AU718673B2

AU718673B2 - Coolant compositions

Info

Publication number: AU718673B2
Application number: AU68798/96A
Authority: AU
Inventors: Jean Mane; Jean-Louis Ponge
Original assignee: V Mane Fils SAS
Current assignee: V Mane Fils SAS
Priority date: 1995-08-29
Filing date: 1996-08-29
Publication date: 2000-04-20
Anticipated expiration: 2016-08-29
Also published as: JP3245744B2; BR9610312A; ES2163651T3; JPH09510627A; DK0847268T3; CA2207457A1; KR100441535B1; RU2174388C2; WO1997007771A1; AU6879896A; ATE205382T1; MX9706270A; EP0847268A1; PT847268E; JP2000354467A; PL325123A1; JP3292883B2; PL184802B1; DE69615208D1; KR19990036418A

Abstract

The invention relates to refreshing compositions, flavouring compositions and ingestible and topical compositions containing at least a refreshing compound selected amongst monomenthyl succinate, alcaline metal salts of monomenthyl succinate, alcaline-earth metal salts of monomenthyl succinate and mixtures thereof. Said compositions provide a durable, bitterness-free, pleasant and refreshing effect, and said refreshing feel is different from that of other known refreshing agents. Consequently, a complementary or synergic effect can be obtained by combination with other refreshing agents. Furthermore, the succinate-based refreshing compounds according to the invention provide for an increase of alcohol feel in alcoholic drinks. Finally, the succinate-based refreshing compounds provide a refreshing taste when they are applied to filters, combustible papers and sheets for wrapping tobacco products for smoking and when they are incorporated into tobacco products for chewing or snuffing.

Description

COOLANT COMPOSITIONS This invention relates to coolant compositions having a unique cooling perception that provides the user with a pleasing cooling effect without bitterness.

The invention also relates to products containing one or more coolant compounds.

A variety of compounds are known which provide a cooling sensation when ingested or contacted vith the body. Perhaps the best known of these compounds is menthol. It is believed that menthol acts on the cold receptors at the nerve endings in order to provide this cooling effect. Since menthol has a strong minty odor and high relative volatility, several other coolant compounds have been developed and reported in the technical literature as potential flavorants or odorants in a variety of topical and ingestible compositions. For example, U.S. Patent No. 5,009,893 proposes the use of menthol in combination with N-substituted-p-menthane carboxamide compounds as coolant compositions in edible products.

International Patent application publication No. WO93/23005 proposes coolant compositions for edible or topical products which comprise a ketal and a secondary coolant which may be selected from menthol, carboxamides and mixtures thereof.

Several other references are mentioned therein which disclose compounds which have a flavor resembling menthol including menthyl carbinol, saccharide esters of menthol and a variety of amides. Also, 2,3-p-menthane diol has been reported as having a sharp cooling taste.

German Patent application 2 339 661 discloses aromatic compositions which include menthol or menthol esters of heterocyclic carboxylic acids. The preferred ester is menthyl-2-pyrrolidone-5-carboxylic acid ester.

German Patent application 26 08 226 discloses a composition which exhibits a physiological cooling effect. The cooling compounds disclosed include menthol esters of naturally occurring hydroxycarboxylic acids having 2-6 carbon atoms which are esterified with a C 1

-C

4 alkyl group. Menthyl acetate and menthyl lactate are the most preferred cooling compounds of this disclosure. Finally, another commercially available coolant compound is 3-menthoxypropane-l,2 diol.

Thus, a variety of compounds are known which provide cooling properties and are useful in a wide variety of products. However, there is still a need to provide coolant compositions having an improved cooling effect and/or taste perception.

Accordingly, it is an object of the present invention to provide improved coolant compositions.

It is a further object of the present invention to provide coolant compositions having a unique cooling sensation and taste perception.

It is a still further object of the present invention to provide coolant S\0. compositions including two or more cooling agents which provide a complementary cooling sensation and taste perception.

It is a still further object of the present invention to provide a novel coolant composition which employs a non-toxic coolant having a unique cooling sensation and taste perception.

2a According to the present invention there is provided a composition selected from topical products for humans and animals, oral care products, nasal care products, toilet articles, filters, combustible papers and leaf wrappers for smoking tobacco products, chewing tobacco products, snuff tobacco products or chewing gum including a product base and an effective amount of coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metals salts of monomenthyl succinate or mixtures thereof.

e* 0* H:\LColes\Keep\Speci\68 7 98-96.doc 15/07/99 In a second aspect, the present invention relates to a composition including a coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate formulated with a diluent selected from the group of flavors, sweetening syrups, flavoring syrups, flavoring oils and herbal oils.

The present invention also relates to coolant compositions which include a primary coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate, and at least one secondary coolant component.

Monomenthyl succinate is a known compound having Chemical Abstracts no.

77341-67-4. It has been used, for example, in smoking tobacco as is disclosed in U.S.

