US3215603A

US3215603A - Aqueous or alcoholic-aqueous lower olefin-maleic anhydride-vinyl crotonate cosmetic compositions

Info

Publication number: US3215603A
Application number: US184554A
Authority: US
Inventors: Gross Robert Thomas; Lehne Richard Karl
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1962-04-02
Filing date: 1962-04-02
Publication date: 1965-11-02
Anticipated expiration: 1982-11-02
Also published as: NL290950A; BE629437A; GB1032926A; DE1300197B; DK109282C; CH468185A

Description

United States Patent AQUEOUS OR ALCOHOLIC-AQUEOUS LOWER OLEFlN-MALEIC ANHYDRlDE-VINYL CRO- TONATE COSMETIC COMPOSITIONS Robert Thomas Gross, Flushing, N.Y., and Richard Karl Lehne, Berkeley Heights, N.J., assignors to Colgate- Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 2, 1962, Ser. No. 184,554 9 Claims. (Cl. 167-87) This invention relates to new compositions of matter. More particularly, the invention relates to compositions which are useful in the field of cosmetics, especially hair grooming preparations.

Many types of cosmetic hair grooming preparations are presently known. Generally, such preparations include at least one hair grooming agent and a vehicle therefor. The vehicle can vary widely in composition. For example, the vehicle may be a constituent which forms an emulsion, solution or gel with the hair grooming agent. Many cosmetic gels do not possess good properties of stability when subjected to heating or cooling. Others have a somewhat grainy feel when rubbed on the palms of the hands. Still others have a drying or stiffening effect on surfaces, such as the skin or hair to which they are to be applied. Accordingly, there exists a need for cosmetic gel compositions which overcome these disadvantages. The present invention provides a composition which fulfills this need, especially in the field of hair grooming preparations. Therefore, the invention will be explained as it applies to the field of hair grooming compositions, although it is to be understood that the compositions of the invention are also useful in other products too, such as wave setting compositions, hair tinting compositions and the like.

In accordance with the present invention, the present cosmetic compositions comprise a major proportion of at least one constituent selected from the group consisting of water and mixtures of at least one low molecular weight monohydroxy alcohol and water, a minor proportion of an at least partially neutralized copol mer of a low molecular weight olefin and maleic anhydride and a minor proportion of at least one compound selected from the group consisting of low molecular weight alcohol esters of higher fatty acids, aliphatic polyoxyalkylene compounds of the formula,

R(OC,,H OR and lower polyoxyalkylene adducts of alkane triols.

Among the low molecular weight monohydroxy alcohols which may be used in the practice of the invention are ethyl, propyl, isopropyl, butyl and isobutyl alcohols, that is, the lower liquid aliphatic alcohols. Of these, ethyl alcohol is the preferred compound. The alcohols can be anhydrous, but dilute alcohols are also suitable. The alcohols can be diluted to a rather large degree with a diluent such as water to as much as about percent or more.

The olefin-maleic anhydride copolymers utilized in the cosmetic compositions of this invention can vary widely. Essentially, they are the linear and cross-linked resinous copolymers of maleic anhydride with an olefin containing from 2 to 4 carbon atoms, that is, ethylene propylene, butylene and isobutylene. Under the usual preliminary conditions for the formation of the copolymers, the olefin and maleic anhydride may be combined in substanice tially equimolar proportions. These copolymers have a broad range of viscosities, those having viscosities of from about 10,000 to 200,000 centipoises being best for use in the new compositions of this invention, depending upon the amount of firmness desired in the particular composition being prepared. The viscosities are measured at 25 C. on a 1.0 percent aqueous solution at pH 9 using a Brookfield viscometer, No. 6 spindle at 25 revolutions per minute. Although both the linear and crosslinked olefin-maleic anhydride copolymers are useful in preparing the cosmetic compositions of this invention, the cross-linked copolymers are preferred. One of the preferred cross-linking agents is vinyl crotonate; but other known difunctional vinyl type cross-linking agents also can be utilized. These cross-linking agents are used dur ing the polymerization of the olefin and maleic anhydride. Difunctional compounds, .such as glycols and diamines, can also be used as cross-linking agents. However, these types are normally utilized after polymerization has taken place. The copolymers may be manufactured by any of the usual vinyl polymerization processes, which are well-known in the art.

