Hair dressing compositions containing a hair substantive quaternary resin
Q United States Patent 11 1 1111 3,876,760  
 Nersesian et a1. A r. 8 1975 HAIR DRESSING COMPOSITIONS 3.123.640 3/1964 LongIey 260/567.6 CONTAINING A HAIR SUBSTANTIVE :32: g y 1 o QUATERNARY RESIN 3.210.251 10/1965 KIug: 424/ X Inventors: Ara Nersesian, Livingston; Fred 3.257.281 6/1966 aeder-m 1 X Hubner, Edison; Taras Durbak, 3,427,382 2/1969 Haefele 424/71 lrvington a&#34; of Ni 3.530.215 9/1970 Greif et al.... 424/70 3.580.853 5/1971 Parran 424/78 x [73] Assignee: Bristol-Myers Company, New York,  
  FOREIGN PATENTS OR APPLICATIONS [22] Filed: July 10, 1972 1,492,597 7/1967 France 424/78 [2]] Appl. No.: 270,409  
 I Primary Examiner-Jerome D. Goldberg Relfned Apphcamm Data Assistant E.\&#39;aminerVera C. Clarke [63] f of 1969&#39; Attorney, Agent, or Firm-Irving Holtzman; David J.  
  an one Mugford; George A. Mentis [52] US. Cl, 424/70; 252/DIG. 252/D1G. 2; 252/DIG. 3; 252/153; 252/305; 252/541;  
  424/010&#39; 1; 424/DIG. 2; 424/1310. 4; ABSTRACT 424/47; 424/71; 424/; 424/172; 424/259;  
  424/1312 A hair dressing composmon compnsmg a ham sub- [51] Int. Cl A6lk 7/06 Stamive quaternary resin to impart hair&#39;holding prop [58] Field of Search l 4 2 71 78 erties to hair when supplied. and a grooming agent; Q i the grooming agent preferably being incompatible [56] References Cited with the quaternary resin.  
  UNITED STATES PATENTS 7 Claims, No Drawings 3.061.519 10/1962 Rosekrans 424/70 HAIR DRESSING COMPOSITIONS CONTAINING A l-IAIR SUBSTANTIVE QUATERNARY RESIN This application is a continuation of Application Ser. No. 868,892 filed Oct. 23, 1969, now abandoned.  
  This invention relates to hair dressing compositions. More particularly, it concerns hair dressing compositions designed to be applied to hair to maintain hair in place, and at the same time to impart thereto certain desirable grooming characteristics, such as lubricity (without greasiness), soft feel, shine, anti-static properties, etc. The properties of these compositions which serve to maintain hair in place is herein referred to as their holding or fixative properties. On the other hand, those properties which give the hair lubricity, soft feel, shine, anti-static properties, etc., are herein described collectively as the grooming and conditioning properties.  
  Hair dressing compositions of the prior art have, in general, suffered from at least two distinct disadvantages. In those compositions containing a hair fixative (which usually was a film forming resin) dissolved or dispersed in a&#39;solvent system, when they were applied to the hair and allowed to dry, tended to cement fibers of hair together giving the hair an overall boardiness. On the other hand, those prior art compositions which leave out the hair fixative and contain only the hair grooming and conditioning agents, as defined above, do not have adequate hair holding properties.  
  It has now been found that these disadvantages can be avoided by formulating a hair dressing composition comprising, in combination, a hair substantive quaternary resin and a hair grooming agent. The quaternary resin is characterized by its great affinity for hair, which is preferably greater than that which the grooming agent has for hair. The grooming agent is preferably one which is incompatible with the resin and which separates therefrom on the evaporation of a solvent in which they are both dissolved.  
  Although applicants do not want to be bound by any theory of operation, it is believed that the excellent results obtained with the instant composition are due in large part to the incompatibility of the resin and grooming agent, and their different affinities for hair. When, for example, the compositions are applied in the form of solutions containing the quaternary resin and grooming agent; on the evaporation of the solvent, the quaternary resin, having a greater affinity for hair, coats the same and imparts thereto its fixative properties. The grooming agent, being incompatible with the quaternary resin and having less affinity for hair, separates therefrom. The results appear to be that substantially each hair fiber is provided with a first coat of hair fixative quaternary resin and an over-coat of grooming and conditioning agent. The holding properties of the fixative resin are imparted to the hair fibers. At the same time, they are maintained substantially as uncemented discrete fibers by virtue of the lubricating properties of the over-coat of grooming and conditioning agents. Furthermore, the over-coat of grooming and conditioning agents imparts its other desirable characteristics to the hair, e.g. soft feel, shine, anti-static properties, natural appearance, etc.  
  It is accordingly an object of the present invention to provide a hair dressing composition capable of simultaneously holding hair in place, and imparting thereto grooming and conditioning characteristics.  
  It is a further object of the present invention to provide a composition of the aforesaid type which comprises a hair substantive quaternary resin in combination with a hair grooming agent which is incompatible with said hair substantive quaternary resin.  
  Other and more detailed objects of the present invention will be apparent from the following description and claims.  
