US3433868A - Two phase fast breaking foam pressurized hair waving composition - Google Patents

Description

United States Patent 3 433,868 TWO PHASE FAST BREAKING FOAM PRES- SURIZED HAIR WAVING COMPOSITION Stanley Brechner, West Orange, Meyer Malakolf, Kendall Park, and Martin M. Rieger, West Englewood, N.J.,

assignors to Warner-Lambert Pharmaceutical Company,

Morris Plains, N.J., a corporation of Delaware No Drawing. Filed July 27, 1964, Ser. No. 385,467 US. Cl. 424-47 Claims Int. Cl. A61k 7/10 ABSTRACT OF THE DISCLOSURE An improved two liquid phase pressurized hair waving composition adapted for discharge from its container as a foam, consisting of a low molecular weight mercaptoalkanoic acid, an alkalizing agent imparting to the composition a pH of above about 7, a propellant, a surface active agent, a polyhydric alcohol, and the balance substantially water.

This invention relates to improved liquid cold waving preparations packaged in pressurized containers for use in the permanent waving of hair. More particularly, the present invention relates to a composition for use in the cold permanent waving of hair which upon release from a pressurized container forms a fast breaking foam.

Cold permanent waving compositions are well known to the art. These compositions accomplish the permanent waving of hair through their ability to break the disulphide bonds of the cystine, which is a major constituent of the keratin of hair, and on the successive transformation of the cystine to cysteine. When the disulphide bonds are broken, the hair tresses become pliable and easily shaped to a new configuration. Upon regeneration of the disulphide bond and conversion from cysteine to cystine by oxidation, the hair tresses then become permanently fixed in the shape of the new configuration. The means used for breaking the disulphide bonds of cystine by chemical agents are numerous with the most widely used and preferred agents being mercaptans such as thioglycolic acid.

Cold permanent waving compositions are usually applied to the hair with cotton pads or small sponge applicators by repeatedly saturating the applicator with the hair waving lotion and thereafter transferring the lotion from the applicator on to the hair. This method is recognized as being cumbersome, tedious and time-consuming with irritation of sensitive skin resulting on prolonged contact with the lotion. In addition, little control is possible through the use of such applicators.

The use of plastic squeeze bottles and special hair combs have been proposed to overcome the many problems which exist in the application of cold permanent waving lotions to the hair, but these devices do not materially overcome the deficiencies inherent in the conventional applicators.

The volatility and susceptibility to oxidation of the active ingredients in hair waving lotions make ordinary methods of packaging inappropriate. Once the containers of permanent hair waving lotion are opened to the atmosphere, they cannot be stored and used repeatedly without loss of activity. One type of packaging which enables alternate use and storage such as is required for touch-up waves as well as for periodic full waving is the aerosol package.

Aerosol packages or pressurized containers have been widely employed for packaging many products for household purposes. In spite of their recognized advantages in other areas, aerosol packaging techniques have not been widespread for application of cold permanent waving 3,433,868 Patented Mar. 18, 1969 compositions. The usual aerosol methods which might be used to dispense hair waving products such as foams or mists are by their very nature less able to meet the demands of cold waving of hair than are the conventional application techniques. A foam, for example, acts as a physical impediment to the penetration of the reducing agent into the hair, whereas a mist is unsatisfactory because of the wide diffusion of the hair lotion, with the outside of a wound tress receiving a heavy concentration of the lotion, while the portion of the hair inside a wound curl may receive a much smaller amount. As a result, portions of the hair may be damaged by over concentration with lotion, while other parts of the wound curl may not be reduced at all because of insuflicient contact by a sufficient amount of lotion which is ordinarly neces sary to break the disulphide bonds. In order then to provide a suitable pressurized cold permanent hair waving composition in an aerosol package, the composition should neither be expelled as a spray nor as a stable foam. It has now been recognized that the problem of providing a pressurized cold permanent waving composition may be overcome by use of a hair waving composition which is dispensed from an aerosol container as a foam which collapses to a liquid promptly after discharge and which is capable of being absorbed by the hair at about the same rate as the foam collapses to a liquid.

