US3639568A

US3639568A - Gas-releasable and foamable compositions

Info

Publication number: US3639568A
Application number: US761876A
Authority: US
Inventors: William H Schmitt
Original assignee: Alberto Culver Co
Current assignee: Alberto Culver Co
Priority date: 1968-09-23
Filing date: 1968-09-23
Publication date: 1972-02-01
Anticipated expiration: 1989-02-01

Abstract

GAS RELEASABLE AND FOAMABLE COMPOSITIONS, ADAPTED TO BE PACKAGED IN CONVENTIONAL NON-PRESSURIZED CONTAINERS AS, FOR EXAMPLE, METAL OR PLASTIC COLLAPSIBLE OR SQUEEZABLE TUBES, COMPRISING SUBSTANTIALLY ANHYDROUS COMPOSITIONS CONTAINING A COMPRESSIBLE WATER-INSOLUBLE GAS, PARTICULARLY IN THE FORM OF AN ALIPHATIC HYDROCARBON OR HALOGENATED HYDROCARBON, DISSOLVED IN AN ORGANIC SOLVENT, SUCH AS A POLYETHYLENE GLYCOL, WHICH ORGANIC SOLVENT IS ALSO WATERSOLUBLE, AND SUPPLEMENTAL AGENTS TO COMPLETE THE COMPOSITIONS FOR THEIR INTENDED USES, SUCH AS SOLID DETERGENT TABLETS, SUPPOSITORIES, SHAVING CREAMS, MOUTHWASHES, ENEMAS, DRAIN CLEANERS, ETC. WHEN SAID COMPOSITIONS ARE WETTED OR ADMIXED WITH WATER, SAID DISSOLVED COMPRESSIBLE GAS IS DISPLACED FROM SAID ORGANIC SOLVENT AND IS RELEASED IN THE FORM OF A GAS OR, IN CERTAIN CASES, A GAS TO FOR A FOAM.

Description

United States Patent O 3,639,568 GAS-RELEASABLE AND FOAMABLE COMPOSITIONS William H. Schmitt, Elmhurst, 111., assignor to Alberto- Culver Company, Melrose Park, Ill. No Drawing. Filed Sept. 23, 1968, Ser. No. 761,876 Int. Cl. A61r 7/00, 7/06, 9/02 US. Cl. 424-43 22 Claims ABSTRACT OF THE DISCLOSURE Gas releasable and foamable compositions, adapted to be packaged in conventional non-pressurized containers as, for example, metal or plastic collapsible or squeezable tubes, comprising substantially anhydrous compositions containing a compressible water-insoluble gas, particularly in the form of an aliphatic hydrocarbon or halogenated hydrocarbon, dissolved in an organic solvent, such as a polyethylene glycol, which organic solvent is also watersoluble, and supplemental agents to complete the compositions for their intended uses, such as solid detergent tablets, suppositories, shaving creams, mouthwashes, enemas, drain cleaners, etc. When said compositions are wetted or admixed with water, said dissolved compressible gas is displaced from said organic solvent and is released in the form of a gas or, in certain cases, a gas to form a foam.

This invention relates to novel gas-releasable compositions which are adapted to be packaged in conventional non-pressurized containers, particularly metal or plastic collapsible or squeezable tubes. It also relates to a novel method of effecting release of gases, utilizing such compositions.

The compositions of my invention are substantially or essentially non-aqueous or anhydrous compositions of that type which, when brought into contact with certain liquids, especially water, in the environments in which they are intended to be used, evolves a gas which, in turn, causes a mechanical action leading, in certain cases, to foam formation and spreading. Broadly speaking, compositions which form and evolve gases on contact with water have long been known, gas formation resulting from the release of oxygen-containing compounds such as perborates, or by the interaction of an acid such as tartaric acid or citric acid with sodium bicarbonate.