Patent No. 3,111,127. In particular, this patent discloses smoking tobacco which Sincorporates a monoester of synthetic or natural menthol and a saturated or unsaturated aliphatic or aromatic polycarboxylic acid or a substituted analog of such an acid. These tobacco products were evaluated and observed to burn slower at smolder than a comparable control product, to have increased firmness, and to require more puffs under a controlled smoking regime. Further, when tested organoleptically, these products were found to deliver smoke having the pleasing and cooling taste and aroma characteristic of menthol. Among the polycarboxylic acid esters are mentioned methylsuccinic acid ester, mono menthylsuccinate, monomenthyla-a-dimethylsuccinate and mono menthol-menthylsuccinate.

The article, "A Molecular Approach to Flavor Synthesis. I. Menthol Esters of Varying Size and Polarity," Jabloner, H. and Dunbar, J. of Polymer Science, Vol.

18, pages 2933-40 (1980) discloses a method for the synthesis of monomenthyl succinate as well as monomenthyl sodium succinate and other menthol esters derived from monomenthyl succinate. Solutions of 5% by weight of several of these menthol esters in mineral oil or water were tasted by a nine person taste panel. 5% of dimenthyl succinate in mineral oil was found to be odorless and tasteless, 5% sodium monomenthyl succinate in water was found to be vile and bitter and monomenthyl succinate itself was not tasted.

It has been surprisingly found that monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate used in a variety of ingestible and topical products at low concentrations of up to 1% by weight, give a pleasing, long-lasting cooling effect rather than the vile and bitter taste observed by the taste panel in the Jabloner article.

The present invention relates to an end use composition selected from topical products, oral care products, nasal care products, toilet articles, ingestible products, chewing gums, chewing tobacco, moist snuff or snuff tobacco products, and smoking tobacco products which include a product base and an effective amount of a cooling compound selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate and alkaline earth metal salts of monomenthyl succinate (hereinafter collectively referred to as "succinate-based coolant compounds").

More preferably, the coolant employed in the compositions of the present invention is selected from monomenthyl succinate, monomenthyl sodium succinate, monomenthyl potassium succinate, monomenthyl lithium succinate, monomenthyl 5 calcium succinate, monomenthyl magnesium succinate and monomenthyl barium succinate, as well as mixtures thereof.

It has been surprisingly found that these succinate-based coolant compounds, preferably when used in low concentrations of up to 1% by weight based on the total weight of the end use composition into which they are incorporated, provide a pleasing and/or long lasting cooling effect without the bitterness which would be expected from the prior art. Further, at concentrations of up to 1% by weight, the succinate-based coolant compounds do not develop a strong minty taste in the mouth or throat as do other coolants such as menthol.

The succinate-based coolant compounds of the present invention also provide a cooling effect in a different area of the mouth and throat when ingested than, for example, menthol or carboxamide-based coolant compounds. As a result, the succinate-based coolants of the present invention provide a complementary or .9* synergistic cooling effect when combined with at least one secondary coolant compound.

Further, the succinate-based coolant compounds of the present invention 25 enhance the taste sensation of alcohol in alcoholic beverages. As a result, alcoholic o** beverages comprising the succinate-based coolant compounds of the present invention taste like they have a higher, alcohol content than equally strong alcoholic beverages 30 without the succinate-based coolant compound.

The choice of the succinate-based coolant compound for use in the coolant composition will depend, to some extent, on the solubility characteristics which are desired of the compound. For example, monomenthyl succinate is sparingly soluble in water and more soluble in oil. Thus, monomenthyl succinate is particularly suitable H:\LColes\Keep\Speci\68798-96.doc 15/07/99 for environments where oil solubility is advantageous, although monomernthyl succinate can be used in aqueous environments if a concentration below the water solubility limit is employed. The alkali metal and alkaline earth metal salts of monomenthyl succinate are substantially more soluble in water and, as a result, are most useful in products where water solubility is advantageous.

The end use compositions in which the succinate-based coolant compounds may be employed include a wide variety of ingestible compositions and topical compositions for application to the human or animal body. Ingestible compositions include foodstuffs for human or animal consumption, beverages and other orally ingested compositions for humans or animals such as medicaments, antacids and laxatives, as well as chewing gum compositions. Topical compositions include a wide variety of compositions for application to humans or animals such as toiletries, oral care products, nasal care products, lotions, oils and ointments. Tobacco products include chewing tobacco, moist snuff, snuff tobacco, as well as filters, combustible papers and leaf wrappers used in smoking tobacco products.

In formulating the compositions of the present invention, the coolant compound can be employed in the form of a coolant composition, a flavoring composition and/or the coolant compound, composition or flavoring composition may be incorporated into a carrier material which may be inert or may contain other active ingredients of the end use composition. A wide variety of carrier materials can be employed including, for example, polar solvents, oils, fats, finely divided solids, maltodextrins, cyclodextrins, gums, natural or synthetic resins and any other known carrier materials for coolant or flavoring compositions.

