|Publication number||US3927199 A|
|Publication date||16 Dec 1975|
|Filing date||13 Aug 1973|
|Priority date||14 Apr 1972|
|Publication number||US 3927199 A, US 3927199A, US-A-3927199, US3927199 A, US3927199A|
|Inventors||Albert L Micchelli, Gerard J Legato, Stuart H Ganslaw, Lawrence D Schuler|
|Original Assignee||Nat Starch Chem Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (8), Referenced by (173), Classifications (25)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent Micchelli et a1.
National Starch and Chemical Corporation, Clifton, NJ.
Filed: Aug. 13, 1973 Appl. No.: 388,325
Related US. Application Data Continuation-impart of Ser. No. 244,264, April 14, 1972, abandoned.
US. Cl 424/47; 260/296 ME; 260/296 T; 260/296 TA; 260/33.4 R; 260/338 UA; 260/785 BB; 260/8013; 260/808; 424/DlG. 1; 424/DIG. 2; 424/71; 424/78; 424/81;
424/359 Int. Cl. A61K 7/11 Field of Search 424/DIG. 1, DIG. 2, 47,
424/71, 81, 78; 260/785 R, 80.73, 29.6 T, 29.6 TA, 29.6 ME, 33.8 UA, 33.4 R
[ Dec. 16, 1975  References Cited UNITED STATES PATENTS 3,257,281 6/1966 Maeder 424/47 3,405,084 10/1968 Bohac et a1... 424/71 X 3,493,500 2/1970 Volk et a1. 260/8073 X 3,577,517 5/1971 Kubot et a1 424/47 3,577,518 5/1971 Shepherd et al. 424/47 3,726,288 4/1973 Nowak et a1 424/71 X 3,735,003 5/1973 Zimmer et al. 424/47 3,753,958 8/1973 Wingler et a1. 260/785 R FOREIGN PATENTS OR APPLICATIONS 1,141,255 1/1969 United Kingdom 424/71 1,814,115 7/1969 Germany 260/8073 2,047,655 4/1971 Germany 424/71 Primary ExaminerSam Rosen Assistant ExaminerVera C. Clarke  ABSTRACT 10 Claims, No Drawings HAIR FIXING COMPOSITIONS CONTAINING N-ALKYL ACRYLAMIDE OR METHACRYLAMIDE INTERPOLYMER This is a continuation-in-part application of our copending application Ser. No. 244,264 filed Apr. 14, 1972, now abandoned.
This invention relates to hair fixing compositions containing unique film forming polymeric binders therein.
In order to be highly effective in hair fixing compositions such as aerosol hair sprays and hair setting tions, 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 sufficient 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 non-tacky state despite humid conditions; they should be clear, transparent and glossy and 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 these stringent requirements. Among these are included: polyvinylpyrrolidone, copolymers of N-vinyl pyrrolidone. with vinyl acetate, 5-5 '-dimethyl hydantoinformaldehyde resins, and copolymers of methyl vinyl ethers and maleic acid half esters, 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.
It is the prime object of this invention to provide film forming polymers for use as binders in hair fixing formulations, said polymers exhibiting most or all of the above-described properties required in such binders.
It is a further object to prepare effective aerosol hair sprays, hair setting lotions and the like utilizing these polymeric binders.
Various other objects and advantages of this invention will become apparent from 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 polymers 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 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.
The film forming polymers (i.e. interpolymers) utilizable as binders in the hair fixing compositions of this invention comprise polymers containing moieties derived from l) at least one comonomer which is an N-alkyl acrylamide or methacrylamide, (2) at least one acidic comonomer containing one or more available carboxyl groups, and (3) at least one comonomer selected from a group of copolymerizable comonomers.
The applicable N-substituted acrylamides or methacrylamides are substituted with alkyl radicals containing from 2-12 carbon atoms. Among the applicable acrylamides and methacrylamides are included N-ethyl acrylamide, N-tettiary-butyl acrylamide, N-n-octyl acrylamide, N-teltiary-octyl acrylamide, N-decyl acrylamide, N-dodecyl acrylamide, as well as the corresponding methacrylamides.
