US3830919A

US3830919A - Antimicrobial haidressing

Info

Publication number: US3830919A
Application number: US00154180A
Authority: US
Inventors: F Olson
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1971-06-17
Filing date: 1971-06-17
Publication date: 1974-08-20
Anticipated expiration: 1991-08-20
Also published as: CH573249A5; FR2141853B1; GB1354990A; FR2141853A1; NL7208318A; IT1048255B; AU466455B2; BE784897A; AR196997A1; CA991548A; DK132256C; AU4349072A; ZA723813B; PH9994A; SE387845B; BR7203916D0; DK132256B; DE2228934A1

Abstract

TRANSPARENT, ANTIMICROBIAL HAIRDRESSING COMPOSITIONS COMPRISING AN ALKYL ISOQUINOLINIUM SLAT, SUCH AS A HIGHER ALKYL ISOQUINOLINIUM HALIDE, A HYDROPHILIC OIL AND A HYDROPHOBIC OIL, BOTH OF WHICH ARE MONOETHERS OF LOWER ALCOHOL(S) AND POLY-LOWER ALKYLENE GLYCOL(S), AND AN AQUEOUS OR AQUEOUS ALCHOLIC MEDIUM.

Description

United States Patent Office 3,830,919 Patented Aug. 20, 1974 ABSTRACT OF THE DISCLOSURE Transparent, antimicrobial hairdressing compositions, comprising an alkyl isoquinolinium salt, such as a higher alkyl isoquinolinium halide, a hydrophil'ic oil and a hydrophobic oil, both of which are monoethers of lower alcohol(s) and poly-lower alkylene glycol (s), and an aqueous or aqueous alcoholic medium.

SUBJECT OF THE INVENTION The present invention relates to clear hairdressings having hair conditioning and antimicrobial properties. In addition to inhibiting the growth of bacteria, fungi, and yeasts, the present preparations are useful in treating the hair so as to make it more readily controlled and combed into place. Such products are especially useful as mens hairdressings but may also find applications in the treatment of Womens hair.

BACKGROUND "OF THE INVENTION For years extensive research has been conducted in efforts to produce cosmetic materials that will also possess antimicrobial activities. Many cosmetics, toiletries and washing agents containing a wide variety of bactericides and fungicides have been formulated. Preparations for the skin have been made which include bactericides that are elfective against Staphylococcus aureus, and compositions for the hair incorporating microbicides effective against Staphylococcus aureus and Pityrosporum ovale have been made, the latter of which has been considered to be a causative agent for the development of dandrufi and excessive scaling of the human scalp.

DESCRIPTION OF THE (INVENTION It has now been found that an effective antimicrobial hairdressing can be produced as a clear product. This fact is especially appreciated when it is realized that other microbicides which have been found to be clinically effective against dandruff, including zinc omadine and selenium disulfide, do not form clear hairdressings in aqueous alcoholic media. The present compositions are unobvious in that they are truly effective antimicrobial hairdressings capable of being made as clear products.

The unobviousness of the present invention is further established by tests which indicate that the combination of alkyl isoquinolinium salt and mixture of polya'lkylene glycol ethers described herein results in an effectively microbicidal composition rather than in diminution of antimicrobial proper-ties, as could have been expected from a combination of the germicide and a surface active nonionic material. Furthermore, the desired properties of the present compositions are obtained whether the compositions are in liquid or gel form.

In accordance with the present invention, there is provided a hairdressing which comprises minor proportions of an antimicrobial alkyl isoquinolinium salt and hydrophilic and lipophilic lower alkyl monoethers of polylower alkylene glycols in an aqueous or aqueous alcoholic carrier medium. More specifically, such hairdressing compositions are either clear liquid or gel preparations and preferably comprise lauryl isoquinolinium bromide, 21

hydrophilic polyethylene-polypropylene glycol monoether of butanol which is of molecular weight from about 1,400 to 1,600 and is derived from equal parts by weight of propylene oxide and ethylene oxide and a lipophilic polypropylene glycol monoether of butanol which has a molecular weight of 2,0002,500 in a carrier medium which is aqueous ethanolic. Also, within the invention are antimicrobial uses of the composition of alkyl isoquinolinium salt and the mixed polyalkylene glycol ethers.