In order to achieve aerosol permanent waving compositions which collapse as a fast breaking foam, a series of important criteria must be met. One is that the cold permanent hair waving composition should contain propellants which are finely dispersed throughout the composition. A true solution or a molecular dispersion is found to be ideal. However, many propellants known and available for use in propelling cold waving compositions are generally not very soluble in aqueous solutions, particularly those containing keratin-reducing agents. Mutual solvents such as alcohols can be employed to overcome this problem, but these compositions are generally less effective in the cold permanent waving of hair. In addition, the alcohol which is required adds to the cost of the final composition.

Use of two liquid phase compositions in pressurized packages is well known and may be recognized in the teaching of Baton, US. Patent No. 2,728,495, wherein there is disclosed a composition having an aqueous liquid phase which floats on top of a liquid propellant phase. This composition does not discharge as a foam although it can be discharged as a foam after violent agitation.

It has now been found that the disadvantages heretofore encountered in conveniently applying cold permanent Waving compositions to the hair may now be overcome by providing a two-phase permanent waving composition containing a keratin-reducing agent in one phase and a liquefied propellant in the second phase such that the hair waving composition may be discharged from a container as a foam which collapses to a liquid promptly upon discharge.

It is an object of this invention, therefore, to provide a cold permanent waving composition packaged in pressurized containers for use in improving methods of cold permanent waving of hair.

It is also an object of this invention to provide a two liquid phase composition dischargeable as a fast breaking foam for use in cold permanent waving hair upon release from a pressurized container.

It is also an object of this invention to provide a pressurized cold permanent hair waving composition which can be used and then stored for subsequent application without material loss of activity between uses.

It is a further object of this invention to provide an improved method of permanent waving of hair with a cold permanent waving composition which eliminates or greatly reduces the possibility of skin irritation which may otherwise result when a liquid waving lotion is applied to the hair in an amount greater than may be absorbed.

Other objects and advantages will appear from the following detailed description.

Generally, the present invention comprises an improved hair waving procedure and composition packaged in a pressurized container such that the composition may be released as a fast-breaking foam which substantially breaks or collapses into a liquid promptly upon discharge from the container. The application of an unstable foam waving lotion to the hair eliminates run off because the foam collapses to a liquid at about the same rate the liquid is absorbed into the hair tresses.

The cold permanent hair waving compositions of this invention generally comprises an aqueous solution of a keratin-reducing agent, a liquefied propellant, and at least one surface active agent packaged in a suitable pressurized container. Particular polyhydric alcohols can also be included and have been found to provide improved hair waving characteristics to the composition. When maintained in a package under pressure, the present composition exists as two liquid phases and a vapor phase. Upon discharge from the container, the composition forms a foam which is unstable and which substantially completely collapses to a liquid within a very short time after discharge.

The keratin-reducing compounds desirably employed as agents for reducing the cystine to cysteine by rupture of the keratin disulphide bonds in the present cold permanent waving composition include low molecular weight watersoluble mercaptans containing as functional groups, in addition to the mercaptan group present, radicals SIlCth as carboxyl, hydroxyl or amide. The mercapto-alkanoic acids described by McDonough in US. Patent No. 2,577,710 are effective keratin-reducing agents for use herein with thioglycolic acid being preferred. Mercaptopropionic acid is almost equally suitable as are ammonium thioglycolate, thioglycerol and the like.

It is desirable to have the pH of the waving lotion above pH 7 to obtain rapid and effective action and to have the pH below 10 to avoid hair damage. A particularly desirable range is from pH 8.5 to pH 9.6. A pH of about 9.3 is especially suitable. Although it is recognized that any suitable alkali may be used to adjust the pH within the indicated range, it is preferred to use a weak base or a mixture of bases containing at least one weak base as the alkali to provide a buffering and hair swelling effect. Suitable weak bases having dissociation constants of less than 10" and preferably less than 10 are useful and include compounds such as ammonia, monoethanolamine, diethanolamine, tris(hydroxymethyl) aminomethane and 3- amino 2 methyl 1,3 propanediol with ammonia being preferred.