Ingestible compositions in accordance with the present invention include, but are not limited to, alcoholic and non-alcoholic beverages, confectionery compositions including confectionery tablets, hard-boiled candies, chewing gums, pectin-based candies, chewy candies, cream-centered candies and fondants; carbonated beverages, powdered beverage mixes, distilled beverages, alcoholic beverages, non-alcoholic beverages, mineral waters, baked goods, dairy products, fruit ices, jams, jellies, gelatins, puddings and animal feeds.

Another type of ingestible composition in accordance with the present invention is sugarless candies. Sugarless candies typically have higher boiling points than the corresponding candies including sugar and thus any flavors added thereto must be stable at higher temperatures in order to be successfully added to the sugarless candy. Sugarless candies may include hard-boiled candies, pectin-based candies, chewy candies and cream-centered candies. In addition, sugarless chewing gums may also be made in accordance with the present invention. The amount of cooling composition incorporating in sugarless candies and/or sugarless gums is the same as would be used for the corresponding candies and/or gums including sugar.

The topical compositions of the present invention include, but are not limited to, toiletries such as face creams, talcum powders, hair oils, shampoos, bath oils and salts, toilet soaps, cologne, antiperspirants, toilet water, perfume, shaving lotions and creams, soaps, creams, dentifrices, mouthwashes, hair tonics and other similar products.

The succinate-based coolant of the present invention may also be incorporated into ingestible or topical medicaments such as cough drops, antacids, lozenges, antiirritants, ointments, lotions, oral analgesics and other similar products. Further, other compositions such as adhesives for a variety of uses where taste percepton is a concern can incorporate the cooling and flavorant compositions of the present invention.

The succinate-based coolant compounds are incorporated in a variety of tobacco products in accordance with the present invention. In one embodiment, the succinate-based coolant compounds are incorporated into chewing tobacco, moist snuff or snuff tobacco. In another embodiment, the succinate-based coolant compositions are associated with smoking tobacco products either by incorporating the succinate-based coolant compounds into the combustible paper, leaf wrapper or filter of the smoking tobacco products or by applying the succinate-based cooling compositions to surface of the combustible paper, leaf wrapper and/or filter of smoking tobacco products.

By tobacco products is meant products such as cigarettes, cigars, chewing tobacco, moist snuff and snuff tobacco which include as a component tobacco, or a tobacco derivative product. For example, clove cigarettes and cigars as well as flavored chewing tobaccos and the like are included within the scope of tobacco products in accordance with the present invention. Moist snuff is a form of snuff which is placed in the mouth either in a hand-made pellet form or contained in a sachet of high porosity paper.

The succinate-based coolant compounds of the present invention provide a refreshing aftertaste when employed in certain tobacco products. Further, when used in combination with a compound material such as menthol, the succinate-based coolant compounds provide a complementary cooling effect without undesirably enhancing the minty flavor of the menthol.

In making the tobacco products of the present invention, the coolhint compound can be employed in the form of a coolant composition or the coolant compound or composition may be incorporated into a carrier material which may be inert or may contain other active ingredients of the end use composition. A wide variety of carrier materials can be employed including, for example, polar solvents, oils, fats, finely divided solids, maltodextrins, cyclodextrins, gums, natural or synthetic resins and any other known carrier materials for such compositions.

The amount of coolant composition incorporated in each of the tobacco products of the invention will vary depending upon the particular compound, the degree of cooling effect desired and the strength of other coolants in the composition.

Typically, the succinate-based coolant compound will make up from 0.01 to 0.5% by weight of the tobacco product. More preferably, the succinate-based coolant compound makes up 0.02 to 0.3% by weight, based on the total weight of the tobacco product.

The succinate-based coolant compounds are applied directly to tobacco in any conventional manner such as by spraying, brushing or injection, for example. When applied to the combustible paper, leaf wrapper or the filter of smoking tobacco products, the succinate-based coolant compounds may be sprayed or brushed on or, in the case of filters, may be injected in the filter. Any other suitable means can be employed.

The present invention also relates to tobacco products including a combination of a primary cooling agent selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof, with at least one secondary coolant component. Generally, the level of the secondary coolant compounds in the tobacco products of the present invention is from about 10% by weight to about 700% by weight, more preferably from about by weight to about 650% by weight, and most preferably from about 30% by weight to about 500% by weight, based on the weight of the primary cooling agent.

Other preferred compositions which incorporate the succinate-based coolant of the present invention are pressed confectionery tablets, hard-boiled candies, chewing gums, chewy candies, pectin candies, cream-centered candies, fondant, toothpastes, mouthwashes, breath fresheners, alcoholic and non-alcoholic beverages, carbonated beverages and dry beverage mixes.

The amount of coolant composition incorporated in each of these end use compositions will vary depending upon the particular compound, the degree of cooling effect desired and the strength of other flavorants in the composition. Typically, the succinate-based coolant compound will make up from 0.001-1.0% by weight of the end use composition. More preferably, the succinate-based coolant compound makes up 0.005-0.5% by weight, based on the total weight of the end use composition.

