CA1105390A - Crystalline metal alumino-silicate in two tone flavoured heat releasing dentrifrice - Google Patents

Abstract

ABSTRACT
There is disclosed an anhydrous heat releasing, two toned flavored dentrifrice which contains an anhydrous synthetic zeolite as the sole or major abrasive, a flavoring agent and a second anhydrous polishing agent as the essential ingredients, the dentifrice composition having an adjustable abra-sivity and heat release.

Description

" 11~!53~0 This invention relates to a novel anhydrous heat-releasing denti-frice capable of delivering a two tone flavor in the oral cavity, immediately upon contact therewith, as when brushing one's teeth, and containing zeolite as the sole or major polishing agent a suitable flavoring agent, and a second anhydrous polishing agent.
This application is divided from applicants copending application serial number 309,904 filed on August 23rd 1978, and directed to an anhydrous heat releasing fluoride dentifrice which generates heat in the mouth enhancing the fluoride anticaries action and which effects a two tone flavor change in the oral cavity consisting of a finely divided anhydrous synthetic zeolite having an appreciable heat of hydration and capable of being reversibly dehy-drated as the sole or major dental polishing agent in amounts of about 10 to 50% by weight which synthetic zeolite is a crystalline metal al~min~ sylicate, said metal being selected from the group consisting of an alkali metal, alkaline earth metal, zinc, copper and mixtures thereof, an effective amount of a fluo-rine containing compound, about 0.1 to 5% by weight of at least one flavoring agent, and ~bout 20 to 75% by weight of an anhydrous liquid vehicle.
The present application concerns a heat releasing dentifrice with a second anhydrous polishing agent.
The prior art discloses self-heating cosmetic preparations as shown in patent No. 3,341,418 to Moses et al. Said patent discloses a two-part aqueous liquid composition, to be applied to the skin as a shaving cream, or to ! the hair as a shampoo, packaged in a dual compartment container and to be simultaneously dispensed for exothermic reaction with each other, one compart-ment containing an oxidant such as hydrogen peroxide or the like in an aqueous medium and the other compartment containing a reducing agent such as thiourea and the like in an aqueous medium.
Patent No. 3,250,680 to Menkart et al also discloses a heat-generat-. .

~ 5~390 ing cosmetic composition adapted to evolve heat when it contacts moisture which is an anhydrous composition containing about 5 to 40~ of an anhydrous adsorbent material such as alkali metal alumino-silicate molecular sieves dispersed in ~ a non-aqueous cosmetically-acceptable vehicle such as mineral oil or liquid ; polyalkylene glycol. The cosmetic compositions disclosed herein include skin and hand creams, shampoos and toothpaste. However, the toothpaste formula therein does not contain any flavoring agents nor is the sodium aluminum sili-cate the sole or major polishing agent. As a matter of fact, its content is less than that of each of the other two polishing agents. The presence of a flavoring agent which is totally absent in this patent is an essential ingre-dient in present novel dentifrice for its unusual and unexpected two-tone flavor in the mouth.
It has been observed that taste and flavor are perhaps the most im-portant single aspects with respect to the consumer acceptance of a dentifrice . formulation. The selection of acceptable sweetener and flavoring ingredients is therefore of significant importance in the formulation of a dentifrice. It has oftentimes been stated that the foregoing is both an art as well as a sci- .;
ence. It is an art in the sense that it requires the blending of the various components with the flavoring agents such that the final composition contains a pleasing taste as well as provides a composition in which the flavor is stable.
The foregoing has presented particular difficulties in incorporating flavoring agents in a dentif~Fice formulation inasmuch as the former must be compatibl~e with the latter and remain essentially unchanged over the shelf life of the product. Some of those flavors which do not have stability problems have the drawback that they are not suitable for use due to the unacceptable timelag prior to the onset of their flavor andtor their associated side tastes. In-asmuch as dentifrices generally contain a detergent-like material, the sweete-ner employed therein must have the quality of a rapid onset of flavor so as to . ::: .:: : : , :- :: ::
,, . ., ::: .:: . .:. - :. : .:

1~5390 mask the generally bitter flavor associated with det-ergent-like ingredients.
The use of low intensity flavors isl therefore, not practical for use in most dentifrice formulations. Merely increasing the amount of low intensity fla-vors so as to overcome the foregoing deficiencies does not prove very helpful inasmuch as a dentifrice generally contains large amounts of humecta~t~ po-lishing agents, water and the like and therefore from a volume point of view, it is not practical.
The sensation of flavor is believed to be made up of taste received by the taste buds on the tongue, o~ors picked up by the ol factory mucosa of io the nose as sensations, such as burning, cooling and astringency transmitted through the tactile nerve endings in the mouth. Flavor sensation is made up essentially of four basic tastes, sweet, sour, bitter and salty, which are registered by the taste buds on the tongue. Bitter flavors are detected by the back of the tongue, sweet at the tip, sour along the sides from midway to the back of the tongue and saltiness is detected more or less equally along the entire tongue.
Accordingly, this invention is directed to providing a dentifrice capable of effecting a unique and unusual flavor-odor sensation in the mouth by including a flavor in conjunction with an anhydrous synthetic zeolite as ~'; 20 the essential polishing agent in an anhydrous formulation.
,~, This invention also aims to provide an anhydrous dentifrice possessing a thermal effect in the oral cavity.
.~, Accordingly, the present invention provides an anhydrous heat rsleas-ing dentifrice which generates heat in the mouth and effects a two tone flavor change in the oral cavity comprising an abrasive system consisting essentially of a finely divided anhydrous crystalline metal alumino-silicate having an appreciable heat of hydration and capable of being reversibly dehydrated in .: : .: .., :

, . , :., .. . :, 3~0 amounts of about 10-50% by weight, said metal being selected from the group consisting of an alkali metal, alkaline earth metal, zinc, copper and miXtures thereof, and a minor amount of up to about 20% by weight of a finely divided anhydrous dental abrasive to decrease the abrasivity and regulate the degree of heat generated by said dentifrice, about 0.1 to 5% by weight of at least one flavoring agent, and about 20 to 75% of an anhydrous liquid vehicle.
The synthetic zeolites useful herein are crystalline metal alumino silicates wherein the metal may be an alkali metal, an alkaline earth metal, zinc, copper or a mixture of metals and having an appreciable heat of hydration, and capable of being dehydrated and at least partially rehydrated without des-troying the framework structure of the zeolite.
Zeolite has been defined by Smith, J.V., Mineralogical Society of America, Special Paper No. 1, 1963, as an alumino-silicate with a framework structure enclosing cavities occupied by large ions and water molecules, both of which have considerable freedom of movement permitting ion exchange and reversible dehydration.
A synthetic zeolite useful in this invention is typically commercial-ly available from the Linde Division of Union Carbide Corporation, New York, New York as molecular sieves. These materials are fully described in United States Patent Numbers 2,882,243 and 2,882,244. The structure of the A and X
crystals may be represented as follows:
A-Crystal C al2(A12)12(Si2)1 ~ 27H20 ., i x_crystal E a86(A12)86(Si2)1 ~ 264H20 On heating, the water is removed leaving the crystal structure intact with an aluminum-oxygen-silicon structure.
The A102 has one negative charge available for cation exchange. By ~53~0 making use of this property, the "pore size" can be varied.
The crystal synmmetry of A-zeolites are cubic and the unit cell dimension is about 12.5 A on each side. In ~he A-crystal the pores range from 3 to 5 A and with the X-crystal from 8 to 12 A. The X-crystal also has a cubic symmetry.
Molecules, if not too large, pass through the pores and are adsorbed on the inner surface and held by electrostatic forces. As materials are ad-sorbed in the sieves, more or less heat is evolved and in some cases where this energy is high, it causes the sieves to glow. The sieves rapidly take up the maximum amount of material (cavities full) and the partial pressure over the loaded sieve in some cases is very low.
The A-crystal with the small pore size is best suited for holding water and hence adapted to techniques and procedures where drying is the primary objective. The X-crystal with the larger pore size is usually pre-ferred for loading since there is less limitation of the molecular size which can pass through the pore. Pore size affects the rate of displacement of ad-sorbed material but not the equilibrium.
The ability of the pores to pass certain molecules and exclude others has been the basis for a number of the present applications for separating similar compounds. For example, normal hydrocarbons readily pass through the pores whereas isohydrocarbons do not.
Materials adsorbed on the sieves may be released by heating, reduced pressure or by displacement by a more strongly adsorbed compound. For instance, water will remove any adsorbed material. The higher the molecular weight, the slower is the displacement by any means. Metal ions such as copper, zinc, alkali metals, magnesium, calcium and other alkaline earth metals are taken up or replaced in these sieves in accordance with the selectivity and capacity of ~ : ''. ' . : ~. - . ..... ~ :

