IL36091A

IL36091A - Cosmetic compositions for the treatment of hair

Info

Publication number: IL36091A
Application number: IL36091A
Authority: IL
Original assignee: Gaf Corp
Priority date: 1970-01-30
Filing date: 1971-01-29
Publication date: 1973-10-25
Also published as: JPS564533B1; SE375691B; BR7100737D0; IL36091A0; ZA71588B; PH10121A; IT1030520B; DK127742B

Description

COSMETIC COMPOSITIONS FOR THE TREATMENT CF HAIR nnm a»a a»?man The present invention relates to novel cosmetic composition, e.g., aerosol hair sprays, hair conditioners, hair setting lotions, and creams, etc., containing a quaternary copolymer of vinyl pyrrolidone. More partic-ularly, the present invention relates to cosmetic compositions containing quaternary copolymers of vinyl pyrrolidone and a further copolymerizable vinyl monomer, such copolymers providing greater adhesion, greater holding power, and less flaking than conventional synthetic polymers used in hair and similar cosmetic preparations.

A number of synthetic polymers are presently used in hair sprays, hair wave set lotions, hair conditioners, etc., the function of such synthetic polymers being generally to contribute "body" and holding power to the hair-do sets.

The holding phenomena of hair sprays and setting lotions are, however, not very well defined. In hair sprays, a polymer globule holds several keratin fibers together so as to produce the necessary holding of the hair in place. In setting and conditioning lotions polymers are deposited over the surface of the hair and again several hair strands are adhered together. Polymer adhesion to the hair is thus an important factor which influences the usefulness of a particular synthetic polymer or resin in a hair preparation. Many of the currently employed synthetic polymers or resins exhibit poor adhesion, causing poor holding of the hair in place and excessive flaking when the hair is combed or brushed.

At the present time the principal synthetic polymers or resins employed in hair sprays, wave set lotions and hair conditioners include polyvinyl pyrrolidone homo-polymers and copolymers, half esters of polyvinyl ethers -maleic anydride, polyvinyl acetate - crotonic acid co- and terpolymers, half esters of ethylene - maleic anhydride as well as various others. With the exception of vinyl pyrrolidone homopolymers , all of the above conventionally employed synthetic polymers and resins used in hair sprays, wave set lotions, and hair conditioners give stiff hair-dos, thereby causing an unnatural look. In addition, such synthetic polymers or resins sometimes result in excessive flaking or excessive fly-away, thereby making preparations containing same unsatisfactory from a commercial standpoint.

Although polyvinyl pyrrolidone homopolymers provide a more natural look in that they are free from some of the disadvantages of other commercially available products, the use of these homopolymers does not provide satisfactory holding of the hair at high humidity levels.

This disadvantage of the use of polyvinyl pyrrolidone homopolymers in hair spray, wave set lotions and hair conditioner compositions has created the desire and necessity for the development of further synthetic polymers and resins substantially free from all of the above recited disadvantages. This has now been accomplished in accordance with the present invention.

It has been discovered in accordance with the present invention that the above disadvantages and inherent deficiencies of previously employed cosmetic compositions have been substantially eliminated by the use of a new type of polymer or resin useful in hair setting compositions including aerosol hair sprays, hair conditioners and hair setting lotions and creams. These new quaternary derivatives of N-vinyl pyrrolidone copolymers are particularly useful in cosmetic compositions and provide excellent holding power and contribute to excellent body without the disadvantag of flaking and stiffening associated with previously employed polymer materials.

The present invention accordingly provides novel cosmetic compositions employing as the film-forming resin a quaternized derivative of a copolymer of N-vinyl pyrrolidone. In hair compositions, for example, such quaternary copolymers exhibit improved substantivity to the hair.

The polymeric materials are adsorbed onto the keratin surface, thereby improving hair strength and increasing hair weight. Furthermore, such adsorption of the quaternary copolymers employed in the novel compositions of the present invention is more uniform and more continuous than the absorption obtained with currently available hair setting resins. This provides a distinct advantage for the compositions of the present invention when compared with conventional prior art compositions.

The quaternary copolymers employed in the novel compositions of the present invention have the formula: wherein n represent 40 - 90 mole p^ecent, m is 5 - 40 mole percent, p is 0 - 50 mole percent, and n+m+p = 100; is H or CH3; R2 is CH2CH-CH2 or C^tt-, where x = 2-18; R3 is CH3 or C2H5; R4 xs CH3, C2H5, HSO . CH SC< ; and M is a monomeric unit resulting from the 4 3 3 ¾ heteropolymerization employing an optional copolymerizable vinyl monomer.

These quaternary copolymers are prepared by the copolymerization of N-vinyl pyrrolidone and di-lower-alkylaminoalkyl (or hydroxyalkyl-) acrylate or methacrylate, and optionally a further copolymerizable vinyl monomer.

Based upon 100 mole percent, the vinyl pyrrolidone units are present in an amount of 40 - 90 mole percent, the units derived from the di-loweralkylaminoalkyl (or hydroxyalkyl-) acrylate or methacrylate constitute from 5 to 40 mole percent, and the units derived from the further copolymerizable vinyl monomer constitute from 0 to 50 mole percent.

Exemplary di-loweralkylaminoalkyl (or hydroxyalkyl-) acrylates or methacrylates suitably employed in the production of the quaternary copolymers for use in the compositions of the present invention include: dimethylaminomethyl acrylate dimethy1aminomethy1 methacry1ate diethylaminomethyl acrylate diethylaminomethyl methacrylate dimethylaminoethyl acrylate dimethylaminoethyl methacrylate dimethylamino-2-hydroxy propyl acrylate dimethylamino-2-hydroxy propyl methacrylate diethylamino-2-hydroxy ethyl acrylate diethylamino-2-hydroxy ethyl methacrylate dimethylaminobutyl acrylate dimethylaminobutyl methacrylate dimethylaminoamyl methacrylate diethylaminoamyl methacrylate dimethylaminohexyl aerylate diethylaminohexyl methacrylate dime hylaminooctyl aer late dimethylaminooctyl methacrylate diethylaminooctyl acrylate diethylaminooctyl methacrylate dimethylaminodecyl methacrylate dimethylaminododecyl methacrylate diethylaminolauryl acrylate diethylaminolauryl methacrylate dimethylaminostearyl acrylate dimethylaminostearyl methacrylate diethylaminostearyl acrylate diethylaminostearyl methacrylate The optional vinyl monomers represented by M in the above structural formula include any conventional vinyl monomer copolymerizable with N-vinyl pyrrolidone.

Thus, for example, suitable conventional vinyl monomers include the alkyl vinyl ethers, e.g., methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, etc.; acrylic and methacrylic acid and esters thereof, e.g., methacrylate, methyl methacrylate, etc.; vinyl aromatic monomers, e.g., styrene, a-methyl styrene, etc.; vinyl acetate; vinylidene chloride, acrylonitrile and substituted derivatives thereof; methacrylonitrile and substituted derivatives thereof; acrylamide and methacrylamxde and N-substxtuted derivatives thereof; vinyl chloride, crotonic acid and esters thereof; etc.