The copolymers are employed in hydrolyzed form in the practice of the instant invention. Any suitable hydrolyzing agent can be employed for this purpose. Among such agents are water; basic compounds, such as sodium, potassium and ammonium hydroxide; inorganic and organic acids, such as sulfuric acid, hydrochloric acid, acetic acid and the like; and other inorganic compounds which are capable of suppling a hydroxyl group. Water, however, since it is already present as one of the constituents in the composition and is the cheapest and most readily available, is the preferred hydrolyzing agent. In those cases, Where the hydrolyzing agent has extremely strong basic or acidic properties, it is generally best to employ it in a dilute concentration. Among other reasons, this is advisable because the final composition is to be applied to hair or skin areas, which are susceptible to damage. Hydrolysis of the copolymer can take place before mixing it with the alcohol and other constituents of the compositions or it can take place in situ in the gel composition itself as the constituents thereof are being mixed together to form the gel.

Neutralizing agents are generally utilized in the new compositions. These agents serve a dual function. Primarily they are employed to at least partially neutralize the copolymer and to adjust the pH of the composition to the desired level in order to attain a composition having a substantially higher viscosity. On the other hand, the alkaline agents also serve to adjust the pH to a desired level which is compatible with the hair and human skin to which the composition is to be applied. Generally, any alkaline agent such as inorganic and organic nitrogen-containing compounds and the like can be employed for these purposes. The inorganic agents include ammonium hydroxide, sodium hydroxide, potassium hydroxide and other hydroxides and inorganic compounds which act as neutralizing agents. The organic agents include alkyl amines, alkanolamines, diamines and triamines, with those containing from 1 to 7 carbon atoms in the hydrocarbon groups performing well in the practice of the invention, whether they be primary, secondary, or tertiary compounds. The alkyl amines include mono-, diand trimethyl and ethyl amines and the like. The alkanolamines include the mono-, ditrimethanolamines and ethanolamines and the like. Among the preferred neutralizing agents are 2-amino-2-methyl-I'-propanol, diisopropanolamine and triethanolamine.

A wide variety of compounds which can be utilized as grooming agents in the compositions of this invention include the low molecular weight alcohol esters of the higher fatty acids, particularly the esters of C to C fatty acids and the lower molecular weight monohydroxy alcohols containing 1 to 6 carbon atoms. Among the preferred esters are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl and hexyl esters of lauric, palmitic, oleic myristic and steari-c acids and the like.

Additional compounds which can be used as grooming agents are aliphatic polyoxyalkylene compounds having the formula.

wherein R and R are selected from the group consisting of hydrogen and a lower aliphatic hydrocarbon radical of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n, the average number of carbon atoms in the lower monoxyalkylene monomeric constituent of the chain, is preferably from 2 to 6 and most preferably from 2 to 3 although the monoxyalkylene monomeric constituents can contain more than an average of 6 carbon atoms and x, the total number of lower monoxy-alkylene groups is such as to give a product of average molecular weight of at least about 300. These aliphatic polyoxyalkylene compounds are preferably water soluble but also include substances that form emul- SlOIIS.

Products of this type may be prepared by condensing lower alkylene oxide with a compound containing an active hydrogen such as an alcohol or glycol. The average degree of alkoxylation or chain links can be regulated in the manufacturing process but due to the nature of this type of regulation, the polyoxyalkylene will normally be a mixture of groups in different polymerization stages. Generally, compounds of this type which are most useful in the present invention are those in which the average molecular weight of the product is from about 300 to as much as about 10,000.

As representative of these compounds there may be mentioned the mono-lower alkyl ethers of poly-lower oxyalkylene glycols. These compounds are of the formula R(OC H OH. They will usually 'be .very satisfactory if the monoxyalkylene groups contain no more than 4 carbon atoms, R contains from 1 to 6 carbon atoms, and the average molecular weight of the compound is at least about 300.

Water insoluble but emulsifiable analogues of the above products may be made by forming the diether n Zn) XOR,

wherein both R and R are alkyl radicals and they satisfy the same conditions as R and R defined hereinabove.

Another sub-class of compounds is the group of water soluble polyalkylene glycol block copolymers. These compounds aremade by polymerizing lower alkylene ox ide and/ or glycol groups to form compounds containing separate hydrophobic and hydrophilic blocks or chains and having terminal hydroxy groups.