The antimicrobial alkyl isoquinolinium salts employed are those of the formula:

wherein R is alkyl and X is a salt-forming anion. Among the R groups that may be employed are the higher alkyls of 8 to 20 carbon atoms, preferably the straight chain alkyls of 8 to 16 carbon atoms, e.g., myristyl, lauryl, and decyl. Of these lauryl is most preferred. Salt-forming groups are usually halogens, including fluorine, iodine, bromine, and chlorine, of which the bromine and chicrine are preferred and the bromine is the most preferred. Other suitable salt-forming anions are also useful in particular applications, including the sulfates, bisulfates, acetates, rand propionates. The salt-forming ions will usu ally be anionic portions of commercially available inorganic acids or of lower carboxylic acids, preferably of 2 to 5 carbon atoms. Although the formula given illustrates the non-substituted alkyl isoquinolinium salts, it is contemplated that equivalent such which are substituted by non-interfering radicals, such as lower alkyl, halogen, nitro, amino or hydroxyl groups, may also be employed in accordance with the teachings of the invention. If such substitution is present, it will usually be found on the aromatic ring or the alkyl chain.

An important consideration in selecting the antimicrobial .alkyl isoquinolinium salt is that it should be strongly antimicrobial, especially eifective against Pityrosporumt ovale, and it should be compatible with the other constituents of the hairdressing compositions, especially with the lower polyialkylene glycol ethers, alcohol, water, and gelling agent if employed to make clear solutions or gels. Thus, the alkyl isoquinolinium salts should be sufiiciently soluble in the carrier solvent medium to make clear products and should not cause clouding or creaming of the hairdressing composition.

The mixed polyethylene-polypropylene glycol ether hydrophilic oil component of the present preparations is one in which the proportions of polyoxyethylene and polyoxypropylene are such that the hydrophilic properties of the product predominant, making it water soluble, while still giving it the thickness and lubricity of an oil. Because the polyethylene glycol or polyethylene oxide component employed to produce the polyoxyethylene portion of the hydrophilic oil is that component which usually favors hydrophilic characteristics, to increase such properties an increase in polyethylene glycol or polyethylene oxide monomer may be effected. Correspondingly, to in crease the lipophilic properties, the properties of polyoxypropylene or, in some cases, polyoxybutylene, can be increased, with greater lipophilic effects being obtained from using some higher polyoxyalkylene, such as polyoxybutylene, due to its increased carbon/oxygen ratio. The lipophilic or hydrophilic properties of the polyalkylene glycol and its solubilities are also related to chain lengths or molecular Weight and these factors, with ethylene oxide-propylene oxide ratios and etherifying monohydric alcohol carbon contents, are chosen to obtain the hydrophile-lipophile balance and water solubility for the hydrophilic oil.

Various types of polyethylene-polypropylene glycol ethers can be used as the present hydrophilic oils, including mixed polymers made by blending the desired ratios of polyethylene oxide and polypropylene oxide with chain terminating compounds, such as lower monohydric alcohols and condensing or sequentially polymerizing polyethylene oxide or glycol monomers, followed by polymerizing polypropylene oxide or glycol monomers, joining onto the previously made chain and terminating the chain made. Variations of these methods can be employed, such as those wherein mixed polymers are first made, which are subsequently block copolymerized with other previously produced polymers of the ethylene oxide or propylene oxide types. Whatever system is used, the product made should be water soluble and possess an oily appearance, with hair conditioning and lubricating properties.

Methods for making the various mixed polyethylenepolypropylene glycol, whether of the block copolymer, sequentially polymerized or copolymerized mixed monomer types, all of which are characterized in the specification as mixed polyethylene-polypropylene glycols, are well known. They are described at length in U.S. Pat. 2,425,755, at columns 6-9 and in the working examples.

The polypropylene glycol ether lipophilic oil compound of the present compositions is related to the hydrophilic oil previously described. Although in some instances polyoxybutylene may be employed in part in the making of a mixed or block copolymer, in most cases the polyalkylene oxide employed will be polypropylene oxide. Of course, instead of the polypropylene oxide, a corresponding polypropylene glycol may be used. Chain length will be terminated by a lower alkanol, preferably butanol. The various polypropylene glycol or polyoxypropylene alkyl ethers are mixtures of polymers of various chain lengths, as are the hydrophilic polymers previously discussed. The chain lengths and the chain terminating compound are chosen so that the product will be desirably lipophilic, oily and clear. The polymers should be soluble in the alcohol or aqueous alcoholic media employed. Solubility in water itself may be very small, often being less than 2%. In preferred embodiments of the invention, mixtures of polyoxypropylene butyl monoethers are used. The described compounds are known and methods for their manufacture are given in U.S. Pat. 2,448,664 at columns -8 and in the working examples. This patent describes the useful class of the lipophilic polymers and a similar description, with respect to the hydrophilic polymers, is found in U.S. Pat. 2,425,755, previously cited.

