US3722752A

US3722752A - Self heating cosmetic

Info

Publication number: US3722752A
Application number: US00867897A
Authority: US
Inventors: D Kenkare; D Shumway
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1969-10-20
Filing date: 1969-10-20
Publication date: 1973-03-27
Anticipated expiration: 1990-03-27
Also published as: ZA706788B; CH548774A; BE757722A; NL7015370A; FR2064433A1; GB1295321A; DE2050554A1; ES384681A1; DK127838B

Abstract

A packaged self-heating cosmetic, such as a shaving cream, includes separate thermogenically reactive thio-di-alkanol or thio-di-lower alkoxy alkanol reductant and an oxidant, which converts the reductant to the corresponding sulfoxide or sulfone, which serves as a nonionic surface-active or solubilizing constituent of the heated cosmetic. Means are provided for dispensing the packaged reductant and oxidant from separate zones and mixing them together so that they react and heat pressurized shaving cream or other cosmetic product constituents with which the thermogenic reaction mixture is contacted. The reducing agent employed is preferably 2,2''-thiodiethanol or thiodiethoxyethanol and the oxidizing agent is aqueous hydrogen peroxide.

Description

Elite States Patent 1191 Kenkare et al.

[54] SELF-HEATING COSMETIC [75] Inventors: Divaker B. Kenkare, North Plainfield', Durland K. Shumway, Piscataway, both of NJ,

[73] As'signee: Colgate-Palmolive Company,. New

York, N.Y.

22 Filed: Oct.20,1969 21 Appl.No.: 867,897

52 U.S. c1. ..222/14 s, 424/45, 424/47, 424/73,252/s9 51 Int. Cl. .........B67d 5/60, A61k 7/14, A61k 7/00 Sawaki, Chem. Abst. Vol.66 (1967) page 94502c.

1 1 Mar. 27, 1973 Primary Examiner-Sam Rosen Attorney-Herbert S. Sylvester, Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, Thomas J. Corum, Richard N. Miller and Robert L. Stone [57] ABSTRACT A packaged self-heating cosmetic, such as a shaving.

cream, includes separate thermogenically reactive thio-di-alkanol or thio-di-lower alkoxy alkanol reductant and an oxidant, which converts the reductant to the corresponding sulfoxide or sulfone, which serves as a nonionic surface-active or solubilizing constituent of the heated cosmetic. Means are provided for dispensing the packaged reductant and oxidant from separate zones and mixing them together so that they react and heat pressurized shaving cream or other cosmetic product constituents with which the thermogenic reaction mixture is contacted. The reducing agent employed is preferably 2,2'-thiodiethanol or thiodiethoxyethanol and the oxidizing agent is aqueous hydrogen peroxide.

9 Claims, No Drawings SELF-HEATING COSMETIC Shaving creams and various other cosmetics have been known to be more effective and more pleasant to use when employed in a warm or hot condition than when applied at room temperature. In the past, such products had been heated or the body surface on which they were to be applied had been warmed by washing with warm water. Among the mechanisms used for generating heated foams, especially in the case of shaving creams, were electric machines containing agitators and resistance heaters. However, recently, with the advent of pressurized foam shaving creams, devices for heating the cream after it is dispensed from the pressurized container have been produced. Some of these utilizeheat transfer between the cream and hot water and others utilize electrical heating in the dispensing spout. Still other devices operate by heating the entire can of pressurized material before dispensing so that the product dispensed, although it loses some heat by vaporization, will be warm.

Although mechanical and electrical means for heating cosmetics, and shaving creams in particular,'have met with some measure of success, many of such devices available are expensive, unwieldy or inefficient in operation. Therefore, researchers have turned to chemical means for heating such products. Despite the difficulties of obtaining chemical systems which will be compatible with other cosmetic ingredients, of sufficient stability and heat-generating powerand that will be cosmetically acceptable to the consumer, a few systems have been discovered that can be utilized to produce heated cosmetics. Usually, the products will be pressurized or aerosol preparations in which the chemically reactive materials are maintained in separate zones and are dispensed together, with other cosmetic ingredients, to produce a heated product. Various chemical mechanisms may be employed to effect the desired thermogenic reaction but the most successful of these is oxidation. Other mechanisms include neutralization, hydration, hydrolysis, metathesis or other suitable exothermic chemical reactions.

Although the reactions mentioned are capable of generating heat and will warm the cosmetic being dispensed, care must be taken to assure that the byproducts of the reactants are cosmetically acceptable. Thus, many sulfur-containing materials are rnalodorous and destroy the appeal of the cosmetic, although they may be functionally effective. Some materials interact with other constituents of the cosmetic with iuhicl'l they are brought into contact and either destroy or adversely affect the functions of such ingredients. Others are toxic or dermatological irritants. Some reactant systems, although compatible and otherwise acceptable,-have to be employed in such proportions that use thereof is not practicable. In some instances, the systems do not lend themselves to use with dispensing apparatuses, which usually comprise separate zones, of which one is two to ten times as large as the other, with the larger zone including the major cosmetic ingredient. Even if the system is acceptable, commercially available and of low enough cost to make the use feasible, the reactants displace cosmetic materials and thereby add weight and volume to the product, without any corresponding cosmetic activity. In other words, in a given dispenser volume, some cosmetic material must be displaced by the thermogenic reactants, thereby diminishing the quantity of cosmetic that may be contained. For example, in the compositions of the U. S. Pat. No. 3,341,418, the byproducts are not functionallyuseful and occupy space designed for containing cosmetic to be dispensed.

In accordance with the present invention, there is provided a packaged self-heating cosmetic, such as a shaving cream, which includes separate thermogenically reactive thio-di-alkanol or thio-di-lower alkoxy alkanol reductant and an oxidant, such as an aqueous solution of hydrogen peroxide, which converts the reductant to the corresponding sulfoxide, and sometimes to the sulfone. The product produced is useful as a solubilizing constituent in the heated cosmetic or, in many cases, possesses surface active or detergent properties. In addition, an advantage of such product is that it is nonionic in nature. In cosmetic compositions, wherein ionic character may sometimes be indicative of skin-irritating properties and wherein ionic reactions between cosmetic constituents are to be avoided, this advantage can be important. In fact, in some cases wherein the cation, e.g., sodium, potassium, is a cause of skin irritation, it is desirable to replace it with a nitrogen-containing cation, such as an alkanolamine or an amine, e.g., triethanolamine, dipropylamine. The

use of such heavy weight cations adds additional,

materials to the cosmetic composition over and above those normally desired and increases the weight of the heat-generating chemicals. This can be avoided and the various advantages of the nonionic solubilizers or surface active agents can be obtained by the use in pressurized cosmetics of the thermogenic systems of the present invention.