An additional sub-class of material is the group composed of water soluble aliphatic lower 1,2-polyalkylene glycols of the formula,

wherein m, the number of carbon atoms in the monoxyalkylene unit is 2 and/or 3 and the molecular weight of which is between about 300 and 10,000. A preferred compound of this sub-class is polyalkylene glycol of a molecular weight of about 600.

An additional class of compounds which can be employed as grooming constituents includes the lower polyoxyalkylene adducts of alkane triols which have a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400. Preferred compounds in this sub-class include the adducts of alkane triols containing from about 3 to 6 carbon atoms such as the polyoxypropylene adducts of glycerine or 1,2,6-hexanetriol, and the like. Regardless of which particular grooming agent, falling within the wide variety of materials defined, is employed in preparing the new compositions of this invention, it may be utilized either alone or in combination with any one or more of the others. It is to be noted, however, that in those cases where a fatty acid ester such as those defined hereinabove are employed, it may be necessary to use a solubilizing agent, such as polyoxyethylene sorbitan fatty acid ester. The use of such an agent is generally preferred in order to prepare a satisfactory composition. However, it is to be understood that the solubilizing agent is not necessary and the fatty acid ester can be incorporated into the composition without solubilization, although a clear gel is not usually then obtained. In addition to the polyoxyethylene sorbitan esters, any other known solubilizing agent can be utilized. Such agents include polyethoxylated fatty alcohols, polyethoxylated lanoline alcohols and the like.

Plasticizing agents are optionally but preferably employed. They serve to plasticize the film formed by the copolymer. Such plasticizers include glycerine, hexylene glycol, propylene glycol, ethylhexane diols and other diol and triol compounds of this type. Additional plasticizers include the diethyl and dimethyl phthalates. One of the preferred plasticizers is methyl phthaloyl ethyl glycolate. In some cases, the plasticizer also can function as an additional grooming agent. On the other hand, some of the polyalkylene glycols set forth above as grooming agents will also have a plasticizing effect on the composition.

Various adjuvants, such as perfumes, colorants, bactericides, and other materials designed to give the compositions special effects may also be present in limited proportions.

The water, alcohols, copolymer, grooming agents, neutralizing agents and plasticizers, where employed, can be present in various proportions in the compositions of this invention. Generally, the new cosmetic gels of the invention comprise a major proportion of water or a mixture of at least one alcohol and water, as stated Previously In a composition which does not contain any alcohol, the water is employed in a range of about 75 to 98 percent, by weight, based on the total weight of the composition. The remaining constituents in such a composition comprise enough copolymer, grooming agent, adjuvants and neutralizing agent to bring the total to 100 percent. Preferably, however, in such a composition the Water is utilized in a range of about to percent by weight. On the other hand, where a mixture of water and alcohol is used, the alcohol can be present in a range of about 30 percent or less to as much as about 65 percent or more by weight, based on the total weight of the composition and preferably is present in a range of about 50 to 60 percent by weight. In such a case, the water is used in a sufficient quantity to bring the total weight of the composition to percent after the addition of the copolymer, grooming agents, adjuvants and neutralizing agent, the water generally being present in a range of about 10 to 65 percent and preferably in a range of about 20 to 40 percent by weight, based on the total composition weight. Where two or more alcohols are employed, they can be utilized in a mixture with each other in any desired amount so long as the total amount of alcohol is Within the ranges set out hereinabove.

The ethylene-maleic anhydride copolymer is generally present in a minor proportion in the new cosmetic gels of this invention. The copolymer is utilized in an amount sufiicient to form a stable gel with the other constituents. However, the gel so formed can be relatively fluid or pourable or it can be relatively viscous,

so that it peaks, when contacted by an object such as a spatula or like, when the object is withdrawn from contact with the surface of the gel. Generally, the copolymer can be used in a range of about 0.1 to about 4.5 per cent by weight, based on the total weight of the composition and preferably in a range of about 1 to 3 percent. In general, those copolymers having viscosities in the upper portion of the viscosity ranges previously given can be employed in smaller amounts, within the established percentage limitations.

The wide variety of grooming agents defined can be employed in a range of about 1 to as much as about 15 percent by weight, based on the total weight of the composition and preferably in a range of about 8 to 12 percent. Where a mixture of two or more grooming agents is utilized, the total amount of grooming agent employed should not fall out-side the established weight percent limitations for best results, although within these limitations the grooming agents may be used in any combination desirable.

