GB1595649A - Aerosol hair spray compositions - Google Patents

Description

(54) AEROSOL HAIR SPRAY COMPOSITIONS (71) We, NATIONAL STARCH AND CHEMICAL CORPORATION, a corporation organised and existing under the laws of the State of Delaware, United States of America, of 10 Finderne Avenue, Bridgewater, New Jersey, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- Ecological considerations have recently resulted in a search for suitable substitutes for conventionally employed halocarbons as propellants for aerosol hair spray formulations. Certain hydrocarbons as well as carbon dioxide have been proposed as the most practical and economical replacements. However, the use of these propellants poses a number of problems, some of which are related to the decreased solubility of hair spray resins in the alcohol carbon dioxide or hydrocarbon-propellant systems, thus, although the commercially favored vinyl acetate/vinyl pyrrolidone copolymers as well as the carboxylated acrylic, maleate and/or acetate based resins are soluble in the anhydrous alcohol-halocarbon systems, the reduced solubility of some of these resins in the proposed anhydrous alcohol-hydrocarbon or carbon dioxide propellent may render the use of these resins unacceptable to the industry. While the use of methylene chloride in amounts of up to about 25% by weight, generally 1520%, has been proposed in order to increase the solubility of the hair spray resins, the use thereof has been questioned from an economic as well as a safety viewpoint.

The issues of shelf life and metal container corrosion are also critical with regard to hair spray resin formulations. Substantially all hair spray resin formulations available heretofore have been anhydrous due to the belief that in water-containing systems the polymer was rendered unstable and corrosion of the metal container would occur resulting in unacceptable shelf life. Industry has been forced to use formulations employing anhydrous alcohol since the use of wateralcohol mixtures, for example, 95% alcohol, has been found to cause an unacceptable rate of corrosion in uncoated metal containers.

We, have now found that the addition of small amounts of water to the hair spray resin not only improves the solubility of the resin in the carbon dioxide or hydrocarbon alcohol aerosol formulations, but will unexpectedly result in an aerosol formulation with improved stability and reduced can corrosion when compared to similar aerosol formulations to which the water has not been added. Thus, we have found that the addition of water improves the color stability of the polymer solution of the aerosol container, Moreover, accelerated aging tests show that aerosol can corrosion diminishes as the water content is increased within the limits given below.

One of the few areas where water has been employed with hair spray resins has been in the "pump-type" non-pressurized aqueous alcoholic hair setting formulations wherein metal containers are not generally used and wherein relatively long drying periods are invoved. Additionally, U.S. Patent 2,995,278 teaches the use of aqueous alcoholic solutions together with halogenated hydrocarbon/hydrocarbon propellent systems, which formulations remain in two separate phases until mixed and propelled using the specialized mixing chamber and valving device.

The present invention is therefore directed to novel aerosol hair spray compositions in aerosol metal containers, said compositions comprising 0.5 to 5.0% by weight of at least one carboxylated or nonionic hair spray resin, 1 to 15% water, a propellent selected from the group consisting of 27% carbon dioxide, 5-35% hydrocarbon and mixtures thereof, the remainder of said composition (to 100(,") comprising ethanol or isopropanol, or mixtures thereof.

The present invention is therefore equally applicable to use with any of the conventionally employed hair spray resins. Such resins may be generally classified as nonionic and carboxylated resins. The nonionic resins (designated group A) include the resin formed from polyvinyl acetates and copolymers thereof hydrolyzed to an extent that from 15 to 60% of its acetate groups are converted into hydroxyl groups, such as are disclosed in U.S. Patent 3,417,180. Nonionic resins also include the copolymers ot vinyl acetate and vinyl pyrrolidone. While these copolymers may contain vinyl acetate in amounts of 20% or more. it is those copolymers containing at least about 50% vinyl acetate which benefit most from the present invention since the solubility of systems containing less that about 50 /" vinyl acetate is satisfactory for most formulations. Representative of the nonionic hair spray resins are those available, for example, from BASF under the tradenames Luviskol VA 28 (20% vinyl pyrrolidone, 80% vinyl acetate) and Luviskol VA 37 (30 /n vinyl pyrrolidone, 70 /O vinyl acetate). The carboxylated resins useful in the present invention and designated Group B are the carboxylated hair spray resins which comprise organic vinyl polymers containing (i) 5-55 mole per cent acidic monomer such as a monomer selected from the group consisting of maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic half esters, fumaric half esters, crotonic acid, aconitic acid, allyl acetic acid, allyl arsenic acid, 2-allyl oxyproplonic acid, 13-benzoyl acrylic acid, N-n-butyl maleamic acid, N-ethyl maleamic acid, N-methyl maleamic acid, N,Ncarboxyl-substituted maleamides, 2-furfuryl acrylic acid, 2-vinyl propionic acid, vinyl acetic acid, sorbic acid, dihydroxy maleic acid and mixtures thereof; and (ii) 9545 mole percent of at least one monomer selected from the group consisting of: (a) styrene and derivatives thereof, (b) methylacrylate and acrylate alkyl esters wherein the alkyl group contains 1 to 18 carbon atoms, (c) vinyl esters of the formula CH2=CH-OCOR where R is C1-C1a, (d) alkyl substituted acrylamides and methacrylamides of the formula CH2=CR-CONR1R2 where R is H or CH3; Rl is H or C1-C12 and R2 is C1-C18.