The following list of monomers are representative of the applicable acidic film forming comonomers which contain at least one available carboxylic acid group: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the C -C alkyl half esters of maleic and fumaric acids such, for example, as methyl hydrogen maleate and butyl hydrogen fumarate as well as any other acidic monomers which are capable of being copolymerized with the particular interpolymer system whose use is desired by the practitioner. As is known to those skilled in the art, the acidic comonomer(s) must be so chosen as to be readily polymerizable with the selected interpolymer system.
The acidic comonomers make it possible for the. resultant copolymer to be neutralized by reaction with an appropriate base in order that it may ultimately exhibit the requisite water solubility. These acidic comonomers may be neutralized prior to their being incorporated into the ultimate hair fixing formulation thus permitting these formulations to be removed from the hair merely by rinsing with water. However, if such copolymers are not pre-neutralized in this manner. removal may still be readily effected by the application of an alkaline aqueous solution, for example, soap and water. It should be noted that for purposes of this invention the term water solubility is meant to include both water solubility in its usual meaning as well as water dispersibility wherein the resulting films are sufficiently hydrated and softened by contact with water so as to be easily removed from the hair by the application of water and either soap or shampoo.
In order to modify or enhance certain properties of I the polymeric binder, for example. adherance to the atoms such as methyl, ethyl, propyl, butyl, octyl and lauryl alcohols; hydroxyalkyl esters of acrylic and methacrylic acids such as hydroxypropyl acrylate and methacrylate, hydroxybutyl acrylate and methacrylate, hydroxystearyl acrylate and methacrylate and hydroxyethyl acrylate and methacrylate; alkyl (C -C amino alkyl (C -C esters of acrylic and methacrylic acids such as N, N diethylaminoethyl acrylate, N-tertbutylaminopropyl acrylate, N, N -dimethylaminoethyl methacrylate, N-tert.-butylaminoethyl methacrylate and the quatemization product of dimethylaminoethyl methacrylate and dimethyl sulfate, diethyl sulfate and the like; diacetone acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; and styrene monomers such as styrene and alpha-methyl styrene.
In order to provide binders which will function particularly efficiently in the novel hair fixing compositions of this invention, the interpolymer will contain from about 30-60% of the N-substituted acrylamide or methacrylamide, from -20%, (and 12-18%, preferrably) of the acidic comonomer, and up to 55% of at least one copolymerizable comonomer; these percentages being based on the total weight of the interpolymer. The percentages given herein and in the claims are to be taken so that the comonomers of the interpolymer will total to 100%.
Applicants preferred composition (preferred because of its combination of excellent properties of curl retention, adherance to the hair, clari'ty, gloss, and the like) will contain from 35-45% of N-tert.-octyl acrylamide. from 12-18% of acrylic or methacrylic acid, from 32-38% of methyl methacrylate, from 2-10% of hydroxypropyl acrylate, and from 2-10% of an alkyl (C -C amino alkyl (C -C acrylate or methacrylate.
As for the actual preparation of these polymeric film forming binders, there may be employed any of the usual vinyl polymerization methods which are well known to those skilled in the art and which are particularly suited for the polymer whose preparation is desired. Thus, the polymers may be prepared by means of free radical initiated processes utilizing bulk, suspension, solution, or emulsion polymerization techniques. The polymers may, if desired, be converted into relatively large particles known as beads or pearls by disp'ersing the solution polymerized polymer in water and thereafter driving off the solvent followed by separating and drying the particles.
It should be noted that the polymer binders of this invention 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 reacting the polymer, in the form of a solution in an organic solvent, with or without added water, with a concentration of an alkaline reagent (neutralizing agent) which is equivalent on a molar basis to a minimum of about 50% of the available carboxyl groups present on the polymer. 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-propanol and 2-amino-2-methyl-l,3-propanediol. However, if such polymers are not pre-neutralized in this manner, their eventual removal may still be readily effected 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 l,l,l-trichloroethane, etc.
Various types of aerosol propellants are well known to those skilled in the art. Thus, the commonly used propellants include trichlorofluoromethane, dichlorodifluoromethane, isobutane and propane, etc., as well as 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 or diluting the polymer in the selected solvents, 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 abovedescribed polymers 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, but may be included in some formulations.