The neutralizing agent is also present in minor proportion in the compositions of the invention. The specific amount of neutralizing agent employed will depend upon the desired physical properties of the final product. In general, although the final product can have a pH as low as 3 and as high as 8 or 9, it is preferred that the compositions have a pH of about 6 to 7. On the other hand, if total and complete neutralization of the copolymer is desired, enough neutralizing agent is employed to adjust the pH of the composition to about 8 or 9. However, enough agent to adjust the pH to at least about 6 will develop a firm gel. Generally, the neutralizing agent is employed in a range of about 0.01 to 5 percent by weight based on the total weight of the composition, depending upon the type and concentration of the particular neutralizing agent being used.

As pointed out hereinabove a plasticizer is preferably utilized in the new compositions of this invention although it is optional. Generally, about 1 to 6 percent by Weight, based on the total weight of the composition, of plasticizer is used. However, about 2 to 4 percent by weight of the plasticizer is preferred. It is to be understood that with the plasticizer, as well as all of the other constituents employed herein, the particular amount of any one constituent employed in a particular composition to achieve the best result is readily determinable by simple tests or trials. Products containing constituents in the ranges established herein exhibit desirable properties of stability, grooming and the like.

The new compositions disclosed and claimed herein can be prepared in a relatively simple manner. The constituents may be mixed together at a temperature in a range extending from about room temperature (20 C.) to the boiling point of the mixture, with agitation, until a homogeneous composition results. In one method of preparation, the lower olefin-maleic anhydride copolymer is dispersed in water and heated to a temperature between about -95 C. and the boiling point of the watercopolymer mixture until a uniformly thick paste results. Even though heating is not necessary it permits hydrolysis of the copolymer in a minimum amount of time. Su-bsequently, this paste is stirred into the required amount of at least one alcohol, where an alcohol is used, at a temperature between about 45 C. and the boiling point of the alcohol and is agitated until a substantially homogeneous gel is obtained. To conserve alcohol, the temperature of mixing is preferably kept as low as practicable within this range. During agitation, the grooming agents, plasticizers and neutralizing agents are added to the mixture as gelation is taking place. The length of the period of agitation necessary to obtain a homogeneous composition can be as long as several hours or more. In those compositions where alcohol is not employed, the grooming agents and the like are simply added to the water-copolymer paste. In another alternative method, the minor components, that is, the copolymer, bacteriostat. grooming and plasticizing constituents may be combined as a fluid paste. Then the water may be added, with agitation, followed by the alcohol. When complete dispersion of the ingredients in the water and alcohol is effected, the neutralizer is added. Regardless of the partlcular sequence of steps carried out in preparing the gels, a good product can be obtained.

The compositions disclosed and claimed herein exhibit desirable properties when employed as a cosmetic in grooming the hair or other similar uses. For example, a hair grooming composition prepared in accordance with the above outlined procedure will result in a product that is characterized by high stability and which is clear, has a pleasing texture, good viscosity and consistency. The preferred range of viscosities is from 1,000 to 100,000 centipoises at 25 C., as measured by a Erookfield RVF viscometer (No. 7 spindle at 20 revolutrons per minute). Moreover, upon reasonable periods of aging (up to periods of 12 months or more) even those compositions which contain as high as 50 percent or more alcohol incorporated therein do not exude the alcohol. In addition, the compositions of the invention do not form gritty particles of gel upon rubbing out between the palms of the hands. However, similar compositions, wherein other gelling agents outside this invention, are substituted for the ethylenemaleic anhydride copolymer-s employed in the instant compositions, objectionably form granules of gel when rubbed out between the palm of the hands. The new compositions of the invention also exhibit extremely good grooming ability and form a film which has a pleasing texture when applied to the hair. Moreover, rewetting of the hair to which these compositions have been applied is very satisfactory.

The present compositions are very versatile and can be employed as wave setting compositions in their less viscous state and as hair tinting compositions when the proper dyes or pigments are incorporated therein. In addition to the constituents set out hereinabove, the compositions of this invention may also contain perfumes and germicidal compounds such as hexachlorophene, quaternary ammonium compounds such as stearyl dimethyl benzyl ammonium chloride and the like. When employed, these adjuvants are used in relatively minor amounts, often less than about 1 percent. Proper utilization of the copolymer in the molecular weight ranges such as those set forth above permits the preparation of a composition which is relatively fluid and pourable or which can be a firm gel composition which may be conveniently extruded from a tube, as desired.