The gas-releasable compositions of my present invention are radically different from those of the previously known types referred to above and operate on an entirely unrelated principle of gas formation and evolution. The compositions of my invention utilize as a base a first solvent, which is a non-aqueous organic solvent, in which certain types of compressible gases are dissolved, thereby reducing their vapor pressures. The first, organic, solvent must also be soluble in a second solvent whereby, when said second solvent is added to the system, the release of the compressible gas in gaseous form is effected by reason of the insolubility of the compressible gas in the mixture of said first and second solvents. In at least most instances, the second solvent will be water (although it may be an organic solvent) and, therefore, the first solvent, namely, the non-aqueous organic solvent, would also be one which is water-soluble.

In broad terms, the gas-releasable compositions of my invention comprise (a) a compressible gas, (b) a solvent for said compressible gas which lowers the vapor pressure of the resultant solution to a point at which said solvent solution of said compressible gas can be maintained at ambient temperatures in conventional non-pressurized containers, and (e) such additional ingredients as are desired or required, as the case may be, to produce parice ticular gas-releasable compositions for specific purposes as, for instance, detergent tablets, suppositories, enemas, etc. The finished gas-releasable compositions of my invention can subsequently, in use, free the dissolved compressible gas by admixture with a second solvent which is soluble in said first organic solvent but in which the compressible gas is insoluble. The system may be illustrated by the following schematic arrangement:

Solution I Use Vehicle Solution II Compressible Gas (Compressible Gas) (Solvents) '7 (Solvent) (Use Vehicle) The gas-releasable or foamable compositions of my invention, which include the solutions of compressible gas in a solvent, may occur as solids, pastes or gels, semisolids, or liquids, uncompressed at normal storage temperatures.

Any volatile organic material which exists as a gas at use temperatures (and ambient or atmospheric pressure) and which exists as a liquid at the same temperatures under superatmospheric pressures, and is soluble in the first, organic, solvent (or mixtures thereof) utilized, and is substantially insoluble in the second solvent, notably water, can be used as the gas-producing agent. Especially suitable are the C -C aliphatic hydrocarbons, namely, liquefied propane, n-butane, isobutane, isobutylene, npentane, isopentane, n-hexane, and hexane-2; and halogenated aliphatic hydrocarbons which contain from 1 to 2 carbon atoms and include, by way of example, vinyl chloride, ethyl chloride, chloroform, trichloroethylene, methylene chloride, dichlorodifiuorornethane, monochlorodifiuoromethane, dichlorotetrafluoroethane, trichlorofluoromethane, trichlorofluoroethane, difluoroethane, difiuoromonochloroethane, trichlorotrifluoroethane, and mixtures of two or more thereof, most desirably the saturated hydrocarbons and halogenated saturated aliphatic hydrocarbons. The boiling points of said aliphatic hydrocarbons and halogenated aliphatic hydrocarbons should fall within the range of about 30 C. to about 60 C. at atmospheric pressure, preferably about 3 C. to about 37 C. The proportions thereof in the compositions of the present invention will, in general, range from about 1 to about 20%, by weight, preferably about 5 to about 10%. The vapor pressure of the finished compositions is, in general, in the range of from 0 to 10 psig. at 25 C. and not greater than about 15 p.s.i.g. at

The first, organic, solvent for the compressed gas is limited only by a solubility for the compressed gas, the resultant vapor pressure of the solution, and the particular utility and purpose for which the system is intended, namely, the specific nature and intended use of the finished gas-releasable composition, which plays a role in the selection of the additional ingredients which are incorporated to make up said finished gas-releasable compositions. Said organic solvent may be normally liquid, semi-solid or solid. Among such organic solvents are, for instance, saturated aliphatic monohydric alcohols containing l to 3 carbon atoms such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and di-allcyl ketones in which the alkyl groups contain 1 to 3 carbon atoms, such as acetone and methyl ethyl ketone. It is, however, especially desirable to utilize water-soluble polyoxyethylene glycols such as polyoxyethylene glycol 200, 400, 600, 800, 1,000, 1,450, and higher po-lyoxyethylene glycols, such as 4,000 or 6,000, and the like. Various aliphatic polyhydric alcohols such as glycerol, monoalkylene and polyoxyalkylene glycols in which the alkylene groups contain from 2 to 4 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, di-