The quaternized copolymers employed in the novel compositions of the present invention are characterized as having a repeating structural unit derived from A) 40 - 90 mole % of vinyl pyrrolidone; B) 5 - 40 mole % of a di-loweralkylaminoalkyl acrylate or methacrylate of a di-loweralkylaminohydroxyalkyl acrylate or methacrylate and C) φ - 50 mole % of a vinyl monomer copoly-merizable with vinyl pyrrolidone.

These copolymers are conveniently prepared by subjecting a solution of vinyl pyrrolidone and the amino acrylate or amino methacrylate monomer, with or without an optional copolymerizable vinyl monomer, to conditions conducive to vinyl polymerization through the double bond. Thus, for example, polymerization may suitably be initiated by the action of free radicals, the polymerization proceeding exothermically once initiated. Suitable free radical catalysts conveniently employed and suitably utilized in accordance with the production of the copolymers include organic and inorganic peroxides, e.g., hydrogen peroxide, t-butyl peroxide, etc., aliphatic azo compounds, e.g., azobisisobutyronitrile as well as other free radical forming catalysts well knowi in the polymerization art.

The polymerization is preferably carried out in solution at temperatures varying from about 50°C to 100°C or more; however, to avoid runaway conditions and to obtain a copolymer of a desirable molecular weight it is sometimes preferred to carry out the copolymerization at a temperature of from about 75 to about 85° C. The copolymerization reaction is preferably carried out in the absence of free oxygen, conveniently under a blanket of an inert gas, such as nitrogen, argon or the like, or at atmospheric pressure.

In order to obtain the copolymers in the form of their quaternary salts, after the completion of the polymerization reaction the polymer is submitted to a treatment conducive to quaternization of the tertiary amino group, utilizing a conventional quaternizing agent. Suitable quaternizing agents include dialkyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, etc; alkyl sulfonic acid, e.g., methyl sulfonic acid, ethyl sulfonic acid, etc.; benzyl halides, e.g., benzyl chloride, benzyl bromide, benzyl iodide, etc.; alkyl halide, etc., as well as other conventional quaternizing agents.

The above copolymers employed in the compositions of the present invention can be prepared over a wide range of molecular weights. Generally, however, the molecular weight of the copolymer employed in the novel composition of the present invention is within the range of 15,000 to 1,000,000, the molecular weight being chosen somewhat with respect to the utility of the cosmetic composition. The copolymers for use in the compositions of the present invention are soluble in both water and alcohol and, thus, can be employed in hair spray and similar cosmetic compositions containing an alcoholic, aqueous, or mixed alcoholic-aqueous base. In addition, the high molecular weight quaternary polymers act as their own thickeners in aqueous or alcoholic solutions, such solutions displaying a slippery feel and an ease of application to the hair. The use of the higher molecular weight quaternary copolymers, i.e., quaternary copolymers within the molecular weight range of 50,000 to 500,000 is particularly applicable to the preparation of hair setting lotions, creams, etc.

A further advantage of the use of the quaternary copolymers in the hair setting and similar cosmetic preparations of the invention is that hair sprayed or otherwise treated with a hair setting composition containing the quaternized copolymers is easy to comb and easy to roll on rollers. The setting and conditioning lotions give a firm and stiff curl yet allow easy combing without corrib drag The quaternary copolymers employed in the novel compositions of the present invention are soluble in both alcohol and water. This makes such copolymers eminently suitable in hair spray and similar compositions which conventionally have an alcoholic, aqueous, or mixed aqueous-alcoholic base.

In the compositions of the present invention the film-forming quaternary copolymer of N-vinyl pyrrolidone is generally employed in an amount of from about 0.1% to about 35% by weight, the precise amount depending on the desired end utility for the composition. For particular purposes it may be desirable to employ slightly less or more of the film-forming polymer, the end use of the composition dictating the precise amount employed in the novel composition of the present invention.

As indicated above, for hair spray compositions, the base can either be aqueous, alcoholic* or a mixture of alcohol and water. The alcohol which is used as the alcoholic base or portion of the water-alcohol solvent system is generally a lower monohydric aliphatic alcohol, preferably, a monohydric aliphatic alcohol having from 2 to 3 carbon atoms, e.g., ethanol, isopropanol or n-propanol, ethanol being preferred. Thus, for example, the alcoholic solvent can comprise the commercially and industrially available ethyl alcohols or any one of the denatured alcohol formulas which are permitted by law for use in hair spray preparations, e.g., any one of those listed for this use in "Formulas for Denatured Alcohol", Part 212, Title 26 CFR, IRS publication 368. Representative formulas having current U.S. Government approval that can be used are, for example: SDA-40 which consists of 100 gallons of ethyl alcohol denatured with 1.5 oz. of brucine sulfate and one-eighth gallon of tertiary butyl alcohol; SDA-23 A which consists of ten gallons of acetone in each one hundred gallons of ethyl alcohol; and SDA-23 H which consists of eight gallons of acetone and one and one half gallons of methyl isobutyl ketone in each one hundred gallons of ethyl alcohol.

In addition to the film-forming quaternary copolymer and the solvent present in the system the hair spray or similar composition may contain minor amounts of other ingredients for their usual purposes. Thus, for example, the compositions may include wetting agents, defoamers, antibiotic agents, perfumes, coloring materials, and like additives which are soluble in the aqueous, alcoholic, or mixed solvent medium.

In addition, the hair spray or similar composition may contain a suitable plasticxzer for the novel quaternary copolymer employed as the film-forming resin. In this regard, the liquid substantially non-volatile polyols have been found particularly useful. Such materials include polyethylene glycols and ethylene oxide derivatives of monohydric alcohols, i.g., the ethylene oxide derivative of isostearyl alcohol.

When the aqueous alcoholic, or mixed solvent system containing the quaternary copolymer film-forming resin is utilized as a spray formulation, the usual aerosol type container and equipment and usual aerosol type propellent may be effectively utilized. The propellant may be any material which can be suitably utilized to propel compositons on the hair. Conventional propellents include liquidified lower hydrocarbons such as propane, N-butane, and isobutane and the low boiling chlorofluoro hydrocarbons identified broadly as freons. Particularly useful are freon 11-trichlorofluoromethane, freon 12-dichlorodifluoromethane and freon 114-1, 2-dichloro-l, 1,2 , 2-tetrafluoroethane.

In an aerosol type hair spray composition in accordance with the present invention the propellant is generally employed in an amount of from about 25% to about 65% by weight based on the total composition. The film-forming quaternary copolymer constitutes from about 0.1% to about 5% by weight, the remainder being the alcohol, water, or water-alcohol mixture. In addition, the hair spray composition can contain minor amounts, i.e., up to about 5% by weight of a surfactant or plasticizer and still lesser amounts of perfumes, i.e., up to about 0.5% by weight and similar agents.