The invention is effected by means of a plural compartment container or other suitable package in which the oxidant and reductant compositions are stored separately, until the intended time of dispensing, when they are simultaneously discharged from separate sources or compartments into contact with each other. At the time of such contact, there are present the other cosmetic or shaving cream constituents and the cosmetic is heated to a satisfactorily high temperature, as it is dispensed, or shortly thereafter. In some instances, where the heating proceeds somewhat more slowly, it may take from 5 to 30 seconds for appreciable warmth to be noted and the temperature of the cosmetic may not reach a maximum until 20 to 60 seconds after initial contact of the oxidant and reductant. P resently preferred formulations reach a maximum temperature within 12 to 18 seconds. Such a heating rate is preferred by many consumers. Instead of using a p ural compartment single container, a combination of containers or sources of oxidant, reductant and cosmetic material may be employed, wherein all three of these elements or suitable mixtures thereof are brought together at approximately the same time, when dispensed. 1

In preferred embodiments of the invention the reductant is 2,2'-thiodiethanol, preferably in a composition with other cosmetic or shaving cream constituents, and the oxidant is an aqueous solution of hydrogen peroxide, kept separate from the other cosmetic constituents until the time of dispensing. However, other dialkanols and oxidizing agents are also useful and may be preferred in particular circumstances.

The plural compartment dispensers which are employed are well known and are commercially available. In these dispensers, a single container usually includes a main compartment of a generally cylindrical shape which contains liquefied gas and other ingredients, plus a smaller compartment or sac, which is collapsible under the pressure of the liquefied gas, as the contents are dispensed. A valve communicates with the contents of the compartments by means of dip tubes or suitable connections and allows simultaneous dispensing of the contents, when opened. Such valve or plural valves, as the case may be, are actuatable by movement of a spout or other dispensing member. Usually, the contents of the compartments are led through the spout member, wherein they are mixed, and then are discharged from it in heated form, ready for use. A suitable dispenser is illustrated in U. S. Pat. No. 3,325,056, wherein the mixing of the reactive components occurs internally. However, it is preferred for such mixing to be effected externally of the container, preferably in the spout member. In addition to the integral dispensing container, one may also employ combinations of dispensers, each of which contains one of the reactive materials, which combination may be such as that illustrated in U. S. Pat. No. 3,451,593.

The proportions of oxidant and reductant used will normally be about stoichiometric. However, in some circumstances, where it is desired to force the reaction by employing an excess of one or the other of the reactants, or where it is desired that the final composition be either of a reducing or oxidizing character, an excess, such as percent, of either oxidant or reductant may be employed. Generally, such excess will be no more than percent of the stoichiometric quantity, and preferably, in the usual case, approximately stoichiometric proportions will be used. The stoichiometric proportions referred to are with respect to reactions for making either the sulfoxide or sulfone. Thus, the mole ratio of hydrogen peroxide to thio-di-alkanol or the corresponding alkoxy alkanol may be from 0.75 to 2.5, depending on whether the sulfoxide or sulfone reaction is to be utilized.

The temperature to which the present cosmetic will be raised is usually controlled by valve design, viscosities of the constituents of the oxidant and reductant compositions, the specific identities of the oxidant and reductant employed, and their proportions. Usually such temperature will be from 100 to 160F., preferably from l20 to 150F. and most preferably from 130 to 145F. Thus, the increase in the temperature of the cosmetic over room temperature will usually be from to 100F. and most often will be about 60 to 80F. Although heating to such temperatures is effected substantially all of the time, nevertheless, the use of the present invention to dispense the materials at other temperatures is contemplated, when the situation demands.

The thio-di-alkanols and derivatives thereof which are used as the reducing agents in the preparations of this invention may be characterized as being of the formula OHRS-R'OH wherein ROH and R'OH, which may be the same or different, are either hydroxyalkyl or lower alkoxy hydroxyalkyl groups including poly-lower alkoxy hydroxyalkyl. The hydroxyalkyls are generally of two to 20 carbon atoms, and the corresponding alkoxy hydroxyalkyls are of four to 20 atoms in the chain. Although the hydroxyl groups are considered to be terminal in preferred compounds, intermediately hydroxylated groups are useful reductants too. The shorter the chain, the more solubilizing activity will normally be possessed by the sulfoxide or sulfone produced, as well as by the reductant. The longer the chain, the more detersive will be the action of the products. Still, short chain length materials are preferred in most cases because of the greater heatgenerating capacities that they possess. Thus, the lower alkylene and lower alkoxy groups preferred are those of 2 to 4 carbon atoms and most preferably are of two carbon atoms. Exemplary thereof are: CH CH -CH -CH CH CH(CH )CH CH CH -CH -CH Among the higher alkanol and lower alkoxy higher alkanol-containing compounds are 2,2'-thiodi-ndodecanol; 2,2-thiodi-n-stearyl alcohol; 2,2'-thiodi-noctanol; 2,2'-thiodioleyl alcohol; 2,2-thiodi-ethoxy propoxy-n-dodecanol; and 2,2-thiodi-(ethoxy) -ndodecanol. Specific examples of the preferred thiodialkanol and corresponding alkoxy-containing reducing agents wherein the alkanol is of up to four carbon atoms and the alkoxy is of up to four carbon atoms, with the chain being of 2 to 11 atoms, include HO CH CH,S-CH CH OH; HO-Cl-l CH(CH S-CH(CH -,)CH,OH; HO(CH,) S(CH,);,- OH; HO(CH S(CH 0H; fro-omen, OCH CH SCH CH OCH CH OH; HO (CH CH O) CH CH SCH CH (CH CH O) a) 2 ]a( 2)2 2)2[ OCH,CH(CH --OH; and HOCl-l,Cl-l OCH Cl-l S(CH CH O) CH CH OH.

In addition to the above-recited compounds, when desired, substituted derivatives thereof may be employed, such as those wherein hydrogen atom(s) of an alkylene group or groups is replaced by a non-interfering radical, such as nitro, amino or hydroxy. Up to three such substituents may be present in the molecule of reductant. Halogenated, e.g., chlorinated and brominated, derivatives should be avoided. In some instances, where otherwise compatible with the formulations, salts of the alcohols may be employed, such as the alkali metal, alkaline earth metal, ammonium,

amine, e.g., lower alkylamines andalkanolamines, e.g., mono-, di-, and tri-lower alkanolamine salts. Of such salts it is preferred to employ the sodium, potassium, triethanolamine, triisopropanolamine, triethylamine and magnesium salts. However, usually the reductant will be added to the preparations as an alcohol rather than as a salt. Although not presently preferred in the cosmetic preparations of this invention, the 2,2-thiodialkanol reductant may be chemically modified by reaction with two molar proportions of an acid anhydride, such as succinic anhydride, maleic anhydride or phthalic anhydride, to produce a di-ester-acid. Such product can be changed to the sulfoxide or sulfone by reaction with oxygen and additionally, in those cases where desired, can be neutralized. Thus, by employing an alkaline oxidizing agent, heat may be generated by both the oxidation and neutralization reactions.