ethylene glycol, triethylene glycol, tetraethylene glycol and higher polyoxyethylene glycols, such as those mentioned above, can be used. In certain types of gas-releasable compositions made in accordance with my invention, the first, organic, solvent can be in the form of one or more organic surface active agents or surfactants, of nonionic, anionic, cationic or amphoteric character. Illustrative of such nonionic surfactants are alkylene oxide, particularly ethylene oxide, adducts of fatty or aliphatic long chain (straight or branched) alcohols, or fat-forming fatty acids, or alkyl phenols as, for example, 8 to 20 mol ethylene oxide adducts of octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl alcohol, oxo-alcohols such as oxo-tridecyl alcohol, oleic acid, palmitic acid, diamylphenol, nonylphenol, dinonylphenol, and the like. Other nonionic surfactants, for example, those sold inder the designation Pluronics, are condensates or adducts of ethylene oxide with polyoxypropylene glycols of molecular weight 1200 or higher and vary in physical properties from liquids through pastes to solids. They are dis closed, for example, in US. Pats. Nos. 2,674,619 and 2,677,700. Illustrative anionic surfactants which, in certain cases, can be used as the first, organic, solvent are sulfated fatty alcohols and sulfated derivatives of fatty alcohols, and sulfonated long chain alkyl benzene or toluene, advantageously in the form of their salts, typical of which are sodium lauryl sulfate, sodium myristyl ether sulfates, dodecylbenzene sodium sulfonate and octadecylbenzene sodium sulfonate, and the corresponding sulfates in the form of their amine salts such as the ethanolamine, diethanolamine, triethanolamine and isopropylamine and isopropanolarnine salts. Illustrative of the cationic surfactants are the quaternary ammonium compounds of which there is a very extensive literature, illustrative examples of which are lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, and lauric acid ester of colaminoformylmethyl pyridinium chloride. The situation is similar in regard to the amphoteric surfactants, illustrative examples of which are dodecyl butaalanine, sulfated imidazolines, and reaction products of dodecyl taurine with hydrophobic tertiary amines.

The organic surfactants should, of course, be chosen, among other considerations, with regard to their adequate solubility for the compressible water-insoluble gas and the resultant vapor pressure of the system. Said surfactants commonly function not only as the first, organic, solvent but, in addition, they impart other properties to the finished gas-releasable compositions of my invention as, for instance, thickening properties, detergent properies, surface tension effects, and the like, depending upon r the particular surfactant selected and the particular environment in which it is utilized.

Other surfactants which are not solvents for the compressible gases can, of course, be incorporated in various proportions in the gas-releasable compositions, or formed in situ in the procedure employed for making the gasreleasable compositions, to obtain certain functions such as detergency, wetting and the like. Illustrative of such surfactants are various soaps as, for instance, alkanolamine soaps of fat-forming fatty acids such as diethanolamine, triethanolamine and diisopropanolamine soaps of coco or coconut oil fatty acids or special cuts or fractions thereof such as those containing mainly lauric acid or myristic acid, and said soaps of such other fatty acids as palmitic acid, oleic acid, stearic acid, and mixtures thereof. Numerous other surfactants, well known to the art, can also be used.

Compatible mixtures of such and/or other first, organic, solvents can be utilized and such mixtures may ineluded monohydric alcohols such as ethyl alcohol and/or other organic solvents to provide for a total first, organic, solvent in which the selected compressible gas is adequately soluble. Generally speaking, because of solvency and other practical considerations, particularly in those instances where the compressible gas utilized is watersoluble and where the second solvent which is to be added thereto is water or an aqueous medium, it is generally particularly advantageous to employ polyoxyethylene glycols or mixtures thereof having molecular weights in the range of about 200 to 6000. The proportions of the first, organic, solvent of solvents utilized in the gas-releasable compositions of my invention are variable but will, in general, lie in the range of about 20 to about 90%, by weight, or somewhat more or less, usually about 40 to about 70%. Commonly, the compressible gas will comprise a distinctly minor percentage by weight of the first, organic solvent solution thereof, generally in the range of from about 3% to about 12%, and usually in the range from about 5% to 10% by Weight of said solution.

