US3810977A - Hair fixing composition and process containing a solid terpolymer - Google Patents

Abstract

THIS APPLICATION DESCRIBES HAIR FIXING TERPOLYMER COMPOSITIONS COMPRISING VINYL ACETATE, CROTONIC ACID AND VINYL ESTERS OF ALPHA-BRANCHED SATURATED ALIPHATIC MONOCARBOXYLIC ACIDS, CONTAINING FROM 5 TO 10 CARBON ATOMS IN THE CARBOXYLIC ACID MOIETY, AND A PROCESS FOR MAKING SUCH COMPOSITIONS. IT ALSO DESCRIBES A METHOD FOR TREATING HAIR WITH SUCH COMPOSITIONS.

Description

United States Patent Oflice 3,810,977 Patented May 14, 1974 Int. Cl. A61k 7/00 US. Cl. 424-47 Claims ABSTRACT OF THE DISCLOSURE This application describes hair fixing terpolymer compositions comprising vinyl acetate, crotonic acid and vinyl esters of alpha-branched saturated aliphatic monocarboxylic acids containing from 5 to 10 carbon atoms in the carboxylic acid moiety, and a process for making such compositions. It also describes a method for treating hair with such compositions.

This application is a continuation-inpart of our application, Ser. No. 625,328, filed Mar. 23, 1967, now abandoned.

In order to be highly effective in hair fixing compositions such as aerosol hair sprays and hair setting lotions, the film forming polymeric binders utilized therein as well as the films derived therefrom must meet a rigid set of requirements. Thus, the binders used in such formulations should be soluble in anhydrous organic solvents, yet the films cast from such hair fixing formulations should, ordinarily, either be Water soluble or water dispersible in order to facilitate their easy removal from the users hair. As is readily visualized, this is an unusual combination of properties which is further complicated by the requirement that the binder used in such formulations be completely compatible with the solvents and/ or propellants ordinarily employed therein. Furthermore, the binders used should show little or no tendency to interact with the perfumes or other optional ingredients utilized in hair fixing formulations.

In addition, the films cast from either aqueous or organic solvent solutions of these binders should be flexible and should simultaneously exhibit sufiicient strength and elasticity; they should exhibit good adhesion to hair so as to avoid the occurrence of dusting or flaking when the hair is subjected to varying stresses; they should readily allow the hair to be recombed; they should maintain a nontacky state despite humid conditions; they should be clear, transparent and glossy and should maintain this clarity on aging; they should possess good antistatic properties; and, they should be easily removable by the use of water and/ or soap or shampoo.

Needless to say, many polymeric systems have been utilized in an attempt to meet those stringent requirements. Among these are included: polyvinylpyrrolidone, copolymers of N-vinyl pyrrolidone with vinyl acetate, 5,5- dimethyl hydantoinformaldehyde resins, copolymers of methyl vinyl ethers and maleic half esters, and terpolymers of N-vinyl pyrrolidone, an acrylate ester and acrylic acid, etc. Though each of the latter systems has met at least some of the above cited requirements, none has exhibited all of these requirements to an optimum degree.

Furthermore, US. Pat. No. 2,996,471, which is assigned to the assignee of the present application, discloses a neutralized vinyl acetate-crotonic acid copolymer which is also applicable for use as a binder in hair fixing formulations. Although such polymeric binders exhibit many of the required properties specified hereinabove, and are superior in performance to many of the prior art binder systems, they are, nevertheless, deficient in certain solubility characteristics. Thus, they do not exhibit the broad range of solubility in aqueous and nonaqueous systems which will enable them to be readily stored at high concentration levels and, thereafter, formulated at relatively low concentrations. This deficiency in their solubility characteristics also limits the utility of these resins when they are sought to be utilized in alcohol-water based wave set lotions as well as in alcohol based aerosol hair sprays. With regard to the latter hair sprays, the neutralized vinyl acetate-crotonic acid copolymers exhibit limited compatibility with the hydrocarbon propellants present therein. Additionally, since these vinyl acetate-crotonic acid copolymers are most frequently utilized when they have been neutralized, the films derived therefrom have been found to be characterized by too great a degree of water sensitivity and thereby provide a reduced degree of bold ing power to the hair.