In accordance with the preferred embodiment of the present invention, the sprayable hair composition is generally formed as an alcoholic or mixed aqueous- alcoholic solvent system. Suitable amounts of the various components in such composition are as follows: Component Amount Quaternary film-forming resin 0.1 - 5% Alcohol 30 - 70% Propellant 25 - 65% Water 0.25% Improved setting and conditioning lotions for the hair can also be provided by the employment of a minor amount, i.e., 0.1 - 5% by weight of the film-forming or mixed aqueous and alcoholic system. Exemplary of the setting and conditioning lotions of the invention are lotions composed as follows : Component Amount Film-forming quaternary copolymer 0.1 - 5% Water 60 - 95% Alcohol 0 - 35% It is preferred in accordance with the present invention to employ the higher molecular weight quaternary copolymers of N-vinyl pyrrolidone. The higher molecular weight copolymers act in the aqueous or mixed aqueous-alcoholic solvent system as their own thickeners thereby providing a creamy lotion consistency to the composition, even when employed in a minor amount of 0.1 - 5% by weight.

The setting and conditioning lotions of the invention may contain minor amounts of other conventional optional materials. These include such materials as perfumes, preservatives, additional organic solvents, lanolin and lanolin derivatives, silicone lubricants, etc. These optional components are conventional and employed in minor amounts, i.e., less than about 2% by weight.

An optional surfactant or plasticizer for the film-forming copolymer can also be employed in an amount up to about 5% by weight.

In addition to the hair preparations, i.e., aerosol hair sprays and setting and conditioning lotions, the cosmetic compositions of the present invention can take the form of creams, particularly protective hand creams .

The use of the film-forming quaternary copolymer of N-vinyl pyrrolidine provides advantageous results in other compositions of the invention wherein film-forming resins are utilized. Thus, for example, compositions for use as wig conditioners, hair coloring preparations hand lotions, protective creams, moisturizing creams, anti-flash creams, deodorant sprays, cream rinses and shampoos as well as pet shampoos and industrial compositions such as sanitizer solutions, detergents, paper adhesive additives, carriers for pigments in printing inks, stencil inks, etc. show distinct advantages through the use of the film-forming quaternized copolymer of N-vinyl pyrrolidone.

An effective protective water-repellent hand cream is provided by employing the quaternized copolymer of N-vinyl pyrrolidone invention. A suitable cream dispensed as a heavy foam can be formulated to comprise an alcoholic solution of the film-forming copolymer, water, emollients, and an aerosol propellant, with or without other conventional additives. A suitable composition contains, for example; water, ethanol, the film-forming copolymer and emollients such as glycerine and derivatives, fatty acids and esters thereof, lanolin and derivatives thereof, silicones and mixtures of the above. The use of the quaternized copolymer of N-vinyl pyrrolidone for this purpose is seen to provide substantially better results than the use of conventional film-forming polymers. The quaternized copolymer is preferably employed in an amount from about 0.1% to 5% by weight, the alcoholic solvent in an amount of up to about 10% by weight, the water solvent in an amount from about 50% - 90% by weight, the propel1ant in an amount from about 15% - 45% by weight and the various emollients in an amount from about 10% - 40% by weight.

As the film-forming quaternary copolymers of N-vinyl pyrrolidone are soluble in both the alcoholic and aqueous systems, it is merely necessary to dissolve the copolymer in the suitable solvent with previous, simultaneous or subsequent addition of the other optional components. Solution of the copolymer in the solvent system may be facilitated by mixing.

The preparation of the copolymers for use in the novel compositions of the present invention is illustrated by the following specific Example: EXAMPLE 1 Production of Film-Forming Quaternary Copolymer A copolymer was produced utilizing polymerization apparatus comprising a 5 liter kettle equipped with mechanical stirrer, reflux condenser, thermometer, and gas inlet tube. Some 1,225 parts of ethanol as a solvent were charged into the kettle and 800 parts of vinyl pyrrolidone and 200 parts of dimethylaminoethyl meth-acrylate were added and agitation was started. To the system was added one part of azobisisobutyronitrile and the system was purged thoroughly with nitrogen. The The polymerization reaction was promoted with further additions of catalysts (one part each) until the amount of residual monomer was below 0.6%. The system was thereafter cooled to 25°C and the speed of the agitation was increased.

In order to provide the quaternary derivative of the copolymer 98.3 parts of diethyl sulfate were added from a dropping funnel over a period of thirty minutes . When the slightly exothermic reaction of quaternization was completed the mixture was agitated for an additional period of thirty minutes. An analysis of the product produced indicated that the same contained 49.19% solids with the residual monomer content being 0.57%. The K value of the copolymer was 74.8, the same having a relative viscosity as measured as a 1% solution in ethanol of 2.837, and an intrinsic viscosity of 1.25 and a Brookfield viscosity of 26,000 cps.

The compositons of the invention are illustrated by reference to the following Examples: EXAMPLE 2 An aerosol hair spray composition was produced by admixing the following components in the weight percent indicated: Low molecular weight vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymer (80:20) quaternized with diethyl sulfate (50% solids in H O) and produced in Example 1 Isostearyl alcohol plus 3 E.O.

Silicon SF-1075 (Gen. Elec.) Perfume Alcohol SD-40 anhydrous Propellents trichlorofluoromethane and dichlorodifluoromethane (65:35 ratio) The aerosol hair spray formulation was prepared by dissolving the film-forming copolymer in the ethanol solvent and thereafter adding the plasticizer with vigorous mixing. After such mixing the perfume oil was added and the composition filtered and transferred to an aerosol can where it was crimped and charged with the necessary propellants.

Such a hair spray composition was found to be easily applied to the hair, the same providing a natural look yet offering excellent holding power. The stiff look associated with the use of half esters of polyvinyl ethers, maleic anhydride or polyvinyl acetate, crotonic acid co- and terpolymer hair setting resins was not present and there appeared to be no flaking associated with the employment of the hair spray composition containing the film-forming quaternary copolymer of N-vinyl pyrrolidone.

EXAMPLE 3 In a manner similar to Example 2 an aerosol hair spray, particularly adapted for men, was prepared in an alcohol-aqueous solvent system. Utilizing a mixing procedure as in Example 2, the following composition was prepared Weight % Low molecular weight vinyl pyrrolidone/ dimethylaminoethyl methacrylate copolymer (80:20) quaternized with diethyl sulfate (50% solids in alcohol) and produced in Example 1 4.00 Isostearyl alcohol plus 3 E.O. 0.65 Perfume oil 0.10 Water deionized 15.00 Alcohol SD-40 anhydrous 50.25 Propellent - CCl F and CClF CClF 2 2 2 2 (50:50 mixture) 30.00 100.00 As was the case with respect to Example 2, the hair spray composition was found to have excellent holding properties providing a natural 16ok to the hair. Here again, the use of the quaternized copolymer of N-vinyl pyrrolidone was seen to be superior to other conventional film-forming resins in that no flaking and no undue stiffness of the hair resulted.