  The compositions of the present invention may take a wide variety of physical forms. Thus, they may take the form of liquids, gels, creams, sticks, pastes, aerosol sprays, etc. As liquids, they may be simple solutions in a variety of solvent systems, such as water, aqueous alcohol, or other organic solvents and mixtures thereof. It may also take the form of an oil-in-water or a waterin-oil emulsion. In the preferred form of this invention, the composition assumes the form of solutions of the active ingredients in an aqueous solvent and particularly, an aqueous alcoholic solvent system. The alcohol is preferably a lower (C to C alkyl alcohol e.g., ethyl, propyl, isopropyl or butyl alcohol.  
  A variety of hair substantive quaternary resins known in the prior art are suitable for the purposes of the present invention. One representative class is described in French Patent 1,492,597, which is incorporated herein by way of reference.  
  These compounds are quaternized cellulose ethers which can be prepared by first etherifying cellulose or alkali cellulose to prepare the ether, e.g., methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl-methyl cellulose, carboxymethyl cellulose or its salts. These may then be quaternized by reacting the respective ethers or mixtures thereof with the halohydrin quaternary salt.  
 in which Z above is a halogen, e.g. Cl, Br or l;  
  R R and R have the values ascribed to them below; 0 is the anion of a strong mineral acid; and t is a whole number equal to the valence of Q. The resulting compounds may be described generally by the formula:  
 C (I! II I III 0 /OR a\ CII 0R wherein:  
  Y indicates the degree of polymerization and is a number from 50 to 20,000; R,, R; or R is a radical of the general formula:  
 in which:  
 a is a whole number 2 or 3;  
 b is a whole number 2 or 3;  
 c is a whole number 1 to 4;  
 m is a number from O to 10;  
 n is a whole number to 3;  
 p is a whole number from 0 to 10;  
 q is zero or 1;  
  R is H or COOMe group in which Me is H, Na, K or NH4;  
  X is an anion, e.g. Cl, Br, I, sulfate, methylsulfate, sulfonate, nitrate, phosphate, acetate, etc.;  
 r is a number equal to the valance of X;  
  R,. R and R are organic radicals (e.g. alkyl, aryl, etc.) any two or three of which may also constitute together a heterocyclic nitrogen radical. In the general polymer defined in Formula lll above, the quaternary group is present on the average of about 0.1 to 3 quaternary groups per anhydroglucose unit.  
  R R and R above may be, by way of example, alkyl, aryl. aralkyl, alkaryl, cycloalkyl, alkoxyalkyl or alkoxyaryl. These radicals will usually contain up to 12 carbon atoms. When they are aryl moieties, they are usually hydrocarbon moieties. When they are alkyl moieties they are usually lower alkyl, e.g. l to 6 carbon atoms (methyl, ethyl, propyl, butyl, t-butyl, amyl, hexyl, etc.). In the case when they are cycloalkyl, they usually have 5 to 6 carbon atoms in the cycloalkyl ring.  
  As noted above. any two or three of R R or R may constitute together a heterocyclic nitrogen radical. These will usually contain 5 to 6 atoms in the heterocyclic nucleus and may contain oxygen as well as nitrogen in the heterocyclic ring. By way of illustration, the following may be mentioned: pyridine, a-methylpyridine; 3,5-dimethylpyridine; 2,4,6-trimethylpyridine; N- methylpiperidine. N-ethylpiperidine; N- methylmorpholine or N-ethylmorpholine.  
  Within the broader class of quaternized cellulose ethers described above, there is a preferred group of materials which are particularly suitable for the purposes of the present invention. These may be described by the formula:  
  c o -oc c c A c \g \L l l E Q 10 I (1 2%) x (3,) a  
  l n on wherein:  
  n a number from 1 to 5; a number from 50 to 20,000 and preferably from 200 to 5000;  
 in which R,,, R and R are the same or different and are lower alkyl having from 1 to 6 carbon atoms; B is hydrogen or lower alkyl having from I to 6 carbon atoms; and X is an anion such as Cl, Br, I, sulfate,  
 methylsulfate, nitrate, sulfonate, phosphate, acetate,  
 etc; at least one A in said Formula V being one of said quaternary groups; v is a number equal to the valence of X.  
  One group of hair fixative quaternary resins of special interest in the present invention are Union Carbides .IR-l Resins. These are advantageous in that they impart holding properties without excessive stiffness;  
  they are effective at low concentrations (0.1%); they form a substantive, elastic film on hair, thus powdering or flaking does not result; they demonstrate good resistance to high humidity conditions; they are soluble in water and can tolerate large concentrations of alcohol (75% they form a clear film, thus do not dull the hair, and they are compatible with quaternary grooming and germicidal agents.  
  .lR-l Resins may be described as 2-hydroxypropyl trimethyl ammonium chloride ethers of hydroxyethyl cellulose. The molecular weights of the resins are in the range 200,000 to 2,000,000. The structural formula of the resins can be represented as follows:  
 Where R is H or -ca -&#39;cH-cu;u (31 7 011 n is n is l to 5 and z is a whole number that represents the degree of polymerization. Thereare currently two viscosity grades of JR-l Resins available. One of them is the low viscosity grade .lR-l L Resin which has at 25C a viscosity of (2% aqueous solution) from about 50 to 1000 cps. The other grade is a high viscosity grade (JR-1H Resin) which has a viscosity of (2% aqueous solution) above 1000 cps.  