When reacted with hydrogen peroxide or suitable oxidant, the thiodialkanols (this term also applies to the corresponding alkoxy compounds) generate heat rapidly and efficiently, especially in the presence of catalysts for the redox reaction. In addition to this, however, the products of the reaction, either the preferred sulfoxide or the sulfone, may include short chain alcohol or alkoxy alcohol groups which are solu-' bilizing in their activity. When the chain of atoms between the hydroxyl 'and sulfur is from 2 to '6 in number, the compounds exert a solubilizing activity, due to their hydrophilic nature. When more than six atoms are in such chain, they assume surface active properties, in addition to their solubilizing functions. When the chain is of 12 to 22 atoms the product is detersive. Thus, the product of the redox reaction serves a useful function in the cosmetic or shaving cream preparation, increasing its degree of homogeneity by helping to solubilize various constituents thereof. It also improves the wetting effect of the product and may increase detergency. This is done without introducing cations into the composition and without increasing the molecular weight of the reducing agent to an objectionable extent. Of course, by mixing the various long and short chain thiodialkanols of this invention or by making different chemical compounds containing both the longer and shorter chains, properties of the reducing agent may be controlled so as to be most preferable for the particular formula employed.

The thiodialkanols may be made by reaction of hydrogen sulfide and the appropriate alkylene oxides, alkanols or alkoxy alkanols, according to 7 known techniques. Alternatively, the thiodialkanols can be reacted with alkylene oxide. These reactions result in the production of no undesirable byproduct. The compounds made, although they contain sulfur, are not objectionably malodorous when converted to the sulfoxide or sulfone and can be employed in cosmetic compositions without destroying or overpowering sensitive perfumes and other cosmetic constituents.

The oxidizing agent which is reacted with the thiodialkanol or thiodialkoxydialkanol may be any suitable such material which converts the sulfide to sulfoxide or sulfone and generates enough heat to increase appreciably the temperature of the cosmetic being dispensed. A great varietyof organic and inorganic oxidizing agents may be employed but it is preferred to use per-compounds. Of these, the inorganic per-compounds (which term is employed in this specification to describe oxygen-releasing compounds, also referred to as per-oxygen compounds) are preferred, especially those which are converted to innocuous or useful byproducts. The best of these appears to be hydrogen peroxide, preferably utilized in stabilized aqueous solution. However, other per-compounds such as sodium peroxide, sodium perborate, potassium percarbonate, sodium persulfate, and urea peroxide may also be satisfactorily employed. Such per-compounds are preferably used as their alkali metal, alkaline earth metal or other metal salts, referred to as per-salts. In addition, materials which release hydrogen peroxide are oxidants useful in the practice of the present invention. Of course, mixtures of these may be utilized to adjust properties or obtain special effects. Hydrogen peroxide is a preferred oxidizing agent, usually in stabilized aqueous solution, because the byproducts of the oxidation reaction are limited to water, when the oxygen is entirely consumed in converting the sulfide to sulfoxide or sulfone. Of course, water is a normal and desired constituent of cosmetic compositions, including shaving cream, and does not add irritating cations or other possibly interfering ions to the product.

Similarly, the water and sulfoxide or sulfone, in combination, help to solubilize cosmetic ingredients and improve the surface activity of the final preparation. The sulfoxide or sulfone, not containing any salt-forming ions, also avoids the possibly irritating and insolubilizing effects of such materials in cosmetics.

The oxidizing agent used is preferably a separate I aqueous solution, not in contact with the other cosmetic and reducing agent constituents of the present preparation until the time of dispensing. There are times when the oxidizing agent may be present with some of the cosmetic materials but these are not the usual cases. The concentration of the oxidant in water may be varied widely, depending on the particular preparations involved. However, usually from 3 to 30 percent of the per-compound will be employed. When hydrogen peroxide is used this will be from 5 to 30 percent and preferably from 8 to 20 percent, with the most usual concentrations being 9 to 15 percent of the hydrogen peroxide in aqueous solution. Use of such higher concentrations aids in keeping container size as small as possible or, stated differently, having a maximum amount of cosmetic contained therein, accompanied by maximum freedom in formulation. Of

course, present with the hydrogen peroxide solution maybe minor proportions of sequestrants, chelating agents and other stabilizers, such as nitrilotriacetic acid or its'trisodium salt, ethylene diamine tetraacetic acid or a salt thereof, stannic chloride, silicates or other known compounds useful to stabilize hydrogen peroxide.

The speed of the redox reaction between the peroxide and the thioalkanol reducing agent is significantly increased by the presence of metal catalysts. Thus, tungstates, molybdates and uranates, and other salts and catalytic materials for, such oxidation reactions, which may operate by activating the peroxide, may be used to increase the reaction efficiency of a redox system employing per-compounds, such as hydrogen peroxide, as the oxidant. Usually, the alkali metal or ammonium salts are used, e.g., ammonium molybdate,

potassium tungstate, or sodium uranate. Because metals that activate hydrogen peroxide systems might also act to convert the hydrogen peroxide to a less stable form, in following the present invention the catalyst will usually be present in the zone containing the thiodialkanol and will not contact the stabilized peroxide until the thermogenic reaction is to be effected. Although the redox reaction will proceed and heat will be generated without use of a catalyst, for rapid generation of heat, in preferred embodiments of the invention, a metal salt catalyst for the redox reaction will usually be employed. Such catalysts are known as those which activate the decomposition or reaction of hydrogen peroxide.

The other components of the cosmetic compositions within the present invention are those known to the cosmetic art to impart desired properties for particular cosmetic purposes. Most cosmetics and shaving cream preparations include both hydrophilic and lipophilic components, often together with emulsifying or wetting agents to help convert them to a stable uniform emulsion. For example, in a hand cream the lipophilic phase may include lanolin, mineral oil, stearic acid, petrolatum, animal fats, vegetable and petroleum waxes and emollients. The aqueous cosmetic phase may contain water, glycerol, solvents, buffers, depilatories, bleaches, waving agents, astringents, stabilizers, deodorants, antiperspirants, or other acitve materials. Soaps or synthetic organic emulsifiers, surface active agents and detergents may also be present in the aqueous phase and assist in maintaining the emulsion form. Of course, some materials, are present in both phases, the greater proportion usually being found in that phase in which the material is most soluble. In some cases, solutions may be used instead of emulsions. The material dispensed may be in any of several physical forms, including liquid, paste, gel or foam. Foams may be created by the action of a dissolved pressurized or liquefied gas dispersed throughout the composition. The gas expands the composition as the pressure on it is released, thereby creating the foam. Preferably, for most cosmetic compositions and especially for shaving creams, a stable foam form is employed, although sometimes one which is easily reduced to a liquid may be preferred.

In shaving preparations, the shaving emulsion dispensed from one compartment of a pressurized container comprises a major proportion, up to about 95 percent of water, usually 50 to 75 percent, and the rest of the material includes soap or other beard softeners, solvents, solubilizers, emulsifying, wetting and conditioning agents. The soap is preferably a stearic acid soap, made from commercial double or triple pressed stearic acid. However, other higher fatty acid soaps, such as those of tallow, coconut oil, corn oil, cottonseed oil, animal greases and other animal fats and vegetable oils may be employed. Usually however, a major proportion of the soap-forming fatty acid of the soap should be of 16 to l8 carbon atoms. The cation of the soap is preferably an alkanolamine, such as triethanolamine, although other tri-, di-, and mono-alkanolamines of one to four carbon atoms per alkyl group are useful, such as diisopropanolamine. If desired, alkali metal soaps, such as sodium and potassium soaps may be employed, as may be ammonium and lower alkyl amine soaps. For best results in producing a soap which does not irritate the skin after shaving and which is fluid enough so as to be dispensed entirely from the container, a triethanolamine soap is used. Minor proportions of sodium and potassium soaps may be added to help stabilize the lather. When superfatting effects are desired, the fatty acid employed, from which the soap is made, may be only partly neutralized by the cation of a neutralizing agent, leaving the free fatty acid present to exert its emollient effect upon the skin. Usually, in such cases the free fatty acid will be from 0.5 to 30 percent, preferably 10 to 25 percent of the soap content.

