US3171784A

US3171784A - Copolymer of vinyl pyrrolidone and vinyl acetate as aerosol hair spray

Info

Publication number: US3171784A
Application number: US621206A
Authority: US
Inventors: Daniel B Witwer
Original assignee: General Aniline and Film Corp
Current assignee: GAF Chemicals Corp
Priority date: 1956-11-09
Filing date: 1956-11-09
Publication date: 1965-03-02
Anticipated expiration: 1982-03-02
Also published as: FR1265403A; DE1129682B; DE1089930B; GB828970A; BE591236A; GB878970A; FR1187884A

Description

United States Patent 3,171,784 COPOLYMER 0F VlNYL PYRROLIDDNE AND VINYL ACETATE AS AEROSOL HAIR SPRAY Daniel B. Witwer, Montclair, Ni, assignor to General Aniline & Film orporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Nov. 9, 1956, Ser. No. 621,206

13 Claims. (Cl. 167-87) The present invention relates to aerosol film forming compositions and particularly to improved hair waving and setting compositions.

There are numerous preparations available for the waving and setting of human hair. Most of them are based on aqueous film forming solutions. The principal ingredient of such Solutions is either a natural gum or resin or synthetic resins which upon evaporation of the liquid medium deposits a film or coating. In addition to natural gums and resins, various alcohol soluble proteids, such as gliadin, zein, and the like, gelatin, a mixture of egg albumen, casein, and sodium silicate, inorganic resinous compounds obtained by treating anhydrous monosodium phosphate with borax, and various water soluble polymeric acrylic acid derivatives have been employed.

Since natural gums, such as, for example, karaya gum, salts of alginic acid, gum acacia, etc., flake off, dry hard, and impart an undesirable stiffness and brittleness, their use has been replaced by water soluble synthetic resins, such as those obtained by incomplete saponification or hydrolysis of polymeric acrylic and a-alkacrylic esters and amides. The disadvantage of waving fluid or hair dressing preparations containing such resins is that the preparations cannot tolerate bleaching agents without the presence of ammonia, or an ammonium salt, such as ammonium carbonate. The latter compounds have the tendency to impart hydroscopicity to the resinous film or coating after evaporation of the liquid medium or carrier. As a result, the film or coating becomes tacky and develops a greasy feel. Moreover, depending upon the nature of the water soluble polymeric acrylic acid derivative, some derivatives have the tendency of rubbing loose and falling off the hair in the form of small flakes resembling dandruff, while others require alkaline media for easy removal from the hair. It is well recognized among hair stylists and beauticians that ammonia has distinct hair stiffening characteristics whereby the fibers of the hair are attacked with a subsequent altering of its natural life.

Alcoholic solutions of shellac have also been employed and are currently sold in limited amounts in a Freon System. The disadvantage of shellac is that it must be solubilized with alkaline media, such as caustic soda or caustic potash for preparation of the solution prior to formulation in a pressurized can. Moreover, the same alkaline media must be employed to remove it from the hair.

Various synthetic polymers have been tried for use in hair grooming preparations, but have not been practical because of their solubility characteristics, i.e., they are not suitable for application and/or removal from the natural hair filaments. For example, gums and many polymers are not soluble in aerosol propellants and hence cannot be used in aerosol sprays. Also, many polymers are affected by changes in the relative humidity and the hair varies from a stiff, boardy feel to a sticky feel. Of the several polymers available, polyvinylpyrrolidone (more popularly termed PVP) is outstanding and currently employed in aerosol hair grooming preparations. When a PVP alcohol solution is applied in an aerosol system to human hair under a relative humidity of less 3,171,784 Patented Mar. 2, 1965 than 50%, the tendency of the resulting film to tackiness is substantially decreased. As a result thereof the preparation is acceptable by all consumers. However, when the relative humidity is above 50%, and particularly at humid atmospheres, films of PVP, sprayed from an aerosol system, pick up considerable moisture. The moisture is retained and results in a tacky film. In view of this property, the aerosol preparation is extremely undesirable where a dry hair condition is required as is the case with most users, especially women. The equilibrium water content of PVP depends upon the relative humidity of the atmosphere. The moisture content varies in a linear fashion with relative humidity, and the equilibrium percentage of moisture is about one-third of the relative humidity. Thus, if PVP is exposed to a relative humidity of 50%, the moisture pickup is approximately one-third of the relative humidity and therefore the resulting film contains about 17% moisture. To overcome the unique hygroscopicity of PVP, it has been suggested to employ detackifying agents such as shellac, cellulose acetate-propionate, etc. The former yields films which become opaque at high humidities, and the latter yields a film insoluble in ethyl alcohol. Carboxy-methylcellulose, cellulose acetate, methyl methacrylate polymer, polyvinyl formal, etc., are not effective as detackifiers under conditions of extremely high humidities.