I have also found that, in gas-releasable compositions of the type contemplated by my present invention, the rate of release of the compressible gas from said compositions can be selectively controlled when said compositions are contacted with water or other second solvent, as the case may be. By way of illustration, 5 to 10% solutions of compressible gases, such as trichlorofluoromethane (Propellant 11), in highly polar compounds or solvents such as ethanol, release such gases almost instantly, without agitation, upon addition of such solutions to a vehicle in which the solvent (ethanol) is soluble but in which the compressible gas (Propellant 11) is insoluble, for instance, water. Another illustrative first, organic, solvent in which said compressible gas (Propellant 11) is soluble but which releases said compressible gas in a much different manner is typified by octylphenoxypolyethyleneoxyethanol (con1- mercially available as Igepal 'CA 630). The Igepal CA 630 is in the class of nonionic surfactants which has both hydrophilic and lipophilic character. A 5 to 10% solution in Igepal CA 630 of a compressible gas such as Propellant 11 when added to water with no agitation releases very little of said compressible gas. Agitation of the mixture over a relatively prolonged period of time does, however, liberate the compressible gas. This system that releases the compressible gas slowly and only with agitation can be modified by addition of a solute for the final vehicle to the solution. For example, the aforesaid solution in Igepal CA 630 of Propellant 11 may be modified by the addition of a minor amount, for instance, 15%, by weight, of a salt such as sodium bicarbonate. This salt is insoluble in said solution, and tends to be held in suspension. The addition of said solution carrying the added sodium bicarbonate in suspension to the water vehicle brings about a very quick release of the compressible gas with little agitation. The rate of release of the compressible gas can be modified by both the amount and the nature of the added solute for the final vehicle. This modifying constituent may be soluble or insoluble in the compressible gas-solvent solution, but must be a solute, or soluble, in the vehicle to which the compressible gas-solvent solution is added. The control of the rate of release of the compressible gas upon addition of the compressible gas-solvent solution to the vehicle is accomplished by either the solvent, a portion of the solvent, or an additive to the compressible gas-solvent solution. If the liberated compressible gas is emulsified or complexed by the resultant vehicle-compressible gas-solvent solution mixture, the release will be slow; whereas, if the liberated gas is completely unassociated, the release will be rapid; additives can accelerate the release from emulsified mixtures.

While sodium bicarbonate has been found to be especially desirable as a compressible gas-release enhancing agent for gas-releasable compositions made in accordance with my invention, other compressible gas-release accelerating agents which can be used are ionic compounds, exemplified by monovalent or polyvalent salts, such as sodium chloride, sodium tartrate, sodium citrate, and calcium citrate. Nonionic compounds, exemplified by sugar alcohols such as sorbitol, mannitol and arabitol, especially sorbitol, said sugar alcohols being insoluble in the gas-releasable composition systems, can also be used to control the rate of release of the compressible gas. The sugar alcohols, of course, are utilized in their anhydrous or essentially anhydrous form, the soribtol being employed in the form of a powder. Generally, speaking, the ionic gas releasing agents are more effective than the nonionic compressible gasreleasing agents. Said agents are employed in minor proportions in the gas-releasable compositions, usually and preferably from about to by weight of the gasreleasable compositions, or somewhat more or less, with about 15% being a good average, the exact amount depending upon the extent of the desired control or acceleration of the rate of release of the compressible gas.

The following table illustrates the effect of the utilization of sodium bicarbonate as a compressible gas-release accelerating agent in given compressible gas-solvent solution systems. The parts given are by volume and the amount of water added in each test was 5 parts by volume for each part of the solution of the compressible gas in the ethanol or ethanol-additive.