Alkylolamides also have a conditioning effect on the hair and skin, in addition to their property of stabilizing foams of cosmetic compositions. lncludcd in the alkylolamide groups are dialkylolamides, such as coconut oil fatty acids diisopropanolamide, lauricmyristic diethanolamide, and other alkylolamides wherein the acyl groups are of 12 to 18 carbon atoms, preferably with 50 percent by weight or more being of 12 to 14 carbon atoms. The alkylol groups are preferably of one to three carbon atoms each. Although desirable in many cosmetic compositions, often the functions of the alkylolamides may be performed by other ingredients or may be unnecessary, in which cases the alkylolamides may be omitted. Suitable substitutes for them as thickeners for foams are the higher fatty acid monoglyceride sulfonates at concentrations of0.l to 1.5 percent.

Various suitable emulsifying or surface active agents may be important ingredients of the present products. These include the nonionic, anionic and cationic compounds. Of these materials it is preferred to use the nonionics to the exclusion of anionics and cationics, except of the soap, and of the nonionics the most preferable group is that of the higher ethers of lower alkoxylated alkyl phenols and of higher fatty alcohols. These compounds, known commercially as lgepals, a trademark of GAF Corporation, usually have an alkyl group of six to 10 carbon atoms on the phenol ring and the degree of alkoxylation (ethoxylation) is from one to 50,

preferably of l0 to 40 ethoxy groups per molecule, with the higher fatty alcohol being of 10 to 18 carbon atoms per molecule, usually averaging about 12 carbon atoms. Other nonionic compounds, such as esters of higher fatty acids and ethoxylated alcohols, condensates of groups of higher ethylene oxide polymers and higher propylene oxide polymers, and esters of ethoxylated fatty acids and sugar alcohols or'hexitans are representative of the nonionics that may be included in the present formulation. Among the anionic surface active agents are the higher alkyl sulfates and alkyl sulfonates, the higher alkyl benzene sulfonates, ethoxylated fatty alcohol sulfates, monoglyceride sulfates, higher fatty acid amides of amines, such as sodium lauroyl sarcoside, phosphates corresponding to the abovementioned sulfates, and sulfates and sulfonates of the mentioned nonionic compounds, where possible. Among the cationic surface active agents may be mentioned the quaternary ammonium and phosphonium compounds, e.g., trimethyl benzyl ammonium chloride, cetyl trimethyl ammonium bromide and lauryl pyridiniurn chloride, all of which exert antiseptic, as well as surface activity. Other emulsifying and surface active agents are described in Cosmetics Science and Technology, by Edward Sagarin (lnterscience Publishers, 1957),

particularly at pages l006l008, 1060-63, 775 and 776. This text also contains descriptions of other cosmetic materials, such as various active ingredients, solvents, emollients, liquefiable gas propellants, conditioning agents, soaps, fatty materials, etc. i

In self-pressurized aerosol" compositions a liquefied gas, such as lower hydrocarbon or a lower halogenated hydrocarbon, may be employed to aid in discharging the oxidant and reductant portions of the cosmetic preparation. Especially when the liquefied gas is emulsified into one or both ofthe portions of the cosmetic, it will assist in generating a foam as .the liquefied propellant is converted to minute gas bubbles. If it is desired to avoid using hydrocarbons or halogenated hydrocarbons, they may be-replaced with compressed nitrogen, carbon dioxide, the inert gases or other non-liquefied gas, which provides the force to discharge the oxidant material. Among the liquefied gas propellants which may usually be employed are the lower hydrocarbons of three to four carbon atoms, which include 'n-butane, isobutane and propane, preferably employed as a mixture of isobutane and propane, preferably 85 to 90 parts isobutane and 10 to 15 parts propane. The halogenated hydrocarbons are preferably those which are at least partially fluorinated, including monochlorotrifluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, monochloropentafluoroethane, trichloromonofluoromethane, tetrachlorodifluoroethane, and similar chlorofluorohydrocarbons, having one to three carbon atoms per molecule. Of course, mixtures of the halogenated hydrocarbons are also employed, desirably to regulate the pressure developed, solubilizing properties, corrosion prevention, emulsion formation, and so forth. In some instances it may be preferable to utilize completely chlorinated or fluorinated hydrocarbons as propellants or diluents, e.g., methylene chloride, where they are acceptable.

Cosmetic compositions contain adjuvant materials to make the product aesthetically acceptable or specially appealing. Perfumes, dyes, pigments, emollients, solvents, thickeners, solubilizers, humectants, buffers, antiseptics, foaming agents, preservatives and similar materials, generally in minor proportions, usually less than percent each and preferably less than 2 percent each and most preferably less than 1 percent each, with the total thereof being less than 25 percent, preferably less than percent and most preferably less than 5 percent of the composition, are often employed.

As emollients or solvents it is preferred to employ polyhydric alcohols of three to six carbon atoms per molecule, having three to six free hydroxyls per molecule. Exemplary of such compounds are glycerol and sorbitol, although other alcohols such as pentaerythritol, mannitol and other sugar alcohols are also used. Of course lanolin and derivatives thereof may also be present.

The proportions of various other constituents of the present compositions are regulated to a large extent by the type of composition being prepared. Usually for cosmetic compositions there will be present from 2 to 50 percent of the active cosmetic ingredient, although more or less may also be employed in special cases. There will also usually be employed from 5 to 90 percent solvent or dispersion medium and from 1 to 50 percent of surface active agent, which group includes soaps. In some circumstances, as in shaving creams, the active ingredient and the surface active agent may be the same, since one compound serves both functions. In pressurized compositions, there will usually be present from 3 to 90 percent of liquefied or compressed gas. Of course, the given proportions apply to most cosmetics,,but it must be realized that for certain compositions proportions outside the given ranges may also be acceptable, even preferred.

Pressurized shaving creams of this invention preferably contain from 50 to 85 percent water, more preferably 65 to 80 percent, 1 to percent of synthetic organic surface active agent, exclusive of that produced by the redox reaction, preferably 2 to 8 percent thereof, or 8 to 35 percent, including such surface active or solubilizing product, and 5 to 20 percent soap,

preferably 8 to 15 percent thereof. There may also be present 2 to 20 percent of humectant, such as glycerine or sorbitol, which may alsoexert a solvent action in the composition. Of course, when the products of the thermogenic reaction also act as humectants, as they often do, or when humectant activity is not considered to be needed, such materials may be omitted. In most compositions minor proportions of foaming agent and perfume, both usually within the range of 0.1 to 5 percent and preferably, from 0.3 to 1 percent are often utilized. In heated shaving creams the soap solution will usually include from 5 to 40 percent, and preferably from 8 to 20 percent of the thiodialkanol reactant (this term applies to those containing alkoxy groups, too), but the thiodialkanol compound may also be separately dispensed. Together with the thiodialkanol or separately dispensed will often be present 0.2 to 2 percent, preferably 0.3 to 1 percent of molybdate or tungstate catalyst, or other suitable catalyst for the reaction in desirable amount. The hydrogen peroxide contained in the separate compartment to avoid premature contact with the reductant will usually be from 2 to 10 percent of the weight of the soap solution and will be present as an aqueous solution of from 5 to 30 percent strength.