  The quantity of quaternary resin that may be incorporated in the compositions of the present invention may vary considerably. In general, however, it will constitute about 0.1 to 7 percent by weight of the total composition.  
  A second essential component of the instant compositions is the grooming agent. A wide variety of grooming agents are known in the prior art which may be used for the present purposes. Since the compositions will ordinarily comprise an aqueous base, it is advantageous that these grooming agents be soluble in aqueous solvent systems such as water or aqueous alcohol. By way of illustrating the grooming agents which can be employed in the composition, the following are mentioned which may be used either alone or in combination:  
  I. Alkoxy polyoxyalkylene glycols such as butoxy polyoxypropylene glycols (Ucon LB series); butoxy polyoxyethylene-polyoxypropylene glycols (Ucon SOHB and 75H series); methoxy polyoxyethylene glycols (Carbowaxes 350. 550, etc.). The preparation of compounds of the Ucon series is described in U.S. Pat. No. 2,425,845 to Toussaint et al. A preferred class of materials is also described in U.S. Pat. No. 3,0615 19. The latter are described as water soluble lower alkoxy polyoxyalkylene glycols or polyoxyalkylene diols in which the oxyalkylene is a mixture of oxyethylene and oxypropylene in a ratio of about 3:1 to about 1:3 and which have an average molecular weight greater than about 900 and not greater than about 4000. Lower alkoxy is intended to include alkoxy radicals ranging in carbon atom content from 1 to about 6.  
  2. Polyoxyalkylene glycols such aspolyoxypropylene glycols; polyoxyethylene glycols (Carbowaxes 400, 600, I000, etc.); p0lyoxypropylene-polyoxyethylene glycols (Wyandottes Polyol WL-360, Pluronics. etc.).  
  3. Alkoxy polyoxyalkylene glycol esters (Ucon oleate) and polyoxyalkylene glycol esters (PPG 2000 monooleate). 1  
  4. Glycerol and trimethylolpropane based triols such as polyoxypropylene triols (Emcol CD-l 8) and polyoxypropylene-polyoxyethylene triols.  
  5. Polyoxyalkylene ethers such as polyoxyethylene ethers (Volpos, Brijs) and polyoxypropylene ethers (Procetyl 6. Diesters of dicarboxylic acids such as diisopropyl adipate, diisopropyl sebacate, etc.  
  7. Lanolin and its derivatives such as polyoxyalkylene lanolin ethers (Polychols) and acetylated ethoxylated ester-ethers (Solulan 98).  
  8. Protein derivatives such as collagen derived hydrolysates (Polypeptide LSN, Wilsons WSP X-250); cassein derived hydrolysates (Cascoloids) and protein hydrolysate esters (Promois).  
 9. Fatty alcohol ethers and fatty acid esters.  
  10. Higher alcohols (hexadecyl), oleyl, lauryl, cetyl, etc.).  
  11. Cationic or quaternary compounds, e.g. substituted amine oxides, substituted ammonium halides and substituted imidazolines.  
  A particularly useful class of grooming agents for the purposes of the present invention are the cationic quaternary ammonium compounds:  
 wherein R and R are alkyl radicals; R, is an aliphatic hydrocarbon group; R is a polyoxyalkylene radical and 41 is an anion; and v is a number equal to the valence of d).  
  In formula VI above, R and R can vary in the number of carbon atoms contained in the alkyl chain. Ordinarily these will be lower alkyl chains containing from 1 to 6 and particularly 1 to 2 carbon atoms. Similarly, R can vary in chain length but will usually be an alkyl or alkenyl group having 1 to 6 carbon atoms.  
  R of formula VI above may be a polyoxyalkylene radical preferably containing at least 18 carbon atoms and derived from an a-epoxide containing at least 3 carbon atoms, e.g., propylene oxide. More specifically, it may be described by the formula:  
 wherein R is hydrogen or alkyl radical containing 1 to 6 carbon atoms; and n is a whole number from 6 to 40 and B is H, acyl radical of a carboxy acid having 2 to 36 carbon atoms or a hydrocarbon radical having 1 to 36 carbon atoms.-  
  When B is an acyl radical, it may be derived from any of a number of acids. These include such acids as acetic, lauric, oleic, stearic, palmitic, lanolin fatty acids, etc. When B is a hydrocarbon radical, the compound is an ether. This ether likewise may be derived from a variety of alcohols such as ethyl, lauryl, oleyl, stearyl and lanolin alcohols.  
  The esters are prepared in the following manner: To a refluxing solution of the acid chloride in anhydrous ethyl ether, the tertiary amine (e.g.  
  3 1 W. as  
 is slowly added. A percent excess of the acid chloride is employed. The acid chloride is added over a period of 75 minutes and the mixture is maintained at reflux for an additional 2 hours. The reaction mixture is cooled to room temperature and 2N HCl is added. Water is added to the reaction mixture which is then extracted with anhydrous ethyl ether. The acid aqueous residue which contains the tertiary amine ester as the HCl salt is now made basic with concentrated ammonia whereby the free amine ester comes out of solution. This product is extracted with ether and the ether is then driven off leaving the tertiary amine ester. This is then quaternized with methyl chloride by heating a mixture of the amine ester with excess methyl chloride (100% excess) in a sealed tube at 60C for 18 hours. The tube is then opened and the solvent and excess methyl chloride is evaporated.  