When the pH of the hair waving lotion is adjusted in the preferred range with a Weak base, there will usually be present free base in excess of that required to form the salt of the mercapto-alkanoic acid. Strong bases may also be used in conjunction with a weak base to form these salts. Examples of strong bases useful in this invention include sodium hydroxide, lithium hydroxide, potassium hydroxide, and strong organic bases such as tetramethylammonium hydroxide. Soluble canbonates and bicarbonates such as the ammonium salts may also be added for their pH stabilizing effect. Use of a thioglycolate salt in preparing the waving lotion is, of course, equivalent to preparing it in situ from thioglycolic acid and the appropriate base.

The keratin-reducing agent may be incorporated into the lotion at a level equivalent to from 1 to about weight per cent, based on the total composition of thioglycolic acid.

The propellant required to force the hair waving composition from the pressurized container may be any liquefiable gas or combination of liquefiable gases having a suitable vapor pressure, but certain halogenated hydrocarbons are preferred for use in this invention.

The halogenated hydrocarbon propellants are the fluorinated, and chlorinated-fluorinated low molecular weight saturated aliphatic hydrocarbons which may be represented generally by the formula C H Cl F wherein n is a whole number (usually 1 or 2), x is zero or a .whole number, y is zero or a whole number, and z is a whole number, and the sum of x, y, and z is equal to 212+2. Examples of useful propellants taken either alone or in combination include monochlorotrifluoromethane, trichloromofluoromethane, dichlorodifluoromethane, dichloromonofiuoromethane, monochlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, difiuoroethane, and difluromonochloroethane.

The amount of propellant which may be employed depends upon the propellant chosen, the other ingredients of the composition and the desired pressure in the package. Desirably, from about 2 weight percent to about 20 weight percent propellant may be employed. The usual amount of propellant employed is in the range of 2.5% to 15% by weight and preferably about 6% to about 8% by weight.

A sunface active agent is included in the compositions of this invention. Its presence within prescribed limits enables the discharge of a suitable foam. If too much surface active agent is employed in the composition, the foam tends to break too slowly. Enough surface active agent must be used to achieve a desirable but fast breaking foam. For use herein, the term fast breaking is intended to mean a foam which breaks or collapses to a liquid in less than 40 seconds and preferably in about 2 to about 10 seconds after discharge on the hair.

Suitable sunface active agents maybe found among the anionic detergents, and among nonionic detergents.

In the case of anionic detergents, it is preferred that the cation of the detergent be one which confers high solubility on the detergent. The choice of a surface active agent is not critical with most of those commonly employed in shampoos and other personal detergent products being satisfactory. Examples of anionic synthetic detergents suitable for use in the practice of this invention include detergents of the sulfonated and sulfated types such as the alkyl (Cg-C13) sulfates, the alkyl (Cg-C18) polyethenoxy (l-10 units of C H O) ether sulfates, the monoor di-alkyl (Cg-C13) esters of sulfosuccinic acid, sulfonated or sulfated amides of higher fatty acids, sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids, higher fatty acid esters of low molecular weight alkylol sulfonic acids, etc., usually in the form of their sodium, potassium, ammonium, or alkanolammonium salts. Some of the particular detergents within this useful category include sodium octyl sulfate, sodium nonyl sulfate, sodium decyl sulfate, monoethanolammonium dodecyl sulfate, ammonium tetradecyl sulfate, monoethanolammonium pentadecyl sulfate, monoethanolammonium hexadecyl sulfate, monoethanolammonium octadecyl sulfate, monoethanolammonium oleyl sulfate, sodium salts of dioctyl sulfosuccinate, sodium salts of the oleic acid ester of isethionic acid, sodium salt of the lauric acid amide of taurine, triethanolammonium coconut oil monoglyceride monosulfate, monosulfate, monoethanolammonium tallow diglyceride monoethanolammonium tallow diglyceride monosulfate. Mixtures of these various anionic surface active agents are also useful and include those which come within the scope of the general class definition.