It is thus the prime object of this invention to improve upon the performance which is displayed by vinyl acetate crotonic acid copolymeric binders when present in hair fixing formulations. More specifically, it is the prime object of this invention to provide a novel class of film forming polymers for use, as binders, in hair fixing formulations, said polymers exhibiting all of the above described properties required in such binders and being particularly characterized by their solubility in both aqueous and organic solvents as well as by their compatibility with the hydrocarbons commonly used as aerosol propellants. Various other objects and advantages of this invention will be apparent upon a reading of the disclosure which follows hereinafter.

We have now discovered that all of the previously described requirements for an effective hair fixing formulation are met by utilizing the novel class of terpolymers hereinafter described as the film forming binder component of the hair fixing compositions of this invention. Particularly significant are the broadened solubility and compatibility characteristics exhibited by these novel binders. Thus, for example, they display a greater degree of solubility in the organic solvents typically used in aerosol hair sprays as well as in the aqueous solvent systems typically utilized in wave set lotions. In addition, they exhibit greater compatibility with the hydrocarbon propellants typically used in aerosol hair sprays. Furthermore, if neutralization of these resins is desired by the practitioner, the lower levels of neutralization that can be used insure the deposition, onto the hair, of films having a minimal degree of water sensitivity which, although they are readily removable by washing, provide a greater degree of holding power and thereby enable the thus treated hair to retain its shape and body. It should also be noted that the preferred class of the terpolymer binders of this invention are not plasticized as a result of the polymerization procedure utilized for their preparation.

The film forming terpolymers utiliza-ble as binders in the hair fixing formulations of this invention comprise terpolymers containing moieties derived from vinyl acetate, crotonic acid, and at least one vinyl ester of an alphabranched saturated aliphatic monocarboxylic acid having from 5 to 10 carbon atoms in the carboxylic acid moiety, said acid having the formula refer to the presence of at least one branch emanating from the carbon atom immediately adjacent to the carboxyl group, such branching being represented by either the R or R radicals in the above described formula. It is the addition of the moieties derived from the latter class of vinyl esters to the prior art vinyl acetate-crotonic acid copolymers which is primarily responsible for providing the resulting polymeric binders with their improved solubility and compatibility characteristics.

It should be noted that one may employ as the third monomeric component a mixture of more than one of these vinyl esters of alpha-branched saturated aliphatic monocarboxylic acids having from 5 to carbon atoms in the carboxylic acid moiety. A preferred mixture of this type would consist of the vinyl esters of a mixture containing 56%, by weight, of 2,2,4,4-tetramethyl valeric acid and 27%, by weight of 2-isopropyl-2,3-dimethyl butyric acid with the remaining acid components comprising isomers of the latter acids. For purposes of brevity, the latter monomer mixture, which contains only vinyl esters of nine carbon atom acids, will be hereinafter referred to as monomeric mixture A.

In order to provide binders which will function efficiently in the novel hair fixing compositions of this invention, it is necessary that resulting terpolymer contain from about 7 to 89% of vinyl acetate, from about 6 to 13% of crotonic acid and from about 5 to 80% of the selected vinyl ester; the latter concentrations all being based on the total weight of the terpolymer.

As for the actual preparation of these polymeric film forming binders, they must be made by a procedure which will provide the terpolymer in the form of solid beads (also referred to in the art as pearls). Thus, they may be prepared by means of free radical initiated processes utilizing bulk, suspension or solution polymerization techniques. Solution polymerization of the comonorners (which involves, as is well known in the art, polymerization in an organic solvent which is a solvent for the various monomers as well as for the resulting copolymer) followed by the step of dispersing the organic solvent solution of the terpolymer in Water to convert the terpolymer into relatively large particles, known as beads or pearls, which are easily separated, washed and dried is preferred, however, because of its convenience. In the case of bulk polymerization, the solid terpolymer may be dissolved in an organic solvent and then converted to bead form, as indicated above, or if so-called suspension polymerization is employed the copolymerization takes place in an aqueous medium, under conditions such that solid beads of the terpolymer are formed, which can then be readily separated from the water. In any event, the novel polymeric film forming binders of this invention, whether prepared by means of bulk, suspension or solution polymerization techniques, are all characterized by their solid bead form and by their solubility in both aqueous and organic solvents as well as by their compatibility with aerosol propellants.