In a second aspect, the present invention relates to a flavoring composition including a succinate-based coolant and a diluent selected from flavorants. This composition is particularly useful as a flavoring composition in a variety of ingestible compositions and/or compositions destined for contact with the human or animal body.

The flavorants may be selected from fruit flavors such as strawberry flavor, herbal oils such as eucalyptus oil, peppermint oil, spearmint oil, as well as other known flavors or flavoring oils which are conventionally employed in ingestible compositions and compositions designed for contact with human or animal bodies including flavors such as flavoring syrups such as sorbitol syrup or other Sweetening or flavoring syrups.

These flavoring compositions can be optionally diluted with a polar solvent such as, for example, ethyl alcohol, ethyl acetate, propylene glycol, isopropyl alcohol and glycerin. The solvent functions as a carrier material which aids in incorporating the flavoring composition into the product. The diluent may optionally comprise one or more additional conventional components selected from the group consisting of colorants, lubricants, thickeners, emulsifiers, plasticizers and encapsulating agents such as gums, starches, dextrins and cyclodextrins.

Typically the flavoring composition will include 1-80% by weight of the succinate-based coolant compound and from 20-99% by weight of the flavorant diluent and optional polar solvent. More preferred flavorant compositions comprise 5-50% by weight of the succinate-based coolant compound and 50-95% by weight of the flavorant diluent and optional polar solvent.

The present invention also relates to a combination of a primary cooling agent selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate and mixtures thereof, with at least one secondary coolant component.

Secondary coolant components which may be used in combination with the primary coolant of the present invention include menthol, carboxamides, ketals, menthyl acetate, menthyl lactate, 3-menthoxypropane-l,2 diol and mixtures thereof.

The carboxamide and ketal coolant compositions are known from the prior art and can be found, for example, in U.S. Patent No. 5,009,893 and international patent application publication No. WO-93/23005, the disclosures of which are hereby I ijB incorporated by reference. The remaining secondary coolants are known cooling agents, some of which are commercially available.

More particularly, the carboxamide secondary coolants are selected from Nsubstituted-p-menthane-3-carboxamides of the formula:

ONR'R"

wherein when taken separately, is hydrogen or an aliphatic radical containing up to 25 carbon atoms; R" when taken separately is hydroxy or an aliphatic radical containing up to 25 carbon atoms, with the proviso that when R' is hydrogen R" may also be an aryl radical of up to 10 carbon atoms and selected from the group consisting of substituted phenyl, phenylalkyl, substituted phenylalkyl, naphthyl, substituted naphthyl and pyridyl; and R' and when taken together with the nitrogen atom to which they are attached, represent a cyclic or heterocylic group of up to 25 carbon atoms; acyclic tertiary and secondary carboxamides of the formula:

R

1

R

2

C*----CONR'R"

R

3 where R' and when taken separately, are each hydrogen, C 1

-C

5 alkyl or C1-Cg hydroxyalkyl and provide a total of no more than 8 carbon atoms, with the proviso that when R' is hydrogen R" may also be alkylcarboxyalkyl of up to 6 carbon atoms; R' and when taken together, represent an alkylene group of up to 6 carbon atoms, the opposite ends of which group are attached to the amide nitrogen atom thereby to form a nitrogen heterocycle, the carbon chain of which may optionally be interrupted by oxygen; R 1 is hydrogen or C 1

-C

5 alkyl; and R 2 and R 3 are each C 1 -Csalkyl; with the provisos that R 1

R

2 and R 3 together provide a total of at least 5 carbon atoms, preferably from 5-10 carbon atoms; and (ii) when R 1 is hydrogen, R z is C 2

-C

alkyl and R 3 is C 2

-C

5 alkyl and at least one of R 2 and R 3 is branched, preferably in an alpha or beta position relative to the carbon atom marked in the formula; and mixtures thereof.

The ketal coolant compositions may be represented by the formula:

R

3 0

R

2 in which R 1 represents a C-C 6 -alkylene radical having at least 1, but not more than 3, hydroxyl group(s), and either R 2 and R 3 independently of one another represent C 1 Clo-alkyl which is optionally substituted by 1 to 3 radicals selected from the group comprising hydroxyl, amino and halogen, Cs-C 7 -cycloalkyl, preferably cyclohexyl, and

C

6

-C

12 -aryl, preferably phenyl, with the proviso that the total of the C atoms of R and R 3 is not less than 3, or R 2 and R 3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R 2 and R 3 forms a 5-7 membered ring, optionally substituted by C 1

-C

6 -alkyl groups.

The relative amounts of the primary and secondary coolants in the composition of the present invention may be varied over a wide range of compositions depending upon the particular flavor desired. For example, when the strong minty taste of menthol is desirable, a combination of a large quantity of menthol with a relatively small quantity of the succinate-based coolant of the present invention may be desirable. Other potential combinations of the primary coolant with one'or more secondary coolant components will be apparent to the man of skill in the art.