Water soluble soaps of fatty acids, such as sodium, potassium, ammonium or triethanolamine salts of tallow or coconut oil fatty acid, may be used, but the synthetic detergents are preferred. When waving lotion containing soap is rinsed from the hair with hard water, soap curd may form and be left as a dulling film on the hair. Synthetic detergents are generally free of this disadvantage.

Water soluble nonionic synthetic organic detergents are wherein R represents long chain alkyl radicals having from about 8 to about 18 carbon atoms and n is an integer from about 4 to about 30; the polyethylene oxide condensates of alkyl phenols, e.g., the condensation prodnets of alkyl phenols having about 6 to 12 carbon atoms in the alkyl group, in either straight chain or branched chain configuration, with ethylene oxide in amounts equal to 2 to 25 moles of ethylene oxide per mole of alkyl phenol; compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. Compounds with ether linkages are preferred because of their resistance to hydrolysis in alkaline solutions.

Specific compounds commercially available for use herein include, for example, Brij 30 (polyoxyethylene (4) lauryl ether by Atlas Chemical Industries of Delaware), Brij 35 (polyoxyethylene (23) lauryl ether also by Atlas), Brij 72 (polyoxyethylene (2) stearyl ether by Atlas), Brij 76 (polyoxyethylene stearyl ether by Atlas), Brij 76 (polyoxyethylene (20) stearyl ether by Atlas), Brij 52 (polyoxyethylene (2) cetyl ether by Atlas), Brij 56 (polyoxyethylene (10) cetyl ether by Atlas), and Brij 58 (polyoxyethylene (20) cetyl ether by Atlas). In addition, surface active agents such as Duponol WAQ (a lauryl alcohol sulfate sodium salt composition by Dupont of Delaware), Ethomid HT- hydrogenated tallow amide containing 5 moles ethylene oxide (a fatty acid amide-ethylene oxide condensate by Armour & Company of Illinois), G-1441 (a polyoxyethylene sorbitol lanolin derivative by Atlas Powder Company of Delaware), G-3910 (a polyoxyethylene oleyl alcohol derivative also by Atlas Powder Company), Emulphor ON-870 (a polyoxyethylene cetyl oleyl alcohol by Antara Chemicals of New York), Siponic Y-100 (a polyoxyethylene oleyl alcohol by Alcolac Chemical Company of Maryland), Siponic Y-500 (a polyoxyethylene oleyl alcohol also by Alcolac), Siponic CD (polyoxyethylene (C branched chain) alcohols by Alcolac), and Ethoxylan 100 (a polyoxyethylene lanolin alcohol by Malmstrom Chemical Company of New York), and Lanogel 31 (a polyoxyethylene lanolin derivative by Robinson Wagner) may also prove useful.

G1441 is composed of 65.1 percent ethylene oxide, 6.7 percent sorbitol and 28.2 percent lanolin by weight (Drug and Cosmetic Industry, June 1957, p. 846). Langel 31 has an iodine value of 4-12 (Hanus), is water soluble and has a saponification value of 9-18 (American Per furner and Cosmetics, March 1964, p. 51). Emulphor ON-870 has a HLB value of 15.4 (Journal of Pharmaceutical Sciences, September 1961, p. 734). G-3910 contains ethylene oxide units (Journal of Pharmaceutical Sciences, September 1961, p. 734). Duponol WAQ and Ethomid HT-15 are identified in Detergents and Emulsifiers 1963 Annual.

The quantity of surface active agent employed in the present composition is from about 0.05% to about 3 /2% by weight. The surface active agent serves the primary purpose of contributing to the production of a foam having the desired characteristics; it also aids in solubilizing or emulsifying the perfume and contributing to the dispersion of the propellant.

Certain polyhydric alcohols are preferably added to the present hair waving composition as they greatly improve the Waving characteristics of the expelled foam. These alcohols are usefully employed in an amount of about 0.5% to about 5% by weight, based on the total amount of the hair Waving phase. Useful compounds include polyhydric alcohols such as glycerine and glycols such as 1,3-butylene glycol, propylene glycol, 1,2,6- hexanetriol, 1,5-pentanediol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, tetraethylene glycol, triethylene glycol, dipropylene glycol, polypropylene glycol 150, tripropylene glycol, Z-methyl pentanediol-2,4, 2-ethyl hexanediol-1,3, and the like. 1,3- butylene glycol and Z-methyl pentanediol-2,4 are preferred.