It is an object of the present invention to provide improved, hairwaving, hair setting, and hair dressing compositions which are free from the foregoing disadvantages and which, in addition, possess new and desirable properties.

Other objects and advantages will become apparent from the following description.

We have found that a composition possessing new and desirable properties for application to human hair comprises an alcoholic solution of a copolymer of an N-vinyl pyrrolidone and a vinyl ester, which is useful in aerosol sprays, atornizers or can be applied directly to hair. Such solution, in combination with an aerosol propellant such as, for example, Freon 11, 12, 112, 113, 114, Freon C-316 and mixtures thereof, when applied to human hair, yields a glossy film which is substantially tack-free under normal conditions of relative humidity. The resulting film when exposed to a relative humidity of 50% and higher contains no more than about 13% moisture and is sufliciently water-sensitive so that it can be removed from the hair by a single washing. The equilibrium percentage of moisture of the copolymer is not more than one-fourth of the relative humidity. Thus, if the copolymer or film thereof is exposed to a relative humidity of 52%. the resulting film contains about 13.4% of one-fourth of the relative humidity. Thus, if the copolymer, it is not necessary to employ de-tackifying agents.

We have further found that in order to achieve the foregoing desirable properties it is necessary to employ from 30 to 60% by weight of a vinyl pyrrolidone monomer and from 40 to 70% by weight of a monomeric vinyl ester. When such weight-percent ratios are employed in preparing the copolymer, films resulting therefrom maintain suflicient water-sensitivity so that they can be removed from the hair. The copolymers in such ratios are also soluble in the lower alcohols such as, for example, methanol, ethanol, isopropanol and the like, and with all of the aforementioned Freons and mixtures thereof. In cases where it is desirable to produce a hair grooming preparation or industrial coating compositions which lack water-sensitivity under all conditions of relative humidity, and may require several washings before the film is removed, the weight-percent ratio of the monomers may be increased from 10 to 50% of a polymerizable vinyl ester 3 and from 50 to 90% by weight of a polymerizable N-vinyl pyrrolidone. Thus, it becomes clearly evident that the ratio of polymerizable monomers used may range widely to yield water-sensitive to water-insoluble copolymers, both of which are soluble in alcohol and 'fluorinated alkane aerosol propellants. For hair grooming preparations, we prefer to employ copolymers in which the monomers are in the ratio of 30:60 of the N-vinyl pyrrolidone and 40 to 70% by weight of the vinyl ester. In these proportions a copolymer is obtained which is readily soluble in the lower alcohols and dissolves in all of the currently employed Freons and mixtures thereof to yield a hair grooming preparation, the films of which do not become opaque or tacky at high humidities. The resulting films are glossy, tack-free and readily removed by a water wash or a water rinse.

The copolymers utilized in preparing the film forming and hair grooming compositions of the present invention are readily prepared by copolymerizing the two monomers in the aforementioned weight-percent ratio by conventional means or in lower alcohol solvent so that the solution thereof can be used directly in the preparation of an aerosol. The method of copolymerization may be either in bulk, in emulsion or in solution. Instead of a lower alcohol as a solvent, the monomers may be dissolved or dispersed in water or an organic solvent such as benzene, dioxane acetone, methyl ethyl ketone, ethylene dichloride or mixture of such organic solvents. The solution or dispersion of the two monomers, in then heated in the usual manner preferably in the absence of air (nitrogen blanket) in the presence of a polymerizing catalyst such as organic peroxides, peracids, hydroperoxides, i.e., benzoyl peroxide, lauryl peroxide,; tertiary butyl perbenzoate, hexoyl peroxide, methyl ethyl ketone peroxide, a-azodiisobutyronitrile and the like.