Generally, the level of the secondary coolant component in the coolant composition of the present invention is from about 0.05% by weight to about 95% by weight, more preferably from about 0.1% by weight to about 70% by weight, and most preferably from about 0.5% by weight to about 50% by weight, based on the total weight of the composition. Typically, the coolant compositions are made by mixing the primary and secondary coolants together in a conventional manner.

Certain compositions of the present invention are illustrated by the following examples.

Experimental Procedure for the Examples For each of examples 1-10 given below, a taste panel composed of 10-12 persons tasted the materials. The tasters were instructed to give information on the cooling effect, any unpleasant tastes and any other comments they might have. The following results were obtained from these tests.

Example 1 Hard Candy A hard candy formulation was made up from 120 grams of sugar, 30 grams of water, 80 grams of corn syrup and 0.1% by weight, based on the weight of the composition, of cinnamon flavor (control formulation). The formulation was divided into three parts. 0.05% by weight, based on the weight of the composition, of monomenthyl succinate was added to one of the hard candy formulations and 0.05% by weight, based on the weight of the composition of a commercially available coolant composition (WS 3 tm) from Wilkinson-Sword) was added to the other hardy candy formulation for the purpose of comparison.

The taste panel found that the hard candy formulation containing the monomenthyl succinate provided a long-lasting, pleasant cooling effect whereas no cooling effect was present in the control. No minty flavor was noticed by the tasting panel. The hard candy formulation containing WS3" also provided a cooling effect although the taste panel concluded that the cooling effect of WS 3 tm manifested itself in a different area of the mouth and throat than the cooling effect of the monomenthyl succinate of the invention.

Example 2 Pressed Tablets Royal Tt Dextrose (tabletting sugar) was pressed into two tablets, one containing only dextrose (control) and one containing 0.1% by weight of monomenthyl succinate. The taste panel noticed a pleasant cooling effect from the tablet containing the monomenthyl succinate and no cooling effect was obtained from the dextrose control tablet.

Example 3 Mouthwash Four samples of a mouthwash formulation having the following composition were tasted, cetyl pyridinium chloride 0.757 grams sodium saccharin 1.75 grams Tweentm 80 0.5 fluid ozs.

D&C Green #5 soln. in propylene glycol) 0.8 fluid ozs.

D&C Yellow #10 (0.1 soln. in propylene glycol) 0.2 fluid ozs.

Flavor N&A Mint Blend soln.) 0.25 fluid ozs.

Specially denatured alcohol 31.0 fluid ozs.

(l These ingredients were blended together until dissolved and then 96 fluid ozs. of water were added to provide a mouthwash formulation. The coolant compounds were then added to the mouthwash formulation in the amounts specified below.

The four mouthwash formulations tested were as follows: one containing no additives (control), one containing .004% by weight of monomenthyl succinate, one containing .004% by weight of WS3tm and one containing .002% by weight of monomenthyl succinate and .002% by weight of WS3tm.

The taste panel noted a cooling effect in all three compositions although the taste panel concluded that each of the four mouthwash samples had a different taste and that the cooling effect of the monomenthyl succinate manifested itself in a different area of the mouth and throat than the cooling effect of WS 3 tm and the mouthwash. The cooling effects of the monomenthyl succinate, mouthwash mint flavor and WS3 tm were found to be complementary in the fourth sample which contained all three coolants.

Example 4 Mouthwash Containing Sodium Monomenthyl Succinate The same four mouthwash formulations as were made in Example 3 were taste tested except that sodium monomenthyl succinate was substituted for the monomenthyl succinate in the same amounts. The tasting panel found a pleasant, long-lasting cooling sensation without bitterness for the sodium monomenthyl succinate-containing mouthwashes. The tasting panel also noted that the cooling sensation of sodium monomenthyl succinate was perceived at a point slightly forward of the point in the mouth and throat where the cooling sensation of monomenthyl succinate was perceived in the taste tests of Example 3. The sodium monomenthyl succinate was also found to have a complementary cooling effect when c?'mbined with WS3tm.

Example 5 Carbonated Beverages Four samples each of lemon-lime carbonated beverage were prepared, one without additives (control), one with .004% by weight of monomenthyl succinate, one with .004% by weight of WS 3 tm and one with 0.002% by weight of monomenthyl succinate and 0.002% by weight of WS3tm. The carbonated beverage formulation was as follows, with all parts being parts by weight: High fructose corn syrup 96.00 parts Water 28.90 parts Sodium benzoate (25% solution w/w in water) 0.50 parts Citric acid (50% solution w/w in water) 2.30 parts Flavor N&A lemon-lime 0.30 parts The carbonated beverage was formulated by combining the first three ingredients and mixing thoroughly, adding the citric acid solution and mixing again followed by adding the flavor to provide a beverage syrup. One part of the beverage syrup was then combined with 5 parts of carbonated water to provide the carbonated beverage. The coolant compounds were then mixed into the carbonated beverages om the amounts specified above.