The preparation of the terpolymer by emulsion polymerization, whereby the terpolymer exists in the form of an emulsion of fine, unfilterable particles in water, is not suitable for the purposes of this invention. The use of an aqueous emulsion of the terpolymer is ruled out for a number of reasons, including the fact that in hair spray formulations one requires a substantially anhydrous composition, and there is no commercially practical way to separate the emulsified terpolymer from its aqueous carrier. Furthermore, even in the case of the so-called hair lotions, where the terpolymer is dissolved in an alcohol-water mixture, the use of a terpolymer emulsion is not practical because of the difficulty in arriving at a composition containing the required relative proportions of ingredients, as well as the often undesirable presence of emulsifying agents and other additives which are normally used in emulsion polymerization processes, all of which detract from the purity of the ultimate product and its usefulness for hair fixing purposes.

It should be noted that the herein described terpolymers may be partially neutralized prior to their being incorporated into the ultimate hair fixing formulation thus permitting them to be removed from the hair merely by rinsing with water. This may be accomplished by mixing the terpolymer in the form of a solution of the beads in an organic solvent, with or without added water, as will be subsequently described, with a concentration of an alkaline reagent which is equivalent on a molar basis to no more than about of the available carboxyl groups present on the terpolymer. Neutralization to an extent greater than about 80% renders the ultimate composition unsuitable for hair fixing purposes. Applicable alkaline materials which may be utilized in this manner include: sodium and potassium hydroxide; ammonia; primary, secondary and tertiary amines; alkanolamines; and, hydroxyamines such as 2-amino-2-methyl-1,3-propanediol. However, if such terpolymers are not preneutralized, in this manner, their eventual removal may still be readily affected by the application of weak alkaline aqueous solution, e.g. soap and water.

In utilizing the above described polymeric binders in the preparation of aerosol hair sprays, the other essential ingredients which must be admixed therewith are a solvent and a propellant, although in some instances the propellant will serve both the latter functions. The preferred solvents are alcohols such as ethanol and isopropanol. In addition to their solubility properties, the prime advantages of these solvents are their ability to dry quickly, their minimal effect on the metal containers ordinarily utilized for these pressurized aerosol formulations and their accepted use in cosmetic applications. Other solvents which may be used include methylene chloride and 1,1,1- trichloroethane, etc.

Various types of aerosol propellants are well known to those skilled in the art. Thus, the commonly used prm pellants include trichlorofluoromethane, dichlorodifluoromethane, isobutane and propane, etc., as well a mixtures of the latter propellants. These propellants are readily compatible with the binder-solvent solutions utilized in this invention.

In general, the method for preparing the hair spray formulations of this invention merely involves dissolving the terpolymer beads in the selected solvent, adding any modifying agents whose presence may be desired, and thereupon combining the resulting solution with the selected aerosol propellant.

Thus, it may be noted that the novel hair spray formulations of this invention will in all cases contain at least three essential components. The first of the latter components will be what may be termed as the active ingredient comprising one or more of the above described terpolymers which serves as the binder for the formulation. Secondly, there will be one or more solvents which serve as vehicles for the binder. And, finally, there is the propellant which serves to effect the discharge of the aforedescribed binder and vehicle from the container wherein the formulation is packaged. Water is not ordinarily present.

With regard to proportions, the final hair spray formulations typically contain the polymeric binder in a concentration ranging from about 0.5 to 7%, by weight; the solvent in a concentration ranging from about 8 to 90%, by weight; and, the propellant in a concentration ranging from about 10 to by weight. The latter proportions should, however, 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.

In addition, it should be noted that the unique film forming terpolymers of this invention are equally as efiective when utilized in hair setting lotions, which usually consist of a solution of the terpolymer beads in a suitable organic solvent, such as alcohol, together with water. Such lotions may be directly applied to the hair or they may be sprayed thereon utilizing conventional spray nozzles. The application of such lotions may take place prior to, during, or after the desired hair style has been achieved.