As illustrative examples of N-vinyl pyrrolidones which may be copolymerized in the aforestated concentrations with a vinyl ester, the following may be mentioned:

As. illustrative examples of polymerizable vinyl esters, the following may be mentioned:

Vinyl acetate Vinyl glycolate Vinyl chloride Vinyl formate Vinyl propionate Vinyl butyrate The copolymers, prepared with the aforementioned monomers as herein described, correspond to a range of a Finkentscher K value of to 60. These valueswapply to both the water-sensitive and water-soluble copolymers. K value as used herein is defined by the following implicit function of Fikentscher, Cellulosechemie, 13, 60 (1932):

0.001K+ 0.O00075K Relative viscosity 10C 1 000151) A definition of K value is also given in Modern Plastics, 23, 157-161 (November 1945). I I

The invention will be described in greater length in conjunction with the following examples. It is to be understood, however, that these examples are merely illustrative and are not intended that the scope of the invention be limited to them and to the details set forth herein.

4 EXAMPLE 1 A one-liter, three-necked flask equipped with stirrer, reflux condenser and a thermometer was charged with grams of vinyl acetate, distilled, 225 grams of N-vinyl-2- pyrrolidone, distilled, and 300 ml. of Z-butanone. The flask was heated to 75 C. with stirring for 5 minutes. After 5 minutes, 3 grams of 2,2'-azodiisobutyronitrile dissolved in 37.5 ml. of 2-butanone was added to the flask. The flask was stirred and maintained at,70 C. for a total of 12 hours. The product was recovered by evaporating the Z-butanone leaving a solid, white, clear polymer containing 75% N-vinyl-2-pyrrolidone and'25% vinyl acetate. The polymer dissolved in Z-butanone gave a Fikentscher K value of 17.

EXAMPLE 2 A two-liter, three-necked, ground-joint, Pyrex flask equipped with two Allihn condensers, mechanical stirrer with half-moon blade, thermometer, and a nitrogen-inlet tube was charged with 139.0 grams (175 ml.) of denatured ethanol, 83.25 grams (0.75 mole) ml.) of distilled N-vinyl-Z-pyrrolidone, 64.57 grams (0.75 mole) (69.3 ml.) of vinyl acetate, distilled, and 0.75 gram of 2,2'-azodiisobutyronitrile dissolved in '30 ml. of denatured ethanol. The flask was flushed with nitrogen and the inlet rate adjusted to about 3060 bubbles per minute. The flask was heated on a steam bath of 70 C. The steam was turned off and the catalyst was added via the condenser.

. The temperature dropped to 56 C. The steam was then when corrected indicates 60% bound N-vinyl-2-pyrrolidone and 40% bound vinyl acetate by difference. Analysis for volatiles gave 4.6%. Analysis for free monomer gave 0.01% calculated as N-vinyl-2-pyrrolidone.

EXAMPLE 3 Into an Autoclave Engineer steel autoclave were placed 73.80 grams of N-vinyl-2-pyrrolidone, 20.80 grams of vinyl chloride, 87.5 grams of 2-butanone and 0.410 gram of 2,2'-azodiisobutyronitrile catalyst. The autoclave was sealed and heated to 60 C. and stirred with an enamel coated stirrer for 20 hours. The autoclave was cooled to room temperature and vented into a Dry Ice trap. The trap did not gain in weight. The contents of the autoclave were poured into a tared Pyrex dish and placed in an air stream to evaporate the solvent. After 18 hours a thick syrup remained. The thick syrup was placed in a desiccator under vacuum and the remaining solvent removed. The polymer obtained was a straw colored, friable material which was easily pulverized with mortar and pestle. Analysis for Volatiles indicated that the actual yield of dry polymer was 93% of the theoretical yield. Analysis for the N content bound in the polymer indicated N-vinyl-2-pyrrolidone content and 10% vinyl chloride content by difference. The polymer gave a Fikentscher K-value of 22 in water.