The hydrogen peroxide solution is usually from 10 to percent of the soap solution weight and is preferably about 20 to 50 percent thereof.

The pH of shaving preparations is normally regulated to be on the alkaline side and is preferably no higher than 10.5. Thus, it is preferable to employ compositions having a pH of 7 to 10, and most preferably 7.7 to 8.7, although those of pH from 5 to l 1 may also be used, when desired for a particular type of application. The pH may be regulated by use of compatible buffers, such as acid-base, salt-base and acid-salt mixtures, e.g., including borates, phosphates, carbonates, sulfates or silicates, or other acceptable inorganic or organic salts, including salts of alkylolamines. The soap or soaps present in the shaving compositions and the sulfoxides or sulfones produced in the thermogenic reaction may exert buffering effects and the soaps may be the primary buffers present.

The cosmetic preparations of this invention are made by simple methods known to the art. The various constituents of the cosmetic portions of the preparations themselves may be combined in the normal manner and then, depending on the nature of the cosmetic, may be further formulated with either the oxidizing agent or the reducing agent employed. If the cosmetic preparation is essentially oxidizing in nature, it will preferably be combined with the oxidizing agent. The reverse situation is also applicable and in most cases, the cosmetic will have the ingredients thereof packed together with the reductant and catalyst, with the oxidant being separately packaged, usually in a different compartment of the dispenser. If some of the constituents of the cosmetic are oxidizing and others are reducing by nature, the composition may be formulated by such parts and one part may accompany the heat-generating oxidant and the other may be stored with the reductant. The main consideration is that no unwanted oxidation-reduction should occur due to premature combination of a heat-generating chemical of this invention with a cosmetic ingredient. Of course, if so desired, the oxidizing agent and the thiodialkanol may be kept separate and not formulated with any other cosmetic component. In such situations, the cosmetic may be separately dispensed from a container and only brought into contact with the heat-generating chemicals upon discharge from the container. In such an arrangement a three-compartment container may be employed or three or other number of separate containers may be used in conjunction.

Self-heating cosmetic preparations of this invention include various compositions intended for application topically to the human body. Usually these are applied to the skin or hair. They include face creams, body tions, depilatories, tanning agents, antiperspirants, sunscreens, personal deodorants, hair creams, hair lotions, hair gels, shampoos, dyes, bleaches, rinses, shaving creams, makeup preparations, bath oils, facial treatments, astringents, aftershave lotions and many other related preparations. In most of these, nonionic surface active agents or solutilizers are important or useful constituents, either as wetting agents, emulsifiers or solvent aids. By the method of the present invention, such compounds are prepared in the dispensing of the cosmetic during the heating thereof and are immediately solubilized or dispersed in the cosmetic, partly due to the heat generated in the exothermic reaction which produced them. The heat generated produces small currents in the cosmetic being dispensed which help to distribute the surface active or solubilizing sulfone or sulfoxide and by distributing it throughout the composition, the ease of wetting the various areas of the cosmetic preparation and solubilizing constituents is further increased. The heat generated also helps further to solubilize cosmetic preparation ingredients and thereby improves homogeneity of the product. This coaction between the surface active agent produced, the heat generated and the other cosmetic preparation ingredients is a useful result of the present invention and helps to avoid poorly dispersed ingredients or products of the exothermic reaction. The surface activity of the thermogenic product made also helps to distribute throughout the cosmetic the water and other byproducts of the heating reaction and thereby effects a better and more even heating of the cosmetic. Thus, pockets of undispersed materials in the cosmetic are avoided and final product is uniform.

The use of the present reductant-oxidant system for generating heat in cosmetic preparations being dispensed allows the employment of relatively small quantities of reductant to generate sufficient heat to raise the temperature of the cosmetic appreciably. Of course, as the molecular weight of the reductant becomes greater, and the heat of reaction does not increase proportionately, more reductant will have to be used. Nevertheless, the heat developed will be sufficient to satisfactorily warm cosmetics, even with the higher molecular weight thiodialkanols. It will be noted from a review of the specification and the examples which follow that it is preferred to employ approximately the stoichiometric quantity of oxidizing agent to react to produce the sulfone from the thiodialkanol. Most of the heat developed is from the reaction which produces the intermediate sulfoxide and in some instances it will be possible and desirable to stop the oxidation reaction at this stage. Thus, less peroxide will be needed to generate a given amount of heat. Although it might be desirable to produce only the sulfoxide, often enough oxidizing agent is employed to make the sulfone, to assure that all of the thiodialkanol will be converted to sulfoxide and that all the heat of such reactions will be obtained. If the reaction is stopped at the sulfoxide stage, it may sometimes be desirable to add extra reducing agent to the cosmetic composition so as to raise the temperature even higher. This will be made possible by the more efficient use of oxidizing agent, since often the smaller sac or zone of a dispensing container in which the oxidizing agent is contained is of a fixed volume and thereby results inthe oxidizing agent being the limiting factor with respect to heat generation.

The sulfoxides and sulfones are of acceptable odor and therefore, the reaction is not critical with respect to such degree of completion and acceptability of product from an aesthetic viewpoint. Furthermore, the nonionic materials produced, in addition to performing the useful functions set forth earlier, chemically resemble the nonionic surface active agents which are frequently employed as emulsifiers, wetting agents, solubilizers or detergents in the present cosmetics. Similarly, they bear a resemblance to the anionic materials, insofar as the sulfone or sulfoxide is concerned, since many anionics are sulfonates or sulfates. The chemical resemblances to other constituents of the cosmetic indicate improved compatibilities with these materials.

The oxidants and reductants are low in corrosivity toward ordinary materials of container construction, such as tinplate or steel coated with resins commonly used for that purpose. Thus, blockages of valve parts are not encountered, due to corrosion byproducts being released into the cosmetic being dispensed through the valve. In addition to low corrosive action, the present oxidants and reductants are remarkably compatible with normal cosmetic ingredients and do not form undesirable products that would adversely affect the cosmetic properties of the preparations. It is considered to be important in many cases that the products of the exothermic reaction are not gaseous, since the present systems are thereby made useful for liquids, emulsions and creams, as well as foams. Of course, by use of propellants, such as liquefied gases,

emulsions may be dispensed as foams and liquids may be dispensed as sprays, when desired. Here again, it is often important that the present exothermic compositions not change the foaming activity of the liquefied gases or other foaming agents, so that the foaming obtained can be pre-planned, being dependent on the ingredients of the composition used, without being affected by additional gases produced in the heating reactions. Thus, except for the expansion of the foam on heating, the ordinary proportions of foaming agents or spraying agents may be used with the cosmetics. Of course, the heat expansion does increase foam volume and can help save propellant, to some extent.