Preferred blends of glycols or lower alkylene oxides to make the present hydrophilic oils are blends of polyethylene oxide and polypropylene oxide or the equivalent glycols, which contain from 25 to 75% of the polyethylene glycol and 75 to 25% of the polypropylene glycol or equivalent oxides, preferably 40 to 60% and 60 to 40%, respectively, exclusive of the etherifying chain terminating radicals. The polymers made are preferably terminated with hydroxyl or alkyl groups of 1 to 8 carbon atoms, preferably a lower alkyl of from 3 to 5 carbon atoms. Usually, the polymers will be terminated at one end with an OH and at the other with a normal alkyl. To obtain the desired hydrophilic oils the molecular Weights should be regulated to average in the range of about 400 to 4,000, preferably from 1,000 to 2,000 and most preferably from 1,400 to 1,600. In a similar manner, with respect to the lipophilic oils, the chain terminating monohydric alcohol is usually of 1 to 8 carbon atoms and is linear. Preferably, it is of 3 to 5 carbon atoms. The molecular weight of the lipophilic oil is normally within the range of 400 to 4,000, preferably from 1,500 to 3,000. The water solubility of such compounds will generally be from 0.2 to 1% at room temperature.

It has been found that mixtures of the lipophilic oils are useful and in such cases, preferred mixtures are of such compounds of molecular weights between 1,800 to 2,200, with those of such weights of 2,3002,700. In some in stances, the etherifying monohydric alcohol is preferably butanol. In the mixtures described, it will generally be preferable to include, as the major constituent of the mixed lipophilic polyalkylene glycol ether, that of the higher molecular weight, and often it will constitute from 70 to of the mixture.

Both the hydrophilic and lipophilic oils may, in appropriate cases, be replaced, usually only in part, by similar oils or slight modifications. Thus, instead of employing monohydric alcohol chain terminators, in some cases glycols or glycerol may be used for this purpose. Polyoxylower alkylene glycols of the Carbitol and Pluronic types may be used, as may similar compounds of equivalent properties. Generally, however, these will constitute only a minor proportion of the oil content of the clear, microbicidal hairdressing.

The aqueous carrier or solvent employed for the alkyl isoquinolinium salts and the hydrophilic and lipophilic oils and adjuvants is usually water, alcohol or a solution of lower alcohol in water. The water employed is usually soft water, especially deionized or distilled water, although waters of ordinary hardnesses may also be used. It will usually be desirable to maintain the hardness of the water under parts per million and waters having hardness equivalents, in terms of calcium carbonate, below 50 ppm. and preferably below 20 ppm. are most desirably employed. Of course, the solvent system should be clear and free of suspended matter or other impurities which might undesirably affect the clarity or color of the product.

The lower alcohols used will normally be either ethanol, which is preferred, or isopropanol. Although minor proportions of n-propanol, n-butanol, isobutanol or tertiary butanol can be present, generally the use of such alcohols, especially those having more than three carbon atoms, will be avoided. Most preferably, ethanol will be the only lower alcohol used and in some cases isopropanol will be employed to replace it in part or in whole.

The aqueous alcoholic carrier or solvent medium may contain lower alkanol of 2 to 3 carbon atoms and water in a wide variety of proportions, depending upon the particular type of hairdressing being made. As little as 5% water may be present, with the balance being lower alcohol or where the presence of alcohol is undesirable, usually because of an alleged drying effect accompanying its use, the alcohol content may be diminished to 5%. Generally, when aqueous alcoholic solvents are being employed they will comprise from 30 to 80% alcohol and 70 to 20% water, with the most preferred embodiments having 50 to 70% alcohol and 50 to 30% water.