EXAMPLE 4 A composition as in Example 3 was prepared except that the film-forming quaternized copolymer of N-vinyl pyrrolidone and diethylaminoethyl methacrylate was replaced with a substantially equivalent amount of a quaternized copolymer of N-vinyl pyrrolidone and the following monomers : a. dimethylaminomethyl acrylate b. dimethylamino-2-hydroxypropyl acrylate c. diethylamino-2-hydroxyethyl methacrylate d. dimethylaminobutyl acrylate e. diethylaminooctyl acrylate f. diethylaminolauryl methacrylate g. diethylaminostearyl methacrylate When the copolymers produced were employed as the film-forming resin in a hair spray composition such as set forth in Example 3, substantially equivalent results were obtained.

EXAMPLE 5 A hair spray composition as set forth in Example 2 was produced except that the quaternized copolymer of N-vinyl pyrrolidone was prepared by employing the following comonomers in the following amounts : a. 800 parts of vinyl pyrrolidone - 100 parts dimethylaminoethyl methacrylate b. 800 parts vinyl pyrrolidone - 300 parts dimethylamino ethyl acrylate d. 800 parts vinyl pyrrolidone - 600 parts dimethylaminoethyl acrylate.

The quaternized copolymers of N-vinyl pyrrolidone were found to be eminently suitable in hair spray compositions.

EXAMPLE 6 A hair spray composition as set forth in Example 2 was again produced except that the quaternized copolymer of N-vinyl pyrrolidone employed was produced by the copolymerization system of Example 1 including the following further copolymerizable vinyl monomers: a. Methylvinylether - 100 parts b. Octylvinylether - 200 parts c. Methacrylic acid - 150 parts d. Methyl methacrylate - 300 parts e. Styrene - 200 parts f„ Vinyl acetate - 100 parts g. Vinylidene chloride - 100 parts - vinyl chloride - 100 parts h. Methacrylonitrile - 300 parts When these quaternized copolymers were employed in the hair spray composition of Example 2 in substantially equivalent amounts, hair spray compositions of substantially equivalent properties were obtained.

EXAMPLE 7 An anhydrous aerosol hair spray was produced Example 2 by combining the following components: Weight % Low molecular weight vinyl pyrrolidone/dimethylaminoethyl methacrylate copolymer (80:20) quaternized with diethyl sulfate and produced in Example 1 50% solution in ethanol 4.00 Isostearyl alcohol plus 3 E.O. 0.50 Perfume oil 0.10 Alcohol SD-40 anhydrous 50.40 Methylene chloride 15.00 Propellants trichlorofluoromethane and dichlorodifluoromethane (50:50 mixture) 30.00 100.00 The above composition containing no water was also found to be extremely suitable for hair spray purposes. The composition exhibited excellent adhesion and holding power when employed as an aerosol hair spray, particularly adapted for men.

EXAMPLE 8 A setting and conditioning lotion for women's hair was produced as follows. A high molecular weight copolymer of vinyl pyrrolidone and dimethyl- aminoethyl methacrylate (80:20) quaternized with diethyl sulfate was dissolved in water and alcohol so as to provide a 2.0% solids content. After mixing the system well, a plasticizer, silicone lubricity agent, and perfume oil were added with additional mixing.

Stirring was stopped and the system was allowed to rest for about 20 minutes so as to allow the escape of air bubbles. This formulation designed for use on damp or towel dried hair was packed in a plunger or tube type dispenser. The composition produced as above had the following formulation: Weight % High molecular weight vinyl pyrrolidone dimethylaminoethy1 methacrylate co- polymer (80:20) quaternized with diethyl sulfate (21.9% solids in H^) 9.10 Isostearyl alcohol plus 10 E.O. 0.10 Silicone Fluid SF-1066 (GE) 0.10 Perfume Oil 0.05 Alcohol SD-40 20.00 Water deionized 70.65 Preservative q.s. 100.00 EXAMPLE 9 In a manner similar to Example 8, a setting and conditioning lotion was prepared from the following formulation: Weight % High molecular weight vinyl pyrrolidone dimethylaminoethyl methacrylate (90- 10 copolymer) quaternized with diethyl sulfate (21.9% solids in H 0) 9.10 2 Isostearyl alcohol plus 10 E.O. 0.10 Partially acetylated lanolin derived complex 0.10 Perfume and preservative q.s. Water deionized 90.70 100.00 The above components provided a setting and conditioning lotion having advantageous properties associated with the use of the copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate.

EXAMPLE 10 The following example illustrates the preparation of a water-repellant protective hand cream produced through the use of a quaternized copolymer of N-vinyl pyrrolidone in accordance with the present invention.

The composition was produced in four parts. Part A comprising the solution of quaternized copolymer, Part B comprising the emollients and various optional additives.

Part c comprising a perfume, and Part D comprising the propellant.

In the preparation of Part A, the low molecular weight copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate (80:20) quaternized with diethyl sulfate was mixed with ethanol, water, and glycerine until all of the copolymer was in solution. Part A, therefore, constituted the following components: Parts by wqt.

Low molecular weight vinyl pyrrolidone/ dimethylaminoethyl methacrylate copolymer (80:20) quaternized with diethyl sulfate and roduced in Exam le 1 50% Glycerin 10.0 Water deionized 876.6 Part B was prepared by mixing the following components Isopropyl Myristate 15.0 Stearic acid 35.0 Triethanolamine 8.2 Cetyl alcohol 4.8 Silicone SF-1075 (Gen. Electric Co.) 15.0 Acetylated lanolin alcohol 5.0 Parts A and B were separately mixed and heated to 160 - 165° F. Thereafter, the aqueous system of part A was added to Part B with vigorous mixing/ the composition slowly cooled and Part C, 0.3 parts by weight of perfume added. 85 parts of the emulsified product were then transferred to an aerosol can and crimped with the can being filled to suitable pressure with 15 parts of the propellants of Part D, i.e., Propellant - CC1„F and CClF CClF (50:50).

The above composition which is dispensed as a heavy foam was found to be particularly suitable as a pro-tective hand cream having excellent film-forming properties and protective properties.

COSMETIC COMPOSITIONS FOR THE TREATMENT CF HAIR n.nyw is*a> a»pnan ' DN-312 The present invention relates to novel cosmetic composition, e.g., aerosol hair sprays, hair conditioners, hair setting lotions, and creams, etc., containing a quaternary copolymer of vinyl pyrrolidone. More particularly, the present invention relates to cosmetic composi- 1 · j lions containing quaternary copolymers of vinyl pyrrolidone I and a further copolymerizable vinyl monomer, such copolymers providing greater adhesion, greater—holding power, ana less flaking than conventional synthetic polymers used .... ziair and similar cosmetic preparations.' A number of synthetic polymers are presently · - 1 The holding phenomena of hair sprays and setting lotions are, however, not very well defined. In hair sprays, a polymer globule holds several keratin fibers ^together so as to produce the necessary holding of the hair in place. In setting and conditioning lotions polymers are deposited over the surface of the hair and again several hair strands are adhered together. Polymer adhesion to the hair is thus an important factor which influences the usefulness of a particular synthetic polymer or resin in a hair preparation. Many of the currently employed synthetic polymers or resins exhibit poor adhesion, causing poor holding of the hair in place and excessive flaking when the hair is combed or brushed.