Various minor ingredients can be included in the compositions of this invention and are generally desirable for the purposes of making the product more pleasant to use and leaving the hair in a particularly good condition. It is generally also recognized that it is possible to include a soluble salt of the disulphide of the keratin-reducing agent, especially the disulphide of the thioglycolic acid, at a level, based on the total composition, equivalent to form about 0.5% to 5% of dithiodiglycolic acid. The soluble salts which can be used include those formed from the bases listed as suitable for making the pH adjustment. These additives protect the hair from over-treatment and leave it in a particularly good condition as is disclosed in US. Patents 2,719,814 and 2,719,815. A perfume will be added in the preferred compositions of this invention.

The compositions of this invention must be packaged in suitable pressure-tight containers. For pressures lower than about 25 p.s.i.g. at 70 F., glass bottles, which may be coated on the outside with plastic, and metal cans are suitable. Metal cans are preferably employed for higher pressures. A metal which is not appreciably corroded :by the product should be chosen and/or a corrosion inhibitor should be added to the formulation. Aluminum cans are preferred because of their lightness, economy and resistance to corrosion. When aluminum cans are used, it is particularly desirable to include in the waving lotion, as a corrosion inhibitor, from about 0.001% to about 0.1% SiO as water soluble sodium silicate. Water soluble sodium silicates having a weight ratio of SiO- :Na O in the range of about 5:1 to about 1:1 are quite satisfactory.

The valves with which the pressurized containers are fitted to control their opening and discharge of product, are those commercially employed for other aerosol products. Nozzles for discharge of the product are not critical except that it is preferred to use a foam type nozzle. This type of nozzle provides opportunity for an appreciable pressure drop while the product is still confined within the nozzle. This pressure drop within the enclosed channel permits the foam to be generated within the nozzle. Foam nozzles are commercially available and have been repeatedly described in the literature. For example, the US. Patent 2,655,480 of Spitzer et al. shows a typical foam nozzle.

The following examples are set forth to further illustrate the practice of the present invention.

Example 1 The following composition is prepared and introduced into pressurized plastic-covered bottles fitted with valves to control the discharge of the product.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.40 Sodium hydroxide 0.39 Ammonia solution (28%) 6.05 Polyoxyethylene cetyl oleyl alcohol (Antara Chemicals Emulphor ON870) 1.30

Ingredients: Percent by weight Polyoxyethylene (l) oleyl alcohol (Atlas Chemicals G-39l0) 0.18 Polyoxyethylene sorbitol lanolin derivative (Atlas Chemicals Gl44l) 0.09 Propylene glycol 1.25 Sodium lauryl sulfate paste (Duponts Duponol WAQ) 1.00 Perfume 0.45 Dichlorodifiuoromethane 1.00

Dichlorotetrafluoroethane 9.00 Distilled water Balance Perfume while having a desirable effect on the product is not essential to the success of the present invention. When packaged, this composition is found to give a pressure of about 25 p.s.i.g. at 70 F. and when used in waving hair, the composition is easy to apply to the hair without run off of excess lotion.

Monoethanolamine, tris(hydroxymethyl) aminomethane, 2-amino2-methyl-1,3-propanediol and diethanolamine can replace ammonia, in whole or in part, and pH adjustment can be from pH 8.5 to pH 9.6 in this example without losing its advantages.

Example 2 The following composition is prepared and introduced into pressurized plastic-covered glass bottles fitted with valves to control the discharge of the product.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.65 Sodium hydroxide 0.41 Ammonia solution (28%) 6.25 Polyoxyethylene cetyl oleyl alcohol (Antara Chemicals Emulphor ON-870) 2.10

Polyoxyethylene oleyl alcohol (Atlas Chemicals G3910) 0.28 Polyoxyethylene lanolin alcohol (Malmstrom Ethoxylan 100) 0.19 2-methyl pentanediol-2,4 2.15 Perfume 0.45 Dichlorodifiuoromethane 2.00 Dichlorotetrafluoroethane 5.00 Distilled water Balance When the above composition is used in waving hair, very satisfactory results are realized as is the advantage that the preparation is easy to apply neatly to the hair without run off of excess lotion.