The taste panel concluded that the samples containing monomenthyl succinate and WS3 tm provided a cooling effect and that the cooling effect of monomenthyl succinate manifested itself in a different area of the mouth and throat than the cooling effect of WS 3 tm. In addition, the cooling effect of monomenthyl succinate was found to be pleasing, not minty and long-lasting. Further, the combination of monomenthyl succinate with WS3tm was found to provide a complementary cooling effect since different areas of the mouth and throat were affected by the'respective coolants.

Examples 6-8 Alcoholic Beverages Three different alcoholic beverages were made by using 17.00 grams of high fructose corn syrup, 140.89 grams of water and 21.05, 42.11 and 84.22 grams of 190 proof alcohol in order to obtain alcoholic drinks of 20, 40 and 80 proof, respectively.

To samples of each of the three alcoholic beverages was added 0.07% by weight of monomenthyl succinate. A cooling effect was noted in the 20 and 40 proof alcoholic beverages containing the monomenthyl succinate but not in the 80 proof beverage.

As a result, a new sample of 80 proof alcoholic beverage was prepared using a higher concentration of monomenthyl succinate and, at this higher concentration level a pleasant, long-lasting cooling effect was noticed by the tasting panel. In addition, the tasting panel concluded that the monomenthyl succinate enhanced the taste sensation of the alcohol in all of the alcoholic beverages and, as a result, the 20, and 80 proof alcoholic beverages including monomenthyl succinate each tasted as if there were a higher alcohol content than the corresponding control beverage having the same alcohol content no coolant compound.

Example 9 Chewing Gum A conventional chewing gum base was employed for this example. To the chewing gum base was added 1.0% by weight of mixed berry flavoring. Then, to one of the chewing gum samples 0.30% by weight of monomenthyl succinate was added.

A pleasant, long-lasting cooling effect in the back of the mouth and throat was noted by the tasting panel in the chewing gum containing monomenthyl succinate. In addition, no minty taste was apparent.

Example 10 Sugarless Candy Sugarless deposited sorbitol candy was prepared by heating one kilogram of sorbitol syrup to 170*C, cooling the sorbitol syrup to 135 0 C, adding 12 grams of citric acid with stirring and cooling this composition down to 110°C. At that point, 20 grams of sorbitol powder and the flavorant including 0.05% by weight, based on the weight of the composition of monomenthyl succinate was added to the sugarless candy formulation by stirring it in slowly. Finally, the candy is deposited and allowed to harden.

A taste panel found that the sugarless hard candy formulation containing the monomenthyl succinate provided a long-lasting, pleasant cooling effect.

Examples 11-14 and Comparative Examples A-B Mono Menthylsuccinate in Cigarette Filters Combined With Menthol in the Tobacco The tobacco rods of some regular international blended cigarettes and of fluecured cigarettes were each injected with 20 pil of a 10% solution of menthol crystals in ethanol. The menthol-injected cigarettes were then divided into five sets. 20 gl, pl, 40 A1, and 50 pjl of a 1% solution of mono menthylsuccinate in triacetine were injected into the filters of the first four sets of cigarettes with the fifth set of cigarettes being used as a control. Each set of cigarettes included a control with no menthol and no mono menthylsuccinate, a cigarette including only menthol, a cigarette including only mono menthylsuccinate and a cigarette including both merthol and mono menthylsuccinate.

An expert smoking panel (ESP) lighted, smoked and tasted each set of the test cigarettes and found that at a level of 0.2 pl of mono menthylsuccinate and no menthol, there was no cooling effect. At 0.3 /l of mono menthylsuccinate with no menthol a slight cooling effect was noted. At a level of 0.4 tl of mono menthylsuccinate a strong cooling effect with a refreshing aftertaste was noted by the ESP. Further, in combination with menthol in the tobacco at this level, no enhancement of the "mint" flavor note of the menthol by the mono menthylsuccinate was detected by the ESP. At a level of 0.5 /l of mono menthylsuccinate the cooling effect was even more evident to the ESP and still no enhancement of the "mint" flavor note of menthol was noted. However, a minor increase in irritation was experienced by the ESP at this level of mono menthysuccinate.

The ESP concluded that the mono menthylsuccinate injected in the filter of cigarettes had a cooling effect on the smoke and provided a lingering refreshing character in the mouth without significantly altering the flavor note of the menthol in the tobacco.

Example Mono Menthylsuccinate Used With WS3tm Coolant in Filters and Menthol in the Tobacco Rod The tobacco rod of selected cigarettes as in Examples 1-4 above was injected with 20 pl of a 10% solution of menthol crystals in ethanol. The menthol injected cigarettes were divided into two sets. 45 pl of a 1% solution of mono menthylsuccinate in triacetine and 15 1 of a 1% solution of WS3tm in triacetine were injected into the filter of one set of the cigarettes containing menthol.