The lack of gas production in this reaction is a protective feature of the invention because accidental rupturing of a sac containing a reactant will not result in gas generation. If it did, the pressure created could cause the container to explode. It has been found that the present exothermic reaction, even if initiated due to sac leakage, will not cause such explosion.

Although all the above-mentioned properties are of importance in producing a satisfactory self-heated cosmetic, a most important property is low toxicity of the heat-generating chemicals. The present materials are low in toxicity and are suitable ingredients for cosmetics. Another very important property of cosmetics is an acceptable odor. The present materials are of low odor and are aesthetically acceptable. This is important when it is considered that many other sulfurcontaining "reducing agents, such as thiourea, for instance, can be oxidized or otherwise converted to malodorous products, thereby making useless any cosmetic in which such reaction occurs. I

With all the above advantages, the present oxidant and reductant are available commercial materials and are comparatively inexpensive. The reductant costs much less than other comparable" organic materials suggested for use in exothermic aerosol products. For example, the present materials are of approximately half the cost of those suggested in U. S. Pat No. 3,341,418 and in addition, of course, perform useful functions in the final cosmetic compositions. Such additional utilities, without additional expenses, further diminish the effective costs of these'reductants.

The following examples illustrate some preferred compositions within the present invention. Of course, such examples are not to be considered as limiting the invention, because they are only exemplary thereof. Those of skill in the art will know how to replace various constituents and procedural steps of the invention with corresponding equivalent materials or operations without departing from the principles or teachings imparted herein. Unless otherwise stated, all parts are given by weight.

EXAM PLE 1 Parts Stearic acid (double pressed) 10.5 Nonyl phenyl polyoxyethylene ethanol of 5.0 30 oxyethylene groups per mole (lgepal CO-880) Laurie myristic diethanolamide 0.5 Trithanolamine 5 .0 Water (deionized) 64.3 2,2'-thiodiethanol 10.0 Sodium tungstate aqueous solution) 4.0 Perfume 0.7

The stearic acid, lauric myristic diethanolamide and nonyl phenyl polyoxyethylene ethanol are mixed together and heated to 185F. The triethanolamine and water are combined and heated to the same temperature and both portions at 185F. are combined. The emulsion produced is cooled to F. and the perfume, 2,2'-thiodiethanol and sodium tungstatesolution are added and the product is cooled further to 80F. This portion of the cosmetic preparation is then added to the larger compartment of a plural compartment dispensing container. Next, 25 parts of a 14 percent hydrogen peroxide solution (aqueous) are filled into the smaller compartment of the dispenser, which is a plastic sac. Both the larger and smaller compartments communicate with a dispensing valve or valves. Such valve is then staked into place at the outlet of the dispensing container and 40.0 parts of liquefied gas propellant are pressure filled into the larger compartment, to desired operating pressure (about 40 lbs./sq. in.). Of course, the gas exerts pressure on the contents of both compartments. The hydrocarbon propellant employed is a mixture of 83.5 percent isobutane and 16.5 percent propane. Immediately after manufacture is completed, the pressurized thermogenic shaving cream is ready for use.

The thermogenic shaving cream made has a good shelf lifeand will not destroy the perfume or lose heating strength to a significant extent during reasonable storage. The product is pleasant to use and the heated cream dispensed when the dispensing spout is depressed and the valve ports are opened is an effective softener for the beard and a good lubricant for the razor. Shaving is almost effortless with this product. The temperature at which the cream is used is l40F., the temperature to which the cream is raised shortly after dispensing (within 15 seconds). The cream is pleasantly perfumed and the lime perfume odor is not affected by any malodor. The lather produced is of excellent stability and is superior in this respect to previously known hot lather aerosol shaving creams.

Similar results are obtained when the amounts of oxidant and reductant are increased and decreased, within a 25 percent variation, but temperature variations are noted. Thus, when the hydrogen peroxide is decreased to 20 parts and the thiodiethanol is decreased to 8 parts the temperature of the shaving cream is raised only to about F., whereas when the amounts are increased to 30 and I2 parts, respectively, the cream is heated to over F. When the ratios of oxidant to reductant are changed, by up to 25 percent, with the weight of one material being approximately that of this example, heating is improved when the effect is to add reactant and is worsened when the opposite result is attained. Concentrations of the oxidant can be changed from 8 to 20 percent in water, without affecting the heat generated, if the amount of hydrogen peroxide remains substantially constant. When other oxygen-releasing materials such as urea hydrogen peroxide, sodium perborate, potassium persulfate and other per-compounds are employed instead of the hydrogen peroxide, in aqueous solution, the reaction also goes and the shaving cream dispensed is heated to approximately the temperature herein obtained, providing that stoichiometric replacement proportions are present. Such comparable effects are also obtained when the 2,2'-thiodialkanol is replaced with an equivalent heatgenerating amount of the other thiodialkanols, including those which are alkoxylated. With the more highly alk-oxylated and longer chain alkanols the product of the thermogenic reaction also adds surface active and detersive as well as solubilizing activities to the cosmetic produced.

In the absence of a catalyst for the redox reaction the heating is somewhat slower but is still useful for cosmetic purposes. Of course, when the sodium tung- I state is replaced by the equivalent amount of ammonium molybdate, potassium uranate or other redox catalyst suitable for use in the present cosmetics, the development of heat is accelerated and is comparable to the action noted in the preparation of this example.

EXAMPLE 2 Stearic acid 13.0

Nonyl phenyl polyoxyethylene ethanol of 30 polyoxyethylene groups per mole Lauric myristic diethanolamide Triethanolamine Water 9 2,2'-thiodiethanol 1 Sodium tungstate (10% aqueous solution) Perfume Hydrogen peroxide (10% aqueous solution) Propellant (5:1 isobutanepropane mixture) This formula is prepared in the same manner as described previously in Example 1. The product resulting has approximately the same properties except for the temperature generated by the thermogenic reaction being lower, approximately at l30-l 35F. The shaving cream is effective in wetting the beard and softening the hairs thereof. It is as stable as the cream of Example 1 and is satisfactorily shelf stable.

When, instead of the shaving cream base of the present example, there is used with the oxidant-reductant combination, catalyst and propellant another cosmetic base, such as a shampoo, depilatory, facial cleanser, sun-screening preparation, skin or hair conditioner, sunburn cream hair dye or other colorant, cold cream or another preparation described or suggested in this specification, a corresponding heated product results, with the temperature thereof being from 120 to 150F. Of course, in the appropriate formulations there may be added various other ingredients, in addition to the active agents, such as thickeners, anti-foam agents, foaming agents, detergents, stabilizers, etc., as will be known to those of skill in the art. The product may be dispensed as foams or as sprays, readily breaking foams, liquids, pastes or dispersions. Combination products may be obtained by mixing such compositions. Such products are all compositions within the ambit of the present disclosure and these examples.

EXAMPLE 3 Parts Stearic acid 12.0 Nonyl phenyl polyoxyalkylcne alkanol 5.0 (30 oxyethylene groups, ethanol) Sodium lauroyl monoglyceride sulfonate 1.0 (Siponate SGS) Triethsnolamine 6.0 Water (deionized) 62.0 2,2-thiodiethanol 13.0 Sodium tungstate 0.25 Perfume 0.75

The above formula is compounded in a manner like that employed to make the composition of Example 1. The monoglyceride sulfonate is added in place of the lauric myristic dialkanolamide. 30 percent more hydrogen peroxide is used, since more reductant is also employed. The product resulting is a good self-heating shaving cream, the temperature of which increases to about 150F. within 18 seconds after dispensing.