~53~3!0 each of these ions. However, the zeolites containing any of the aforemention-ed metal ions are equally effective in ~njointly releasing heat and the absorb-ed flavor components upon contact with water.
Commercially available synthetic zeolites are suitable for use as the sole or major dental polishing agent in instant dentifrice formulations and possess acceptable abrasivity for effective cleaning and polishing of the teeth, with the added advantage of releasing appreciable heat of hydration within the oral cavity substantially instantaneously so as to afford a pleasurable warm sensation which is coupled with an immediate flavor release, thereby eliminating any objectionable time lag prior to the onset of the flavored taste. Heat is evident in 30 seconds. The thermal effects are illustrated by the following tests, wherein 20 gms of dried zeolites were added to 80 gms deionized distilled water and the temperature recorded at in-tervals of minutes and seconds:
Water temperature prior to addition: 24C 22C 22C 23C
Zeolites added: Cu Zn 5A SK40 Minutes SecondsTem~ C TempC TempC TempC

2 0 31 34 3~ 35

3 0 31 33 37 35 0 30 32 35 3~

- : .: i , ~l~S3~0 Zeolites particularly useful herein include the molecular sieves named zeolite A which has the following properties:
A chemical compositon defined heretofore, a cubic crystalline sym-metry, the cell dimension being equal to 12.32 A (calculated for dehydrated zeolite), a density of 1.33 g/cc (calculated for dehydrated zeolite), a void volume of 0.3 cc/g (based on the amount of water contained per gram of de-hydrated zeolite), and an aperture size of 4.2 A;
Zeolite X which has the following properties: a chemical composition previously defined herein, a cubic crystalline symmetry, a cell dimension of 10 24.95 A (dehydrated zeolite), a density of 1.29 g/cc (dehydrated zeolite), a void volume~of 0.36 cc/g,,and an aperture size of 8 A;
Zeolite Y of the following chemical composition:
N 56 [A12)56(Si2)13~, 264H20 O
which has a cubic symmetry and a cell dimension of 24.7 A, a density of 1.30 g/cc (dehydrated), a void volume of 0.35 cc/g and an aperture size of 8 A;
. Zeolite B of the following chemical composition:
Na6 ~A102)6(SiO2)1~.15H2 which is cubic in symmetry and has a cell dimension of 10.0 A, a density of 1.47 g/cc (dehydrated), a void volume of 0.15 cc/g, and an aperture size of 20 3.5 A;
Synthetic mordenite of the following chemical composition:
Na8 ~12)8(Si2)4~ 24H20 which is orthorhombic in symmetry, has a density of 1.72 g/cc (dehydrated), has a void volume of 0.14 cc/g and an aperture size of 6.6 A.
The a~ove described zeolites may be varied by exchanging all or part of the sodium ions with other cations such as hydrogen and/or metal ions including the alkali metals, alkaline earth metals, zinc or copper or mixtures .

, . : :. : :, .