In the manufacture of gelled hairdressings, a gelling agent is employed to thicken and set the dressing into gel form. Many such thickening agents are known in the cosmetic arts, including both organic and inorganic thickeners. Useful gelling agents form hairdressings that are clear. Generally, organic gums or thickeners are employed. Useful colloidal organic thickeners include the carboxyalkyl cellulose, the hydroxyalkyl celluloses, carboxypolymethylene, Carbopols, and the various natural gums. Also useful are the polyvinyl pyrrolidones, polyvinyl alcohols, and dextrans. Among the natural gums are karaya, tragacanth, gum acacia, algine, agar agar, pectin, carrageenin, guar, locust bean gum, Irish moss extractives and various derivatives thereof.

Specific cellulose compounds that can be used include ethers or esters such as methyl cellulose, methyl ethyl cellulose, sodium carboxymethyl cellulose, sodium carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose. Among the starches are hydroxymethyl starch, alkali metal starch phosphates, and carboxymethyl starch. The synthetic materials include ethylene maleic anhydride copolymers, having viscosities of about 10,000 to 200,000 centipoises disclosed in U.S. 3,215,603, polyvinyl alcohol, polyvinyl pyrrolidone, vinyl pyrrolidone copolymers and the carboxyvinyl polymers, e.g. Carbopol 934. The various synthetic and natural organic gums, hydrocolloid thickeners and gelling agents are described at length in The Chemistry and Manufacture of Cosmetics, Vol. II, Secnd Edition by Maison G. De Navarre (D. Van Nostrand Company, Inc., 1963), at pages 109-154. Especially useful thickening agents which yield clear solutions are carrageenin gum, polyvinyl alcohol, polyvinyl pyrrolidone and the ethylene maleic anhydride copolymers, such as Copolymer No. DX 840-91 (Monsanto Corp.) having a viscosity of 160,000. (Viscosity is determined on a 1% resin solution neutralized to a pH of 9 with sodium hydroxide using a Brookfield Viscometer, spindle No. 6 at r.p.m.)

Often it will be desirable to employ mixtures of the various thickening agents, so as to modify the thickening or gelling effects to obtain best results for a particular application. Generally, no more than two or three gums will be mixed and usually a significant proportion of each will be present. Thus, for example, in a preferred hydrocolloid mixture for gelling purposes, there will be present from 5 to 25% of hydroxypropyl methyl cellulose capable of producing an aqueous solution of 4,000 centipoises viscosity at standard conditions and from 75 to 95% of ethylene maleic anhydride copolymer, such as Copolymer No. DX 840-91.

Various adjuvants may be present in the hairdressings. Included among such adjuvants are colorants, perfumes, buffers or pH regulating chemicals, antioxidants, ultraviolet ray absorbers, stabilizers and supplementary microbicides. The coloring agents and perfumes which are used are standard water or alcohol soluble materials which do not cloud or form films in the present compositions. Ultraviolet light absorbers, e.g., 2,2, 4,4'-tetrahydroxybenzophenone, by GAF Corp., may also be employed to stabilize color and perfume, both in the product and during use.

The proportions of the various constituents of the hairdressings are maintained within desired ranges to produce the best product. The antimicrobial alkyl isoquinolinium salt generally comprises at least 0.1% of the final product and more than 5% is generally unneces sary. Within the 0.1 to 5% range, a preferred concentration is 0.3 to 1%.

The water insoluble polyethylene-polypropylene glycols are used to increase the conditioning properties of the hairdressing and, because their structure is so similar to that of the hydrophilic oil present, this can be done readily without creating unstable products, emulsions or hairdressings which tend to separate. Normally, for best results, the proportions of hydrophilic and lipophilic glycol ethers will be such that from 40 to 95% 0f the polyalkylene glycol content will be of the hydrophilic oil type. For liquid preparations it is preferred that the hydrophilic oil should constitute a major proportion, usually from 80 to 100% and preferably from 90 to 95 of the mixture. When gels are made, from 40 to 60%, preferably about 50% of hydrophilic glycol will be used. Exemplary of the lipophilic alkylene oxide random copolymers which may be employed in suitable compositions are Ucons manufactured by Union Carbide Corp. and identified as LB-65, LB-1145, LB-1715, LB-3000, LB- 70-X, LB-400-X and LB-1800-X. The characteristics of these products, including specific gravities, viscosity indexes, viscosities at 100 F., pour points and flash points are given in Table IV-22 at page 232 of the text Polyethers, Part I, edited by N. Gaylord and published in 1963 by Interscience Publishers. Also in Table IV-22 are descriptions of the properties of the water soluble oils of this type, identified as Ucons 50-HB-55, 50-HB660, 50-HB-5l00, 75-H-450, 75H-1400, 75H90,000, and Dow Chemical Co. Polyglycols 15-100, l5200, 15-1000. The Dow compounds are terminated by glycerol.