EXAMPLE 4 Into'a metal aerosol can partially submerged in a solid carbon dioxide acetone bath were condensed 40 grams of Freon 12, 40 grams of Freon 11, and to this was added 20 grams of an alcoholic solution containing a copolymer of N-vinyl-Z-pyrrolidone and vinyl acetate (Example 2). A nozzle and valve assembly was attached to the can and the entire assembly was held together in a brass cage. The can was checked for leaks by submerging in water. The aerosol sprayer was allowed to warm to room temperatu're. Glass panels were sprayed giving films which dried almost immediately to an odor-free, clear, somewhat flexible film. The films were not tacky. Also, the films when rubbed with a wet finger were not as sensitive as films containing polyvinylpyrrolidone. The compounded aerosol was used to spray hair and allowed to dry. The film resulting on the hair brightened and gave the hair a pleasing appearance and retained the shape and condition that the hair was held in while being sprayed. That is to say, it is useful in retaining artificial curls in hair.

Two manufacturing steps were saved by using the alcoholic solution: (1) the normal spray drying step to recover the polymer, and (2) the dissolving of the polymer into ethanol prior to the preparation of the aerosol.

EXAMPLE 5 Into a three-necked, one-liter Pyrex flask equipped with an Allihn condenser, a thermometer, a mechanical stirrer, and a nitrogen inlet was charged 60.0 grams of distilled N-vinyl-2-pyrrolidone, 40.0 grams of distilled vinyl propionate and 200 grams of anhydrous ethanol. The flask was flushed with nitrogen and the inlet rate of the gas adjusted to about 30 bubbles per minute. The flask was heated and stirred for 30 minutes at 60 C. At this point 0.1 gram of 2,2-azodiisobutyronitrile was added as the catalyst. The flask was maintained at 80 C. and was stirred for a total of 12 hours. At this point the reaction mixture gave an analysis of 3 residual unsaturation.

0.1 gram of 2,2azodiisobutyronitrile was added and the flask was heated for an additional 3 hours. The prodnot was recovered for /2 of the reaction mixture by vacuum stripping. The product consisted of a white, friable, transparent polymer. The remaining half of the reaction solution was bottled for use in its original condition.

Analysis indicated the polymer contained 60% vinylpyrrolidone and 40% vinyl propionate. A sample of the dried polymer gave a Fikentscher K-value of 33 in 2- butanone.

EXAMPLE 6 Into a three-necked flask equipped with an Allihn condenser, a thermometer, a nitrogen inlet, and a mechanical stirrer was charged 55.0 grams of N-vinyl-2-pyrrolidone, 45.0 grams of vinyl propionate and 200 grams of Z-butanone. The flask was flushed with nitrogen and the inlet rate of the gas was adjusted to about 30 bubbles per minute. The flask was stirred and heated to 60 C. for 30 minutes. At this point 0.1 gram of 2,2'- azodiisobutyronitrile was added as the catalyst. The flask was stirred and maintained at 30 C. for a total of 12 hours. The polymer was recovered from the reaction solution by drying in a vacuum desiccator for 24 hours at less than 0.2 mm. of mercury vacuum.

The white, brittle, translucent polymer was analyzed and the analysis indicated that it contained 55% vinylpyrrolidone and 45% vinyl propionate. A sample of the dried polymer gave a Fikentscher K-value of 30 in 2- butanone.

EXAMPLE 7 Into a 4 ounce aerosol can were condensed 25 grams of trichloromonofluoromethane and 25 grams of dichlorodifluoromethane. To this was added 6 grams of the reaction solution from Example 5, and a nozzle assembly was attached to the can and the can allowed to warm to room temperature.

The filled aerosol was used to spray glass panels 8 inches by 10 inches, 21 hank of human hair and a head of human hair. The panels contained continuous film of the polymer and it was noticed they dried rapidly to a tack-free, transparent, odorless film. The hair sprayed with the aerosol contained a clear, transparent coating which brightened the appearance of the hair. It was observed that when the head of human hair was sprayed and allowed to dry that the polymer did show hair fixative properties, that is to say, the hair coated with the polymer tended to hold the shape imposed upon it.