53~

thereof.
T he uniformity in composition and physical properties of the syn-thetic zeolites renders it particularly useful herein as opposed to natural occurring zeolites wherein the physical properties are non-uniform.
The synthetic zeolites can readily be dehydrated to remove subs-tantially all the water by heating it in air or vacuum to temperatures up to 600C, and preferably to a temperature of about 350C in a vacuum of 10 5mmHg, without destroying the crystal structure thereof. Stability to heat has been observed up to temperaturesof about 700C. The proportion of anhydrous syn-thetic zeolite in the dentifrice may be from about 10 to 50% by weight andpreferably about 20 to 35%.
The anhydrous synthetic zeolite has the property of generating heat of hydration when water is added thereto. Accordingly, the presence of said anhydrous zeolite in an anhydrous liquid vehicle containing a flavoring agent imparts a thermal effect in the oral cavity, as well as yields a unique and unusual flavor-odor sensation therein. ~ore particularly, there is a sequential two tone flavor, a change in flavor, first a burst of one flavor which rapidly changes to another flavor. For example, when utilizing a single flavoring agent such as oil of peppermint in the zeolite containing dentifrice, the warmth due to the generation of heat in the oral cavity initially produced a burst of a cinnamon flavor which then tasted minty as the heat subsided.
This change in flavor experience affords a pleasurable sensation and provides an unusual brushing experience. Thus, it is apparent that a variety of se-quential two tone flavored dentifrices can be formulated by incorporating a single flavoring agent or a mixture of suitable flavoring agents.
Any suitable flavoring or sweetening sialagogues or mixture thereof may be employed in formulating a flavor for the compositions of the present 53~0 invention. Examples of suitable flavoring constituents include the flav~ring oils, e.g. oils of spearmint, peppermint, wintergreen, sassafras, clove, sage, eucalyptus, marjoram, cinnamon, lemon, lime, grapefruit and orange, as well as flavoring aldehydes, esters such as methyl salicylate, alcohols, and higher fatty compounds known in the art. Also useful are such chemical5 as menthol, carvone and anethole. Of these, the most commonly employed are the oils of peppermint, spearmint, and eucalyptus and anethole, menthol and carvone. In some cases flavorful solvents, such as chloroform and mock chloroform, may be employed. Such flavorings may be used as liquids or may be solidified by being mixed with a particulate carrier material, such as starch, calcium car-bonate, paraffin, vegetable wax, fat, higher fatty acid or other suitable carrier substances. In the cases of solid flavors, such as vanillin, sage, citric acid or licorice, the flavor may be converted to liquid form, if so desired, by dissolving it in the solvent or emulsifying it, usually with the help of a synthetic or natural emulsifying agent. The choice as to whether to utilize particulate solid or liquid flavors or to convert such flavors to a particulate solid or liquid form, respectively, will often depend on the pro-perties desired in the flavor and its compatibility with the sweetener and any other material to be present with it. Suitable sweetening agents include man-nitol, sucrose, lactose, maltose, sorbitol, xylitol, sodium cyclamate, saccha-rin, the dipeptides of United States Patent No. 3,939,261 and the oxathiazin salts of United States Patent No. 3,932,606. Suitably, flavor and sweetening agent may together comprise from about O.l to 10% or more of the compositions of the instant invention.
The anhydrous zeolite containing dentifrice exhibits anti-odor ac-tivity as evidenced by an in vitro onion test, wherein 4 jars were filled with 1 gm onion. To each jar except one, was added lOgms dried zinc loaded zeolite, - , '' . : :
- ~ , ;

, : , . :.-, .;: : :
,: ,.
,. '':

3~0 10 g dried copper loaded zeolite and 10 g anhydrous dicalcium phosphate, res-pectively, and stored. After 3 days the odors were evaluated by smelling the headspace in the jar and rating it from 1 to 4, with 4 being the pure onion odor and the control. An average of 6 ratings per jar gave the following re-sults:
Jars Additive Odor rating :
A Zn zeolite 2.4 ; B Cu zeolite 1.1 C Dicalcium phosphate 2.7 D None 4.0 These results are indicative of enhanced anti-odor activity in comparison to dentifrices containing the conventional abrasives such as di-calcium phosphate.
The substantially anhydrous vehicle of this invention is prefer-ably formulated from the following: (1) humectant or an oil; (2) gelling or binding agent; (3) standard toothpaste additives; and optionally, (4) water incompatible dentifrice additives, additional abrasives and inert ingredients.
The above-mentioned ingredients must, of course, be non-toxic and substantially anhydrous.
; 20 The dentifrice formulation of this invention includes liquids and solids that are proportioned as further defined hereinafter to form a creamy mass of desired consistency which is extrudable from an aerosol or other pres-surized container or a collapsible tube (for example aluminum). In general, the liquids in the dental cream will comprise chiefly glycerine or an oil, propy-lene glycol, polyethylene glycol 400, etc., including suitable mixtures there-of. It is advantageous usually to use a mixture of both humectant and binder such as glycerine and Carbowax 600. The total liquid content will generally be about 20 to 75 percent by weight of the formulation.