The foam of this shaving cream is thick and stable, such properties being contributed to by the monoglyceride sulfonate. When 0.5 percent or less of the sulfonate is used the foam becomes appreciably thinner. At 1.5 percent content a very thick foam results. Usually, no more than 1.5 percent of the monoglyceride sulfonate will be employed to avoid overthickening. Also the cation may be changed to other alkali metal, alkaline earth metal, ammonium, alkylamine or lower alkanolamine salt and similar results are obtained, if the acyl group is of 10 to 18 carbon atoms.

When the stearic acid and triethanolamine content are cut to 10 and 5 percent, respectively, and the monoglyceride sulfonate is omitted, with water content adjusted to 66 percent, a thinner but usable foam results.

EXAMPLE 4 Parts Stearic acid 10.0 Nonyl phenyl polyoxyethylene ethanol of 5.0 30 oxyethylene groups per mole Aqueous sorbitol solution (70% sorbitol) 10.0 Triethanolamine 5.30 Water (deionized) 52.95 2,2'-thiodiethanol 14.0 Sodium tungstate (25% aqueous solution) 2.0 Perfume 0.75

The various ingredientsare combined, as described in Example 1, with the exception that sorbitol solution is added after neutralization of the stearic acid by the triethanolamine. 144 parts of the composition are then added to the larger compartment of a two compartment dispenser. Following this, 36 parts ofa 14 percent hydrogen peroxide aqueous solution are added to the smaller compartment of the dispenser. Both compartments communicate with a dispensing valve, which is staked into place at the top of the dispenser and is actuatable by finger pressure. Next, six parts of hydrocarbon propellant (5/6 isobutane and H6 propane) are back-filled by pressure into the larger compartment. The product is now ready for use.

As was mentioned with respect to the other shaving creams of this invention, this product has good shelf life and does 'not destroy the pleasant aroma of its' perfume on standing. Neither does it lose heating power on reasonable storage. The temperature to which the dispensed product is raised by the chemical reaction of the 2,2-thiodiethanol and the hydrogen peroxide is over F. and this temperature is reached shortly after dispensing, usually within 12 to 18 seconds. No objectionable malodor is noted, after dispensing. The lather produced is a very stable one and the foam is long lasting and apparently of very finely divided bubbles. It feels especially pleasant on the skin. The improved properties of this lather are considered to be due in part to the presence of the sorbitol in the formulation. This polyhydric alcohol exerts emollient effects,

as has been mentioned in the specification, and additionally, aids in producing a highly acceptable rich, stable foam. Similar results are obtained when other polyhydric alcohols, e.g., mannitol, glycerol, are included in the formulation.

In other compositions, the proportion of propellant is changed, so that from 2 to 8 parts are used, instead of the six parts shown in this formula. Acceptable products are obtainable in'this range, althoughthose with the lesser amounts of propellant are dispensed more slowly and do not possess as fine bubble structure as do those in which more propellant is employed. Care must be taken to avoid using too little or too much propellant to avoid dripping of product or running on the one hand, and sputtering, on the other.

The invention has been describedand illustrated. Of course, it is not limited to specific examples given but includes various compositions and methods in which equivalents are employed, providing that such are within the spirit of the invention and in accord with the present teachings.

What is claimed is:

1. A self-heating cosmetic product comprising constituents of a cosmetic composition stored in separate zones of a package containing a plurality of compartments, in one of which there is present an aqueous medium including an organic reductant of the formula HO-R-S-R'-OH, wherein ROH and ROH, which may be the same or different, are selected from the group consisting of hydroxyalkyl, lower alkoxy hydroxyalkyl, di-lower alkoxy hydroxyalkyl and poly-lower alkoxy hydroxyalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of nitro, amino and hydroxy, which replace alkylene hydrogens and are limited to three per reductant molecule, and salts thereof, the hydroxyalkyls being of twoto carbon atoms and the alkoxy hydroxyalkyls, di-alkoxy hydroxyalkyls and poly-alkoxy hydroxyalkyls being of four to 20 atoms in a chain, with the alkoxies being of two to four carbon atoms, and in the other of which compartments there is present an oxidizing agent which is a per-oxygen compound selected from the group consisting of hydrogen peroxide, urea peroxide, and .metal per-salts, ther mogenically reactive with the reductant to convert it to a compound selected from the group consisting of the corresponding sulfoxides and sulfones having surface active or solubilizing effects on the cosmetic-composition ingredients and simultaneously to heat the cosmetic when dispensed, and means for dispensing contents from both zones so that they are brought into contact with each other and cosmetic ingredients to produce a heated cosmetic including therein a sulfoxide or sulfone product of the thermogenic reaction.

2. A self-heating cosmetic product according to claim 1 wherein ROH and R'OH are unsubstituted hydroxyalkyls, and the oxidant is hydrogen peroxide or a metal per-oxygen salt.

3. A self-heating cosmetic product according to claim 2 wherein ROH and R'OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide, the proportion of reductant to oxidant is from 0.9 times the stoichiometric quantity to produce the corresponding sulfoxide to 1.25 times the stoichiometric quantity to produce the corresponding sulfone, and there is present in the same compartment as the reductant the cosmetic material to be dispensed and a catalyst for the redox reaction, in an effective proportion and amount to accelerate the thermogenic reaction and heat the cosmetic to a temperature of at least F. within 30 seconds after dispensing, said catalyst being an alkali metal or ammonium molybdate, tungstate or uranate.

I 4. A self-heating shaving cream product comprising constituents of a shaving cream composition stored in separate zones of a package containing a plurality of compartments, in one of which is present an aqueous medium including an organic reductant of the formula HO-R-S-R-OH wherein ROH and ROH, which may be the same or different, are selected from the group consisting of hydroxyalkyl, lower alkoxy hydroxyalkyl,-

di-lower alkoxy hydroxyalkyl and poly-lower alkoxy hydroxyalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of nitro, amino and hydroxy, which replace alkylene hydrogens and are limited to three per reductant molecule, and salts thereof, the hydroxyalkyls being of two to 20 carbon atoms and the alkoxy hydroxyalkyls, di-alkoxy hydroxyalkyls and poly-alkoxy hydroxyalkyls being of four to 20 atoms in a chain, with the alkoxies' being of two to four carbon atoms, higher fatty acid soap having a cation selected from the group consisting of alkanolamines, amines, ammonium, and alkali metal and in which the fatty acids content comprises a major proportion of fatty acid(s) of [6 to 18 carbon atoms, and water, and in the other of which compartments there is present an oxidizing agent which is a per-oxygen compound selected from the group consisting of hydrogen peroxide, urea peroxide and metal per-salts, thermogenically reactive with the reductant to convert it to a compound selected from the group consisting of the corresponding sulfoxides and sulfones having surface active or solubilizing effects on the shaving cream composition ingredients and simultaneously to heat the shaving cream when dispensed, and means for dispensing contents from both zones so that they are brought into contact with each other and the shaving cream ingredients to produce a heated shaving cream including therein a sulfoxide or sulfone product of the thermogenic reaction.