The latter hair lotions are prepared by merely admixing the film forming terpolymer with the selected solvent, such solvents usually comprising a mixture, with water, of an alcohol such as ethanol or isopropanol. With regard to proportions, the lotion typically contain from about .5 to 7%, by weight, of the polymeric binder, while any desired ratio of alcohol to water in the solvent system may be utilized therein.

Optional additives may be incorporated into the hair fixing 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 hydrolyzates and other protein derivatives, ethylene oxide adducts, and polyoxyethylene cholesterol; dyes and other colorants; and, perfumes. As previously noted, the polymeric binders of this invention show little or no tendency to chemically interact with such additives.

The resulting hair fixing formulations exhibit all of the characteristics required of such a product. Their films are transparent, glossy, flexible, and strong. They possess good anti-static properties, adhere well to hair, are easily removed by soapy water or shampoos, allow the hair to be readily recombed, do not yellow on aging, and do not become tacky when exposed to high humidities.

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

EXAMPLE I This example illustrates a method for the polymerization of a typical terpolymer applicable for use in the novel hair fixing formulations of this invention.

The initial reaction mixture consisted of 75.0 parts of vinyl acetate, 2.5 parts of crotonic acid, 15.0 parts of monomeric mixture A and 4 parts of benzoyl peroxide, the latter reagents being dissolved in 20 parts of ethyl acetate. The solution was maintained at the reflux temperature whereupon 7.5 parts of crotonic acid were added. Ethyl acetate was also added, as required, in order to maintain a workable viscosity during the polymerization; the total amount of ethyl acetate thus introduced comprising 70 parts. At the completion of the polymerization reaction, the terpolymer solution was dispersed, with agitation, in water containing 0.1% of polyvinyl alcohol, as based on the weight of the polymer solids, thereby converting the terpolymer into the form of pearls. The ethyl acetate and any residual vinyl acetate monomer were then removed by distillation. The aqueous dispersion of the terpolymer was then centrifuged to separate the terpolymer pearls, which were washed and dried. The resulting terpolymer will hereinafter he referred to as terpolymer #1.

Additional terpolymers applicable for use in our novel hair fixing formulations were thereafter prepared by means of the procedure described hereinabove; the reagents and the concentrations in which they were used to prepare the respective terpolymers being set forth in the following table:

Terpolymer 2 3 4 5 6 7 8 6 EXAMPLE n This example illustrates another method for preparing the terpolymer beads, namely, the so-called suspension polymerization method.

The initial reaction mixture consisted of 56.5 parts of vinyl acetate, 10.0 parts of monomeric mixture A, 2.65 parts of crotonic acid and 2.0 parts of benzoyl peroxide. The mixture was heated to reflux, in a suitable reaction vessel, and after five minutes of heating there was added slowly, over a period of 1 /2 hours, a mixture of 20.0 parts vinyl acetate, 3.5 parts monomeric mixture A and 7.35 parts of crotonic acid. The reaction was continued under reflux until the temperature reached 175 F. Agitation was stopped, and there was added a solution, preheated to 175 F., of 0.22 part polyvinyl polyvinylpyrrolidone and 0.01 part polyvinyl alcohol in 100 parts water. Agitation was resumed and the reaction continued until the temperature reached 202 F. Unreacted monomer was distilled off by passing steam through the reaction mass until the temperature reached 212 F. The mixture was permitted to cool, and the solid terpolymer pearls were separated by filtration, washed and dried.

EXAMPLE III This example illustrates the improved performance characteristics exhibited by the novel terpolymers utilized in the hair fixing formulations of this invention.

Alcohol solubility-Anhydrous ethanol solutions containing, respectively, 3 and 30%, by weight, of the terpolymer composition whose complete preparation is described in Example I, hereinabove, and 3 and 30%, by weight, of a control polymer, i.e. a polymer consisting of 90 parts of vinyl acetate and 10 parts of crotonic acid, were prepared by admixing the required ingredients at 72 F. and subsequently heating them to a temperature of F. The resulting solutions were then cooled at a rate of 2 F./minute and observations made of the temperature at which the polymer first appeared to come out of solution, i.e. the Cloud Point. A lower cloud point is thus indicative of greater solubility in the anhydrous ethanol which, it should be noted, is a typical aerosol solvent.