  The corresponding ethers may be prepared by reacting the tertiary amine alcohol (e.g.  
 with a fatty alcohol, e.g. lauryl alcohol, ethyl alcohol or stearyl alcohol in the presence of a small quantity of a catalyst (e.g. p-toluene sulfonic acid). Excess HCl is added and the reaction mass is extracted with ethyl ether. The aqueous acidic residue is made basic with concentrated ammonia and reextracted with ether. The ether is then evaporated and the amine ether is quaternized with methyl chloride in a fashion similar to that described above for the preparation of the quaternized amine ester.  
  The radical d) of formula VI can be any negative or salt-forming radical as, for instance, halide such as chloride, bromide and iodide; hydroxy; sulfate, alkyl sulfate (methosulfate or ethosulfate); nitrate; phosphate; acetate; formate; carbonate; lower alkyl (l to 4 carbon atoms) sulfonates; and the like. Of particular interest are those of the cation-active surface active agents in which the anion is chloride, bromide, methyl chloroacetate, methosulfate, and ethosulfate.  
  Cationic surface active quaternary ammonium grooming compounds that are useful for the purpose of the present invention and the manner of preparing the same are described in U.S. Pat. Nos. 3,123,640; 3,123,641 and 3,141,904 which are incorporated herein by way of reference. Of special interest are compounds described by the formula:  
 in which n has an average value of about 8, 25 and 40 respectively and whose apparent molecular weights are 600, 1600 and 2500 respectively.  
  A number of the cationic surface active quaternary ammonium compounds mentioned above are available commercially. By way of example, mention may be made of products sold under the trade designations EMCOL CC-9, EMCOL CC-36 and EMCOL CC-42.  
  The quantity of grooming agent incorporated in the present composition also will obviously vary with the intended purpose. In general, however, this will constitute between 1.0 to 60 percent by weight of the total composition.  
  Optimum results are obtainable by maintaining the grooming agent at a higher level than the quaternary resin in the composition. The preferred ratio is 1 part of quaternary resin to 10 to 30 parts of grooming agent.  
  It is sometimes advantageous to modify the properties of the aforesaid composition by including therein one or more auxiliary resins. A number of resins are known in the prior art which could serve as auxiliary resins. In this connection, mention may be made of the following:  
 AUXILIARY RESINS l. Polyvinyl pyrrolidone (PVP) and its derivatives such as alkylated polyvinylpyrrolidone (Ganex) polyvinylpyrrolidone-vinyl acetate copolymers (PVP/VA), etc.  
  2. Hydroxyalkyl cellulose derivatives such as hydroxyethyl cellulose (Cellosize, Natrosol); hydroxypropyl cellulose (Klucel); hydroxymethylhydroxypropyl cellulose (Methocel), etc.  
 3. Polyvinyl alcohols (Elvanol).  
 4. Polyoxyethylene resins (Polvox).  
  The above list is given by illustration only and does not enumerate all possible auxilliary resins.  
  The quantity of auxiliary resins that may be employed can also vary considerably. In general, it may constitute between 0 to about 3 percent by weight of the total composition.  
  In addition to the aforesaid ingredients, if desired, other conventional ingredients commonly found in hair grooming preparations may be included in the present composition. These include such agents such as slip agents, plasticizers, germicides, fragrance, colors. solvents and other vehicles, etc. By way of illustration, the following may be mentioned:  
  1. Plasticizers which are compatible with the resin may be incorporated to control the hardness and elasticity of the resin film are as follows: glycerol, glycols (propylene, dipropylene, polyoxyethylene, etc.), phthalic acid esters. quaternary compounds (stearyl dimethyl benzyl ammonium chloride, etc.) and others as used in the art.  
  2. Germieides and preservatives such as quaternary nitrogen compounds (benzethonium chloride, cetyl pyridinum chloride, etc.); p-hydroxy benzoate esters (Parabens), chlorinated phenols (e.g. hexachlorophene) etc.  
 TABLE I PERCENT BY WEIGHT INGREDIENTS GENERAL PREFERRED RANGE CONCENTRATION Quaternary Resin 0.1 7.0 0.3 Ethyl alcohol 0.0 75.0 50.0 Water 25.0 98.0 44.7 Grooming agents 1.0 60.0 5.0 Auxilliary agents q.s. q.s.  
  The following Examples are further illustrative of the present invention. It is to be understood. however, that the invention is not limited thereto. In these Examples when the following terms appear. they have the meaning described&#39;below:  
  1. JR-l L Resin: For description see specification above;  
 2. Emcol CC-9; Emcol CC-36 and Emcol CC-42- Emcol CC-9; n in above formula has an average value of 8; average M. W. 600;  
 Emcol CC-36; n in above formula has an average value of average M. W. 1600;  
 Emcol CC-42; n in above formula has an average value of average M. W. 2500;  
  3. Grooming Agent No. 2000: Butoxypolyoxyethyleneoxypropylcne glycol having an M. W. of 2650 and a viscosity of 2000 Saybolt Universal seconds at 100F; the oxycthylene and oxypropylene are in equal parts; 4. Grooming Agent No. 450: Polyoxyethyleneoxypropylene diol having a M. W. of 990 and a viscosity of 450 Saybolt Universal seconds at 100F; the ratio of oxyethylene to oxypropylene is 3:1;  
  5. Triol 700 polyoxypropylene triol having an average M. W. of about 700 (reaction product of glycerine and propylene oxide);  
 6. Emcol CC-9 Laurate, Emcol CC-9 Stearate:  
 Emcol CC-9 Laurate, n in the formula above has an average value of about 8 and R is lauroyl, i.e.  