(e) diesters of fumaric, itaconic and maleic acids, and, (f) vinyl ethers such as methyl vinyl ether, isobutyl vinyl ether, etc.

In addition to the two monomeric components described above, the carboxylated resin polymer (B) may also contain up to about 30 mole per cent of at least one of the following functional monomers: a) hydroxy functional acrylates and methacrylates such as hydroxy ethyl acrylate, hydroxy propyl acrylate, hydroxy ethyl methacrylate, etc.

b) cationic monomers such as t-butyl aminoethyl methacrylate, dimethyl aminoethyl methacrylate, diethyl aminoethyl methacrylate and the quaternized derivatives thereof such as the quaternized product of l-chloromethacrylate and trimethylamine or of dimethylaminoethyl methacrylate and dimethyl sulfate; c) acrylamide and non-alkyl substituted acrylamides such as diacetone acrylamide; d) cyclic amides such as vinyl pyrrolidone.

Examplary of such carboxylated hair spray resins are the copolymers of vinyl methyl ether and mono-alkyl esters of maleic anhydride sold by GAF under the GANTREZ trademark; vinyl acetate-crotonic acid copolymers and carboxylated terpolymers of vinyl acetate, crotonic acid and a vinyl ester of an alpha-branched saturated aliphatic monocarboxylated acid containing from 5 to 10 carbon atoms in the carboxylic acid moiety (the latter two resins are respectively described in U.S.

Patents 2,996,471 and 3,810,977 and are available from National Starch and Chemical Corporation under the RESYN trademark; styrene maleic anhydride copolymers and esters thereof (e.g. ARCO's SMA); terpolymers of alkyl acrylamide, acrylamide or methacrylamide, N-vinyl pyrrolidone and acrylic or methacrylic acid sold by American Cyamamid as QUADRAMER; copolymers of octylacrylamide, acrylate, butylaminoethyl methacrylate sold by National Starch and Chemical Corporation under the AMPHOMER trademark, partially hydrolyzed copolymers of acrylic ester with other vinyl monomers (e.g. CIBA 325); terpolymers of vinyl type monomers containing carboxylic groups (e.g. VEM 640-B from the Barr Co.); the interpolymers of various alkyl methacylates and acrylic acid (e.g. Resin E-1139 available from Rohm and Haas); etc.

All of the previously mentioned carboxylated resins must be reacted with an alkaline reagent to neutralize at least 3% of the available carboxyl functionalities.

As is recognized by those skilled in the art, the preferred degree of neutralization will vary depending upon the specific carboxylated polymer employed. Thus, the copolymer of octylacrylamide, acrylate and butylaminoethyl methacrylate is generally neutrallized to an extent of 7090% while the copolymers of vinyl methyl ether and the monoalkyl esters of maleic acid are usually neutralized to only about 57%. The neutralization may be accomplished using suitable alkaline reagents including sodium and potassium hydroxide, ammonia, primary, secondary and tertiary amines; alkanolamides and hydroxyamines such as 2-amino-2-methyl I-propanol (AMP) and 2-amino-2-methyl-1,3-propanediol (AMPD).