The results of the above-determination, which clearly indicate the increased solubility of the terpolymer of this invention in anhydrous ethanol, are presented in the following table:

Cloud point F.)

3%. y 30%, by

Weight, welg t,

solusolution tion Control 82 68 Terpolymer #1 58 38 The improved alcohol solubility of the novel terpolymers employed in the products of this invention was further illustrated by the preparation, at a temperature of 77 C. of 3%, by weight, anhydrous ethanol solutions of a variety of the novel terpolymers of this invention. Acceptable solubility properties were indicated by the resulting appearance, after about 20 minutes of agitation, of clear or relatively clear solutions which were free of insolubles. The resulting data is presented in the following table:

{Water solubility.--Each of the 30% anhydrous ethanol solutions of the various terpolymers, including the control, were neutralized by the addition of 2-amino-2- methyl-1,3-propanediol to the extent of 60% of the theoretical equimolar amount of carboxylic acid groups present in the terpolymer. Thereafter, 2 parts of each of the partially neutralized terpolymer solutions were diluted with 18 parts of water and observations made as to the clarity of the resulting solution.

In addition, small portions of water were added in small increments amounting to one part in each instance, to similar samples comprising 2 parts of a 30%, by weight, anhydrous ethanol solution of the partially neutralized terpolymer. Observations were made as to the amount of water thus required to produce turbidity in the solution. Since the addition of 18 parts of water without a significant change in clarity is sufiicient to indicate excellent water solubility, all the samples that remained clear after the addition of 18 parts of water were removed from the test and assigned a value of 18.

The results of these tests are set forth in the following table:

The results summarized hereinabove clearly indicate the increased water solubility of the novel terpolymers employed in the products of this invention.

Propellant compatibility-The terpolymers utilized in this test procedure were initially partially neutralized by mixing the aforementioned 3% anhydrous ethanol solutions of each of the terpolymers, as well as the control, with 2-amino-2-methyl-1,3-propanediol to the extent of 80% of the theoretical equimolar amount of the carboxylic acid groups present in the terpolymer. Thereupon isobutane, a typical aerosol propellant, was added in one part, by weight, increments to parts of each of the partially neutralized 3% solutions. When the point of turbidity was reached, the ratio of isobutane to ethanol was noted with higher values of isobutane indicating a greater degree of compatibility with the isobutane on the part of the terpolymer.

The results of this test procedure are presented in the following table:

Terpolymer: Isobutane:ethanol ratio Control 05:99.5 Terpolymer #1 of Example I 33:67 Terpolymer #5 of Example I 46:54 Terpolymer #6 of Example I 54:46 Terpolymer #7 of Example I 68:32 Terpolymer #8 of Example I 70230 Film Hardness-A series of films having a wet thickness of 1.5 mils were cast on glass plates from by weight, solutions of the terpolymers in anhydrous ethanol. These films were dried for 24 hours at a temperature of 72 F. and a relative humidity of The surface hardness of these films were then tested using a Sward Hardness Rocker. The results of the hardness tests were rated on a numerical scale of from 0 to 100. Thus, a glass plate gives a value of 100, while a value of 0 implies a surface which is so soft as to be tacky.

The results of this test procedure are described in the following table:

Sward rocker Terpolymer: hardness Control 30 Terpolymer #1 of Example I 26 Terpolymer #2 of Example I 26 Terpolymer #5 of Example I 26 Terpolymer #6 of Example I 28 The results presented hereinabove clearly indicate that the films derived from terpolymers which contain the preferred alpha-branched vinyl esters as the third component therein, display a degree of hardness which is equivalent to the hardness exhibited by the films derived from copolymers of vinyl acetate and crotonic acid.

EXAMPLE IV This example illustrates the preparation of an aerosol hair spray formulation typical of the novel products of this invention utilizing the 75.0:10:l5.0 vinyl acetate: crotonic acid:monomer mixture A terpolymer, i.e. terpolymer #1, whose preparation was described in Example I, hereinabove.