, ,!, ~ ~

~53~0 It is preferred to use also a gelling agent in dental creams and gels, such as the natural and synthetic gums and gum-like materials, for example, Irish moss, gum tragacanth, methyl cellulose, polyvinylpyrrolidone, hydrophilic col-loidal carboxyvinyl polymers such as those sold under the trademark Carbopol ; 934 and 940, hydroxyethyl cellulose, Indian gum, acacia gums, agar agarj lo-cust bean gum, synthetic silicated clays such as those sold under the trade-mark Laponite CP and Laponite SP, pectin and finely divided pyrogenic silica, sold under the trademarks Cab-O-Sil M5, Syloid 244, Syloid 266 and Aerosil D
200. The solid portion of the vehicle is usually present in an amount of up 10 to about 10 percent and preferably about 0.2 to 5 percent by weight of the formulation.
The proportions of gelling agents or thickeners in the present dentifrices are sufficient to form an extrudable, shape-retaining product which can be squeezed from a tube onto a toothbrush and will not fall between the bristles of the brush but rather, will substantially maintain its shape thereon. In almost all cases no:more than about 10% of gelling agent need be used and in most instances about 0.5 to 10% will suffice, and preferably about 1 to 5%.
Sùitable oils for use in the practice of this inve~tion include 20 those which have viscosities ranging from about 100 to about 300 centipoises at 70F., and can be mineral oil, light liquid petrolatum thickened to the necessary viscosity; and vegetable oils. The preferred mineral oil is Mineral Oil U.S.P. (also known as Liquid Petrolatum U.S.P., mineral oil (heavy medi-cinal), white mineral oil, liquid paraffin, and heavy liquid petrolatum).
Mineral oil U.S.P. is defined in Remington's Pharmaceutical Sciences, 13th edition, Mack Publishing Co., Easton, Pa. 1965 as "a mixtu~e of liquid hydro-carbons obtained from petroleum; a colorless transparent, oily liquid, free or ~1~!53~0 nearly free from fluorescene". It is tasteless and odorless when cold and develops not more than a faint odor of petroleum when heated.
The preferred light liquid petrolatum is Light Liquid Petrolatum N.F. also known as light liquid paraffin and light white mineral oil. It is described in Remington's Pharmaceutical Sciences, as "... a mixture of liquid hydrocarbons obtained from petroleum, it may contain a stabilizer". If the Light Liquid Petrolatum N.F. is used as the oil it must be thickened to the required viscosity of from about 100 to about 300 centipoises at 70F. with - one of the well-known commercially available inert thickening materials, such as a pyrogenic silica sold under the trademark Cab-O-Sil, or a hydrogenated castor oil, sold under the tradename THIXIN.
Suitable vegetable oils which may be used as the oil ingredient include coconut oil, cotton-seed oil, sesame oil and similar non-toxic vege-table oils, as described in Vegetable Fats and Oils by E.W. Eckey, Reinhold Publishing Corp., New York, 1954. The vegetable oil selected must, of course, fall within the required viscosity range of from about 100 to about 300 centi-poises. A particular vegetable oil falling within this range is NEOBFE M-5, a fractional triglyceride of coconut oil. It is desirable that the vegetable oil ingredient contain a minor amount of an antioxidant such as butylated hy-droxyanisole or butylated hydroxytoluene, preferably in an amount ranging fromabout 0.1% to about 3~ by weight, based on the weight of the vegetable oil employed.
The liquid vehicle of the dentifrice, together with the gelling agent (s) and other constituents, forms an extrudable mass of a non-dripping consistency when extruded from a collapsible tube, such as an aluminum tube.
Thus, by the addition of more vehicle, the dental cream can be thinned and conversely, by the addition of more solids, especially more gelling agents, ,; ~ - . - . :, :.; .,.; - .;: ,. : :, ~53~0 the products can be thickened. In most dentifrices, the liquid portion com-prises glycerine. Although it is preferred to employ glycerine, other suit-able vehicles in place thereof or in addition thereto may also be present, either with the mentioned polyhydric alcohols or in replacement for them.
Thus, propylene glycol, polyethylene glycol, and polypropylene glycol may be employed providing that they are physiologically acceptable and produce pro-ducts having a desired refractive index, in the case of the manufacture of visually clear dentifrices. Normally the proportion of vehicle is determined by the physical properties of the extrudate. Usually, however, from about 10 to 90% of the vehicle will be employed, with about 10 to 35% being a typical range for the production of opaque dentifrices and about 40 to 90% being use-ful for the manufacture of clear dental preparations.
It is to be understood that whiIe ordinarily where sorbitol or mannitol is employed in a dentifrice, it is used as an aqueous solution, they may be employed herein, with-the proviso, however, that it be substantially anhydrous ~i.e., crystalline).
The preferred liquid vehicle is an anhydrous humectant or oil selected from the group consisting of glycerine, propylene glycol, polyethy-lene glycol, polypropylene glycol, liquid light petrolatum, mineral oil, vegetable oil and suitable mixtures thereof.
The preferred gelling agents are selected from the group consist-ing of sodium carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl al-cohol, Irish moss, silica aerogel or mixtures thereof.
In the preparation of tooth powders, it is usually sufficient to adm~ mechanically, e.g., by milling, the various solid ingredients, in appro-priate quantities and particle sizes and thereafter carrying out procedures known in the art for containerization of the product.