The ESP observed an intense cooling effect and a slight enhancement of the mint and aromatic flavor notes of the menthol, as compared to the mentholcontaining control. No increase in irritation was found. The panel concluded that at these levels, a synergistic effect occurred between the two cooling agents.

Examples 16-17 Mono Menthylsuccinate in Chewing Tobacco and Snuff Tobacco 0.08% and 0.12% by weight of mono menthylsuccinate were added by injection to chewing tobacco using a 10 pjl gas chromotography syringe and the same levels of mono menthylsuccinate were added to snuff by spraying using a thin atomizer.

Each sample of the tobacco was kept in the mouth of the ESP members for a one minute test period after which the mouth was cleaned with pure water and a waiting period of five minutes was observed before starting a new evaluation.

At a level of 0.08% by weight, a refreshing effect was observed by the ESP after a period of 2-3 minutes. At 0.12% by weight an even higher intensity of cooling was observed approximately two minutes after the tobacco was removed from the mouth, whereby the interior of the mouth was judged as being cleaner. Also, the ESP concluded that a more pleasant refreshing aftertaste was present. The aftertaste lasted for up to five minutes following the removal of the tobacco from the mouth.

Examples 18-19 Mono Menthylsuccinate in Filter Tipping Paper of Indonesian Cigarettes 1 and 20 gl of a 1% solution of mono menthylsuccinate in triacetine was distributed in the form of a thin film applied with a soft brush over the first third of the mouth end of the filter tipping paper of different types of Kretek cigarettes obtained from the Indonesian market.

At 0.10 pil of mono menthylsuccinate, the ESP found a slight refreshing effect on the lips after 2-3 minutes following insertion of the Kretek cigarette in the mouth.

At 20 pl a cooling effect associated with a refreshing character started approximately one minute after insertion of the Kretek cigarette in the mouth and lasted for up to five minutes on the lips and inner part of the mouth. The ESP concluded that the mono menthylsuccinate had an effect that can be efficaceous in retaining a refreshing, clean character on the lips and inner part of the mouth when applied on the mouth end of a Kretek cigarette.

These examples have been given for the purpose of illustration and description only and are not to be construed as limiting the scope of the invention in any way.

The scope of the invention is to be determined from the claims appended hereto.

Claims

1. A composition selected from topical products for humans and animals, oral care products, nasal care products, toilet articles, filters, combustible papers and leaf wrappers for smoking tobacco products, chewing tobacco products, snuff tobacco products or chewing gum including a product base and an effective amount of coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metals salts of monomenthyl succinate or mixtures thereof, wherein the coolant is present in an amount of up to 1% by weight based on the total weight of the product. 15 2. A composition as claimed in claim 1 wherein the products are topical products for humans and animals, oral care products, nasal care products or toilet articles. e*

3. A composition as claimed in claim 1 wherein the 20 products are chewing tobacco products, moist snuff tobacco products and snuff tobacco products or the filters of smoking tobacco products.

4. An ingestible product for humans and animals selected from baked goods, dairy products, fruit ices, confectionery products, jams, jellies, gelatins, puddings, I: animal feeds, lozenges, cough mixtures, decongestants, anti-irritants, antacids, anti-indigestion preparations, oral analgesics, pressed confectionery tablets, hard boiled candies, chewing gums, pectin-based candies, chewy candies, cream-centered candies, fondants, toothpastes, mouthwashes, breath fresheners, carbonated beverages, mineral waters, powdered beverage mixes, non-alcoholic beverages, alcoholic beverages or distilled beverages, including a product base and an effective amount of a coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl H:\Caroline\Keep\Speci\p23919.doc 14/02/00 23a succinate or mixtures thereof, with the proviso that when said ingestible product is an alcoholic beverage or a a.. S a a a aSSa a S *Saa a a a. S a S H:\Caroline\Keep\speci\p23919 .doc 14/02/00 24 distilled beverage the amount of the coolant is from 0.001- by weight, based on the total weight of the ingestible product.

5. A products as claimed in claim 4 wherein the ingestible product is a foodstuff selected from baked goods, dairy products, fruit ices, confectionery products, sugarless candies, jams, jellies, gelatins, puddings or animal feeds.

6. A product as claimed in claim 4 wherein the ingestible product is selected from lozenges, cough mixtures, decongestants, anti-irritants, antacids, anti- indigestion preparations or oral analgesics.

7. A product as claimed in claim 4 wherein the ingestible product is selected from pressed confectionery tablets, hard boiled candies, chewing gums, pectin-based candies, chewy candies, creme-centered candies, fondants B S 20 sugarless hard-boiled candies, sugarless pectin-based candies, sugarless chewy candies, sugarless cream-centered candies, toothpastes, mouthwashes, breath fresheners, alcoholic beverages, carbonated beverages, mineral waters, powered beverage mixes, non-alcoholic beverages, or 25 distilled beverages. *0*

8. A composition as claimed in any one of claims 1-7 which includes from 0.001-1.0% by weight of said coolant based on the total weight of the product.