Rate of release cc./sec. of gas on addition to water at C.

Solvent, Igepal ethanol CA 630 -As indicated above, gas-releasable compositions can be made in accordance with the teachings of my present invention for a wide variety of purposes where enhancement of the utility of the compositions results from controllable gas or, in certain cases, foam production. Illustrative, but not limitative, of such compositions are suppositories, enemas, vaginal preparations, acne treatment preparations; shave creams, after-shaves, pre-shave lotions, cleasning creams, astringent lotions, mouthwashes, hair dyes, shampoos, hair conditioners, hair dressings, analgesic rubs, underarm deodorants, bath oils, colognes and perfumes; scouring powders, detergent tablets, rug and upholstery cleaners and wall cleaners; paint removers; and insecticide treatments.

The following examples are illustrative of gas-releasable compositions made in accordance with my invention. It will be understood that numerous other gas-releasable compositions can readily be made in the light of the guiding principles and teachings of the present invention disclosed above. The examples given are, therefore, by way of illustration and not by way of limitation. All parts listed are in terms of weight.

EXAMPLE l.'SOLID CLEANSER Composition:

Polyoxyethylene Glycol 6000 5S Trichlorofiuoromethane (Propellant l1) 5 Pumice 20 Sodium hexametaphosphate 10 Sodium lauryl sulfate .10

All of said ingredients are combined in a pressure mixing vessel at 70 C. until solution of the polyoxyethylene glycol 6000 and Propellant 11 is effected. Then said mixture is congealed by lowering the temperature thereof, for instance, by direct cooling or by placement in a chilled atmosphere to make a congealed solid bead. The finished product may be stored in a conventional powder can, When it is applied to a Water-dampened surface, such as a sink, it liberates the gas as a foaming action, which facilitates the lifting of soil from the surface.

. 6 EXAMPLE 2.--DETERGENT TABLET Composition:

Sodium lauryl sulfate 74.9 Trichlorofluoromethane (Propellant 11) 5 Sodium tripolyphosphate 20 Perfume 0.1

The ingredients are melted and combined under pressure. The mixture is then cooled to a point just above the congealing point and poured into a chilled mold. The resulting detergent tablet, when added to hot water, as in a washing machine, facilitates dissolution by the action of the escaping compressible gas on the tablet.

EXAMPLE 3.SEMISOLID SUPPOSITORY Composition:

Polyoxyethylene glycol 1000 45 Polyoxyethylene glycol 4000 45 Trichlorofluoromethane (Propellant ll) 10 The polyoxyethylene glycols are melted at 60 C. and the Propellant 11 is added and mixed in to make a solution in a pressure vessel. The resulting solution is then cooled and the suppository masses are molded with an Armstrong suppository extruder, or poured slightly above the congealing point into foil molds, sealed and chilled. Either method forms a semi-solid form of suppository that is easily inserted rectally, and releases the compressible gas, by reason of contact with moisture in the rectal area, which stimulates the normal peristallic and defecation reflexes which bring about evacuation.

EXAMPLE 4.SHAVE CREAM Composition:

Stearic acid (triple pressed) 12.6 Coconut oil mixed fatty acids 3 Diethanolamine 10.4 Polyoxyethylene glycol 400 53.5 Cetyl alcohol l0 Polyoxyethylene glycol 400 monostearate 5 Isopentane 5 Perfume 0.5

All of the ingredients, other than the perfume and the isopentane, are melted together at about 60 C. and stirred and then, while continuing the stirring and while cooling, the perfume is added and then the isopentane is added. The resulting cream, when rubbed with hot water in the hands, produces a thick foam which is applied as a lather to the face to facilitate shaving.

EXAMPLE 5 .SI-LAV'E CREAM Composition:

Polyoxyethylene glycol 600 55.6 Lauryl alcohol 3.4 Sodium lauryl sulfate 5 Magnesium aluminum silicate 10 Sodium bicarbonate 20 Isopentane 5 Perfume 0.1

The ingredients, other than the perfume and the isopentane, are melted together at about 6070 C. and, while stirring and cooling, the perfume is added and then the isopentane is added. The resulting cream functions in a manner similar to that of the shave cream of Example 4.