Example 3 The following composition is prepared and packed in a pressurized aluminum can fitted with a valve to control discharge of the product with a foam nozzle.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.65 Sodium hydroxide 0.41 Ammonia solution (28%) 6.25

Polyoxyethylene oleyl alcohol (Alcolac Chemicals Siponic Y-lOO) 0.28 Polyoxyethylene oleyl Alcohol (Alcolac Chemicals Siponic Y-500) 2.10 Polyoxyethylene lanolin alcohol (Robinson Wagner's Lanogel 31) 0.19 1,3-butylene glycol 1.80 Sodium silicate (Na O:SiO ratio of 3.22:1) 0.08 Perfume 0.45 Monochlorodifiuoroethane 3.40 Difiuoroethane 3.40 Distilled water Balance Perfume and sodium silicate while having a desirable effect on the product are not essential to the success thereof. When the composition is used in waving hair, satisfactory results are noted as is the advantage that the composition is easy to apply to the hair without run off of excess lotion.

Monoethanolamine, tris(hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol and diethanolamine can replace ammonia, in whole or in part, and pH adjustment can be from pH 8.5 to pH 9.6 in this example without losing its advantages.

Example 4 The following composition is prepared and packed in a pressurized aluminum can fitted with a valve to con trol the discharge of the product with a foam nozzle.

When packaged in aerosol form, the vapor pressure of the composition is found to be about 55 p.s.i.g. at 70 F. When discharged, the composition appears as a foam which substantially collapses to a liquid within about 20 seconds. The propellant is found to float on the aqueous phase on prolonged standing but upon shaking is readily redispersed. When the composition is used in waving hair, very satisfactory results are recognized over leading commercial waving preparations. The compsition has ing commercial waving preparations. The composition has without run off of excess lotion.

Example 5 The following composition is prepared and introduced into pressurized aluminum cans fitted with valves to control the discharge of the product from a foam nozzle.

Ingredients: Percent by weight Thioglycolic acid (70%) 7.90 Sodium hydroxide 0.41 Ammonia solution (28%) 6.25 Polyoxyethylene (4) lauryl alcohol (Atlas Chemicals Brij 30) 0.23

Polyoxyethylene (23) lauryl alcohol (Atlas Chemicals Brij 35) 1.63 1,3-buty1ene glycol 2.30 Sodium silicate (Na O:SiO ratio of 3.22:1) 0.08 Perfume 0.45

Monochlorodifluoroethane 3.40 Difiuoroethane 3.40 Distilled water Balance Perfume and sodium silicate while having a desirable effect on the packaged product are not essential to the success of the invention. The composition is found to give a pressure of about 55 p.s.i.g. at 70 F. and about p.s.i.g. at F. Upon discharge from the container the composition appears as a foam which substantially collapses to a liquid within about 5 seconds. When the composition is used in waving hair, very satisfactory results are recognized over leading commercial waving compositions. The composition has the further advantage of being easy to apply to the hair without run off of excess lotion.

9 Example 6 [be following composition is prepared and introduced into pressurized cans fitted with valves to control the discharge of the product from a foam nozzle.

Perfume and sodium silicate while having a desirable effect on the packaged product are not essential to the success of the invention. The composition is found to give a pressure of about 55 p.s.i.g. at 70 F. and about 115 p.s.i.g. at 130 F. Upon discharge from the container the composition appears as a foam which substantially collapses to a liquid within about seconds. When the composition is used in waving hair, very satisfactory results are recognized. The composition has the further advantage of being easy to apply to the hair without run oif of excess lotion.