 Emcol CC-9 Stearate; n in the formula above has an average value of about 8 and R is stearyl.  
 7. Freon 12 Dichlorodifluoromethane;  
  8. Carbowax 400 Polyoxyethyleneglycol M. W. 400;  
  9. Polyoxyethylene glycol (400) Monooleate The monooleate of polyoxyethylene glycol having an M. W. of 400;  
  10. Ucon 50 HB 660 Butoxypolyoxyethylenepolyoxypropylene glycol having a polyoxyethylene to polyoxypropylene ratio of 1:1 and a viscosity of 660 Saybolt Universal seconds at F; M. W. about 2000;  
  l l. Ucon LB 17.15 Butoxypolyoxypropyleneglycol having a viscosity of 1715 Saybolt Universal seconds at 100F; M: W. about 2000;  
  12. Methocel 60 HG 4000; hydroxypropyl methylcellulose ether having 28 to 30 percent by weight of methoxy substituents and 7 to 12 percent by weight of hydroxypropyl substituents; the degree of substitution with methoxy and hydroxypropyl substituents is from 1.68 to 1.82 and from 0.17 to 0.3 respectively; viscosity 3500-5600 cps. (2% aqueous solution at 20C). (See US. Pat. No. 3,427,382).  
  13. Carbopol 940: (purified form of Carbopol 934) water soluble polymer of acrylic acid cross linked with 1 percent of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each molecule of sucrose (See US. Pat. No. 3,133,865).  
  14. P.V.P.: See THE MERCK INDEX, eighth edition, page 849-850.  
  15. Stepans Polypeptide AAS-207c Active: This is an alcohol soluble base hydrolyzed collagen protein derivative. (See Protein, Some New Derivatives&#34; by Richard Riso Proceedings of the Toilet Goods Association No. 42, pages 36-39, December, 1964.  
 The perfume and color may be omitted from this composition if desired. in which event they are replaced by an equal quantity of water.  
 EXAMPLE IA TO IE The composition similar to that of Example I is prepared excepting that for the .IR Resin of Example I an -equal quantity of the product of Example I of French Patent No. 1,492,597 is utilized as the quaternary resin. In a similar fashion, a series of compositions are prepared similar to that of Example I above excepting that each contains an equal quantity of the material prepared by the Examples of 2, 5, 7, 9 and 12 of French Patent No. 1,492,597 in place of the JR-IL Resin of Example I as the quaternary resin.  
  The following Examples 2 through l9 are given in The following examples illustrate the use of auxilliary tabular form. They illustrate other aqueous or aqueous resins in combination with the quaternary resin in acalcoholic systems in which the quaternary resin and the cordance with the present invention.  
 TABLE 2 PERCENT BY WEIGHT INGREDIENT EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX. EX.  
 2 3 4 5 6 7 8 9 l l l l2 l3 l4 l l6 l7 l8 l9 PRODUCT OF EX.l French Patent 0.] 0.5 1.0 2.0 0.3 0.3 0.3 0.3 2.85 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3  
 1.492.597 WATER 44.9 44.5 44.0 43.0 44.7 47.7 39.7 94.7 44.7 74.7 49.7 29.7 29.7 24.7 44.7 44.7 44.7  
 ETHYL ALCOHOL (957!) 50.0 50.0 50.0 50.0 50.0 50.0 50.0 30.0 65.0 60.0 60.0 50.0 50.0 50.0 IEIODUCT OF U.S.Patent 5.0 5.0 5.0 5.0 5.0 2.0 I00 2.5  
 GROOMING AGENT No.2000 5.0 5.0 25.0 25.0 50.0 GROOMING AGENT No.450 5.0100150 TRlOL-700 grooming agents are dissolved in the solvent system.  