The neutralization is accomplished by mixing the resin in the form of a solution in an organic solvent, with or without added water, with a concentration of the alkaline reagent approximately equimolar to the percent of the carboxyl groups to be neutralized. The choice of the alkaline reagent as well as the degree of neutralization affects not only the water solubility or dispersibility of the resultant resin thus permitting easy removal of the resin from the hair by merely washing with shampoo but also affects the flexibility of the resultant film when sprayed on the hair. Thus, a particular reagent may be selected or the degree of neutralization can be regulated to produce a soft film, normal film or a film suitable for "hard-tohold" hair. A further description of the neutralization is presented, for example, in U.S. Patent 2,996,471.

The selected resin, dissolved in ethanol and/or isopropanol is then admixed with water prior to being charged into the aerosol container. The amount of water employed is from I to 15% by weight of the total formulation. It will be apparent that the higher levels of water will result in a hair spray film which will take longer to dry when applied to the hair. Formulations using water in amounts of 3 to 8% by weight of the total formulation are preferred. It is noted that according to prior art formulations, it was required that alcohols used as solvents be employed as anhydrous alcohols and it is therefore an added feature of the present invention that alcohol-water mixtures may be employed in the present formulations thus presenting substantial economic savings. If aqueous alcohol mixtures are employed, the amount of water in the non-anhydrous alcohol is included when calculating the total water present in the aerosol formulation.

The propellent employed in the present formulation is either carbon dioxide or a suitable hydrocarbon propellent or mixtures thereof. Suitable hydrocarbon propellents include, for example, propane, isobutane, n-butane, 2,2-dimethyl propane and isopentane. If only carbon dioxide is employed, amounts of 2 to 7% are satisfactory. In the case of hydrocarbon propellents, amounts of 5 to 35% may be employed. It will be understood that when mixtures of carbon dioxide and hydrocarbon are used as propellents, the amount required will vary based on the relative proportions of the propellent components. Among the most commonly employed propellent mixtures are. those which use propane and/or isobutane together with the carbon dioxide. Typical of such propellent mixtures is a blend of approximately 1 part carbon dioxide and 6 parts A46 (a blend of isobutane and propane).

Optional additives may be incorporated into the aerosol formulations of this invention in order to modify certain properties thereof. Among these additives may be included: plasticizers such as glycols, phthalate esters and glycerine; silicones; emollients, lubricants and penetrants such as lanolin compounds; protein hydrolizates and other protein derivatives, ethylene oxide adducts and polyoxyethylene cholesterol; dyes, tints, and other colorants; and perfumes. As used hereinafter, the phrase 'consisting essentially of' is intended to embrace compositions containing minor amounts of such additives as are conventionally employed in aerosol hair spray formulations.

In general, the formulations of the present invention can be prepared by merely dissolving the resin in the solvent, adding the neutralizing agent if required, and the desired amount of water, as well as any modifying agents, and then charging this "concentrate" into the aerosol container. The aerosol valve is then crimped in place and the propellent added. Carbon dioxide is added either as a gas or in the form of an alcoholic solution using conventional techniques.

Hydrocarbons are added in liquid form under pressure.

With regard to proportions, the final aerosol formulations contain the hair spray resin which, in the case of the carboxylated resins, has been neutralized to the degree desired, in a concentration of from 0.5 by weight to 5.0%',), preferably 0.5 to 2.5%; water in an amount of I to 15%, preferably 3 to 8%, carbon dioxide propellent in an amount of 2 to 7%, preferably 4 to 6% or hydrocarbon propellent in an amount of 5 to 35%, preferably 15 to 20%, with the remainder of the composition (to a total of 100%) being ethanol or isopropanol or mixtures thereof.

It should be recognized that the latter proportions should be considered as being merely illustrative inasmuch as it may well be possible to prepare operable formulations having concentrations of components which fall outside the above suggested ranges.

The resulting hair fixing formulations exhibit all of the characteristics required of such product, resulting in films which hold the hair well and which are easily removed by shampooing.

In the following examples, which further illustrate this invention, all parts given are by weight unless otherwise indicated.

EXAMPLE I This example illustrates the preparation of an aerosol hair spray formulation representative of the present invention Two parts of a carboxylated acrylic copolymer (available from Rohm and Haas as Resin E-1139) was neutralized with 0.18 parts of 2-amino-2-methyl-1- propanol (AMP). The neutralized resin was then dissolved in 87.82 parts anhydrous ethanol and 5 parts water were added thereto. The thus prepared concentrate was then added to an aerosol can (half pound tinplate with tin side seam) which was purged to eliminate air. The aerosol valve was then emplaced and crimped onto the can and carbon dioxide was added through the valve until 5 parts by weight had been picked up.