EXAMPLE 8 Into a glass aerosol compatability tube (obtained from Fischer Porter of Hatboro, Pennsylvania) was condensed, when the tube was cooled in an acetone solid carbon dioxide bath, 20 grams of trichloromonofluoromethane and 20 grams of dichlorodifluoromethane. To the tube Was added 5 grams of a 50% solution of the polymer from Example 6 dissolved in anhydrous ethanol. The compatibility tube was sealed and a nozzle assembly attached to it. The completed aerosol in the compatibility tube was allowed to warm to room temperature and it was observed that a solution of all the ingredients took place.

The completed aerosol was used to spray a glass panel 8 inches by 10 inches and a head of human hair. A quick drying, continuous, clear, tough film was observed. It was observed that the hair was held in place by the dried coating of polymer. The polymer was observed to have hair fixing properties.

EXAMPLE 9 Into a metal aerosol can partially submerged into an acetone solid carbon dioxide cooling bath was condensed 35 grams of trichloromonofluoromethane, and 35 grams of dichlorodifluoromethane. To the can was added 10 grams of a 50% solution obtained from Example 2. A nozzle assembly was attached to the can and the can was sealed in a brass cage. The completed aerosol can was allowed to warm to room temperature.

The aerosol was used to spray a human finger and allowed to dry. It was observed for an area of about 2 square inches a clear, continuous film covered the finger. This cover could be used in place of the ordinary cloth tape bandage. The aerosol was used to spray a human finger which had a slight topical cut (about A: inch long and inch deep) and it was observed that a film was obtained on the finger. The finger was sprayed after the wound had closed by coagulation of the blood. A slight smarting sensation was noticed.

The coating did offer protection to the wound and did not rub off if care was taken not to vigorously scrub the finger with water.

EXAMPLE 10 As noted in Example 4 of application, Serial No. 535,262, filed on September 19, 1955, there was prepared a complex of a copolymer of N-vinyl-2-pyrrolidone and vinyl acetate and pulverized granular iodine. Also, as noted, the iodine complex was treated at 55 C. for 4 hours and after heat treatment the complex analyzed 1.4% available iodine.

Into a metal aerosol can partially submerged into a solid carbon dioxide acetone bath was condensed 40 grams of trichloromonofiuoromethane and 40 grams of dichlorodifluoromethane. To the can was added 5 grams of the 50% solution from Example 2 and 2 grams of the iodine polymer complex described above. An aerosol nozzle assembly was attached to the can and the can was sealed in a brass cage. The completed aerosol was allowed to warm to room temperature.

The aerosol was used to spray a human finger and the coating obtained was allowed to dry. A slightly brown, continuous, protective coating was obtained on about 1 square inch of the finger surface. The coating adhered well to the finger and was not sticky and did not rub oif when massaged with a dry hand. It was observed the finger could be flexed without cracking or breaking the continuous film.

The aerosol was used to spray a finger which had a slight surface cut (about inch long and about ,4 inch deep). The finger was sprayed after the blood had coagulated. After the film dried, it was observed that the wounded area was covered by a light brown film.

7 EXAMPLE 11 Into a one-liter beaker was placed 500 cc. of anhydrous ethanol, 40 grams of. reaction solution from Example 2 and 10 grams of the iodine complex described in Example 10. The contents of the flask was stirred and a solution resulted which was brownish in color and which when cast onto a glass plate dried rapidly.

The solution was used to prepare an antiseptic area on human skin by applying a coating with a brush or similar instrument and allowing it to dry.

EXAMPLE 12 The solution given in Example 11 was used to prepare a pair of antiseptic gloves or coatings on human hands. The hands were carefully Washed and dried. The hands were then submerged into the solution and withdrawn and allowed to dry. A continuous light brown coating was obtained on the portion of the hands which had been submerged into the solution. The antiseptic coating functioned and took the place of the common surgeons rubber gloves. Any small area of the continuous film coating the hands could be easily repaired if damaged by brushing on enough of the solution to cover the damaged area and allowing it to dry to a film. The hands could be flexed and used and no cracking or peeling of the film was observed. 1 V

In order to ascertain the criticality of the weight-percent ratio of the monomers in the copolymer, several copolymers were made in which the N-vinyl-Z-pyrrolidone content ranged from 20 to 60% by weight. Films of such copolymers were both air dried and heated and their dissolving tendencies in water observed. The results obtained are shown in the following table:

Comparison of VP/ VA copolymers FILMS IMMERSED IN WATER Air-dried Films-Time for Film t 1 Soluble.

