>2nd Selexsorb CDX fraction</td><td> 7,4</td><td> 96</td>

<td> 6</td><td>1st fraction CP 366</td><td> 173</td><td> 12</td>

<td> 7</td><td>2nd fraction CP 366</td><td> 138</td><td> 30</td>

<td> 8</td><td>1st fraction CP 367</td><td> 142</td><td> 28</td>

<td> 9</td><td>2nd fraction CP 367</td><td> 130</td><td> 34</td>

Countercurrent extraction (CCE)

The countercurrent extraction (CCE) technique can also be used to remove unwanted components from flavor oils.

This technique is used in the flavoring sector for the production of deterpenated oils. In the original patented process, the essential oils are detached in the two-solvent extraction process using polar and non-polar solvents. Essential oils pass through the mixing chamber and are moved by the counter-current flow of the two solvents, which results in continuous extraction of terpenes into the polar solvent. In one variation of the original CCE process, the citrus oil is separated by pumping it in the opposite direction of the pumped hydroalcoholic solvent. Terpenes are extracted from citrus oil by an aqueous alcoholic solvent. Similarly, the CCE technique can be used to extract DMSO and other sulfur compounds, using water as the extraction solution. The CCE technique was discussed by RL Swaine

EP2 038 012 in the article "Flavoring Agents" in Food Additive Toxicology (1995), Maga &amp; Tu (ed.).

Distillation

Mint oils can be fractionated using standard distillation and / or extraction methods to remove unwanted ingredients. This can be done by standard distillation procedures, such as using a vacuum distillation apparatus or a rotating web column. The final flavor oil can be re-engineered or produced by selecting the desired ingredients and combining them with each other. For example, peppermint oils, in particular those derived from peppermint or peppermint-like sources, such as peppermint oil, have so far identified over 225 volatile compounds. However, it has also been found that only a limited number of this pool of volatile compounds really contribute significantly to the overall odor of the product. Therefore, in order to separate the compounds that most affect the odor from the large amount of volatile compounds that do not affect the odor or only slightly influence it, it is necessary to use effective screening methods. It is preferable to add as many ingredients as possible that are often found in natural peppermint oils to provide a full, well-balanced mint flavor with no undesirable aftertaste or unpleasant smell. If less peppermint oil is fractionated or refined, and more of the ingredients that are not added again are removed, the resulting flavor of the peppermint oil will not be as desired. Therefore, it is desirable to fractionate peppermint oil selectively to provide the most pleasant aesthetic mint flavor.

Mint oils, including the widely known peppermint, spearmint or field mint oils, can be fractionated by distillation to remove unwanted volatile polar compounds (characterized by low boiling point), in particular DMSO and other sulfur-containing compounds such as sulfides and disulphides. Low-boiling polar compounds are compounds for which the boiling point is less than about 120 ° C, less than about 140 ° C, less than about 160 ° C, and even less than about 180 ° C. The distillation process can also

EP2 038 012 cause the removal of low molecular weight compounds such as aldehydes and C3-C9 alcohols.

Fractionated or selected peppermint oil may be essentially free of low boiling point polar compounds, including DMSO and dimethyl sulfide. Other compounds that are removed or their content is significantly reduced include branched alkanals such as 2-methylpropanal, 2-methylbutanal and 3-methylbutanal; branched alkanols such as 2-methylpropanol, 2-methylbutanol and 3-methylbutanol; alkenols such as Z-3-hexanol; alkenals such as E-2-hexanal;

other aldehydes, alcohols and ketones, such as 3-methylcyclohexanone, benzaldehyde, 1-octen-3-ol, 3-octanone and 2,3-dehydro-1,8-cyneol. Certain compounds that may contain selected peppermint oil are α-pinene, β-pinene, sabinen, myrcene, a - fellandren, α-terpinene, limonene, cis-ocymene, eucalyptol, trans-ocymene, gamma-terpinene, 3- octanol, terpineol, sabinene hydrate, linalool, mentofuran, isopulegol, mentone, neomenthol, terpinen-4-ol, isomentone, menthol, neoisomenthol, isomenthol, alpha-terpineol, pulegone, mentyl acetate, carvone, neoisomenyl acetate, piperitonyl acetate , beta-caryophyllene, thymol, trans-beta-farnesene, alpha-humulene, germacrene B, elemol, viridiflorol, eucalyptol, gamma-terpinene, 1-octanol, namylisovalerate, 1-methyl-4- (1-methylethyl) -trans-2-cyclohexene-1-ol, 1-terpineol, alpha-terpineol, 4 , 7-dimethyl-benzofuran, citronellol, neomentyl acetate, eugenol, jagodlin, alpha-kopaen, longifolen, alpha-gurjunene, caryophyllene, (+) - epibicyclosequivellandren, trans-beta-farnezene, beta-caryophylene, allo-aromatadendren, gamma murolen, D germacren, bicyclermermacren, 8-cadinene and terpinolene.