In order to illustrate the present invention more fully, the following illustrative examples are set forth. In the examples, all parts and percents are by weight except where otherwise stated.

Example I A hair grooming composition was prepared which contained the following constituents:

. Percent Ethylene maleic anhydride copolymer cross-linked with vinyl crotonate, having a viscosity of 160,-

000 centipoises 1.5 Deionized water 30.90 Ethyl alcohol (SDA 40), percent alcohol 55.0 Polyethylene glycol, average molecular weight 600 8.00 Trihydroxy polypropylene glycol, average molecular weight 4,000 3.20 2-amino-2-methyl-l-propanol Hexachlorophene 0.25 Perfume -a 0.25

The water and alcohol were placed in a mixer equipped with counter-rotating blades. Agitation was begun and copolymer and hexachlorophene were sifted into the mixture. Next, the polyethylene glycol was added and subsequently, the trihydroxy polypropylene glycol was poured into the mixing vessel. Mixing was continued for approximately 3 hours at atmospheric pressure and room temperature (ca. 20 C.). The perfume was then added and agitation was stopped. Finally, the 2-arnino-2-methyl-l-propanol was added to the composition and .agitation was carried out for minutes, using the counterrotating blades only.

The product so obtained was a clear stable firm gel which had good hair grooming qualities and conditioned the hair without leaving an objectionable flaky coating thereon. The gel was smooth when rubbed out be tween the palms of the hands and did not produce objectionable granules as did a similar composition containing a difierent commercial gelling agent. The product had an apparent viscosity of 28,000 centipoises on a Brookfield RVF viscometer at 25 C. using a number 7 Spindle at revolutions per minute.

Example 11 ular weight 4,000 3.20 Polyethylene glycol, average molecular weight 600 8.00 2-amino-2-methyl-l-propanol 0.12

The copolymer, trihydroxy polypropylene glycol and polyethylene glycol were mixed in an Eppenbach mixer to form a paste at room temperature (ca. 20 (3.). Subsequently, the water was added to the mixture and the reaction mass was agitated at room temperature until complete dispersion of the other constituents in the water and alcohol had taken place which took about 3 hours. The 2-amino-2-methyl-l-propanol was then added to the mixture which was then agitated another 15 minutes.

The product was a clear, stable pourable gel suitable for use as a wave setting composition. When applied to the hair, a small quantity conditions the hair, makes it more manageable and holds it in place, without the production of undesirable flaky scales of dried out wave set. The product viscosity was 3,000 centipoises on a Brookfield RVF viscometer at C. using a number 7 spindle at 20 revolutions per minute. It had a pH of 7 taken on a Beckman pH meter.

Example Ill A composition was prepared which contained the following constituents:

Percent Ethylene maleic anhydride copolymer crosslinked with vinyl crotonate, having .a viscosity of The constituents were mixed together in accordance with the procedure in Example II.

The product was a nearly clear, stable firm gel capable 8 of extrusion from a tube and had properties similar to the composition of Example I. The gel so formed had a viscosity of 84,000 centipoises on a Brookfield RVF viscometer at 250 C. using a number 7 spindle at 20 revolutions per minute. The product had a pH of 7 taken on a Beckman apparatus.

Example IV A composition was prepared which contained the following constituents:

Percent Ethylene maleic anhydride copolymer crosslinked with vinyl crotonate, having a viscosity of 160,000 centipoises 1.50 Deionizer Water 31.10 Ethyl alcohol (SDA 40), percent alcohol 55.00 Trihydroxy polypropylene glycol, average molecular weight 4,000 6.00 Polypropylene glycol, average molecular weight 600 3.00 Polyethoxylated lanolin 2.00 Hexachlorophene 0.25 Perfume 0.25 2-amino-2-methyl-l-propanol 0.90

The constituents were mixed together in accordance with the procedure of Example II except that ethyl alcohol was added with the water and hexachlorophene and perfume were added before neutralization with the 2-amino-2-methyl-l-propanol.