The resulting aerosol formulation was stable over an extended period of time and when sprayed resulted in a satisfactory hair holding film which could be readily removed by shampooing.

EXAMPLE II This example demonstrates the beneficial effects contributed by the presence of water in the hair spray formulations of the present invention.

Two series of. samples, each series comprising 10 (6 oz.) cans (half pound tinplate with tin side seam) were prepared. One series was charged with the formulation of Ex. I (designated series A) and the other series (designated series B) charged with a similar formulation containing 92.82 parts anhydrous ethanol and no water. The cans were incubated at 1200 F. At six week intervals (each equivalent to approximately 1 year at room temperature), for a period of 18 weeks, two cans of each formulation were removed from the oven, cooled to room temperature and then opened and the concentrate evaluated for colder and pH. The amount of can corrosion was also observed.

The results are as follows: 1. After the first six weeks, detinning (a sign of corrosion of the tin lining as evidenced by the formation of black spots and blotches) was evident throughout the interiors of the can filled with formulations of Series B which contained no water. The condition became worse with time and at 18 weeks was of significant proportion.

2. During the 18 week period insignificant detinning was noted (in some cases none at all) on the cans of Series A containing formulations of the present invention.

3. No difference in concentrate color or pH was observed between the two samples.

4. All cans were relatively stable in pressure.

EXAMPLE Ill The following experiment was performed in order to show the improvement in solubility with increased water content in accordance with the present invention.

Three formulations were prepared using the general procedure of Example 1.

The formulations were filled in glass vessels fitted with a thermocouple device. The filled vessels were chilled slowly until turbidity signifying resin insolubility developed. The resultant "cloud point", i.e. the temperature at which the polymer can be seen to precipitate from the solution, was recorded. A lower cloud point indicates better solubility.

The specific formulations and corresponding cloud points are shown in Table 1.

TABLE I Formulations A B C Resin E-1139 2.00 2.00 2.00 AMP 0.18 0.18 0.18 Anhydrous Ethanol 92.82 87.82 82.82 Distilled water - 5.00 10.00 Carbon Dioxide 5.00 5.00 5.00 Cloud Point F +48 -22" below -58" As is shown by the observed results, the addition of water to the hair spray formulation provides an impressive improvement in the solubility of the carboxylated vinyl polymer contained therein.

EXAMPLE IV This example illustrated the use of vinyl acetate-crotonic acid type polymers in the aerosol composition of the present invention.

Two carboxylated polymers available from National Starch and Chemical corporation under the tradenames RESYN 28-1310 and RESYN 28-2930 comprising respectively a copolymer of vinyl acetate and crotonic acid and a terpolymer of vinyl acetate, crotonic acid and vinyl neodecanoate were employed to produce aerosol formulations using the procedure outlined in Example I. The specific formulations using the procedure outlined in Example I are shown in Table II below: TABLE II Formulations A B C D E F RESYN 28-2930 1.50 1.50 1.50 1 50 RESYN 28-1310 1 I 1 1.50 1.50 1.50 AMP 0.12 0.12 0.12 0.12 0.12 0.12 Anhydrous Ethanol 93.38 90.88 88.38 93.38 90.88 88.38 Distilled water - 2.50 5.00 2 2.50 5.00 Carbon dioxide 5.00 5.00 5.00 5.00 5.00 5.00 The aerosol formulations were stored and evaluated at 2, 4, 6, 12 and 24 week intervals following the procedure used in Example I. The observed results follow: Formulations A-C I. Less discoloration of the concentrate was observed in the samples containing larger amounts of water for all the time periods.

2. Less detinning was observed in formulations containing water at 6, 12 and 24 week intervals. No differences in can corrosion were observed at the 2 and 4 week intervals.

Formulations D-F 1. Less concentrate discoloration was observed at all time intervals in the samples containing larger amounts of water.

2. Less detinning was observed in formulations containing water at all time intervals.

3. The resin precipitated at the 24 week interval in the formulations containing no water. The samples containing water remained homogeneous.

EXAMPLE V This example illustrates the increased solubility obtained by the addition of water to hair spray formulations containing carboxylated resins and the effect of increased neutralization and solid content of the polymer on the level of solubility.

A series of aerosol formulations were prepared using the vinyl acetate crotonic acid polymers of Example IV. The formulations were tested for solubility using the cloud point testing procedure described in Example III. Formulations and results are shown in Table III.