With regard to proportions, the final hair spray formulations typically contain the polymeric binder in a concentration ranging from about 0.25 to 7%, by weight; the solvent in a concentration ranging from about 8 to 90%, by weight; and, the propellant concentration ranging from 10 to by weight. The latter proportions should, however, be considered asbeing 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 polymers of this invention are equally effective when utilized in hair setting lotions, which usually consist of a solution (or dispersion) of the polymer 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 polymer 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 lotions typically contain from about 0.5 to 7%. by weight. of the polymeric binder. while any desired ratio of alcohol to water in the solvent system may be utilized therein. An all alcohol system may also be used in some cases.
Comonomers N-tert.-octyl methacrylamide N-tert.-octyl acrylamide N tert=butyl acrylamide Acrylic Acid Methacrylic Acid ltaconic Acid Methyl Methacrylate Methyl Acrylate Tert.Butyl 'Methacrylate Hydroxypropyl Methacrylate Hydroxypropyl Acrylate Tert.-butyl Aminoethyl Methacrylate Dimethyl Aminoethyl Methacrylate N.N'-Dieth vlaminoethyl Acrylate Vinyl Acetate Diacetone Acrylamide to prepare the respective polymers being set forth in the following table:
Parts Polymer (Example No.)
Azobisisobulyronitrile substituted for benzoyl peroxide as free radical initiator.
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; U.V. absorbers; 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 antistatic 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, do not become tacky when exposed to high humiditie's, and have excellent curl retention under high humidity conditions.
In the following examples, which further illustrate the embodiment of this invention, all parts given are by weight unless otherwise indicated.
EXAMPLES l-l 1 methyl methacrylate, 1.0 part benzoyl peroxide and 100 parts of ethanol. The contents were heated to the reflux temperature of the system and held there for a period of 6 hours whereupon an additional 1.0 part of benzoyl peroxide was added thereto. The system was then held at reflux for an additional 4 hours whereafter the reaction was cooled to 30C and the polymer No.1 recovered.
Additional polymers applicable for use in the hair fixing formulations of this invention were also prepared by means of the above-described procedure; the reagents and the concentrations in which they were used EXAMPLES 12-17 vessel was charged with 25% of a monomer mix con-- taining 40 parts tertiary-octyl acrylamide, l5 parts acrylic acid, 35 parts methyl methacrylate, 5 parts hydroxpropyl acrylate and 5 parts tertiary-butyl aminoethyl methacrylate. The system was heated to its reflux temperature whereupon the remainder of the monomer mix was added over a period of 4 hours. Upon completion of the monomer addition, an additional 1.0 part of benzoyl peroxide was added and the reaction held at reflux for further 4 hours. The system was cooled and polymer No.12 recovered therefrom.
Additional copolymers applicable for use in the hair fixing formulations of this invention were also prepared by the above described procedure; the reagents and the concentrations in which they were used to prepare the respective polymers being set forth in the following table:
Parts Polymer (Example No.)
Comonome rs 'lgl llllllll llE EEI'JIIII" EXAMPLES 18-23 Parts These examples illustrate the preparation of aerosol Wave Set Lem) (Example N0.) hair spray formulations typ1cal of the novel products of 34 25 26 5 thls lnverltlon' Anhydrous ethanol 4625 9170 A solution of the desired polymer in anhydrous ethawater 99344 50,000 nol was prepared and subsequently introduced into an available cflrbfmylic 100 6U acid groups neutrahzed aerosol container wh1ch had been charged with the in polymer desired propellant to an internal pressure of 30 lbs. per square inch gauge. The various modifying agents were 10 added to the Polymer-alcohol Solutlens Prior to When utilized, each of these wave setting lotions mtteduetton Into the propellant-Charged aerosol deposited a clear, glossy, flexible film which was readily tametremoved from the hair by a thorough washing with The reagents and the concentrations utilized for prewater. paring the Venous aerosol hair p y are Set forth l5 Summarizing, it is seen that this invention provides the tollowmg table: for the preparation of novel hair fixing formulations Parts Aerosol Spray (Example No.) 1s 19 20 21 22 23 Polymer No. 1 (dried) 0.50 Polymer No. 2 (dried) 0 250 7.000 Polymer No. 3 (dried) 0.500 2.000 Polymer No. 12 (dried) 0 50 2amino-2 methyl propanol 0.042 1.750 2amino-2 methyl- 0.059 0.136 1.3-propanediol Perfume oil 0.10 0.10 0.10 0.10 0.10 0.10
Polymethylpolysiloxane 0.250 Ethoxylated lanolin oil 0.50 0.500 0.50 Propoxylated oleyl alcohol 0.400 Hydrolyzed protein 0.70 Anhydrous ethanol 63.9 49.358 63.826 37.330 10.450 63.90 A :60 propellant mixture of dichlorodifluoromethane and trichlorofluoromethane 50.0 80.00 A :45:10 propellant mixture of trichlorofluoromethane: dichlorodifluoromethane: isobutane 35.0 35.0 35.00
Methylene Chloride 15.00 Vinyl Chloride 15.00 lsobutane 10.00
Dichlorodifluoromethane 20.00 7r of available carboxylic acid groups neutralized in polymer 55 100 58 81 EXAMPLES 24-26 These examples illustrate the preparation of wave setting lotions typical of the products of this invention.