2 Partly sol. 2 Do.

D0. 1 Not dispersible.

l The film of copolymer was coated on a glass slide and air dried.

2 VP =N-vinyl-Z-pyrrolidone/VA=vinyl acetate.

3 Solutions (0.5% in water) and shaken for 1 hr.

From the foregoing table it becomes clearly manifest that the Weight-percent ratio of the monomers is very critical and that copolymers outside the aforementioned desired ratio will lead to films which are insoluble, thereby requiring several vigorous washings before removal. In other words, the desired ratio in which all of the aforementioned desired properties are found is in 30 to 60% by weight N-vinyl-Z-pyrrolidone and from 40 to 70% by weight of vinyl ester.

I claim: V

l. A sprayable film forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of 30-60% by weight of N-vinylpyrrolidone and 40-70% by weight of a vinyl ester in solution of a mixture of a low boiling aliphatic alcohol of 1 to 3 carbon atoms and at least one aerosol propellant from the class of liquified chlorofiuoro hydrocarbons of one to. two carbon atoms, the said mixture being present in suficient amount to dissolve the said copolymer and render it sprayable, the said'vinyl ester being characterized by the following formula:

CHZ=RCHR wherein R represents a member selected from the class consisting of chlorine, formyl, acetyl, hydroxyacetyl, propionyl and butyryl. 2. A sprayable hair grooming preparation substantially tack-free under normal conditions of relative humidity and having water-solubility 'for removal from the hair consisting essentially of a copolymer of N-vinylpyrrolidone and a vinyl ester in solution of a low boiling aliphatic alcohol of 1 to 3 carbon atoms and at least one aerosol propellant from the class of liquified chloro-fiuoro bydrocrabons of one to two carbon atoms, the said alcohol and propellant being present in sufficient quantities to dissolve the said copolymer and render it sprayable, said copolymer having a Fikentscher K value of 15 to 60 and consisting of from about 30 to about 60% by weight of N-vinylpyrrolidone and from about 40 to 70% I by weight of a vinyl ester'having the following formula:

CH =CHR wherein R represents a member selected from the class consisting of chlorine, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

3. A sprayable hair grooming preparation according to claim 2 wherein the aerosol propellant is a mixture of trichloromonofiuoromethane and dichlorodifluromethane.

4. A sprayable hair grooming preparation according to claim 2 where the aerosol propellant is trifluoromethylchloride.

5. A sprayable hair grooming preparation according to claim 2 wherein the copolymer is a copolymer of 30% by weight of N-vinylpyrrolidone and 70% by weight of vinyl acetate.

6. The process of keeping human hair in place which comprises spraying said hair with a fine mist dispensed fro-m an aerosol container whose essential contents consist of a volatile, chloro-fluoro-substituted lower aliphatic hydrocarbon propellent having dissolved therein a copolymer consisting of about 50% vinyl pyrrolidone and about 50% of vinyl acetate, and a low boiling aliphatic alcohol of 1 to 3 carbon atoms.

7. The process of keeping human hair in place which comprises spraying said hair with a fine mist dispensed from an aerosol container whose essential contents consist of a volatile, chloro-fluoro-substituted lower aliphatic hydrocarbon propellent having dissolved therein a copolymer consisting of about 30-90% vinyl pyrrolidone and about lO-70% by weight of vinyl acetate, and ethyl alcohol.