:, ' , . '., ' , ` '''.,: . :' 53~) In chewable dental tablets the solids and liquids are proportioned similarly to the amounts in dental creams and the flavor is blended with the solids and liquids, and a waxy matrix such as polyethylene glycol having a molecular weight of about 6,000 by weight, generally in amounts of about 4-20 percent by weight, in order to facilitate the formation of a tablet of the desired size and shape.
The formulation of this invention includes an additional dentally acceptable, substantially water insoluble anhydrous polishing agent of the type commonly employed in dental creams. The polishing agents are usually finely divided water insoluble powdered materials. Preferably, they are from 1 to 40 microns, most preferably from 2 to 20 microns in particle sizes, with distribution of particle sizes being normal over the range. Representative polishing agents include, for example, dicalcium phosphate, tricalcium phos-phate, insoluble sodium m~taphosphate, aluminum hydroxide, colloidal silica, magnesium carbonate, calcium carbonate, calcium pyrophosphate, bentonite, etc., including suitable mixtures thereof. When employed, it is preferred to use a minor amount thereof, up to a maximum of 20% by weight of the formulation and preferably no more than 10%.
The above listing of polishing agents, and other listings of other constituents of the dentifrice composition to be given in the present specifi-cation are not intended to be exhaustive and therefore, for other materials of these types reference should be made to a standard handbook, such as Cosmetics:
Science and Technology, by Sagarin, 2nd printing, 1963, published by Inter-science Publishers, Inc.
Grganic surface-active agents are used in the compositions of the present invention to assist in achieving thorough and complete dispersion of the instant compositions throughout the oral cavity and render the instant ~ .

' ~5390 compositions more cosmetically acceptable. The organic surface-active material may be anionic, nonionic, ampholytic, or cationic in nature, and it is prefer-red to employ as the surface-active agent a detersive material which imparts to the composition detersive and foaming properties. Suitably such detergents are water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monosul~ated monoglyceride of hydrogenated coconut oil fatty acids, higher alkyl sulfates, such as sodium lauryl sulfate, alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate, higher alkyl sul-foacetates, higher fatty acid ester of 1,2-dihydroxy propane sulfonates, and the substantially saturated high aliphatic acyl amides of lower aliphatic ami-no carboxylic acid compounds, such as those having 12 to 16 carbon atoms in the fatty acid, or acyl radicals, and the like. Examples of the last mentioned amides are N-lauroyl sarcosine, and the sodium potassium and ethanolamine salts of N-laurGyl, N-myristoyl, or N-palmitoyl sarcosine which shou~ld be substantially free from soap or similar higher fatty acid material which tends to substantially reduce the effect of these compounds. The use of those sar-cosinate compounds in the dentifrice compositions of the present invention is particularly advantageous since these materials exhibit a prolonged and marked effect in the inhibition of acid formation in the oral cavity due to carbo-hydrate breakdown in addition to exerting some reduction in the solubility oftooth enamel in acid solutions.
Other particularly suitable surface-active materials include no-nionic agents such as condensates of sorbitan monostearate with approximately 20 moles of ethylene oxide, condensates of ethylene oxide with propylene oxide, condensates of propylene glycol ("Pluronics"), and amphoteric agents such as quaternized imidazole derivatives which are available under the trademark "Miranol" such as Miranol C2M.

,.