At the present time the principal synthetic polymers or resins employed in hair sprays, wave set lotions and hair conditioners include polyvinyl pyrrolidorie horoo- polymers and copolymers, half esters of polyvinyl ethers - rv.aleic anydride, polyvinyl acetate - crotonic acid co- and erpolymers , half esters of ethylene - maleic anhydride as well as various others. With the exception of vinyl pyrrolidone homopolymers , all of the above conventionally employed synthetic polymers and resins—used in hair sprays, wave set lotions, and hair conditioners give stiff hair-dos, thereby causing an unnatural look. In addition, such / synthetic polymers or resins sometimes result in excessive provide a more natural look in that they are free jfrom some of the disadvantages of other commercially available roducts, the use of these homopolymers does not provide satisfactory holding of the hair at high humidity levels.

This disadvantage of the use of polyvinyl pyrrolidone homopolymers in hair spray, wave set lotions and hair conditioner compositions has created the desire and necessity for the development of further synthetic polymers and resins substantially free from all of the above recited disadvantages. This has now 1 sen accomplished in accordance with the present invention.

It has been discovered in accordance with the present invention that the above disadvantages and inherent deficiencies of previously employed cosmetic compositions have been substantially eliminated by the use of a new type of polymer or resin useful in hair setting compositions including aerosol hair sprays, hair conditioners and hair setting lotions and creams. These new quaternary derivatives of N-vinyl pyrrolidone copolymers are particularly useful in cosmetic compositions and provide excellent holding power and contribute to excellent body without the disadvantages of flaking and stiffening associatec with previously employed polymer materials.

The present invention accordingly provides noy&l cosmetic compositions employing as the film-forming resin ^ copolymers exhibit improved substantivity to the hair.

The polymeric materials are adsorbed onto the keratin surface, thereby improving hair strength and increasing hair weight. Furthermore, such adsorption of the quaternary copolymers employed in the novel compositions of the present invention is more uniform and more continuous than the absorption obtained with currently available hair setting resins. This provides a distinct advantage for the compositions of the present invention when compared with conventional prior art compositions.1 1 The quaternary copolymers employed in the novel compositions of the present invention have the formula: wherein n represent 40 - 90 mole pf^ecent, m is 5 - 40 mole percent, p is 0 - 50 mole percent, and ri+m+p = 100; i is H or CH3; ¾ is CH2CH-CH2 or C^IL, where x = 2-18; R3 is OH CEL or C2H5; is CH HSO , CH SO ; and M is a monomeric unit resulting frcra the 4 3 3 X. copolymerization of N-vinyl pyrrolidone and di-lower-aikylarainoalkyl (er hydroxyalkyl-) acrylate or methacrylate, and optionally a further copolymerizable vinyl monomer.

Based upon 100 mole percent, the vinyl pyrrolidone units are present in an amount of 40 - 90 mole percent, the units derived from the di-loweralkylaminoalkyl (or hydroxy- I alkyl-) acrylate or methacrylate constitute from 5> 40 mole percent, and the units derived from the further copolymerizable vinyl monomer constitute from 0 to 50 mole percent.

Exemplary di-loweralkylaminoalkyl (or hydroxy- alkyl-) acrylates or methacrylates suitably employed in •che production of the quaternary copolymers for use in the compositions of the present invention include: dimethylaminometh 1 acrylate dimethylaminomethyl methacrylate ! ; diethylaminomethyl acrylate diethylaminomethyl methacrylate dimethylaminoethyl acrylate dimethylaminoethyl methacrylate dimethylamino-2-hydroxy propyl acrylate dimethylamino-2-hydroxy propyl methacrylate diethylamino-2-hydroxy ethyl acrylate diethylamino-2-hydroxy ethyl methacrylate dimethylaminobutyl acrylate diethylaminoamyl methacrylate dimethylaminohexyl aerylate \ diethylaminohexyl methacrylate dimethylaminooctyl acrylate! dimethylaminooctyl methacrylate diethylaminooctyl acrylate diethylaminooctyl methacrylate 1 dimethylaminodecyl methacrylate dimethylaminododecyl methacrylate diethylaminolauryl acrylate diethylaminolauryl methacrylate dimethylaminostearyl acrylate dimethylaminostearyl methacrylate diethylaminostearyl acrylate diethylaminostearyl methacrylate The optional vinyl monomers represented by in the above structural formula include any conventional vinyl monomer copolymerizable with N-vinyl pyrrolidone. Thus, for example, suitable conventional vinyl monomers include the alkyl vinyl ethers, e.g., methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, etc.; acrylic ana methacrylic acid and esters thereof, e.g., methacrylate, methyl methacrylate, etc.; vinyl aromatic monomers, e.g., styrene, cr-methyl styrene, etc.; vinyl acetate; vinyii ene chloride, acrylonitrile and substituted derivatives thereof thereof; vinyl chloride, crotonic acid and esters I thereof ; stc- The quaternized copolymers employed\ in the novel compositions of the present invention are characterized as having a repeating structural unit derived from A) 40 - 90 mole % of vinyl pyrrolidone i B) 5 - 40 mole % of a di-loweralkylaminoalkyl acrylate or methacrylate of a di-lowexalkylaminohydroxyalkyl acrylate or methacrylate and C) 0 - 50 mole % of a vinyl monomer copoly-iiiarizabie with vinyl pyrrolidone.

These copolymers are conveniently prepared by subjecting a solution of vinyl pyrrolidone and the amino acrylate or amino methacrylate monomer, with or without a optional copolymer!zable vinyl monomer, to conditions conducive to vinyl polymerization through the double bond. hus, for example, polymerization may suitably be initiated by the action of free radicals, the polymerization proceeding exothermically once initiated. Suitable free radical catalysts conveniently employed and suitably utilized in accordance with the production of the copolymers include organic and inorganic peroxides, e.g., hydrogen peroxide, t-butyl peroxide, etc., aliphatic azo compounds, e.g., azobisisobutyronitrile as well as other free radical forming^ catalysts well knovn in the polymerization art. or mere; however, to avoid runaway conditions and to obtain a copolymer of a desirable molecular weight it is sometimes preferred to carry out the copolymerization at a temperature of from about 75 to about 85° C. '. The copolymerization reaction is preferably carried o.t in the absence of free oxygen, conveniently under a blanket of an inert gas, such as nitrogen, argon or the like, or at atmospheric pressure.

In order to obtain the copolymers in the form of their quaternary salts, after the completion of the polymerization reaction the polymer is submitted to a treatment conducive to quaternization of the tertiary amino group, utilizing a conventional quaternizing agent. Suitable quaternizing agents include dialkyl sulfates, e.g., dimethyl sulfate, diethyl sulfate, etc; alkyl sulfonic acid, e.g., methyl sulfonic acid, ethyl sulfonic acid, etc.; benzyl hal des, e.g., benzyl chloride, benzyl bromide, benzyl iodide, etc.; alkyl halide, etc., as well as other conventional quaternizing agents.