8. A sprayable film-forming preparationsubstantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of about 30 to about percent by weight of N-vinyl pyrrolidone and from about 25 to about 70 percent by weight of a vinyl ester in solution of a mixture of a low-boiling aliphatic alcohol of l-3 carbon atoms and at least one aerosol propellant from the group of liquified chloro-fluoro hydrocarbons of from 1 to 2 carbon atoms, the said mixture being present in sufiicient amount to dissolve the said copolymer and render it sprayable, the said vinyl ester being of the formula:

CH2=CHR V wherein R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

9. A sprayable film-forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of from about 30 to about percent by weight of N-vinyl pyrrolidone and from about 10 to about 70 percent by weight of a vinyl ester in solution ofa mixture of a low-boiling aliphatic alcohol of l3 carbon atoms and at least one aerosol propellant from the group of liquified chloro-fluoro hydrocarbons of l to 2 carbon atoms, the said mixture being present in sufficient amount to dissolve the said copolymer and render it sprayable, the said vinyl ester being of the formula:

CH CHR wherein R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

10. A sprayable film-forming preparation substantially tack-free under normal conditions of relative humidity consisting essentially of a copolymer of from about to about 60 percent by weight of N-vinyl pyrrolidone and from about to about 70 percent by weight of a vinyl ester in solution of a mixture of a low-boiling aliphatic alcohol of 1-3 carbon atoms and at least one aerosol propellant from the group of liquified chloro-fluoro hydrocarbons of 1 to 2 carbon atoms, the said mixture being present in suflicient amount to dissolve the said copolymer and render it sprayable, the said vinyl ester being of the formula:

CH =CHR wherein R is a member of the group consisting of chloro, formyl, acetyl, hydroxy acetyl, propionyl and butyryl.

11. A sprayable hair-grooming preparation substantially tack-free under normal conditions of relative humidity and having water solubility for the removal from the hair consisting essentially of a copolymer of N-vinyl pyrrolidone and a vinyl ester in solution of a low-boiling aliphatic alcohol of 1-3 carbon atoms and at least one aerosol propellant from the group of liquified chlorofluoro hydrocarbons of 1 to 2 carbon atoms, the said alcohol and propellant being present in sufiicient quantities to dissolve the said copolymer and render it sprayable, said copolymer having a Fikentscher K value of 15 to and consisting of from about 30 to about 75 percent by weight of N-vinyl pyrrolidone and from about 25 to about percent by weight of a vinyl ester having the formula:

12. A sprayable hair-grooming preparation substantially tack-free under normal conditions of relative humidity and having water solubility for removal from the hair, consisting essentially of a copolymer of N-vinyl pyrrolidone and vinyl acetate in solution of a low-boiling aliphatic alcohol of 1-3 carbon atoms and at least one aerosol propellant from the group of liquified chlorofluoro hydrocarbons of 1 to 2 carbon atoms, said copolymer having a Fikentscher K value of 15 to 60 and consisting of from about 30 to about percent by weight of N-vinyl pyrrolidone and from about 25 to about 70 percent by weight of vinyl acetate, the said mixture being present in sufficient amount to dissolve the said copolymer and render it sprayable.

13. The process of keeping human hair in place which comprises spraying said hair with a fine mist dispensed from an aerosol container whose essential contents consist of a volatile chloro-fluoro substituted lower aliphatic hydrocarbon propellant having dissolved therein a copolymer consisting of from about 30 to about percent by weight of N-vinyl pyrrolidone and from about 10 to about 70 percent by weight of a vinyl ester having the formula:

References Cited by the Examiner UNITED STATES PATENTS 2/50 Werntz. 1/54 Morner et a1. 26085.7

OTHER REFERENCES JULIAN S. LEVITT, Primary Examiner.

W. B. KNIGHT, M. O. WOLK, Examiners.

Claims

1. THE PROCESS OF KEEPING HUMAN HAIR IN PLACE WHICH COMPRISES SPRAYING SAID HAIR WITH A FINE MIST DISPENSED FROM AN AEROSOL CONTAINER WHOSE ESSENTIAL CONTENTS CONSIST OF A VOLATILE, CHLORO-FLUORO-SUBSTITUTED LOWER ALIPHATIC HYDROCARBON PROPELLENT HAVING DISSOLVED THEREIN A COPOLYMER CONSISTING OF ABOUT 30-90% VINYL PYRROLIDONE AND ABOUT 10-70% BY WEIGHT OF VINYL ACETATE, AND ETHYL ALCOHOL.