 The following examples further illustrate aqueous al- INGREDIENT PERCENT BY WEIGHT coholic systems in which the active ingredients are EXAMPLE present In solutIon. In these examples different quater- 26 nary grooming agents are employed: JR-lL Resin 0.5 0.5 30 Methocel 00 HG 4000 0.5 WP 0.5  
 l (C-36 5.0 5. INGREDIENT PERCENT BY WEIGHT E$f 500 3 Water 44.0 64.0 EXAMPLE Perfume. color. etc. q.s. q.s. 2 21 22 JR-lL Resin 0.3 0.5 0.3 EnlCnI Q09 5.0 The following example Illustrates the present Inven- I tion in which it takes the form of a gel. Ethyl Alcohol 50.0 50.0 50.0 Water 44.7 44.7 44.7 Perfume. Color. etc. q.s. q.s. q.s. 4O  
 INGREDIENT PERCENT BY WEIGHT The following examples also illustrate the use of cerlg tain quaternary grooming agents in combination with Carbon 940 the quaternary resin. JR-lL Resin 05 Tricthanolaminc l.5 Emcol (C-36 5.0 Water 62.0 Eth l -l h I 30.0 INGREDIENT PERCENT BY WEIGHT I QS QI cm qii EXAMPLE 23 24 The following examples illustrate the present inven- Emcol CC-9 Laurate 15.0 tion in the form Of an aerosol spray. Emcol CC-9 Stearate 5.0 JR-lL Resin 1.0 0.3 Ethyl Alcohol 40.0 50.0 Water 44.0 44.7 Perfume. Color, etc. q.s. q.s. INGREDIENT PERCENT BY WEIGHT EXAMPLE 29 30 The following example Illustrates the use of a substl- JRJL Resin 03 0.3 tuted amine oxide-type grooming agent. Emcol CC-36 4.0 4.0 Water 25.7 30.7  
  Ethyl alcohol 30.0 30. 7 INGREDIENT PERCENT BY WEIGHT 263 &amp; 350 EXAMPLE 25 Perfume. color. etc. q.s. q.s.  
 Lauryl amine oxide 5.0 JR-IL Resin 0.3 Ethyl alcohol 50.0 The followlng examples are a miscellaneous group of exam les illustratin a variet of as ects of the resent Perfume. color. etc. q.sp g y p p invention.  
  EXAMPLE INGREDIENT PERCENT BY WEIGHT 45 4e 47 .lR-lL Resin 0.3 0.3 0.3 EXAMPLE Emcol (C-36 50 5.0 5.0 31 32 33 34 35 Hc tachlorophene 0.5 JR-lL Resin 0.3 0.3 0.3 0.3 0.3 sll&#39;cylw 9&#34; Ethyl alcohoI 50) 65.0 501) 501) 65 Benzethomum chloride 4 0 3 Water 44.7 29.7 44.7 39.7 29.7 Biphcmlminc hidmchlorlde L0 Polyoxyethylene Ethyl alcohol 50.0 50.0 glycol (Carbo- 0.0 wax 400) 5.0 Water Polyoxyethylene glycol 400 Perfume. color. etc. q.s. q.s. q.s. monooleate .0 5.0 Acetylaled Polypeptide LSN (Average M.W. 900 I500) may he used in place of Stepans ethoxylated Polypeptide AAS. ester ether of [5 123E333? W The following examples further illustrate cream and Collagen protein lotion formulations within the scope of the present inhydrolysate (Stepmfs P0|y ventlon. peptide AAS-ZOV: active) 5.0 INGREDIENT PERCENT BY WEIGHT Lauryl lactate 5.0 Perfume. color. etc. q.s. q.s. q.s. q.s. q.s. EXAMPLE IN E I N 48 49 50 51 GR D E T PERCENT BY JR-lL Resin 0.5 0.5 0.5 0.5 WEIGHT Emcol CC-36 5.0 5.0  
  lsopropyl myristate 2.0 EXAMPLE Glyceryl monostearate 7 0 4.0 2.0 2.0 36 37 3 8 an lin 1.0 .IR-lL Resin 0 3 2,0 N-(lauryl colaminoformyl- Ethyl alcohol 50.0 50.0 methyl )pyridinium chloride 0.5 Glycerine 2.0 w 44 9 43 Mineral Oil (55-65Vis) 2.0 5.0 3.0  
  3 Cetyl alcohol l.0 Emcol cost. 5.0 3.0 5.0 I P L0 L0 Collagen protein hydrolysate Tncthanoli-mme LO (Stephans Polypeptide LSN) 0.5 Ethmylmcd. 15 Perfume. color. etc. q.s. q.s. q.s. i i ox&#39;de) coconut oil amine (Ethomeen C125 Amour) 1.0 1.0 &#39;NGREDlENT Q ESJ Water 85.5 89 0 89.5 86.5 3 Perfume. color. preservative q.s. q.s. q.s. q.s. EXAMPLE 7 39 41 .IR-IL Resin 2.85 0.3 0.3 What 15 l im 15: Ethylfllwhfll l. A hair dressing composition comprising a hair- Water 92.15 44.7 74.7 t. t u I th h h. h Buwx). pnlymycthylcnb 40 me tve qua e rnary ce u ose e er resin av mg a lg polyoxypropylcne glycol affimty for hair and a hatr grooming agent dissolved in 2 2 an aqueous alkyl alcoholic solvent in which the alkyl alcohol has from 2 to 6 carbons wherein: INGREDIENT &amp; gg a. said resin is present in the range of from about 0.1 to 7.0 percent by weight based on the total weight EXAMPLE of the composition; 2 3 44 b. said hair grooming agent is present in the range of k from about 1 to 60 percent by weight based on the in; 3 4 total weight of the composition; Butoxy polyoxypropylcne c. the ratio of said resin to said hair grooming agent (Umn L817) being present in the ratio of about 1 part of resin Emcol (C-36 2.5 2.5 Bum). polyoxycthykng to 10 to 30 parts of grooming agent, s y y tgw g zz glywl 1 said resin being 2-hydroxypropyltrimethyl ammog g g mkm nium chloride ether of hydroxyethyl cellulose having a viscosity in 2 percent aqueous solution INGREDIENT Q Q g BY from about 50 to 1000 cps at 25C and being of the formula:  
  H 0A 0 I I E 2 C \C/H I? H/ \C c H l IEI 5 3 O 2 4 n 0 in n I a 0A L 0A ux wherein:  
 n a number from 1 to 5; is a number from 50 to 20,000; A is hydrogen or said hair grooming agent being of the formula:  
 in which n has an average value of 25.  