The product was a clear, stable, pale yellow extrudable gel which had properties similar to the composition of Example I. The composition had a viscosity of 17,000 centipoises taken on a Brookfield RVF viscometer at 25 C. using a number 7 spindle at 20 revolutions per minute. The product had a pH of 7 taken on a Beckman pH meter.

Example V A composition was prepared which contained the following constituents:

Percent Ethylene maleic anhydride copolymer crosslinked with vinyl crotonate, having a viscosity of 160,000 centipoises 1.50 Deionized Water 27.00 Ethyl alcohol (SDA 40), 95 percent alcohol 50.00 Trihydroxy polypropylene glycol, average molecular weight 64,000 2.80 Polyethylene glycol, average molecular weight 600 8.00 Polyoxyethylene sorbitan, palmitate, average molecular weight 1,200 6.80 Isopropyl palmitate 3.00 2-amino-2-methyl-l-propanol 0.90

The procedure of Example I was followed and the product obtained had properties similar to that of Example I.

Example VI A composition was prepared which contained the following constituents:

Percent Ethylene-maleic anhydride copolymer, crosslinked with vinyl crotonate and having a viscosity of 160,000 centipoises 1.50 Deionized water 30.90

Ethyl alcohol (SDA 40), 95 percent alcohol 55.00 Polyethylene glycol, average molecular weight 600 8.00 Trihydroxy polypropylene glycol, average molecular weight 4,000 3.20 Stearyl dirnethyl benzyl ammonium chloride 0.25 Perfume 0.25 2-amino-2-methyl-l-propanol 0.90

9 The constituents were mixed together in accordance with the procedure of Example I. The gel so formed exhibited similar properties although it was slightly less clear.

Example VII A composition was prepared which contained the following constituents:

Percent Ethylene-maleic anhydride copolymer, cross-linked with vinyl crotonate and having a viscosity of Polyethylene glycol, average molecular weight 300 2.20

Methyl phthaloyl ethyl glycolate 5.00 Perfume 0.25 2-amino-2-methyl-l-propanol 0.90

The constituents were mixed together in accordance with the procedure of Example I. The gel so formed exhibited similar properties although it was slightly less clear.

The above invention has been described in conjunction with illustrative examples thereof. It will be obvious to those skilled in the art who read this specification that other variations and modifications of the invention can be made and various equivalents substituted therein without departing from the principles disclosed or going outside the scope of the specification or purview of the claims.

What is claimed is:

1. A composition comprising a major proportion of a constituent selected from the group consisting of water and mixtures of at least one low molecular weight monohydroxy alcohol and water, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, a minor proportion of an at least partially neutralized copolymer of a low molecular weight olefin and maleic anhydride, said olefin containing from 2 to 4 carbon atoms and said copolymers being cross-linked with vinyl crotonate, and a minor proportion of at least one compound selected from the group consisting of low molecular weight alcohol esters of higher fatty acids containing from 12 to 18 carbon atoms, aliphatic polyoxyalkylene compounds of the formula,

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n is the average number of carbon atoms in the lower oxyalkylene constituents of the chain, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300, and lower polyoxyalkylene adducts of alkane triols having a molecular weight in the range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400, said alkane triols containing from 3 to 6 carbon atoms.

2. A stable cosmetic gel composition comprising by weight, based on the total weight of the composition, about 75 to 98 percent of a constituent selected from the group consisting of water and mixtures of at least one low molecular weight monohydroxy alcohol and water, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, about 0.1 to 4.5 percent of an at least partially neutralized copolymer of a low molecular weight olefin and maleic anhydride, said olefin containing from 2 to 4 carbon atoms and said copolymers being cross-linked with vinyl crotonate, and about 1 to percent of at least one compound selected from the group consisting of low molecular weight alcohol esters of higher fatty acids containing from 12 to 18 carbon atoms, aliphatic polyoxyalkylene compounds of the formula,

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n is the average number of carbon atoms in the lower oxyalkylene constituents of the chain, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300, and lower polyoxyalkylene adducts of alkane triols having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400, said composition having a pH of about 3 to 9, said alkane triols containing from 3 to 6 carbon atoms.