EXAMPLE 6.-FOAMING MOUTHWASH Composition:

Ethanol (200 proof USP) 76.275 1,1 dichloro-l,2,2,2-tetrafluoroethane (Propellant 114) 3 Cetyl pyridinum chloride 0.025 Propylene glycol 20 Sodium saccharin 0.1 Sodium cyclamate 0.4 Peppermint oil (terpeneless) 0.2

The ethanol and Propellant 114 are intially admixed and there is then admixed therewith a mixed solution of the sodium saccharin, sodium cyclamate, cetyl pyridinum chloride, and peppermint oil in the propylene glycol. The resulting solution can be stored in conventional glass bottles. When said solution is added to tap water, it foams slightly and releases a small proportion of the compressed gas; but, when swished and gargled in the mouth, the gas is rapidly released with a pleasant oral sensation and a foaming action which aids in removing debris and food particles.

EXAMPLE 7.-LIQUID DRAIN CLEANER Composition:

Diethanolamine 94 Trichlorofiuoromethane 6 The ingredients are mixed together to form a solution which has a specific gravity greater than that of water. Although diethanolamine is soluble in water, the composi tion has such a high viscosity that it flows through Water before it goes into solution. When it does start to go into solution with the water in a given area, the result is to liberate the compressed gas, thereby causing a churning action. This, in turn, aids in the saponification of any fat particles that are present in the obstruction or restriction. Heat produced by the saponification of the fat by the diethanolamine further aids in the release of gas which also facilitates churning and agitation.

EXAMPLE 8.GAS-PRODUCING "ENEMA Composition:

Polyoxyethylene glycol 400 90 The ingredients are mixed together to form a solution. The said solution is placed into a laminated plastic collapsible tube with a rectal tip covered by a protective cap. At the time of administration, the protective cap is removed, the rectal tip screwed on and the contents inserted into the rectum. This causes the quick release of the compressible gas, by reason of contact with moisture in the rectum, which acts on the defecation reflex causing defecation.

EXAMPLE 9.MODIFIED GAS-PRODUCING Trichlorofluoromethane RETENTION ENEMA Composition:

Polyoxyethylene glycol 400 85 Trichlorofluoromethane l Dioctyl sodium sulfosuccinate The ingredients are mixed together to form a solution. The said solution is administered in the same manner as in Example 8. However, with the composition of 'Example 9, the compressible gas is released slowly, the dioctyl sodium sulfosuccinate acting both to retard release of gas and as a stool softener. This composition is useful as a retention enema.

EXAMPLE l'0.HAlR SHAMPOO The ingredients, except the isopentane and the perfume, are melted together at 6070 C. and, while stirring and cooling, the perfume is added and then the isopentane is added. On contact and admixing of the resulting shampoo with water, gas release is etfected.

I am aware that it has herefore been disclosed to prepare self-foaming or gas-releasable compositions, which are adapted to be packaged in non-pressure containers, such as collapsible or squeezable metallic tubes, plastic containers, and the like and which, when spread out in a thin layer, foam spontaneously. Such compositions, which are disclosed in US. Pat. No. 2,995,521, and may be in the form of shaving creams, toothpastes, etc., comprise a mixture of (a) at least one substance of the class of C to C saturated aliphatic hydrocarbons and various Freons, which may be jellified with aluminum octoate, and (b) a mixture of a plurality of ingredients comprising, in the case of a toothpaste, precipitated calcium carbonate, soap, sugar, talc, glycerine and a substantial content of water, the water constituting about 20% of the (b) mixture and about 16% of the toothpaste as a whole. The gas is suspended in a metastable state in the examples as described in the above patent, and the release of the gas is effected by the spreading out of the compositions in a thin layer. The gas-releasable compositions of my invention are sharply distinguishable therefrom in a number of particulars in that, for instance, my gas-releasable compositions are anhydrous or substantially anhydrous, and the gas-producing agent or agents are in solution in an organic solvent and are displaced or released from said solution when contacted with water and issue as a gas at the temperature encountered in the environment of their use.