The above copolymers employed in the compositions of the present invention can be prepared over a wide range of molecular weights. Generally, however, the molecular weight of the copolymer employed in the novel composition of the present invention is within the range of 15,000 ^ invention are soluble in both water and alcohol and, thus, can be employed in hair spray and similar cosmetic compositions containing an alcoholic, aqueous, or mixed alcoholic-aqueous base. In addition, the high molecular weight quaternary polymers act as their own thickeners in aqueous or alcoholic solutions, such solutions displaying a slippery feel and an ease of application to the hair.

The use of the higher molecular weight quaternary copoly¬ mers, i.e., quaternary copolymers within the molecular i weight range of 50,000 to 500,000 is particularly applicable to the preparation of hair setting lotions, creams, etc. \ A further advantage of the use of the quaternary copolymers in the hair setting and similar cosmetic prep¬ arations of the invention is that hair sprayed or otherwise treated with a hair setting composition containing the quaternized copolymers is easy to comb and easy to roll on rollers'. The setting and conditioning lotions give a firm and stiff curl yet allow easy combing without comb drag.

The quaternary copolymers employed in the novel compositions of the present invention are soluble in both alcohol and water. This makes such copolymers eminently suitable in hair spray and similar compositions which conventionally have an alcoholic, aqueous, or mixed aqueous-alcoholic base.

In the compositions of the present invention about 35% by weight, the precise amount depending on the desired end utility for the composition. For particular purposes it may be desirable to employ slightly less or more of the film-forming polymer, the and use of the composition dictating the precise amount nployed in the novel composition of the present invention.

As indicated above, for hair spray compositions, the base can either be aqueous, alcoholic, or a mixture of alcohol and water. The alcohol which is used as the alcoholic base or portion of the water-alcohol solvent, r jtem is generally a lower monohydric aliphatic alcohol, preferably, a monohydric aliphatic alcohol having from 2 to 3 carbon atoms, e.g., ethanol, isopropanol or n-propanol, ethanol being preferred. Thus, for example, . alcoholic solvent can comprise the commercially and industrially available ethyl alcohols or any one of the denatured alcohol formulas which are permitted by law for use in' '..air spray preparations, e.g., any one of those listed for this use in "Formulas for Denatured Alcohol", part 212, Title 26 CFR, IRS publication 368. Representative formulas .ving current U.S. Government approval that can be used are, for example: SDA-40 which consists of 100 gallons , £ ethyl alcohol denatured with 1.5 02. of brucine sulfate / ,.id cne-eighth gallon of tertiary butyl alcohol; SDA-23 A mathyI isobutyl ketone in each one hundred gallons of s hyl alcohol.

! In addition to the film-forming quaternary copolymer and the solvent present in the system the hair spray or similar composition may contain , minor amounts of other ingredients for their usual purposes. Thus, for example, the compositions may include wetting agents, • -v defoamers, antibiotic agents, perfumes, coloring ma'te :ials, and like additives which are soluble in the aqueous, alcoholic, or mixed solvent medium.

In addition, the hair spray or similar composition may contain a suitable plasticizer for the novel quaternary copolymer employed as the film-forming resin. In this regard, the liquid substantially non-volatile polyols have been found particularly useful. Such materials include polyethylene glycols and ethylene oxide derivatives of I t ncnohydric alcohols, i.g., the ethylene oxide derivative I f isostearyl alcohol.

When the aqueous alcoholic, or mixed solvent system containing the quaternary copolyme film-forming resin is utilized as a spray formulation, the usual1 aerosol type container and equipment and usual aerosol type w propt-llant may be effectively utilized. The propellant may La any material which can be suitably utilized to propel compositons on the hair. Conventional propellants include liquidified lower hydrocarbons such as propane, useful are freon 11-trichloro luoromethane, freon 12-dichlorodifluoromethane and freon 114-1, 2-dichloro-l , 1,2 , 2-tetrafluoroethane, ! I In an aerosol type hair spray composition in accordance with the present invention the propellant is generally employed in an amount of frbm about 2,5% to about 65% by weight based on the total compositjion. The film-forming quaternary copolymer constitutes from about i 0.1% to about 5% by weight, the remainder being! the alcohol, water, or water-alcohol mixture. In addition, the hair spray composition can contain minor amounts, i.e., up to I j about 5% by weight of a surfactant or plasticizer and ; . A still lesser amounts of perfumes, i.e., up to about 0.5% by weight and similar agents.

In accordance with the preferred embodiment of the present invention, the sprayable hair composition components in such composition are as follows: j Component Amount . j * j Quaternary film-forming resin 0.1 - 5% Alcohol 30j- 70% Propellant 25 - 65% Water 0.25% Improved setting and conditioning lotions for ! / the hair can also be provided by the employment of a or mixed aqueous and alcoholic system. Exemplary of the sattiag and conditioning lotions of the invention are lotions composed as follows : \ Component Amount i Film-forming quaternary copolymer 0.1 - 5% Water 60 - '' 5% Alcohol 0 - 35% It is preferred in accordance with the present invention to employ the higher molecular weight quaternary copolymers of N-vinyl pyrrolidone. The higher molecular weight copolymers act in the aqueous or mixed aqueous-alcoholic solvent system as their own thickeners " thereby providing a creamy lotion consistency to the composition, even when employed in a minor amount of 0.1 - 5% by weight.

The setting and conditioning lotions of the invention may contain minor amounts of other conventional optional materials. These include such materials as ' perfumes, preservatives, additional organic, solvents, lanolin and lanolin derivatives, silicone lubricants, etc.

These optional components are conventional' and employed xn minor amounts, i.e., less than about 2% by weight.

An optional surfactant or plasticizer for the film- forming copolymer can also be employed in an amount up •co about 5% by weight.

In addition to the hair preparations, i.e., / aeros l hai s ra s and settin d d creams .

The use of the film-forming quaternary copolymer of N-vinyl pyrrolidone provides advantageous results in other compositions of the invention wherein film- forming resins are utilized. Thus, for example, compositions for use as wig conditioners, hair coloring preparations hand lotions, protective creams, moisturizing creams, anti-flash creams, deodorant sprays, cream rinses and shampoos as well as pet shampoos and industrial compositions such as sanitizer solutions, detergents, paper adhesive additives, carriers for pigments in printing inks, stencil inks, etc. show distinct advantages through the use of the film- \ forming quaternized copolymer of N-vinyl pyrrolidone.