A solution consisting of 1.2 parts of the terpolymer in 38.8 parts of anhydrous ethanol was prepared and subsequently introduced into an aerosol container which had been charged with 60 parts of a 60:40 propellant mixture of trichlorofluoromethane and dichlorodifluoromethane to an internal pressure of 30 pounds per square inch gauge. "It is to be noted that the resulting system was found to be completely compatible.

When utilized, the resulting hair spray deposited a film which was characterized by its clarity, gloss and flexibility. It served to hold the desired hair style in place while also allowing for its recombing. Of greater significance was the fact that it was readily removed from the hair by the use of a conventional shampoo.

EXAMPLE V Parts Solid beads of a 75.0: 10: 15.0 vinyl acetatezcrotonic acidzmonomer mixture A terpolymer (as prepared in Example I) 2-amino-2-methyl-1,3-propanediol Anhydrous ethanol 14.7 Water 82.0

The resulting clear solution which comprised the wave set lotion thus contained a polymeric binder which had been neutralized to the extent of of the theoretical equimolar amount of carboxylic acid groups present in the terpolymer.

When utilized, this wave setting lotion deposited a clear, glossy, flexible film which was readily removed from the hair by a thorough washing with water.

Summarizing, it is thus seen that this invention provides for the preparation of novel, improved terpolymer compositions which are ideally suited for use as the polymeric binder in a wide variety of hair fixing compositions.

Variations may be made in proportions, procedures and materials without departing from the scope of this invention which is defined by the following claims.

We claim:

1. An aerosol hair fixing composition, in an aerosol container, comprising a solution of solid beads of a terpolymer of vinyl acetate, crotonic acid and at least one vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid having between five and ten carbon atoms in the carboxylic acid moiety, said acid corresponding to the formula wherein R and R is alkyl and R is selected from the group consisting of hydrogen and alkyl; wherein said terpolymer said vinyl acetate is present in a concentration of from about 7 to 89%, said crotonic acid is present in a concentration of from about 6 to 13%, and said vinyl ester is present in a concentration of from about to 80%; the latter concentrations being based on the total weight of said terpolymer, and the solvent in said terpolymer solution being selected from the group consisting of ethanol, isopropanol, methylene chloride and 1,1,1-trichloroethane, said terpolymer being present in said solution in a concentration of from about 0.5% to 7% by weight and an efiective amount of a compatible propellant.

2. The hair fixing composition of claim 1 in which the terpolymer has been partially neutralized with an alkaline reagent in an amount equivalent on a molar basis to no more than about 80% of the available carboxyl groups on said terpolymer.

3. The hair fixing composition of claim 1 in which the vinyl ester component of the terpolymer is vinyl pivalate.

4. A process for fixing hair comprising spraying upon the hair an eifective amount of an aerosol hair fixing composition, in an aerosol container, as defined in Claim 1.

5. A process for fixing hair comprising applying to the hair an efiective amount of a hair fixing composition comprising a solution of solid beads of a terpolymer of vinyl acetate, crotonic acid, and at least one vinyl ester of an alpha-branched saturated aliphatic monocarboxylic acid having between five and ten carbon atoms in the carboxylic acid moiety, said acid corresponding to the formula wherein R and R is alkyl and R is selected from the group consisting of hydrogen and alkyl; wherein said terpolymer said vinyl acetate is present in a concentration of from about 7 to 89%, said crotonic acid is present in a concentration of from about 6 to 13%, and said vinyl ester is present in a concentration of from 5 to the latter concentrations being based on the total weight of said terpolymer, said composition being in the form of a solution of said terpolymer beads in a mixture of a solvent for said terpolymer selected from the group consisting of ethanol and isopropanol and water, said terpolymer being present in said solution in a concentration of from about 0.5% to 7% by weight.

References Cited UNITED STATES PATENTS 2,948,656 8/1960 Tousignant et a1. 424-71 X 3,321,408 5/1967 Briggs 252-161 3,503,916 3/1970 Warson et a1 260-80.8 X

ALBERT T. MEYERS, Primary Examiner D. R. ORE, Assistant Examiner U.S. C1. X.R.

260--29.6 TA, 33.4 R,33.8 UA; 424-71