The water soluble hydrophilic oil is present in minor proportion, generally from 0.5 to 30% and preferably from 5 to 25 of the product. The water insoluble polyalkylene glycol may comprise from 0.5 to 15% of the product and is preferably from 1 to 8% thereof. From 1 to 4% is preferably present in liquids and from 4 to 8% in the gels.

The carrier or solvent medium of the hairdressing may constitute the balance of the product if no thickeners and other adjuvants are present. The water or aqueous alcoholic medium which is often used instead will constitute a significant proportion of the hairdressing, usually being from 40 to 98.9% thereof, with a major proportion, 50.1 to being preferred.

When a gel hairdressing is made, it will normally contain from 0.3 to 5% of an organic gelling agent to thicken the composition. Small proportions, from 0.1 to 0.4% of such products may be employed to increase the viscosity of a liquid hairdressing. Of course, the thickening effect is dependent on the particular gelling agent being used and the composition being thickened.

The adjuvants described will usually be present to the extent of no more than about 10% each of these compositions, with the total adjuvant quantity generally being less than 25 By utilizing the proportions of various ingredients given, clear hairdressings having exceptionally good antimicrobial properties are obtained. This is surprising because the nonionic hydrophilic oil and the related lipophilic oils contain polyoxyalkylene groups and may also contain free hydroxyls which would lead one to expect that they would behave similarly to surface active materials of related structures. In the past it has been observed that such surface active compounds have had detrimental effects upon the microbicidal properties of compounds. Yet, in the present case, the hydrophilic oils of these hairdressings do not have such detrimental effects and indeed have been shown to improve microbicidal activity of the particular germicides of this invention, the alkyl isoquinolinium salts. At the same time, the hydrophilic oils help condition the hair and give it a satisfactory lustre. Even after application of the hairdressing to the hair and evaporation of carrier components, including the water or aqueous alcoholic carrier, the use of a damp comb is enough to revitalize the hair because of the combination of the moisture with the hydrophilic oil and the combined action of both on the hair. The hydrophilic oils and the microbicides of this invention are compatible with the other constituents which may be employed to thicken liquid preparations or to make gels. They are also compatible with the usual adjuvants employed for hairdressings. The hydrophilic oil gives body to the liquid hairdressings, compensating for the thinning effects of alcohol and water. The alcohol helps to solubilize the various constituents, as does the water, and improves the evaporation rate of the product so that the hair returns to a dry, lustrous state soon after application of the hairdressing. Thus, it is seen that the various components of the present products co-act to produce a hairdressing preparation of superior qualities. Although a hairdressing can be intentionally made opaque or can be formed into an emulsion or cream, according to known techniques, it is most frequently desired that modern hairdressings leave no creamy or greasy deposit on the hair and it is usually important that the product, as applied, should appear to be transparent. The various effective microbicides, useful against fungi and bacteria found on the hair are insoluble in conventional hairdressing compositions and in the present hydrophilic oils.

The combinations of hydrophilic and lipophilic polyethylene-polypropylene glycol oils or monoether derivatives thereof with the higher alkyl isoquinolinium halide microbicide result in improved hair conditioning properties, while still maintaining the microbicides effects. This is somewhat unexpected because the hydrophilic oils appear to possess no antimicrobial activity and the lipophilic oils, in mixture, do not inhibit microbial growths. Yet, with the alkyl isoquinolinium halide rnicrobicide, the disclosed oils appear to increase the effectiveness by enlarging the area over which the rnicrobicide may work. Thus, it is highly desirable for antimicrobial activity, as well as for conditioning effects, that the present compositions contain both hydrophilic and lipophilic oils and preferably include a mixture of the lipophilic oils, such as were mentioned herein with one or more of the hydrophilic polyoxyethylene-polyoxypropylene polymers.

The following examples illustrate some preferred embodiments of the invention. Unless otherwise indicated, all parts and percents given are by weight and temperatures are in degrees Centigrade.