~1~53gO

Other suitable nonionic detergents are the condensation products of an ~-olefin oxide containing 10 to 20 carbon atoms, a polyhydric alcohol containing 2 to 10 carbons and 2 to 6 hydroxyl groups and either ethylene oxide or a heteric mixture of ethylene oxide and propylene oxide. The result-ant detergents are heteric polymers having a molecular weight in the range of 400 to about 1600 and containing 40% to 80% by weight of ethylene oxide, with an a-olefin oxide to polyhydric alcohol mole ratio in the range of about 1:1 to 1:3. These detergents are manufactured using well-known polymerization techniques under conditions of high temperature and high pressure. The olefin oxide and polyhydric alcohol usually are added to the reactor prior to the addition of ethylene oxide. These nonionic detergents may be mixed with similar nonionic detergents as well as other types of nonionic detergents described herein.
T here may also be employed olefin sulfonate detergents, typically long chain alkenyl sulfonates.
The a-olefin feedstock preferably contains olefins of 8-25 carbon atoms, most preferably 12-21 carbon atoms. The feedstock may contain minor amounts of other constituents, such as secondary or internal olefins, diolefins, cyclic olefins, aromatics, naphthalenes, and alkanes. Best results have been obtained when ~-olefins (where Rl is H) constitute a major proportion. A
typical olefin feedstock contains in the range of about 12 to 21 carbon atoms in the molecule and yields olefin sulfonates having excellent detergency properties. Especially good foaming characteristics have been obtained by the us~ of a feedstock whose ~-olefin content consists essentially of compounds of 15 to 18 carbon atoms.
The detergent material above produced, typically contains at least about 50% by weight of long-chain alkenyl sulfonate, up to about 33% by weight 539~
of hydroxy alkane sulfonate, and up to about 15% of impurities, such as long chain water-insoluble sultones, most of which impurities are characterized as being soluble in acetone.
The olefin sulfonate is generally employed in the form of its sodium salt. It is within the scope of this invention to use other water-soluble salts, for example, salts of other alkali metals such as potassium, salts of alkaline earth metalsJ such as magnesium and calcium, triethanolamine, salts and the like as well as mixtures of a salt such as a sodium salt with the free olefin sulfonic acid.
It is preferred to use from about 0.05 to 5% by weight and pre-ferably about 0.5 to 5% of the foregoing surface-active materials in the ins-tant oral preparations.
Various other compatible and suitable materials may be incorporated in the dentifrice formulations of ~his invention. Examples thereof are colo-; ring or whitening agents or dyestuffs, preservatives, silicones, chlorophyll compounds, ammoniated materials such as urea, diammonium phosphate and mixtures thereof and other constituents. These adjuvants are incorporated in the ins-tant compositions in amounts which do not substantially adversely affect the properties and characteristics desired and are selected and used in proper amount depending upon the particular type of preparation involved.
Antibacterial agents may also be employed in the oral preparation of the instant invention to provide a total content of such agents of up to about 5% by weight, preferably about 0.01 to5.~%,most preferably about 0.05 to 1.0%. Typical antibacterial agents include:
Nl-(4-chlorobenzyl)-N5-(2,4-dichlorobenzyl) biguanide;
p-chlorophenyl biguanide;

4-chlorobenzhydryl biguanide;

, ., ::

~: :

53~0 4 -chlorobenzhydrylguanylurea;
N-3-lauroxypropyl-N5-p-chlorobenzylbiguanide;
l-(lauryldimethylammonium)-8-(p-chlorobenzyldimethylammonium~octane dichloride;

5~6-dichloro-2-guanidinobenzimidazole;
N -p-chlorophenyl-N5-laurylbiguanide;
1,6-di-p-chlorophenyl b1guanidohexane;
1,6-bis(2-ethylhexyl biguanido) hexane;
5-amino-1,3-bis(2ethylhexyl)-5-methylhexahydropyrimidine;
and their non-toxic acid addition salts.
T he dentifrice may be prepared by suitably mixing the ingredients.
For instance in making a toothpaste, a gelling agent such as silica aerogel or Carbopol 934 and a preservative such as dried benzoic acid, and sweetener, if used, is dispersed with a humectant such as glycerine. Dental abrasive agents, including the anhydrous zeolite, surface-active agent and flavor are then separately added and uniformly dispersed. The toothpaste is then thoroughly deaerated (e.g., in vacuo) and tubed.
Preferably the amount of water-soluble essential flavoring oil is above 0.5% and below 2%. Strongly flavored toothpastes contain above about 1% of such flavoring oil, e.g., about 1.2 to 1.5%.
The following examples are given to illustrate this invention further. In this application all proportions are by weight unless indicated.

Dental Cream Ingredients %
Glycerin 59.59 ; Carbowax 600(~po]yethylene glycol of app.3.00 molecular weight of 600-Union Carbide) .. . , . , , . . : ~ - . ; : :-53~0 Benzoic acid 0.15 Na2P03F 0.76 Sodium zeolite 3A (anhydrous) 10.00 Silica aerogel (Syloîd 244) 4.00 Sodium lauryl sulfate 1.50 Peppermint flavor 1.00 Amorphous sodium alumino-silicate 20.00 The zeolite 3A was dried at 300C prior to incorporation into this composition.
The glycerin, carbowax, benzoic acid sodium alumino-silicate and the sodium monofluorophosphate are thoroughly mixed until uniform. The zeo-lite powder is added and mixed therewith until a uniform dispersion is obtained.
The silica aerogel, sodium lauryl sulfate and flavor are each separately added to the mixture and each is thoroughly mixed until uniformly dispersed in the cream. The mixing process takes place in a low humidity room. This dental cream is packaged in the conventional manner.
The resultant product exhibits thermal effects when used in the brushing of teeth as well as a concurrent two tone flavor effect in the mouth, ,., such as a burst of an initial flavor (ciDnamOn) which changes to another 20~ taste (mint) leaving a clean and refreshed feeling in the mou~and a feeling of smoothness on the teeth.
When 2 gms of this formulation are added to 1 ml water, the tem-perature rises from 72F to 76F.