5. A self-heating shaving cream product according to claim 4 wherein ROH and R'OH are unsubstituted hydroxyalkyls, the oxidant is hydrogen peroxideor a metal per-oxygen salt and the means for dispensing the contents of the zones is a liquefied gas under pressure selected from the group consisting of lower hydrocarbons, lower halogenated hydrocarbons and mixtures thereof.

6. A self-heating shaving cream product according to claim 5 wherein ROH and R'OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide, the proportion of reductant to oxidant is from 0.9 times the stoichiometric quantity to produce the corresponding sulfoxide to 1.25 times the stoichiometric quantity to produce the corresponding sulfone, and there is present in the same compartment as the reductant, soap and water, a catalyst for the redox reaction, in an effective proportion and amount to accelerate the thermogenic reaction and heat the shaving cream to a temperature of at least lOOfF. within 30 seconds after dispensing, said catalyst being an alkali metal or ammonium molybdate, tungstate or uranate.

7. A self-heating shaving cream product according to claim 6 wherein the reductant component comprises from to 40 percent of the composition in the reductant compartment, the catalyst for the redox reaction comprises 0.2 to 2 percent thereof and the soap is triethanolamine soap, and the oxidant component is an aqueous solution of hydrogen peroxide in which the active hydrogen peroxide content is from 2 to 10 percent of the weight of the reductant component.

8. A self-heating shaving cream product according to claim 7 wherein the shaving cream dispensed is propelled by a mixture of propane and isobutane, is exothermically heated to a temperature of at least 130F.,

and comprises 50 to percent water, I to 35 percent of a surface active agent which is a nonionic higher alkylphenyl poly-lower alkoxy lower alkanol, 5 to 20 percent of triethanolamine soap and less than 25 percent of adjuvants, with the pH at dispensing being from 7 to 10.

9. A self-heating shaving cream product according to claim 8 which comprises about 15 parts of trietha'nolamine stearate, 5 parts of nonyl phenyl polyoxyethylene ethanol of 30 oxyethylene groups per mole, 10 parts of 2,2'-thiodiethanol, 0.5 part of lauric myristic diethanolamide, 0.4 part of sodium tungstate, 3.5 parts of hydrogen peroxide and parts of water, before dispensing.

* III

Claims

2. A self-heating cosmetic product according to claim 1 wherein ROH and R''OH are unsubstituted hydroxyalkyls, and the oxidant is hydrogen peroxide or a metal per-oxygen salt.
3. A self-heating cosmetic product according to claim 2 wherein ROH and R''OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide, the proportion of reductant to oxidant is from 0.9 times the stoichiometric quantity to produce the corresponding sulfoxide to 1.25 times the stoichiometric quantity to produce the corresponding sulfone, and there is present in the same compartment as the reductant the cosmetic material to be dispensed and a catalyst for the redox reaction, in an effective proportion and amount to accelerate the thermogenic reaction and heat the cosmetic to a temperature of at least 100* F. within 30 seconds after dispensing, said catalyst being an alkali metal or ammonium molybdate, tungstate or uranate.
4. A self-heating shaving cream product comprising constituents of a shaving cream composition stored in separate zones of a package containing a plurality of compartments, in one of which is present an aqueous medium including an organic reductant of the formula HO-R-S-R''-OH wherein ROH and R''OH, which may be the same or different, are selected from the group consisting of hydroxyalkyl, lower alkoxy hydroxyalkyl, di-lower alkoxy hydroxyalkyl and poly-lower alkoxy hydroxyalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of nitro, amino and hydroxy, which replace alkylene hydrogens and are limited to three per reductant molecule, and salts thereof, the hydroxyalkyls being of two to 20 carbon atoms and the alkoxy hydroxyalkyls, di-alkoxy hydroxyalkyls and poly-alkoxy hydroxyalkyls being of four to 20 atoms in a chain, with the alkoxies being of two to four carbon atoms, higher fatty acid soap having a cation selected from the group consisting of alkanolamines, amines, ammonium, and alkali metal and in which the fatty acids content comprises a major proportion of fatty acid(s) of 16 to 18 carbon atoms, and water, and in the other of which compartments there is present an oxidizing agent which is a per-oxygen compound selected from the group consisting of hydrogen peroxide, urea peroxide and metal per-salts, thermogenically reactive with the reductant to convert it to a compound selected from the group consisting of the corresponding sulfoxides and sulfones having surface active or solubilizing effects on the shaving cream composition ingredients and simultaneously to heat the shaving cream when dispensed, and means for dispensing contents from both zones so that they are brought into contact with each other and the shaving cream ingredients to produce a heated shaving cream including therein a sulfoxide or sulfone product of the thermogenic reaction.
5. A self-heating shaving cream product according to claim 4 wherein ROH and R''OH are unsubstituted hydroxyalkyls, the oxidant is hydrogen peroxide or a metal per-oxygen salt and the means for dispensing the contents of the zones is a liquefied gas under pressure selected from the group consisting of lower hydrocarbons, lower halogenated hydrocarbons and mixtures thereof.
6. A self-heating shaving cream product according to claim 5 wherein ROH and R''OH are hydroxyethyl, the oxidant is aqueous hydrogen peroxide, the proportion of reductant to oxidant is from 0.9 times the stoichiometric quantity to produce the corresponding sulfoxide to 1.25 times the stoichiometric quantity to produce the corresponding sulfone, and there is present in the same compartment as the reductant, soap and water, a catalyst for the redox reaction, in an effective proportion and amount to accelerate the thermogenic reaction and heat the shaving cream to a temperature of at least 100* F. within 30 seconds after dispensing, said catalysT being an alkali metal or ammonium molybdate, tungstate or uranate.
7. A self-heating shaving cream product according to claim 6 wherein the reductant component comprises from 5 to 40 percent of the composition in the reductant compartment, the catalyst for the redox reaction comprises 0.2 to 2 percent thereof and the soap is triethanolamine soap, and the oxidant component is an aqueous solution of hydrogen peroxide in which the active hydrogen peroxide content is from 2 to 10 percent of the weight of the reductant component.
8. A self-heating shaving cream product according to claim 7 wherein the shaving cream dispensed is propelled by a mixture of propane and isobutane, is exothermically heated to a temperature of at least 130* F., and comprises 50 to 85 percent water, 1 to 35 percent of a surface active agent which is a nonionic higher alkylphenyl poly-lower alkoxy lower alkanol, 5 to 20 percent of triethanolamine soap and less than 25 percent of adjuvants, with the pH at dispensing being from 7 to 10.
9. A self-heating shaving cream product according to claim 8 which comprises about 15 parts of triethanolamine stearate, 5 parts of nonyl phenyl polyoxyethylene ethanol of 30 oxyethylene groups per mole, 10 parts of 2,2''-thiodiethanol, 0.5 part of lauric myristic diethanolamide, 0.4 part of sodium tungstate, 3.5 parts of hydrogen peroxide and 90 parts of water, before dispensing.