3. A stable composition for grooming the hair comprising by weight, based on the total weight of the composition, about to percent of a constituent selected from the group consisting of water and mixtures of at least one low molecular weight alcohol and water, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, about 1 to 3 percent of an at least partially neutralized copolymer of a low molecular weight olefin and maleic anhydride, said olefin containing from 2 to 4 carbon atoms and said copolymers being cross-linked with vinyl crotonate, and about 8 to 12 percent of at lease one compound selected from the group consisting of low molecular weight alcohol esters of fatty acids of 12 to 18 carbon atoms, aliphatic polyoxyalkylene compounds of the formula,

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC I-l is a polyoxyalkylene chain of lower monoxyalkylene groups, n, the average number of carbon atoms in the lower oxyalkylene constituents of the chain, is from 2 to 6 and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300, and lower polyoxyalkylene adducts of alkane triols containing 3 to 6 carbon atoms and having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400.

4. A stable gel composition for grooming the hair comprising by weight, based on the total weight of the composition about 80 to 90 percent of a constituent selected from the group consisting of Water and mixtures of at least one low molecular weight monohydroxy alcohol and water, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, about 1 to 3 percent of an at least partially neutralized copolymer of low molecular Weight olefin and maleic anhydride, said copolymer being neutralized with about 0.01 to 5 percent of a neutralizing agent selected from the group consisting of mono-, diand tri-alkanolamines containing 1 to 7 carbon atoms in the hydrocarbon groups, said olefin containing from 2 to 4 carbon atoms and said copolymers being cross-linked with vinyl crotonate, and about 8 to 12 percent of at least one compound selected from the group consisting of low molecular weight alcohol esters of fatty acids of 12 to 18 carbon atoms, aliphatic polyoxyalkylene compounds of the formula,

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC l-I Q is a polyoxyalkylene chain of lower monoxyalkylene groups n, the average number of carbon atoms in the lower oxyalkylene constituents of the chain, is from 2 to 3 and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300, and lower polyoxyalkylene adducts of alkane triols containing 3 to 6 carbon atoms and having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400, said composition having a pH of about 6 to 7.

5. A stable gel composition for grooming the hair comprising by weight, based on the total weight of the composition, about 80 to 90 percent of a constituent selected from the group consisting of water and mixtures of at least one low molecular weight monohydroxy alcohol and water, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, about 1 to 3 percent of an at least partially neutralized copolymer of a low molecular weight olefin and maleic anhydride cross-linked with vinyl crotonate, said copolymer being neutralized with about 0.01 to percent of a neutralizing agent selected from the group consisting of mono-, diand tri-alkanolamines containing 1 to 7 carbon atoms in the hydrocarbon groups, said olefin containing from 2 to 4 carbon atoms, and about 8 to 12 percent of at least one compound selected from the group consisting of lower molecular weight alcohol esters of C to C fatty acids, aliphatic polyoxyalkylene compounds of the formula,

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n, the average number of carbon atoms in the lower oxyalkylene constituents of the chain, is from 2 to 3, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300 and lower polyoxyalkylene adducts of alkane triols containing 3 to 6 carbon atoms and having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400 said composition having a pH of about 6 to 7.

6. A stable gel composition for grooming the hair comprising by weight, based on the total weight of the composition, about 75 to 98 percent of a constituent containing water in a range of about to 65 percent and lower molecular weight monohydroxy alcohol in a range of about 30 to 65 percent, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, about 0.1 to 4.5 percent of an at least partially neutralized copolymer of a lower molecular weight olefin and maleic anhydride, said olefin containing from 2 to 4 carbon atoms and said copolymers being cross-linked with vinyl crotonate, and about 1 to 15 percent of a compound selected from the group consisting of low molecular weight alcohol esters of fatty acids, of 12 to 18 carbon atoms, aliphatic polyoxyalkylene compounds of the formula,

wherein R ano R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC H J is a polyoxyalkylene chain of lower monoxyalkylene groups, n is the average number of carbon atoms in the lower oxyalkylene constituents of the chain, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300, and lower polyoxyalkylene adducts of alkane triols and having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400, said alkane triols containing from 3 to 6 carbon atoms.

7. A stable gel composition for grooming the hair comprising by weight, based on the total weight of the composition about 75 to 98 percent of water, about 0.1 to 4.5 percent of an at least partially neutralized copolymer of a low molecular weight olefin and maleic anhydride, said olefin containing from 2 to 4 carbon atoms and said copolymers being cross-linked with vinyl crotonate, and about 1 to 15 percent of a compound selected from the group consisting of low molecular weight alcohol esters of C to C fatty acids, aliphatic polyoxyalkylene compounds of the formula,

wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n is the average number of carbon atoms in the lower oxyalkylene constituents of the chain, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight of at least about 300 and lower polyoxyalkylene adducts of alkane triols having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400, said alkane triols containing from 3 to 6 carbon atoms.