I am also aware that it has been suggested to prepare gas-releasable or foam-producing compositions for dispensing from aerosol containers, as disclosed, for instance, in US. Pats. Nos. 3,055,834 and 3,131,153, the compositions of said latter patent containing (a) an alcohol or dialkyl ketone, (b) glycerol or an alkylene glycol such as polyoxyethylene glycol 200, 400, 600 etc., (c) a surface active agent, and (d) a propellant in the form of a liquified normally gaseous aliphatic hydrocarbon or halogenated aliphatic hydrocarbon such as butanes or pentanes or dichlorodifluoromethane or dichlorotetrafluoroethane. Such gas-releasable or foam-producing compositions are suggested for use as pre-electric shave lotions, after-shave lotions, astringents, colognes, sun tan lotions, hair-coloring tints, hair dressings, paint removers, etc. The said compositions are dispensed by means of conventional aerosol propellants and contained in conventional aerosol packaging. Again, my gas-releasable compositions and their manner of use and the basis upon which gas release is achieved are sharply distinguishable from the disclosures and teachings in said patents in that a requirement of the latter is the dispensing from aerosol or pressure containers. My gas-releasable compositions, in sharp contrast, not only are packaged in ordinary or conventional non-pressurized containers, such as squeezable metal or plastic toothpaste tubes, or rigid non-pressure containers, but, indeed, if simply placed as such, and without more, in an aerosol container, would not be dispensable therefrom. Aspreviously described, the gas-releasable compositions of my invention depend fundamentally for the release of gas upon the discharge from solution of a compressible gas in a first, organic solvent by means of another solvent ingredient which is soluble in said first, organic, solvent and in which said other solvent ingredient said compressible gas is insouble.

I claim:

1. A method of effecting gas release from a gas-releasable composition as hereafter defined, which comprises providing a composition comprising a substantially non-aqeous mixture containing, as essential ingredients, from about 20 to about of a water-soluble organic solvent having dissolved therein from about 1 to 20% of a compressible gas which exists as a gas at substantially ambient temperature to the temperature of use of the composition and which exists as a liquid at said temperature under superatmospheric pressure, said organic solvent being selected from the group consisting of saturated aliphatic monohydric alcohols containing 1 to 3 carbon atoms, di-alkyl ketones in which the alkyl groups contain 1 to 3 carbon atoms, glycols, aliphatic polyhydric alcohols, monalkylene and polyalkylene glycols in which the alkylene groups contain from 2 to 4 carbon atoms, non-ionic surface active agents in the form of alkylene oxide adducts of aliphatic long chain alcohols and of alkyl phenols, ethylene oxide adducts of polypropylene glycols, sulfated long chain fatty alcohols, sulfonated long chain alkyl benzenes and sulfonated long chain alkyl toluenes, cationic surfactants and amphoteric surfactants; said compressible gas being selected from the group consisting of C -C aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons containing from 1 to 2 carbon atoms, fiuorinated aliphatic hydrocarbons containing from 1 to 2 carbon atoms, and chlorinated-fluorinated aliphatic hydrocarbons containing from 1 to 2'carbon atoms; and then admixing with said composition an aqueous solvent which is soluble in said organic solvent and in which said compressible gas is insoluble, whereby to release said compressible gas, the vapor pressure of said gas-releasable composition, prior to the addition thereto of said aqueous solvent, being in the range of from to 10 p.s.i.g. measured at 25 C. and not greater than about p.s.i.g. measured at 50 C.

2. The method of claim 1, in which the temperature at which the compressible gas exists as a gas is substantially ambient temperature, and in which said second solvent is water.