The lotions noted in the following table were prepared by charging the specified ingredients into a reaction vessel equipped with means for mechanical agitation.
Parts Wave Set Lotion (Example N0.) 24 25 26 Polymer N0. 2 (dried) 0.500 3.000 7,000 2umino-2 methyl 0.156 0.750 1.300
propanol which are characterized by their excellent holding power as well as by their ready removability.
Variations may be made in preparations. procedures and materials without departing from the scope of the invention as defined by the following claims:
We claim: e
1. A hair fixing composition containing a solvent selected from the group consisting of 1,1, l-trichloroethane, methylene chloride, ethanol, isopropanol, and water, and from 0.25 to 7%, by weight, of an interpolymer of 1') 30-60% of a comonomer selected from the group consisting of N-alkyl acrylamide and N-alkyl methacrylamide wherein the alkyl group thereof contains from 2 to 12 carbon atoms, (2) 12-18% of an acidic copolymerizable comonomer selected from the group consisting of acrylic acid, methacrylic acid. crotonic acid, itaconic acid, maleic acid, fumaric acid, and the (C -C alkyl half esters of maleic and fumaric acids, and '(3) 20-55% of at lest one copolymerizable comonomer selected from the group consisting of (C -C alkyl acrylates. C1 'C12) alkyl methacrylates, (C -C hydroxyalkyl acrylates. hydroxystearyl acrylate. hydroxyalkyl methacrylates, hydroxystearyl methacrylate, (C -C alkyl (C -C amino alkyl acrylates. (C 4: alkyl (Cg-C aminoalkyl methacrylates. vinyl 9 acetate, vinyl propionate, diacetone acrylamide, styrene, and alpha-methyl styrene; said interpolymer being sufficiently neutralized with an alkaline reagent to effect its solubility in water.
2. The hair fixing composition of claim 1, wherein from 50 to 100% of the available carboxyl groups of the interpolymer are neutralized with an alkaline reagent.
3. The hair fixing composition of claim 1, containing an interpolymer of (1) 30-45% N-tert.octyl acrylamide, (2) 12-18% acrylic or methacrylic acid, (3)
5. The hair fixing composition of claim 1, wherein the composition is in an aerosol container and also contains an aerosol propellant therefor.
6. The hair fixing composition of claim 2, wherein the composition is in an aerosol container and also contains an aerosol propellant therefor.
7. The hair fixing composition of claim 3, wherein the composition is in an aerosol container and also contains an aerosol propellant therefor.
8. The hair fixing composition of claim 4, wherein the composition is in an aerosol container and also contains an aerosol propellant therefor.
9. A process for fixing hair comprising applying to the hair an effective amount of the hair fixing composition of claim 1.
10. A process for fixing hair comprising spraying upon the hair an effective amount of the hair fixing composition of claim 5.
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|U.S. Classification||424/47, 526/303.1, 525/329.4, 526/923, 424/DIG.200, 424/70.17, 524/555, 524/379, 424/DIG.100, 524/473|
|International Classification||A61K8/81, C08F20/54, C08F20/52, A61Q5/06|
|Cooperative Classification||Y10S424/01, C08F20/52, Y10S526/923, A61K8/8158, C08F20/54, A61Q5/06, Y10S424/02|
|European Classification||C08F20/52, C08F20/54, A61K8/81K6, A61Q5/06|