Usage

The present invention also relates to methods of cleaning teeth and preventing undesirable conditions in the oral cavity, such as caries, microbial infection, sediment, tartar, discoloration and odor from the mouth, as well as erosion of the teeth.

The method used herein is to bring the oral hygiene composition into contact with the surfaces of the dental enamel and mucosa in a patient's mouth in accordance with the present invention. The method of use includes brushing with a dentifrice, rinsing with a dental suspension or mouthwash or chewing gum. Other methods include contacting the oral gel

EP2 038 012 for topical application, mouth spray or other form with the patient's teeth and mucosa. The patient can be any person or animal whose tooth surface has contact with the oral composition. By animal is meant a term comprising household or other domestic animals, or captive animals.

For example, the method of treatment may include human brushing a dog's teeth with one of the dentifrice compositions. Another example could include rinsing the cat's mouth with an oral composition for a time sufficient to notice the effect. Pet care products, such as chews and toys, can be made to contain the oral compositions of the invention. The composition is incorporated into a relatively flexible but strong and durable material such as raw leather, ropes made of natural or synthetic fibers and polymer articles made of nylon, polyester or thermoplastic polyurethane. When an animal chews, licks or bites this product, the active ingredients introduced are released into the animal's mouth, into saliva, comparable to effective brushing or rinsing.

Examples

The following examples further describe and demonstrate embodiments specific to the scope of the present invention. These examples are given for illustration only and should not be construed as limiting the present invention, since many variations are possible without departing from the spirit and scope of the invention.

The following are the main components of the selected peppermint oils in accordance with the present invention.