  2. A hair dressing composition comprising a hairfixative quaternary cellulose ether resin having a high affinity for hair and a hair grooming agent dissolved in an aqueous alkyl alcoholic solvent in which the alkyl alcohol has from 2 to 6 carbons wherein:  
 a. said resin is present in the range of from about 0.1 to 7.0 percent by weight based on the total weight of the composition;  
 b. said hair grooming agent is present in the range of from about 1 to 60 percent by weight based on the total weight of the composition;  
 c. the ratio of said resin to said hair grooming agent being present in the ratio of about 1 part of resin to 10 to 30 parts of grooming agent wherein:  
 said resin is of the formula:  
 Y indicates the degree of polymerization and is a number from 50 to 20,000; R R or R is a radical of the formula:  
 (II) -(c H -o) -(cH iH-o-) -(c H 2 3 R N R X 3 1 2 in which:  
 a is a whole number 2 or 3;  
 b is a whole number 2 or 3;  
 c is a whole number 1 to 4;  
 m is a number from to 10;  
 n is a whole number from 0 to 3;  
 p is a whole number from 0 to 10;  
 q is zero or l;  
 R; is H or COOMe group in which Me is H, Na, K or X is a salt forming anion;  
 v is a number equal to the valence of X;  
 R R and R are alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties have up to 6 carbon atoms; the aryl moieties having up to 12 carbon atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and wherein two or three of the radicals R,, R and R may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms in the nucleus, one atom of which may also be oxygen;  
 and wherein the resin defined by the formula 1 above contains the quaternary group:  
 in the average of about 0.1 to 3 quaternary groups per anhydroglucose unit;  
 said hair grooming agent being a quaternary compound of the formula:  
 wherein R and R, are alkyl radicals having 1 to 6 carbon atoms; R is an aliphatic hydrocarbon group having 1 to 6 carbon atoms; R, is hydrogen or alkyl having I to 6 carbons, n is a whole number from 6 to 40, B is H, carboxy acyl having 2 to 36 carbons or hydrocarbon having 1 to 36 carbons, d) is a salt forming anion selected from the group consisting of chloride, bromide, iodide, hydroxy, sulfate, methosulfate, ethosulfate, nitrate, phosphate, acetate, formate, carbonate, 1 to 4 C sulfonate and methyl chloroacetate; and v is a number equal to the valence of qb.  
  3 A composition according to claim 2 wherein the hair-fixative quaternary cellulose ether resin is of the formula:  
  H CA G I *&#34;K A H C C C C H 0 $1.12 v Q C H :2 4 n m l... 0A x wherein: 4. A hair dressing composition comprising a hairn a number from 1 to 5; fixative quaternary cellulose ether resin having a high A a number from 50 to 20,000; affinity for hair and a hair grooming agent dissolved in A is selected from the group consisting of: an aqueous alkyl alcoholic solvent in which the alkyl alcohol has from 2 to 6 carbons wherein:  
 a. said resin is present in the range of from about 0.]  
 (1) hydrogen and the quaternary g p to 7.0 percent by weight based on the total weight of the composition; (2) X b. said hair grooming agent is present in the range of l 9 T; from about l to 60 percent by weight based on the R total weight of the composition;  
 (3) -CH -HC on g 2 t 2 (Q n -CH-H -cH-m.&#39;x i W m x (5) CH H? CH I 3 1 in which R R and R are the same or different and c. the ratio of said resin to said grooming agent being are lower alkyl having from I to 6 carbon atoms; B is present in the ratio of about 1 part of resin to 10 hydrogen or lower alkyl having from 1 to 6 carbon to 30 parts of grooming agent wherein atoms; and X is a salt forming anion selected from the said resin is of the formula:  
  OR H (I) C 5 C l CH OR group consisting of chloride, bromide. iodide, sulfate. wherein: methylsulfate, nitrate, sulfonate, phosphate and ace- 65 Y indicates the degree of polymerization and IS a tate; at least one A being one of said quaternary groups; number from to 20,000;  
 and equals the valence of X. R R or R is a radical of the formula:  
 a is a whole number 2 or 3;  
 b is a whole number 2 or 3;  
 c is a whole number 1 to 4;  
 m is a number from to l0;  
 )1 is a whole number from 0 to 3;  
 p is a whole number from 0 to q is zero or 1;  
 R is H or COOMe group in which Me is H, Na, K or NH4Z X is a salt forming anion;  
 v is a number equal to the valence of X;  
 R,, R and R are alkyl, aryl, aralkyl, alkaryl, cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties have up to 6 carbon atoms; the aryl moieties having up to 12 carbon atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and wherein two or three of the radicals R R and R may constitute a nitrogen heterocyclic nucleus oxy polyoxyalkylene glycol which has an average molecular weight greater than about 900 and not greater than about 4000, the lowr alkoxy ranging in carbon atom content from 1 to about 6.  