8. A stable gel composition for grooming the hair comprising by weight, based on the total weight of the composition, about to percent of a constituent selected from the group consisting of water and mixtures of at least one low molecular weight monohydroxyalcohol and Water, said alcohol being selected from the group consisting of ethyl, propyl, isopropyl, butyl and isobutyl, about 1 to 3 percent of an at least partially neutralized copolymer of a low molecular weight olefin and maleic anhydride, cross-linked with vinyl crotonate, said copolymer being neutralized with about 0.01 to 5 percent of a neutralizing agent to adjust the pH of the composition to about 6-7, said olefin containing from 2 to 4 carbon atoms, and about 8 to 12 percent of at least one compound selected from the group consisting of low molecular weight alcohol esters of fatty acids, of 12 to 18 carbon atoms, aliphatic polyoxyalkylene compounds of the formula,

R (OC H OR wherein R and R are selected from the group consisting of hydrogen and lower aliphatic hydrocarbon of up to 6 carbon atoms, (OC H is a polyoxyalkylene chain of lower monoxyalkylene groups, n, the average number of carbon atoms is the lower oxyalkylene constituents of the chain, is from 2 to 6, and x, the total number of lower monoxyalkylene groups, is such as to give a product of average molecular weight at least about 300, and lower polyoxyalkylene adducts of alkane triols containing 3 to 6 carbon atoms and having a molecular weight in a range of about 300 to 5,000 and an average hydroxyl number of about 30 to 400.

9. A clear, stable alcoholic gel composition for grooming the hair comprising by weight, based on the total weight of the composition, about 50 percent of ethyl alcohol, about 2.0 percent of a substantially completely neutralized copolymer of ethylene andmaleic anhydride cross' linked with vinyl crotonate, about 8 percent of polyethylene glycol having a molecular weight of about 600, about 4 percent of trihydroxy polypropylene glycol having a molecular weight of about 4,000, about 0.90 percent of 2-amino-2-methyl-l-propanol, and about 30.0 percent of water.

References Cited by the Examiner UNITED STATES PATENTS 2,309,722 2/43 Wilkes et al 16787 XR 2,771,394 11/56 Mehaffey 16787 (Other references on following page) 13 UNITED STATES PATENTS Mills l6787.2 XR Sundberg et a1. 16787 XR Zopf et a1. 26078.5 Johnson 260-785 Cohen et a1. 260-785 Reinhard 16763 XR Tarpey 16787.2

14 OTHER REFERENCES Atlas Powder 00., A Guide to Cosmetic and Pharmaceutica'l Formulations with Atlas Products, Wilmington, Delaware (1954).

JULIAN S. LEVIT T, Primary Examiner.

FRANK CACCIAPAGLIA, JR., LEWIS GOTTS,

Examiners.

Claims

1. A COMPOUND COMPRISING A MAJOR PROPORTION OF A CONSTITUENT SELECTED FROM THE GROUP CONSISTING OF WATER AND MIXTURES OF AT LEAST ONE LOW MOLECULAR WEIGHT MONOHYDROXY ALCOHOL AND WATER, SAID ALCOHOL BEING SELECTED FROM THE GROUP CONSISTING OF ETHYL, PROPYL, ISOPROPYL, BUTYL AND ISOBUTYL, A MINOR PROPORTION OF AN AT LEAST PARTIALLY NEUTRALIZED COPOLYMER OF A LOW MOLECULAR WEIGHT OLEFIN AND MALEIC ANHYDRIDE, SAID OLEFIN CONTAINING FROM 2 TO 4 CARBON ATOMS AND SAID COPOLYMERS BEING CROSS-LINKED WITH VINLY CROTONATE, AND A MINOR PROPORTION OF AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF LOW MOLECULAR WEIGHT ALCOHOL ESTERS OF HIGHER FATTY ACIDS CONTAINING FROM 12 TO 18 CARBON ATOMS, ALIPHATIC POLYOXYALKYLENE COMPOUNDS OF THE FORMULA,