Example 1

<td>Ingredient</td><td> %</td><td> %</td>

<td>α-pinene</td><td> 0,63</td><td> 0,19</td>

<td>β-pinene</td><td> 0,90</td><td> 0,23</td>

<td>sabinene</td><td> 0,03</td><td> 0,01</td>

<td>myrcene</td><td> 0,03</td><td> 0,01</td>

<td>α-terpinene</td><td> 0,01</td><td> 0,01</td>

EP2 038 012

<td>limonene</td><td> 0,50</td><td> 0,05</td>

<td>cis-ocymen</td><td> 0,01</td><td> 0,01</td>

<td>eucalyptol</td><td> 2,64</td><td> 4,71</td>

<td>trans-ocymen</td><td> 0,01</td><td> 0,01</td>

<td>γ-terpinene</td><td> 0,01</td><td> 0,01</td>

<td>3 octanol</td><td> 0,05</td><td> 0,05</td>

<td>terpineol</td><td> 0,01</td><td> 0,00</td>

<td>Sabinene hydrate</td><td> 0,04</td><td> 0,34</td>

<td>linalool</td><td> 0,07</td><td> 0,59</td>

<td>menthofuran</td><td> 0,14</td><td> 2,16</td>

<td>isopulegol</td><td> 0,02</td><td> 0,02</td>

<td>Menton</td><td> 16,89</td><td> 2,27</td>

<td>neomenthol</td><td> 2,22</td><td> 0,86</td>

<td>Terpinene-4-ol</td><td> 0,03</td><td> 0,04</td>

<td>isomenthone</td><td> 3,56</td><td> 0,40</td>

<td>Menthol</td><td> 66,42</td><td> 73,87</td>

<td>Izomentol</td><td> 0,04</td><td> 0,14</td>

<td>α-terpineol</td><td> 0,35</td><td> 0,58</td>

<td>Pulegone</td><td> 0,14</td><td> 0,04</td>

<td>Mentyl acetate</td><td> 3,53</td><td> 5,95</td>

<td>Neoisomentyl acetate</td><td> 0,01</td><td> 0,00</td>

<td>piperitone</td><td> 0,06</td><td> 1,35</td>

<td>β-bourbonen</td><td> 0,02</td><td></td>

<td>β-caryophyllene</td><td> 0,11</td><td> 3,12</td>

<td>thymol</td><td> 0,03</td><td> 0,02</td>

<td>trans-e-farnesene</td><td> 0,08</td><td> 0,01</td>

<td>α-humulene</td><td> 0,02</td><td> 0,24</td>

<td>Germakren D</td><td> 0,32</td><td> 0,05</td>

<td>triacetin</td><td></td><td> 0,17</td>

<td>Germakren B.</td><td></td><td> 0,08</td>

<td>Elemol</td><td></td><td> 0,89</td>

<td>Wiridiflorol</td><td> 0,03</td><td> 0,03</td>

<td>Menthol Acetone</td><td></td><td> 0,17</td>

EP2 038 012

The following are flavor ingredients for selected peppermint oils processed in accordance with the present invention. Selected peppermint oils are essentially free of DMSO and other sulfur compounds that are precursors of an unpleasant odor. Flavor compositions containing the present peppermint oils are evaluated by the organoleptic tests as aesthetically pleasing and can be added to oral care compositions containing reducing agents such as stannous substances and tea polyphenols without producing undesirable taste and smell.

and Example II

<td>Ingredient</td><td> %</td>

<td>Selected peppermint oil</td><td> 60%</td>

<td>anethole</td><td> 10%</td>

<td>Menthol</td><td> 25%</td>

<td>eucalyptol</td><td> 5%</td>

Example III

<td>Ingredient</td><td> %</td>

<td>Selected peppermint oil</td><td> 42%</td>

<td>Selected garden mint oil</td><td> 5%</td>

<td>Cooling medium WS-3</td><td> 10%</td>

<td>anethole</td><td> 7%</td>

<td>Menthol</td><td> 35%</td>

<td>Aloe</td><td> 1%</td>

Oral compositions containing stannous ions, selected peppermint oils in the flavor composition, and orally acceptable carriers are listed below with the percentages of the ingredients given by weight. These compositions are prepared using conventional methods. Example IV illustrates two-phase dentifrice compositions; the first and second phases can be packed in two physically separated

EP2 038 012 dispenser chambers and be dispensed side by side usually in a ratio of 50:50. Example V illustrates single-phase dentifrice compositions.

Example IV

<td>First composition</td><td>measure to</td><td>Second composition</td><td>measure to</td>

<td>teeth cleaning</td><td></td><td>teeth cleaning</td><td></td>

<td>Ingredient</td><td>% by weight</td><td>Ingredient</td><td>% by weight</td>

<td>carboxymethylcellulose</td><td> 0,500</td><td>Sodium hydroxide^(B)</td><td> 1,000</td>

<td>Water</td><td> 2,768</td><td>Coloring agent</td><td> 0,300</td>

<td>Aroma</td><td> 1,000</td><td>Water</td><td> 21,840</td>

<td>Glycerine</td><td> 36,432</td><td>Aroma</td><td> 1,000</td>

<td>Polyethylene glycol</td><td> 1,500</td><td>Glycerine</td><td> 28,992</td>

<td>Propylene glycol</td><td> 8,000</td><td>Sodium gluconate</td><td> 4,160</td>

<td>Sodium lauryl sulfate (a)</td><td> 4,000</td><td>Stannous chloride</td><td> 3,000</td>

<td>Silica</td><td> 28,000</td><td>Silica</td><td> 23,000</td>

<td>Benzoic acid</td><td> 0,600</td><td>Sodium Saccharinate</td><td> 0,300</td>

<td>Sodium benzoate</td><td> 0,600</td><td>poloxamer</td><td> 15,500</td>

<td>Sodium Saccharinate</td><td> 0,300</td><td>Stannous fluoride</td><td> 0,908</td>

<td>Titanium dioxide</td><td> 1,000</td><td></td><td></td>

<td>Xanthan gum</td><td> 0,300</td><td></td><td></td>

<td>Glass H Polyphosphate</td><td> 15,000</td><td></td><td></td>

<td>(a) 27.9% solution</td><td></td><td>(b) 50% solution</td><td></td>

Example V

<td>Ingredient</td><td>IVA</td><td>IVB</td><td>IVC</td><td>IVD</td><td>IVE</td><td>IVF</td><td>IVG</td>

<td>Phytic acid (20% solution)</td><td> 4,000</td><td> 2,000</td><td></td><td></td><td> 10,000</td><td></td><td></td>