Any other propellant such as monochlorotrifluoromethane, trichloromonofiuoromethane, dichlorodifluoromethane, dichloromonofluorometihane, trichlorotrifiuoroethane, dichlorotetrafluoroethane, and difluoromonochloroethane may be substituted for the above propellants of the example separately or in suitable combination with vapor pressure adjustment obtained by regulating the amounts of additives of the combinations for preparation of suitable fast-breaking foams without departing from the advantages of the invention.

It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of this invention.

What is claimed is:

1. A two liquid phase pressurized hair waving composition adapted for discharge from its container as a foam, which collapses to a liquid promptly after discharge, consisting essentially of: from about 1% to about of a member selected from the group consisting of thioglycolic acid, ammonium thioglycolate, and thioglycerol, an alkalizing agent a substantial part of which is a base with a dissociation constant less than 10- imparting to the composition a pH above about 7 but below 10; from about 2 to about 20% by weight of a propellant selected from the group consisting of fluorinated, and chlorinated-fluorinated low molecular weight saturated aliphatic hydrocarbons represented by the formula C H Cl F wherein n represents a whole number 1 and 2; x represents zero, 1 to 4; y represents zero, 1 and 2; and'z represents 1 to 4 and the sum of x, y and z is equal to 2n+2; from about 0.05% to about 3 /2 by weight of a surface active agent selected from the group consisting of nonionic and anionic surface active agents; as a polyhydric alcohol from about 0.5% to about 5% by weight of an organic compound selected from the group consisting of propylene glycol, 1,3-butylene glycol, Z-methyl pentanediol-2,4, and mixtures thereof; and the balance substantially water.

2. A pressure tight aluminum container which contains the composition of claim 1, said composition containing additionally as a corrosion inhibitor from about 001% to about 0.1% SiO added as 'water soluble sodium silicate.

3. A two-liquid phase pressurized hair waving composition adapted for discharge from its container as a foam, which collapses to a liquid promptly after discharge, consisting essentially of: from about 3% to about 6% of thioglycolic acid, an alkalizing agent, a substantial part of which is a base selected from the group consisting of ammonia, monoethanolamine, diethanolamine, tris- (hydroxymethyl) aminomethane, 2-amino-2-methyl-l,3- propanediol and mixtures thereof imparting to the composition a pH in the range of 8.5 to 9.5; from about 2% to about 20% of a propellant selected from the group consisting of dichlorodifluoromethane, dichlorotetrafluoroethane, difluoroethane and monochlorodifluoroethane; from about 0.05% to about 3 /2% of a surface active agent selected from the group consisting of nonionic and anionic surface active agents; as a polyhydric alcohol from about 0.5% to about 5% by weight of an organic glycol selected from the group consisting of propylene glycol, 1,3-butylene glycol, Z-methyl pentanediol-2,4, and mixtures thereof; and the balance substantially water.

4. A two liquid phase pressurized hair waving composition adapted for discharge from its container as a foam, which collapses to a liquid promptly after discharge, consisting essentially of: from about 1% to about 10% of a member selected from the group consisting of thioglycolic acid, ammonium thioglycolate, and thioglycerol, an alkalizing agent a substantial part of which is a base with a dissociation constant less than 10' imparting to the composition a pH above about 7 but below 10; from about 2% to about 20% by weight of a fluorinated, and chlorinated-fluorinated low molecular weight saturated aliphatic hydrocarbon propellants; as a polyhydric alcohol from about 0.5% to about 5% by weight of an organic compound selected from the group consisting of propylene glycol, 1,3-butylene glycol and 2-methyl pentanediol-2,4 and mixtures thereof; from about 0.05 to about 3 /2% of a surface active agent selected from the group consisting of nonionic and anionic surface active agents; and the balance substantially water.

5. A two liquid phase pressurized hair waving composition adapted for discharge from its container as a foam, which collapses to a liquid promptly after discharge consisting essentially of: from about 3% to about 6% of thioglycolic acid, an alkalizing agent, a substantial part of which is a base selected from the group consisting of ammonia, monoethanolamine, diethanolamine, tris-(hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol and mixtures thereof imparting to the composition a pH of about 9.3; as a propellant, not less than about 2.5% and not more than about 15% by weight of a propellant selected from the group consisting of fluorinated, and chlorinated-fiuorinated low molecular weight saturated aliphatic hydrocarbon propellants; as a polyhydric alcohol from about 1% to about 10% by weight of an organic compound selected from the group consisting of propylene glycol, 1,3-butylene glycol, Z-methyl pentanediol-2,4 and mixtures thereof; and from about 0.05% to about 3 /2% of a surface active agent selected from the group consisting of nonionic and anionic surface active'agents; and the balance substantially water.