EXAMPLE 1 Parts Polyethylene-polypropylene glycol (hydrophilic oil, Ucon 50HB660, Union Carbide Corp., cosmetic grade) 15.7 Lauryl isoquinolinium bromide, 90% active ingredient, (Isothan Q-90, Onyx Chemical Company) 0.55 Deionized water 17.7

Ethanol 62.95 Lipophilic polyalkylene glycol (Ucon LB-1715,

Union Carbide Corp., cosmetic grade) 1.8 Lipophilic polyalkylene glycol (Ucon LB-1145,

Union Carbide Corp.) 0.5 2,2, 4,4-tetrahydroxybenzophenone (Uvinul D-50, Ultraviolet absorber, GAF Corp.) 0.2 Perfume 0.5 Colorant, RD. and C. Blue Dye No. l 1% aqueous solution) 0.1

A liquid hairdressing of the above formulation is made by sequentially adding to a mixing vessel, with stirring, the formula amounts of ethanol, Ucon LB-1715, Ucon LB-1145, Ucon 50-HB-660, perfume, lauryl isoquinolinium bromide, water, colorant and Uvinul D-50. No difficulties in formulation are noted and the sequential addition of the various constituents to the alcohol base results in a clear liquid product.

After preparation, all of which may take place at room temperature, the product is packaged and made ready for shipment. It is stable on storage and the lauryl isoquinolinium bromide is effective upon use, despite lengthy storage.

When applied to the hair in usual quantities, about two to five cubic centimeters per application or 3 to 5 grams per day, the product has a microbicidal action against Pityrosporum ovale due to the presence of the lauryl isoquinolinium bromide, in combination with the hydrophilic oil (Ucon 50-HB660). Such action is also ob served when the product is applied to other sites of microbial growths. This is verified by standard agar plate halo tests, wherein improved indications of germicidal actions are noted when the hydrophilic polyethylene-polypropylene glycol is present with the lauryl isoquinolinium bromide in aqueous media. The hairdressing also acts to condition the hair, making it easy to comb and giving it a lustre during and after application. It also improves manageability of the hair after re-moistening hours after hairdressing applications.

Other liquid hairdressing preparations utilizing similar hydrophilic oils and alkyl isoquinolinium salts, with water or aqueous-alcoholic medium bases, as described in the foregoing specification, when used in the proportions therein given produce similarly acceptable products. Such products are notable for being clear liquids, while yet containing an effective rnicrobicide. Even after several restylings of the hair with a damp comb after a single application of such a product, the hair is still readily restyled and maintains its lustre. The conditioning effect of the composition is still obtained and the hair is not dulled by the composition, which stays transparent on the hair. Conditioning effects are also improved by the presence of the lipophilic type oils in the products, in addition to the hydrophilic oils.

EXAMPLE 2 Parts Part I:

Deionized water 30.5 Hydroxypropyl methyl cellulose (Methocel 60 HG 4000, Dow Chemical Company) 0.3 Ethylene maleic anhydride copolymer (Copolymer No. DX 840-91, Monsanto Corp.) 2.0 Colorant, F. D. and C. Blue Dye No. 1 (1% aqueous solution) 0.1 Part II:

Ethanol (SD 40, 190 proof) 49.2 Polyethylene-polypropylene glycol, viscosity of 660 Saybolt Universal Seconds at 100 F. (hydrophilic oil, Ucon 50HB660, Union Carbide Corp., cosmetic grade) 7.5 Lipophilic polyalkylene glycol Ucon LB- 1145, Union Carbide Corp.) 7.5 Perfume 0.2 Lauryl isoquinolinium bromide, 75% active ingredient (Culversan AIB, Culver Chemical Company) 0.7 Part III:

Aminoethylpropanol, 50% alcoholic solution (Commercial Solvents Corp.) 2.0

A gel hairdressing of the above formula is made by admixing the various constituents of Parts I, II, and III, respectively and then blending them together at room temperature. Part I is made by dispersing the ethylene maleic anhydride polymer in water and heating the mixture to about 7580 C. The hydroxypropyl methyl cellulose is added to the mixture and dispersed therein at a temperature of about 70 C. during the heating step. The mixture is held at 7580 C. for about 10-20 minutes to complete the hydrolysis of the anhydride and thereafter the thickened solution is cooled to room temperature, about 25 C., and the colorant is added, completing the making of Part I.

Part II is made by admixing, at about room temperature, the alcohol, Ucon 50-HB-660, Ucon LB-1l45, perfume and lauryl isoquinolinium bromide. Parts I and II are admixed and then a neutralizing quantity of aminomethylpropanol, Part III, is added.