TABLE Ill Formulations AA RESYN 28-1310 1.50 1.50 1.50 1.50 1.50 AMP 0.12 0.12 0.12 0.12 0.12 Anhydrous ethanol 93.38 92.38 90.88 88.38 83.38 Distilled water 0.0 1.00 2.50 5.0() 10.00 Carbon dioxide 5.00 5.00 5.00 5.()0 5.00 Cloud Point ( F) 75 66 57 37 -11 Formulations BB RESYN 28-1310 200 2.00 200 4.00 4.()0 4.00 AMP 0.16 0.16 0.16 0.32 0.32 0.32 Anhydrous ethanol 92.84 87.84 82.84 90.68 85.68 80.68 Distilled water 0.0 5.00 10.00 0.0 5.00 10.00 Carbon dioxide 5.00 5.00 5.00 5.00 5.00 5.00 Cloud Point ( F) +61 -1" -20 +56 -10 -20 Formulations CC RESYN 28-2930 2.00 2.00 2.00 2.00 2.00 AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 92.83 92.33 89.83 86.78 80.73 Distilled water 0.0 0.50 3.00 6.05 12.10 Carbon dioxide 5.00 5.00 5.00 5.00 5.00 Cloud Point ( F) +33 +23 -50 -10 -26 Formulations DD RESYN 28-2930 2.00 2.00 2.()() 2.00 4.00 4.00 AMP 0.20 0.20 0.20 0.20 0.33 0.33 Anhydrous ethanol 92.80 92.30 89.80 86.80 90.67 80.67 Distilled water 0.0 0.50 3.00 6.00 0.0 10.00 Carbon dioxide 5.00 5.00 5.00 5.00 5.00 5.00 Cloud Point ( F) +28 +16 -10 -25 +4 -20 The cloud points shown above indicated the improved solubility characteristic of the compositions of the present invention.

EXAMPLE VI In this example the Resyn 28-2930 polymer was used in a hair spray formulation wherein a hydrocarbon mixture was used as propellent. The procedure and Cloud Point test discussed in the previous examples were repeated using the following formulation: RESYN 28-2930 2.00 2.00 2.00 AMP 0.17 0.17 0.17 Anhydrous ethanol 77.83 74.83 71.83 H2O - 3.00 6.00 Isobutane 18.00 18.00 18.00 Propane 2.00 2.00 2.00 Cloud Point ( F) 16 < -30 < -30 EXAMPLE VII As already discussed, carbon dioxide-propelled aerosol formulations can be prepared using the basic procedure dcscribed in Example I with any carboxylated resins comprising the following monomeric components: TABLE IV Formulations A B C D E F G H Vinyl Acetate 90 80 70 70 70 t-Octyl Methacrylamide 50 50 Methyl Methacrylate 20 Methyl Acrylate 10 10 Isobutyl Vinyl Ether 15 Styrene 60 15 Crotonic Acid 10 Acrylic Acid 10 10 Mono-ethyl Maleate 10 10 15 30 Maleic Acid 15 Hydroxy Propyl Acrylate 5 10 Diacetone Acrylamide 5 5 10 Vinyl Pyrrolidone 15 Di-Octyl Maleate 10 10 Acrylamide 10 In all cases, aerosol formulations containing the above carboxylated polymers, when neutralized to the desired extent, will exhibit improved solubility and shelf life in carbon dioxide/alcohol systems when water is added according to the teachings of the present invention.

EXAMPLE VIII The example illustrates the use of 95% ethanol in the formulation of the present invention.

Two parts of a carboxylated polyvinyl acetate copolymer used in Sample D, E and F of Example IV were mixed with 0.16 parts of 2-amino-2-methyl-l-propanol and 92.84 parts of 95% ethanol. Mixing was continued until solution was complete.

The thus prepared concentrate was then added to an aerosol can which was purged to eliminate air. The aerosol valve was then emplaced and crimped onto the can and carbon dioxide was added through the valve until 5 parts by weight had been picked up.

It was found that the resulting aerosol hair spray formulation when sprayed resulted in a satisfactory hair holding film which could be readily removed by shampooing. Moreover, the aerosol formulation displayed superior low temperature stability and can stability when compared to a formulation made with anhydrous ethanol and no externally added water.