<td>Sodium phytate (20% solution)</td><td></td><td></td><td> 10,000</td><td> 4,000</td><td></td><td></td><td></td>

<td>Zinc carbonate¹</td><td> 2,000</td><td> 1,000</td><td></td><td> 2,000</td><td></td><td></td><td></td>

<td>Zinc oxide</td><td></td><td></td><td> 5,000</td><td></td><td></td><td></td><td></td>

<td>pyrophosphate zinc</td><td></td><td></td><td></td><td></td><td> 8,000</td><td></td><td></td>

<td>Zinc lactate</td><td></td><td></td><td></td><td></td><td></td><td> 2,500</td><td></td>

<td>polyphosphate sodium</td><td></td><td></td><td></td><td></td><td></td><td> 13,000</td><td></td>

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<td>Stannous fluoride</td><td> 0,454</td><td> 0,454</td><td></td><td> 0,454</td><td></td><td> 0,454</td><td> 0,454</td>

<td>Sodium Fluoride</td><td></td><td></td><td> 0,243</td><td></td><td> 0,243</td><td></td><td></td>

<td>Stannous chloride</td><td></td><td></td><td> 1,500</td><td></td><td> 1,000</td><td></td><td> 1,500</td>

<td>Tea extract</td><td></td><td></td><td></td><td> 2,000</td><td></td><td></td><td></td>

<td>EGCG</td><td></td><td></td><td></td><td></td><td></td><td> 1,000</td><td> 1,000</td>

<td>Sodium gluconate</td><td> 0,672</td><td> 0,600</td><td> 0,672</td><td> 0,600</td><td> 0,672</td><td> 0,652</td><td> 2,100</td>

<td>Solution sorbitol</td><td> 34,275</td><td> 35,785</td><td> 34,275</td><td> 35,785</td><td> 34,275</td><td></td><td> 37,496</td>

<td>Glycerine</td><td></td><td></td><td></td><td></td><td></td><td> 38,519</td><td> 14,425</td>

<td>HEC</td><td> 0,300</td><td> 0,300</td><td> 0,300</td><td> 0,300</td><td> 0,300</td><td></td><td></td>

<td>CMC zinc</td><td> 1,200</td><td> 1,300</td><td> 1,200</td><td> 1,300</td><td> 1,200</td><td></td><td> 0,600</td>

<td>carrageenan</td><td> 0,500</td><td> 0,500</td><td> 0,500</td><td> 0,500</td><td> 0,500</td><td> 0,600</td><td></td>

<td>Gum gum</td><td></td><td></td><td></td><td></td><td></td><td> 0,350</td><td> 0,700</td>

<td>PEG</td><td></td><td></td><td></td><td></td><td></td><td> 7,000</td><td></td>

<td>glycol propylene</td><td></td><td></td><td></td><td></td><td></td><td> 7,000</td><td></td>

<td>Silica abrasive</td><td> 20,000</td><td> 16,000</td><td> 20,000</td><td> 16,000</td><td> 20,000</td><td> 25,000</td><td> 20,000</td>

<td>TiO2 (anatase)</td><td> 0,525</td><td> 0,525</td><td> 0,525</td><td> 0,525</td><td> 0,525</td><td></td><td> 0,525</td>

<td>SLS (solution 28%)</td><td> 4,000</td><td> 7,500</td><td> 4,000</td><td> 7,500</td><td> 4,000</td><td> 2,500</td><td> 5,000</td>

<td>saccharin sodium</td><td> 0,250</td><td> 0,250</td><td> 0,250</td><td> 0,250</td><td> 0,250</td><td> 0,500</td><td> 0,300</td>

<td>Aroma</td><td> 0,950</td><td> 0,950</td><td> 0,950</td><td> 0,950</td><td> 0,950</td><td> 0,800</td><td> 1,000</td>

<td>NaOH</td><td> 0,006</td><td> 0,122</td><td> 0,006</td><td> 0,122</td><td> 0,006</td><td></td><td> 0,600</td>

<td>Tribasic sodium phosphate</td><td></td><td></td><td></td><td></td><td></td><td> 1,100</td><td></td>

<td>Water and minor components, e.g. resources coloring</td><td>Supplement</td><td>Supplement</td><td>Supplement</td><td>Supplement</td><td>Supplement</td><td>Supplement</td><td>Supplement</td>

¹ AC Zinc Carbonate supplied by Bruggemann Chemical: Newtown Square, PA, United States

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