The product is poured into jars and forms an unpourable gel when allowed to set. It is an excellent transparent antimicrobial hairdressing and may be used on the hair in a manner similar to that in which other such hair preparations are employed. It is satisfactorily microbicidal, being effective against Staphylococcus aureus and Pityrosporum ovale. Except for its different physical form the product exhibits all the properties described for the liquid preparation of Example 1.

When, in place of the hydrophilic and lipophilic oils, the carrier and gelling agent, other such materials which are described in the specification are employed within the mentioned proportions, other useful gel hairdressings of exceptional microbicidal effects are produced.

EXAMPLE 3 Parts Ethanol (SD No. 40) 53.2 Ultraviolet light absorber (Uvinul N-35, GAP) 0.1 Lauryl isoquinolinium bromide, solution 0.6 Lipophilic oil, Ucon LB-17l5 (Union Carbide) 11.0 Lipophilic oil, Ucon LB-3000 (Union Carbide) 11.0

Surface active agent, Tween 20 (Atlas Chemical Corp.) 1.2 Perfume 0.4 Deionized water 22.3 F. D. & C. dyes, 0.1% solution 0.2

A liquid hairdressing of the above formula is made by substantially following the method of Example 1, sequentially mixing, with stirring, the formula amounts of ethanol, ultraviolet ray absorber, lauryl isoquinolinium bromide, Ucons, perfume, water and colorants at approximately room temperature. The product produced is a clear liquid having a specific gravity of about 0.91, a pH of 5.5 to 6.0, an alcohol content 49.2% by weight and a content of lauryl isoquinolinium bromide of 0.5%. If necessary, pH adjustment may be effected, by addition of 50% aqueous citric acid solution or a 19.1% Na O caustic soda solution.

The product made has bactericidal and fungicidal properties but is inferior to the hairdressings of this invention because it does not contain a hydrophilic Ucon or equivalent hydrophilic polyoxyalkylated oil. Continued applications of compositions which do not contain these hydrophilic ingredients results in a tendency toward buildup of oil and a development of stickiness on the hair. When, in accordance with the present invention, hydrophilic Ucon oils, such as Ucon 50HB660, Ucon 50-I-IB-55, Ucon 75H1400 are added, in amounts from 2 to 8%, alone or in mixture, the applied hairdressing becomes more hydrophilic in nature and is more readily distributed over the hair when the hair is wetted and combed, and it appears that undesirable buildup and stickiness are decreased. Such results are also obtainable when the combinations of hydrophilic and lipophilic oils are employed at lower total proportions, with totals of about 15% being preferred in formulations of this type and with a major proportion of the oil content being hydrophilic.

The presence of hydrophilic Ucon also aids in maintaining the product clear in the bottle as well as after application to the hair. The conditioning elfects obtained are surprising, considering that the hydrophilic Ucons are much less hygroscopic than other water soluble oily carriers, such as polyethylene glycol, polypropylene glycol, glycerol and sorbitol.

EXAMPLE 4 Part I: Parts Deionized water 31.7 Ethylene maleic anhydride copolymer resin,

*Viseosity of 1% solution of hydrolyzed resin neutralized to pH 9 with sodium hydroxide using a Brookfield viscometer, spindle No. 6 at 4 r.p.m.

A clear gel hairdressing of the above formula is made by heating the Part 1 ingredients to 93 C. while stirring with a homogenizing mixer, adding the Part II materials, in combination, to the mixing combination of Part I, cooling to 31 C., while continuing mixing, and adding the Part II ingredients, after which Parts 1V and V are blended in with the mixing gel. The product is found to have a viscosity of 14,000 centipoises at 30 C. and is a useful, clear, microbicidal gel hairdressing. It is found to diminish the growth of Pityrosporum ovale both in vivo and in vitro.

In a variation of this formula, when a lower molecular weight EMA gelling agent identified as resin a Lot D-1256, Monsanto, is substituted for Lot D-627, a viscosity of 6,800 centipoises results. Again, this product is a useful clear, microbicidal gel hairdressing.