EXAMPLE IX This example shows the superior solubility experienced by the formulations of the present invention as compared with those of the prior art wherein methylene chloride is used to improve solubility. The example also shows the use of both hydrocarbon and carbon dioxide propellents in the present formulations.

The preparative and testing procedures described in the previous examples were repeated using the formulations shown below.

Formulation IX-A RESYN 28-2930 2.00 2.00 2.00 2.00 2.00 AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 77.83 72.83 62.83 76.83 75.33 Distilled water - - - 1.00 2.50 Methylene Chloride - 5.00 15.00 - Isobutane 18.00 18.00 18.00 18.00 18.00 Propane 2.00 2.00 2.00 2.00 2.00 Cloud Point ("F) 18 20 -27" -5" < -30" Formulation IX-B RESYN 28-1310 2.00 2.00 2.00 2.00 2.00 AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 77.83 72.83 57.83 75.33 72.83 Distilled water 2 5 - 2.5 5.00 Methylene Chloride - 5.00 20.00 - - Isobutane 18.00 18.00 18.00 18.00 18.00 Propane 2.00 2.00 2.00 2.00 2.00 Cloud Point ("F) 65O 50O 5O 25O -12" Formulation IX-C RESYN 28-2930 2.00 2.00 2.00 2.00 2.()() AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 92.83 X7.X3 82.83 90.83 86.83 Distilled water - - - 2.00 6.00 Methylene Chloride 5.00 10.()() Carbon Dioxide 5.00 5.00 5.()0 5.()0 5.00 Cloud Point ( F) 31O 13 -3 4 -20 Formulation IX-D RESYN 28-1310 2.00 2.()0 2.00 2.00 2.(H) AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 92.X3 87.83 67.83 90.X3 X6.83 Distilled water - - - 2.00 6.00 Methylene Chloride 5.00 20.00 - Carbon Dioxide 5.00 5.00 5.00 5.()0 5.()0 Cloud Point ( F) 62 47 7 35 -15 As is shown by the above results, the addition of relatively small amounts of water to the aerosol hair spray formulations results in a marked improvement in solubility over that obtained using much larger amounts of methylene chloride.

EXAMPLE X This example illustrates the use of conventional nonionic hair spray resins in accordance with the present invention. The preparative and testing procedures described in Example I were used to prepare the aerosol formulations shown in the following table.

RESYN 959C (1) 3.33 3.33 - - - - Luviskol VA55 1(2) - - 4.00 4.00 - - Luviskol VA37 1(3) - - - - 4.00 4.00 Anhydrous Ethanol 76.67 70.67 - - 76.00 70.00 Anhydrous Isopropanol - - 71.00 65.00 - Distilled Water - 6.00 - 6.00 - 6.00 Isobutane 18.00 18.00 22.50 22.50 18.00 18.00 Propane 2.00 2.00 2.50 2.50 2.00 2.00 Cloud Point (0F) 70 4 80 300 27 -30 (1) 40% Hydrolyzed polyvinyl acetate (avg. Molecular wt. 11,000

Claims (9)

**WARNING** start of CLMS field may overlap end of DESC **. Formulation IX-C RESYN 28-2930 2.00 2.00 2.00 2.00 2.()() AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 92.83 X7.X3 82.83 90.83 86.83 Distilled water - - - 2.00 6.00 Methylene Chloride 5.00 10.()() Carbon Dioxide 5.00 5.00 5.()0 5.()0 5.00 Cloud Point ( F) 31O 13 -3 4 -20 Formulation IX-D RESYN 28-1310 2.00 2.()0 2.00 2.00 2.(H) AMP 0.17 0.17 0.17 0.17 0.17 Anhydrous ethanol 92.X3 87.83 67.83 90.X3 X6.83 Distilled water - - - 2.00 6.00 Methylene Chloride 5.00 20.00 - Carbon Dioxide 5.00 5.00 5.00 5.()0 5.()0 Cloud Point ( F) 62 47 7 35 -15 As is shown by the above results, the addition of relatively small amounts of water to the aerosol hair spray formulations results in a marked improvement in solubility over that obtained using much larger amounts of methylene chloride. EXAMPLE X This example illustrates the use of conventional nonionic hair spray resins in accordance with the present invention. The preparative and testing procedures described in Example I were used to prepare the aerosol formulations shown in the following table. RESYN 959C (1) 3.33 3.33 - - - - Luviskol VA55 1(2) - - 4.00 4.00 - - Luviskol VA37 1(3) - - - - 4.00 4.00 Anhydrous Ethanol 76.67 70.67 - - 76.00 70.00 Anhydrous Isopropanol - - 71.00 65.00 - Distilled Water - 6.00 - 6.00 - 6.00 Isobutane 18.00 18.00 22.50 22.50 18.00 18.00 Propane 2.00 2.00 2.50 2.50 2.00 2.00 Cloud Point (0F) 70 4 80 300 27 -30 (1) 40% Hydrolyzed polyvinyl acetate (avg. Molecular wt. 11,000). (2) Copolymer of 50% vinyl pyrrolidone and 50% vinyl acetate. (3) Copolymer of 30% vinyl pyrrolidone and 70n;" vinyl acetate. Summarizing, it is illustrated by the examples presented herein that the addition of small amounts of water to a carbon dioxide or hydrocarbon-propelled aerosol hair spray formulation unexpectedly greatly increases the solubility of the conventional hair spray resin while increasing the shelf stability of the aerosol mixture in the container. WHAT WE CLAIM IS:

1. An aerosol hair spray composition, in a metal aerosol dispensing container, said composition consisting essentially of: i) 0.5 to 5.0% of at least one carboxylated or nonionic hair spray resin, said carboxylated resin being one in which at least 3% of the available carboxylic acid groups are neutralized; ii) 1 to 150/" water; iii) 2 to 7% carbon dioxide and/or 5-35% hydrocarbon aerosol propellant; and iv) ethanol and/or isopropanol to 100 /", said percentages being based on the total weight of the composition.

2. A composition according to claim 1, containing 3 to 8% water.

3. A composition according to claim I or 2, wherein the hair spray resin is a carboxylated organic vinyl polymer containing: i) 5-55 mole percent of an acidic monomer selected from maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic half esters, fumaric half esters, crotonic acid, aconitic acid, allyl acetic acid, allyl arsonic acid, 2-allyl oxypropionic acid, ss-benzoyl acrylic acid, N-n-butyl maleamic

acid, N-ethyl maleamic acid, N-methyl maleamic acid, N,N- carboxyl substituted maleamides, 2-furfuryl acrylic acid, 2-vinyl propionic acid, vinyl acetic acid, sorbic acid, dihydroxy maleic acid and mixtures thereof; ii) 9545 mole percent of one or more comonomers selected from: (a) styrene and derivatives thereof; (b) methacrylate and acrylate alkyl esters wherein the alkyl group contains 1 to 18 carbon atoms, (c) vinyl esters of the formula CHCH--OCOR wherein R is C1-C18 alkyl, (d) alkyl substituted acrylamides and methacrylamides of the formula CH2=CR-CONR1R2, wherein R is H or CH3, R, is H or C1-C12 alkyl and R2 is C1-C18 alkyl; (e) diesters of fumaric, itaconic and maleic acids, and (f) vinyl ethers; and iii) 0--30 mole percent of one or more comonomers selected from: (a) hydroxy functional acrylates and methacrylates, (b) t-butyl aminoethyl methacrylate, dimethyl aminoethyl methacrylate, diethyl aminoethyl methacrylate, or a quaternized derivative thereof, (c) acrylamide and non-alkyl substituted acrylamides, and (d) cyclic amides, wherein said carboxylated polymer is neutralized to an extent that at least 3% of the carboxyl groups have been reacted.

4. A composition according to claim 3, wherein the carboxylated hair spray resin is a copolymer of vinyl acetate and crotonic acid.

5. A composition according to claim 3, wherein the carboxylated hair spray resin is a terpolymer of vinyl acetate, crotonic acid and a vinyl ester of an alphabranched saturated aliphatic monocarboxylic acid containing from 5 to 10 carbon atoms in the carboxylic acid moiety.

6. A composition according to claim I or 2, wherein the hair spray resin is a nonionic resin selected from: polyvinyl acetate hydrolyzed to an extent that from 15 to 60% of its acetate groups are converted into hydroxyl groups, and copolymers of vinyl acetate and vinyl pyrrolidone containing at least 50% by weight vinyl acetate.

7. A composition according to claim 6, wherein the hair spray resin is a copolymer of 20--30% vinyl pyrrolidone and 780% vinyl acetate.

8. A composition according to any one of the preceding claims, containing as the propellant in a mixture of isobutane and propane.

9. A composition according to claim 1, substantially as hereinbefore described in any one of the foregoing Examples.