Example 1 is repeated, but the zeolite content is increased to 15%
and the amorpho~s sodium alumino-silicate content is decreased to 15%.
2 grams of the above plus l ml H20 effects a temperature rise from : : ~ . ;

-~53~0 70F to 80F.

~ ample 2 is repeated, but the zeolite content is reduced to 12.5%
and the amorphous alumino-silicate content is increased to 17.5%.
2 grams of above product plus 1 ml H20 effects a temperature rise from 72F to 78F.

Example 3 is repeated but zeolite 4A is used and the zeolite con~
tent is increased to 20% and the amorphous alumino-silicate content is reduced to 10%.
- 2 grams of the above product plus 1 ml H20 increases the tempera-ture of the water from 70F to 82F.

Example 4 is repeated but the zeolite content is increased to 25%
and the amorphous alumino-silicate content is reduced to 5%.
. 2 grams of the above product plus 1 ml H20 raises the temperature of the water from 70F to 85F.

Example 5 is repeated but zeolite 3A is used and its content is reduced to 5% and the amorphous alumino-silicate content is increased to 25%.
2 grams of this product plus H20 to liquify the product at 72F
effects no increase in temperature, whereas 1 gm dried zeolite 3A plus water to suspend the zeolite resulted in a temperature rise from 72F to 88F.
~ ese examples clearly show that by increasing the amounts of zeo-lite in the dentifrice, a greater increase in the water temperature is obtained with a minimum temperature rise occurring with 10% zeolite. Accordingly, the dentifrice must contain a minimum o 10% zeolite and preferably 20-35% in order , , , , ~ , ~, . . : .

~lQ5390 to achieve optimum results. It is also noted that all the zeolites, regard-less of type, effect a similar elevation in the water temperature.
Other examples may be compounded wherein the flavor or flavors are changed to spearmint, eucalyptus, anethole, menthol, carvone, lemon~ oran-ge, etc., and the proportions varied over a 0.5 to 5% range, and preferably 0.5 to 2% for best taste effects.
S imilarly, examples may be formulated wherein other surfactants such as sodium-N-lauroylsarcosinate and any of the other listed surfactants or mixtures thereof are substituted for the sodium lauryl sulfateJ as well as other gelling agents, humectants or mixtures thereof.
The pH of the dentifrices is generally within the range of about 7 to 9.5.
It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention. The "Abstract" given above is merely for the convenience of technical searchers and is not to be given any .:~
weight with respect to the scope of the invention.

';
, ,, .t:

~ - 21 -'

Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An anhydrous heat releasing dentifrice which generates heat in the mouth and effects a two tone flavor change in the oral cavity comprising an abrasive system consisting essentially of a finely divided anhydrous crystal-line metal alumino-silicate having an appreciable heat of hydration and ca-pable of being reversibly dehydrated in amounts of about 10-50% by weight, said metal being selected from the group consisting of an alkali metal, alka-line earth metal, zinc, copper and mixtures thereof, and a minor amount of up to about 20% by weight of a finely divided anhydrous dental abrasive to de-crease the abrasivity and regulate the degree of heat generated by said den-tifrice, about 0.1 to 5% by weight of at least one flavoring agent, and about 20 to 75% of an anhydrous liquid vehicle.

2. A dentifrice according to claim 1, wherein the liquid vehicle is an anhydrous humectant or oil selected from the group consisting of glycerine, propylene glycol, polyethylene glycol, polypropylenge glycol, liquid light petrolatum, mineral oil, vegetable oil, and suitable mixtures thereof.

3. A dentifrice in accordance with claim 1, which additionally contains about 0.5 to 5% by weight of a surface-active agent.

4. A dentifrice in accordance with claim 2, which also includes a gel-ling agent selected from the group consisting of sodium carboxymethyl cellu-lose, hydroxyethyl cellulose, polyvinyl alcohol, Irish moss, silica aerogel, and mixtures thereof.

5. A dentifrice according to claim 4, which also includes about 0.5 to 5% by weight of a synthetic anionic surface-active agent.

6. A dentifrice in accordance with claim 5, which also contains a sweetening agent and wherein the flavoring agent is a flavoring oil in an amount of about 0.5 to 2% by weight.

7. A dentifrice in accordance with claim 1, wherein the dental abrasive is colloidal silica.