3. The method of claim 1, in which the compressible gas is a chlorofluoro C to C saturated aliphatic hydrocarbon.

4. The method of claim 1, in which the organic solvent comprises a Water-soluble polyoxyethylene glycol.

5. The method of claim 1, in which the composition is solid at room temperature.

6. The method of claim 1, in which the composition is a paste at room temperature.

7. The method of claim 1, in which the composition is liquid at room temperature.

8. The method of claim 1 in which the composition contains a gas-release control agent which is substantially insoluble in the composition and is selected from the group consisting of sodium chloride, sodium tartrate, sodium citrate, calcium citrate and sugar alcohols.

9. The method of claim 8, in which the gas-release control agent is sodium bicarbonate, said sodium bicarbonate being present in proportions in the range of 10 to by weight of the composition.

10. The method of claim 1, in which the composition is a suppository.

11. The method of claim 1, in which the composition is a solid cleaner.

12. The method of claim 1, in which the composition is a cosmetic.

13. A nonpressurized container containing therein a gas-releasable composition comprising a substantially nonaqueous mixture containing, as essential ingredients, from about 20 to about 90% of a Water-soluble organic solvent having dissolved therein from about 1 to 20% of a compressible gas which exists as a gas at a temperature in the range of substantially ambient temperature to the temperature of use of the composition and existing as a liquid at said temperature under superatmospheric pressure, said organic solvent being selected from the group consisting of saturated aliphatic monohydric alcohols containing 1 to 3 carbon atoms, di-alkyl ketones in which the alkyl groups contain 1 to 3 carbon atoms, glycols, aliphatic polyhydric alcohols, monoalkene and polyalkylene glycols in which the alkylene groups contain from 2 to 4 carbon atoms, non-ionic surface active agents in the form of alkylene oxide adducts of aliphatic long chain alcohols and of alkyl phenols, ethylene oxide adducts of polypropylene glycols, sulfated long chain fatty alcohols, sulfonated long chain alkyl benzenes and sulfonated long chain alkyl toluenes, cationic surfactants and amphoteric surfactants; said compressible gas being selected from the group consisting of C -C aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons containing from 1 to 2 carbon atoms, fiuorinated aliphatic hydrocarbons containing from 1 to 2 carbon atoms, and chlorinated-fluorinated aliphatic hydrocarbons containing from 1 to 2 carbon atoms; said composition, when admixed with an aqueous solvent which is soluble in said organic solvent but in which said compressible gas is insoluble, elfecting release of said compressible gas from said composition, the vapor pressure of said composition being in the range of from 0 to 10 p.s.i.g. at 25 C. and not greater than about 15 p.s.i.g. at 50 C.

14. An article according to claim 13, in which the compressible gas constitutes from about 5 to about 10% by weight of the solution thereof in said organic solvent, and is at least one member selected from. the group consisting of C to C saturated aliphatic hydrocarbons and chlorinated-fluorinated C to C saturated aliphatic hydrocarbons.

15. An article according to claim 13, in which the water-soluble organic solvent comprises diethanolamine.

16. An article according to claim. 13, in which the water-soluble organic solvent comprises a mixture comprising a diethanolamine soap of coco fatty acids and a polyoxyethylene glycol having a molecular weight in the range from about 200 to about 6000.

17. An article according to claim 13, in which the composition is a hair shampoo.

18. An article according to claim 13, in which the water-soluble organic solvent comprises a polyoxyethylene glycol having a molecular weight in the range from about 200 to about 6000.

19. An article according to claim 14, in which the composition is a suppository.

20. An article according to claim 13, in which the composition is a solid cleanser and in which the water-soluble organic solvent comprises at least one detergent selected from the group consisting of anionic detergents and nonionic detergents.

21. An article according to claim 20, in which the anionic detergent comprises a diethanolamine soap of coco fatty acids.

22. An article according to claim 20, in which the nonionic detergent comprises octylphenoxypolyoxyethyleneoxyethanol.

References Cited UNITED STATES PATENTS 3,131,153 4/1964 Klausner 424--- RICHARD L. HUFF, Primary Examiner US. Cl. X.R.