An effective protective water-repellent hand cream is provided by employing the quaternized copolymer of N-vinyl pyrrolidone invention. A suitable cream dispensed as a heavy foam can be formulated to comprise an alcoholic solution of the film-forming copolymer, water, emollients, and an aerosol propellant, with or without other conventional additives. A suitable composition contains, for example; water, ethanol, the film-forming copolymer and emollients such as glycerine and derivatives, fatty acids and esters thereof, lanolin and derivatives thereof, silicones and mixtures of the above. The use of the quaternized copolymer of N-vinyl pyrrolidone for this purpose is seen to provide substantially in an amount from about 0.1% to 5% by weight, jthe alcoholic solvent in an amount of up to about 10% by weight, the water solvent in an amount from about 50% - 90% by weight, the propellant in an amount from about 15% - 45% by \ ' I weight and the various emollients i an amountj from about 10% - 40% by weight.

As the film-forming quaternary copolymers of N-vinyl pyrrolxdone are soluble in both the alcoholic and aqueous systems, it is merely necessary to dissolve the copolymer in the suitable solvent with previous, ■ i simultaneous or subsequent addition of the other optional 1 components. Solution of the copolymer in the solvent" system may be facilitated by mixing.

The preparation of the copolymers for use in I the novel compositions of the present invention is illustrated by the following specific Example: j EXAMPLE 1 Production of Film-Forming Quaternary Copolymer A copolymer was produced utilizing polymerization apparatus comprising a 5 liter kettle equipped with mechanical stirrer, reflux condenser, thermometer, and gas inlet tube. Some 1,225 parts of ethanol as ί a solvent were charged into the kettle and 800 parts of vinyl i pyrrolidone and 200 parts of dimethylaminoethyl meth- acrylate were added and agitation was started. |το the system was added one part of azobisisobutyronitrile and The polymerization reaction was promoted with further additions of catalysts (one part each) until the amount of residual monomer was below 0.6%. The system was thereafter cooled to 25°C land the speed of the agitation was increased.

In order to provide the quaternary derivative of the copolymer 98.3 parts of diethyl sulfate were added f om a dropping funnel' over a period of thirty minutes .

When the slightly exothermic reacti n of quaternization was completed the mixture was agitated for an additional \ \ period of thirty minutes. An analysis of the product produced indicated that the same contained 49.19% solids with the residual monomer content being 0.57%. The K value of the copolymer was 74.8, the same having a relative viscosity as measured as a 1% solution in ethanol of r 2.837, and an intrinsic viscosity of 1.25 and a Brookfield viscosity of 26,000 cps.

The compositons of the invention are illustrated by reference to the following Examples : EXAMPLE 2 An aerosol hair spray composition was produced by admixing the following components in the weight percent indicated: Weight % Low molecular weight vinyl pyrrolidone/dimethylaminoethy1 methacrylate copolymer (80:20) quaternized with diethyl sulfate ! (50% solids in H O) and produced in Example 1 ' , ,4, 00 Iso^tearyl alcohol plus 3 E.O. C.10 Silicon SF-1075 (Gen. Elec.) 0.05 Perfume 0.05 Alcohol SD-40 anhydrous 35.80 Propellants trichlorofluoromethane and dichlorodifluoromethane (65:35 ratio) 60.00 100.00 The aerosol hair spray formulation was prepared by dissolving the film-forming copolymer in the ethanol solvent and thereafter adding the plasticizer with vigorous mixing. After such mixing the perfume oil was added and the composition—fxltered and transferred to an aerosol can where it was crimped and charged with the necessary propellants.

Such a hair spray composition. was found to be easily applied to the hair, the same providing a natural look yet offering excellent holding power. The stiff look associated with the use of half esters of polyvinyl ethers, maleic anhydride or polyvinyl acetate, crotonic acid co- and terpolymer hair setting renins / was not present and there appeared to be no flaking containing the film-forming quaternary copolymer of si-vinyl pyr olidene.

EXAMPLE 3 In a manner similar to Example 2 an aerosol hair spray, particularly adapted for men, was prepared in an alcohol-aqueous solvent system. Utilizing a mixing procedure as in Example 2, the following composition was prepared Weight % Low molecular weight vinyl pyrrolidone/ dimethylaminoethy1 methacrylate copolymer (80:20) quaternized with diethyl sulfate (50% solids in alcohol) and produced in Example 1 4.00 Isostearyl alcohol plus 3 E.O. 0.65 Perfume oil 0.10 Water deionized 15.00 Alcohol SD-40 anhydrous 50.25 Propellant - CCl F and CCIF CClF 2 2 2 2 (50:50 mixture) 30.00 100.00 As was the case with respect to Example 2, the hair spray composition was found to have excellent holding properties providing- a natural look to the hair. . Here again, the use of the quaternized copolymer of N-vinyl pyrrolidone was seen to be superior to other conventional ! ί EXAMPLE 4 A composition as in Example 3 was prepared except that the film-forming qu&tem ged co olymer of i N-vinyl pyrrolxdone and diethylaminoethyl^ methacrylate was replaced with a substantially equivalent amount of a quaternized copolymer of N-vinyl pyrrolxdone and the following monomers : i i a. dimethylaminomethyl acrylate b. dimethylamino-2-hydroxy ropy 1 acrylate c. diethylamino-2-hydroxyethyl methacrylate d. dimethylaminobutyl acrylate e. diethylaminooctyl acrylate f. diethylaminolauryl methacrylate g. diethylaminostearyl methacrylate When the copolymers produced were employed as the film-forming resin in a hair "pray composition such as set forth in Example 3 , substantially equivalent results were obtained.

EXAMPLE 5 A hair spray composition as set forth in Example 2 was produced except that the quaternized copolymer of N-vinyl pyrrolxdone was prepared by employing the following comonomers in the following amounts : a. 800 parts of vinyl pyrrolxdone - 100 / parts dimethylarainoethyl methacrylate dimethylamino ethyl acrylate d. 800 parts vinyl pyrrolidone - 600 parts dimethylaminoethyl acrylate.

EXAMPLE 6 ! A hair spray composition as set for!th in Example 2 was again produced except that the quaternized copolymer of N-vinyl pyrrolidone employed was produced by the copolymerization system of Example 1 including the following further copoly erizable vinyl monomers : a. Methylvinylether - 100 parts b. Octylvinylether - 200 parts c. Methacrylic acid - 150: parts d. Methyl methacrylate - 300 parts e. Styrene - 200 parts Vinyl acetate - 100 parts j ώ g. Vinylidene chloride - 100 parts - vinyl chloride - 100 parts ! h. Methacrylonitrile - 300 parts When these quaternized copolymers were employed in the hair spray composition of Example 2 in substantially equivalent amounts, hair spray compositions of substan¬ tially equivalent properties were obtained. / Example 2 by combining the following components : eight ¾ Low molecular weight vinyl \ pyrrolidone/dimethylaminoethyl ' methacrylate copolymer (80:20) quaternized with diethyl sulfate and produced in Example 1 50% solution in ethanol 4.00 Isostearyl alcohol plus 3 E.O. 0.50 Perfume oil 0.10 Alcohol SD-40 anhydrous 50.40 Methylene chloride 15.00 Propellants trichlorofluoromethane and dichlorodifluoromethane (50:50 mixture) 30.00 100.00 The above composition containing no water was also found to be extremely suitable for hair spray purposes. The composition exhibited excellent adhesion and holding power when employed as an aerosol hair spray, particularly adapted for- men.