When, in the above formulas, the lauryl isoquinolinium bromide is replaced by other higher alkyl isoquinolinium halides, e.g., palmityl isoquinolinium chloride, or equivalent higher alkyl isoquinolinium salts, and proportions are kept within the ranges described, useful clear hairdressings are produced. Similarly, when the Ucons are varied within limits given in the description, the products are clear, substantially non-hygroscopic and aid in conditioning and controlling the hair in use. The proportions of lipophilic Ucon or equivalent material may be diminished so that the essential or sole Ucon component is the hydrophilic material, which is found to aid in producing an acceptable microbicidal product. Yet, for the best balanced hairdressing, a combination of lipophilic and hydrophilic oil is used and in such products, mixed lipophilic oils of the types described are preferred. In a similar manner, variations may be made in the alcohol- Water contents within the ranges described, to obtain products of diiferent viscosities and utilities. The hairdressings may be produced as gels, solids and liquids, and may be incorporated in aeroso sprays by the use of a propellant and standard valved aerosol spray container.

The invention has been described with respect to illustrations and working examples. It is not to be considered as limited to the compositions described because it is clear that one of skill in the art will be able to substitute equivalents for elements of the invented compositions and processes without departing from the spirit of the invention.

Resin viscosity of 57,700 centipoises uslng the (Example 4, Part 1) test method.

What is claimed is:

1. A transparent liquid hairdressing comprising from about 0.1 to 5% of an antimicrobial salt of the formula:

wherein R is higher alkyl of 8 to 20 carbon atoms and X is a salt-forming anion selected from the group consisting of halogen, sulfate, bisulfate, acetate, and pro pionate; 0.5 to 30% of a hydrophilic polyethylene-polypropylene glycol ether containing 25-75% of the polyethylene glycol and 75 to 25% of the polypropylene glycol, said ether having hydroxyls and alkyls of 1-8 carbon atoms as chain terminating radicals, and said ether having a molecular weight from about 400 to 4,000; 0.5 to 15% of a lipophilic poly-lower alkylene glycol ether having a molecular weight from about 400 to 4,000;and 40'98.9% of an aqueous or aqueous-alcoholic carrier medium.

2. A hairdressing according to Claim 1 wherein said salt is lauryl isoquinolinium bromide.

3. A hairdressing according to claim 1 wherein the hydrophilic oil is a clear, liquid, water soluble polymer of molecular weight from about 400 to 4,000, comprising from 25 to 75% polyethylene oxide and from 75 to 25% polypropylene oxide components, and the lipophilic oil is a clear liquid, substantially water insoluble polymer of propylene oxide of molecular weight from about 400 to 4,000.

4. A clear hairdressing according to claim 1 comprising from 0.3 to 1% of lauryl isoquinolinium bromide, 5 to 25% of hydrophilic oil, 1 to 8% of lipophilic oil and 50.1 to 90% of aqueous ethanolic medium.

5. A clear hairdressing according to claim 4 wherein the hydrophilic oil is a C to C alkyl ether of molecular weight of 1,000 to 2,000 and the lipophilic oil is a C to C alkyl ether of molecular weight of 1,500 to 3,000.

6. A hairdressing according to Claim 1, which includes from 0.5 to 5% of an organic gelling agent selected from the group consisting of natural gums, natural thickeners, synthetic gums, synthetic thickeners and mixtures thereof, said amount being sufficient to form a gel.

7. A clear hairdressing according to claim 6 which comprises from 0.1 to 0.5% of methyl cellulose and from 1 t 4% ethylene maleic anhydride copolymer as gelling agents.

8. A clear hairdressing according to Claim wherein the hydrophilic oil is a butyl ether of molecular weight of 1,400 to 1,600 and comprises approximately equal proportions of ethylene oxide and propylene oxide and the lipophilic oil is a mixture of polypropylene glycol butyl ethers of molecular weights in the ranges of 1,500 to 2,200 and 2,300 to 2,700 wherein those butyl ethers having a molecular Weight of 2,300 to 2,700 comprise to of the mixture.

References Cited UNITED STATES PATENTS 2,876,210 3/1959 Wynn 124-4-70 X 3,215,603 11/1965 Gross et al. 4247O 3,223,704 12/1965 Shibe et al. 424258 X 3,235,556 2/1966 Wakeman et a1. 424-258 X 3,427,382 2/1969 Haefele 42471 3,536,810 10/1970 Moculeski 424-70 X FOREIGN PATENTS 1,061,034 3/ 1967 Great Britain 42470 OTHER REFERENCES Lubowe: Drug and Cosmetic Industry, Vol. 81, No. 5, November 1957, pp. 602-603 and 674.

STANLEY J. FRIEDMAN, Primary Examiner U.S.-C1. X.R.

424-70, 71, Dig. 2 and 4