9. A flavoring composition which comprises from 1- by weight of a coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, alkaline earth metal salts of monomenthyl succinate or mixtures thereof and 20-99% by weight of flavorant diluent having at least one flavorant selected from fruit flavors, herbal oils, sweetening syrups, flavoring syrups or H:\LCole\Keep\peci\68 7

98-96.doc 15/07/99, 25 flavoring oils. A flavoring composition as claimed in claim 9 which comprises from 5-50% by weight of the coolant and from 50-95% of the flavorant diluent. 11. A flavoring composition as claimed in claim 9 or wherein the flavorant diluent further comprises a polar solvent selected from ethanol, ethyl acetate, propylene glycol, isopropyl alcohol or glycerin. 12. A flavoring composition as claimed in any one of claims 1-11 which further includes at least one secondary coolant component. 13. A coolant composition having an effective amount of at least on primary coolant selected from monomenthyl succinate, alkali metal salts of monomenthyl succinate, or alkaline earth metal salts of monomenthyl succinate, and at 20 least one secondary coolant component, wherein the coolant is present in an amount of up to 1% by weight based on the total weight of the composition. 0 14. A coolant composition as claimed in claim 12 or 0 13 wherein the secondary coolant component is selected from menthol, carboxamides, ketals, menthyl acetate, menthyl lactate, 3-menthoxypropane-l, 2 diol or mixtures thereof. A coolant composition as claimed in claim 14 wherein the carboxamide coolant component is selected from: SCONR'R" where when taken separately, is hydrogen or H:\Caroline\Keep\Speci\p23919.doc 14/02/00 25a an aliphatic radical containing up to 25 carbon atoms; R when taken separately is hydroxy, or an aliphatic radical 4 *4 C C C C p. C C eq C PC. C CC.. P.C. C p *4CC *C P .4 PC P 6P p p P. **PPC C P H:\Caroline\Keep\Speci\p23 9 19.doc 14/02/00 26 containing up to 25 carbon atoms, with the proviso that when R' is hydrogen Re* may also be an aryl radical of up to 10 carbon atoms and selected from substituted phenyl, phenalkyl, substituted phenalkyl, naphthyl, substituted naphthyl or pyridyl; and R' and Roe, when taken together with the nitrogen atom to which they are attached, represent a cyclic or heterocylic group of up to 25 carbon atoms; acyclic tertiary and secondary carboxamides of the formula: R, R2 C*---CONR'R" Rz SR3 where R' and Re*, when taken separately, are each hydrogen, C 1 -Cs alkyl or Ci-Ce hydroxyalkyl and provide a total of no more than 8 carbon atoms, with the proviso that :when R' is hydrogen Roe may also be alkylcarboxyalkyl of up to 6 carbon atoms; R' and Roe, when taken together, represent an 25 alkylene group of up to 6 carbon atoms, the opposite ends of which group are attached to the amide nitrogen atom thereby to from a nitrogen heterocycle, the carbon chain of which may optionally be interrupted by oxygen; RI is hydrogen of Cj-C 5 alkyl; and R 2 and R 3 are each Cl-Cs alkyl; S" with the provisos that R 1 R 2 and R 3 together provide a total of at least 5 carbon atoms; and (ii) when Ri is hydrogen, R 2 is C 2 -C 5 alkyl and R 3 is C 2 -Cs alkyl and at least one of R 2 and R 3 is branched and mixtures thereof. l 16. A coolant composition as claimed in claim 14 H:\LColes\Keep\Speci\68798-96.doc 15/07/99 27 wherein the ketal coolant component is selected from: R 3 1 R in which R 1 represents a C 2 -C 6 -alkylene radical having at least 1, but not more than 3, hydroxyl group(s), and either R 2 and R 3 independently of one another represent CI-Clo- alkyl which is optionally substituted by 1 to 3 radicals selected from the group comprising hydroxyl, amino, halogen, Cs-C 7 -cycloalkyl, Cs-C 12 -aryl, with the proviso that the total on the C atoms of R 2 and R 3 is not less than 15 3, or R 2 and R 3 together represent an alkylene radical which, together with the carbon atom which carries the radicals R 2 and R 3 forms 5-7 membered ring, optionally substituted by C 1 -C 6 -alkyl groups. 17. A composition including a product base and an effective amount of coolant substantially as herein described with reference to any one of the foregoing examples. 18. An ingestible product including a product base and an effective amount of coolant substantially as herein described with reference to any one of the foregoing examples. 19. A flavoring composition including 1-80% by weight of a coolant and 20-99% by weight of a flavorant diluent substantially as herein described with reference to any one of the foregoing examples. H:\Caroline\Keep\Speci\p23919.doc 14/02/00 28 A coolant composition including an effective amount of a primary coolant and a secondary coolant substantially as herein described with reference to any one of the foregoing examples. Dated this 14th day of February 2000 V. MANE FILS S.A. By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia H:\Caroline\Keep\Speci\p23919.doc 14/02/00