6. A pressure tight aluminum container which contains the composition of claim 5, said composition containing additionally as a corrosion inhibitor, from about 001% to about 0.1% SiO added as water soluble sodium silicate.

7. A two liquid phase pressurized hair waving composition adapted for discharge from its container as a foam, which collapses to a liquid promptly after discharge, consisting essentially of: from about 3% to about 6% of thioglycolic acid, an alkalizing agent a substantial part of which is a base selected from the group consisting of ammonia, monoethanolamine, diethanolamine, tris- (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3- propanediol and mixtures thereof imparting to the composition a pH of about 9.3; as a propellant, from about 2% to about 20% of one selected from the group consisting of dichlorodifiuoromethane, dichlorotetrafiuoroethane,

and difluoroethane and monochlorodifiuoroethane; as a polyhydric alcohol from about 1% to about 20% of an organic compound selected from the group consisting of propylene glycol, 1,3-butylene glycol, 2-methyl pentanediol-'2,4 and mixtures thereof; and from about 0.05% to about 3 /2% of a surface active agent selected from the group consisting of nonionic and anionic surface active agents; and the balance substantially water.

8. A two liquid phase pressurized hair waving composition adapted for discharge from its containers of foam which collapses to a liquid promptly after discharge, consisting essentially of about 90% by weight of a waving lotion, comprising to 6 percent thioglycolic acid, 0.05 to 0.5 percent sodium hydroxide, 4 to 7 percent ammonium hydroxide, 0.5 to 2.0 percent a nonionic surface active agent, 0.5 to 5.0 percent 1,3-butylene glycol and distilled water, and about by weight of a propellant selected from the group consisting of dichlorodifluoromethane, dichlorotetrafiuoroethane, monochlorodifiuoroethane, and difluoroethane.

9. A two liquid phase pressurized hair waving composition adapted for discharge from its containers of foam which collapses to a liquid promptly after discharge, consisting essentially of about 90% by weight of a waving lotion, comprising 5 to 6 percent thioglycolic acid, 0.05 to 0.5 percent sodium hydroxide, 4 to 7 percent ammonium hydroxide, 0.5 to 2.0 percent a nonionic surface active agent, 0.5 to 5.0 percent 2-methyl propanediol-2,4 and distilled water, and about 10% by weight of a propellant selected from the group consisting of dichlorodifluoromethane, dichlorotetrafluoroethane, monochlorodifiuoroethane, and difluoroethane.

10. A two liquid phase pressurized hair waving composition adapted for discharge from its containers of foam which collapses to a liquid promptly after discharge, consisting essentially of about by weight of a waving lotion, comprising 5 to 6 percent thioglycolic acid, 0.05 to 0.5 percent sodium hydroxide, 4 to 7 percent ammonium hydroxide, 0.5 to 2.0 percent a nonionic surface active agent, 0.5 to 5.0 percent propylene glycol and distilled water, and about 10% by weight of a propellant selected from the group consisting of dichlorodifiuoromethane, dichlorotetrafluoroethane, monochlorodifiuoroethane, and difluoroethane.

References Cited UNITED STATES PATENTS 3,039,934 6/1962 Whitman et al. l67-87.l 3,099,603 7/1963 Banker et al. 167 -87.1

FOREIGN PATENTS 107,057 4/1939 Australia.

OTHER REFERENCES Lehne: American Perfumes and Cosmetics, vol. 78, No. 10, pp. 103-107, October 1963.

Guillaume: German printed application N 8,064, August 1956.

ALBERT T. MEYERS, Primary Examiner.

VERA C. CLARKE, Assistant Examiner.