EXAMPLE 8 A setting and conditioning lotion for women's hair was produced as follows. A high molecular weight copolymer of vinyl pyrrolidone and dimethyl- amxnoethyl methacrylate (80:20) quaternized with diethyl sulfate was dissolved in water and alcohol sc. as to provide a 2.0% solids content. After mixing the ■' i ' Stirring was stopped and the system was allowed to irt^t for about 20 minutes so as to allow the escape of air bubbles. This formulation designed for use on damp or towel dried hair was packed in a plunger ,or tube type dispenser. The composition produced as above had the following formulation: ί Weight % High molecular weight vinyl pyrrolidone dimethylaminoethyl methacrylate copolymer (80:20) quaternized with diethyl sulfate (21.9% solids in H^) I 9.10 Isostearyl alcohol plus 10 E.O. .-0.10 Silicone Fluid SF-1066 (GE) 0.10 ' Perfume Oil ' 0.05 Alcohol SD-40 20.00 Water deionized Preservative q.s. 100.00 EXAMPLE 9 In a manner similar to Example 8, a setting and conditioning lotion was prepared from the following formulation: j Weight % High molecular weight vinyl pyrrolidone dimethylaminoethyl methacrylate (90- 10 copolymer) quaternized with diethyl sulfate (21.9% solids in ^O) 9.10 Partially acetylated lanolin derived complex * 0.10 Perfume and preservative q.s. i Water deionized I 90.70 ' : N i *· 100.00 The above components provided a setting and conditioning lotion having advantageous properties associated with the use of the copolymer of vinyl pyrrolidone and dimethylaminoethy1 methacry1ate .

The composition was produced in four parts, Part A comprising the solution of quaternized copolymer, Part B comprising the emollients and various optional additives, Part C comprising a perfume, and Part D comprising the ; propellant. I In the preparation of Part A, tfre low molecular weight copolymer of vinyl pyrrolidone and dimethylaminoethy1 methacrylate (80:20) quaternized with diethyl sulfate was I j mixed with ethanol, water, and glycerine until all of the copolymer was in solution. ' Part A, therefore, constituted the following components: 1 Parts by wqt.

Low molecular weight vinyl pyrrolidone/ Λ·≤¾βί Qpiani¾e3 876.6 Part B was prepared by mixing the following component I_iopropyl y istate 15.0 Stearic acid 35.0 riethanolamine 8.2 Cetyl alcohol 4.8 Silicone SF-1075 (Gen. Electric Co.) 15.0 Acetylated lanolin alcohol 5.0 Parts A and B were separately mixed and heated to 160 - 165°F. Thereafter, the aqueous system of Part A was added to Part B with vigorous mixing, the composition slowly cooled and Part C, 0.3 parts by weight of perfume added. 85 parts of the emulsified product were then transferred to an aerosol can and crimped with the can being filled to suitable pressure with 15 parts of the propel1ants of Part D, i.e., propellant - CCl^F and CClF CClF (50:50). -» -2 2 2 ί The above composition which is dispensed as a heavy foam was found to be particularly suitable as a protective hand cream having excellent film-forming properties and protective properties.

Claims

WHAT WE CLAIM IS: 1. A cosmetic composition comprising a solvent base selected from water, lower monohydric alcohols, and a water-lower monohydric alcohol mixture, containing a minor amount of a film-forming quaternized polymer having a repeating structural unit derived from: A) 40 - 90 mole % vinyl pyrrolidone; B) 5 - 40 mole % of a di-loweralkylaminoalkyl acrylate or methacrylate or a di-loweralkylaminohydroxyalkyl acrylate or methacrylate; and C) 0 - 50 mole % of a vinyl monomer copolymerizable with said vinyl pyrrolidone. 2. The composition of Claim 1, wherein component (B) is dimethylaminoethyl methacrylate. 3. The composition of Claim 2, wherein the film-forming quaternized polymer is a copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate. 4. The composition of Claim 1, in the form of an aerosol hair spray containing an effective amount of an aerosol propellant. 5. The aerosol hair spray composition of Claim 4, comprising: A) 30 - 70 % by weight of a lower aliphatic alcohol solvent; B) 0 - 25% by weight water; C) 25 - 65% by weight of an aerosol propellant; and D) 0.1 - 5% by weight of the film-forming quaternized polymer. 6. The composition of Claim 1 useful as a hair setting and conditioning lotion comprising: A) 60 95% by weight water; B) 0 35% by weight of a lower aliphatic alcohol ; and C) 0.1 5% by weight of the film-forming quaternized polymer. 7. The composition of Claim 5 or Claim 6, additionally containing minor amounts of one or more optional components selected from organic solvents, perfumes, plasticizers, surfactants and silicone lubricants. —8-;— he compooition of Claim 5 or claim 6, wherein' component—(-2- —is dimethylaminoothyl mothacrylafce. ¾. The composition of Claim 6, wherein the film-forming quaternized polymer has a molecular range within the range of 15,000 to 1,000,000. - 26 - ·:.-;ΛΤ WE CLAIM IS: !

1. A cosmetic composition comprising a solvent base selected from water, lower monohydric alcohols, and a water-lower monohydric alcohol mixture, containing a minor amount of a film-forming quaternized polymer having a re eating structural unit derived from: , A) 40 - 90 mole % vinyl pyrrolidone; B) 5 - 40 mole % of a di-loweralkylaminoalkyl acryiate or methacrylate or a di-loweralkylaminohydroxyalkyl acrylate or methacrylate; and C) 0 - 50 mole % of a vinyl monomer copolymerizabl » wath said vinyl pyrrolidone.

2. The composition of Claim 1, wherein component (B) is dimethylaminoethyl methacrylate.

3. The composition of Claim 2 , wherein the film-forming quaternized polymer is a copolymer of vinyl pyrrolidone and dimethylaminoethyl methacrylate.

4. The composition of Claim 1, in the form of an aerosol hair spray containing an effective amount of an aerosol propellant.

5. The aerosol hair spray composition of Claim 4, comprising : A) 30 70 % by weight of a lower aliphatic alcohol solvent; / B) 0 25% by weight water;

6. The composition of Claim 1 Ufaeful a he.: - setting and conditioning lotion comprising: A) 60 95% by weight water; B) 0 35% by weight of a lower aliphatic C) 0.1 - 5% by weight of the film-forming quaternized polymer.

7. The composition of Claim 5 or Claim 6, additionally containing minor amounts of one or more optional components selected from organic solvents, perfumes, plasi eizers -rirfactants and silicone lubricants. —8-s—The compooition of Claim G- or Claim 6, wherein" -component (2)—is dimethylaminoe hy1 mothacrylatc. ¾. The composition of Claim 6, wherein the film-forming quaternized polymer has a molecular range within r the range of 15,000 to 1,000,000. AGENTS FOR APPLICANTS