  5. A hair dressing composition comprising a hairfixative quaternary cellulose ether resin having a high 15 affinity for hair and a hair grooming agent dissolved in an aqueous alkyl alcoholic solvent in which the alkyl alcohol has from 2 to 6 carbons wherein:  
 a. said resin is present in the range of from about 0.] to 7.0 percent by weight based on the total weight of the composition;  
 b. said hair grooming agent is present in the range of from about 1 to 60 percent by weight based on the total weight of the composition;  
 c. the ratio of said resin to said hair grooming agent being present in the ratio of about 1 part of resin to 10 to parts of grooming agent wherein said resin is of the formula:  
 having 5 to 6 atoms in the nucleus. one atom of which may also be oxygen;  
 wherein the resin defined by the formula I above contains the quaternary group:  
 (II) -(C (ca es-0+ i R N R X 3 l 1 ii in the average of about 0.1 to 3 quaternary groups per 65 anhydroglucose unit;  
 and wherein said hair grooming agent is a lower alk- R bi- R X in which:  
 a is a whole number 2 or 3;  
 b is a whole number 2 or 3;  
 c is a whole number 1 to 4;  
 m is a number from 0 to 10;  
 n is a whole number from 0 to 3;  
 p is a whole number from 0 to 10;  
 q is zero or 1;  
 R; is H or COOMe group in which Me is H, Na, K or X is a salt forming anion;  
 \&#39; is a number equal to the valence of X;  
 R, R and R are alkyl, aryl. aralkyl, alkaryl. cycloalkyl; alkoxyalkyl or alkoxyaryl in which the alkyl moieties have up to 6 carbon atoms; the aryl moieties having up to 12 carbon atoms and the cycloalkyl moieties having to 6 carbon atoms and wherein two or three of the radicals R R and R may constitute a nitrogen heterocyclic nucleus having 5 to 6 atoms in the nucleus, one atom of which may also be oxygen;  
 wherein the resin defined by the formula I above contains the quaternary group:  
 in the average of about 0.1 to 3 quaternary groups per anhydroglucose unit;  
 and wherein&#39;said hair grooming agent is a polyoxypropylene triol having a M. W. of about 700.  
  6. A hair dressing composition comprising a hairfixative quaternary cellulose ether resin having a high affinity for hair and a hair grooming agent dissolved in an aqueous alkyl alcoholic solvent in which the alkyl alcohol has from 2 to 6 carbons wherein:  
 a. said resin is present in the range of from about 0.1 to 7.0 percent by weight based on the total weight of the composition;  
 b. said grooming agent is present in the range of from about 1 to 60 percent by weight based on the total weight of the composition;  
 c. the ratio of said resin to said hair grooming agent being present in the ratio of about 1 part of resin to 10 to parts of grooming agent wherein:  
 said resin is of the formula:  
 Y indicates the degree of polymerization and is a number from to 20,000; V R R or R is a radical of the formula:  
 m is a number from 0 to 10;  
 n is a whole number from O to 3;  
 p is a whole number from 0 to l0;  
 q is zero or l;  
 R; is H or COOMe group in which Me is H. Na, K or X is a salt forming anion;  
 \- is a number equal to the valence of X;  
 R R and R are alkyl, aryl aralkyl, alkaryl, cycloalkyl, alkoxyalkyl or alkoxyaryl in which the alkyl moieties have up to 6 carbon atoms; the aryl moieties having up to 12 carbon atoms and the cycloalkyl moieties having 5 to 6 carbon atoms and wherein two or three of the radicals R R and R may constitute a nitrogen heterocyclic nucleus having-5 to 6 atoms in the nucleus, one atom of which may also be oxygen;  
 wherein the resin defined by the formula 1 above contains the quaternary group:  
 in the average of about 0.1 to 3 quaternary groups per anhydroglucose unit;  
 and wherein said hair grooming agent is a higher alcohol 7. A hair dressing composition comprising a hairfixative quaternary cellulose ether resin having a high affinity for hair and a hair grooming agent dissolved in an aqueous alkyl alcoholic solvent in which the alkyl alcohol has from 2 to 6 carbons wherein:  
 a. said resin is present in the range of from about 0.1 to 7.0 percent by weight based on the total weight of the composition;  
 b. said hair grooming agent is present in the range of a is a whole number 2 or 3; b is a whole number 2 m3; 6 is a whole number 1 to 4;  
 from about l to percent by weight based on the total weight of the composition;  
 0. the ratio of said resin to said hair grooming agent being present in the ratio of about 1 part of resin 23 24 to 10 to 30 parts of grooming agent wherein eties having up to 12 carbon atoms and the cycloalsaid resin is of the formula: kyl moieties having 5 t 6 carbon atoms and H OR 1 6 (I) C (I l 0R H C I 29 i Y wherein: wherein two or three of the radicals R,, R and R, Y indicates the degree of polymerization and is a may constitute a nitrogen heterocyclic nucleus number from 50 to 20,000; having 5 to 6 atoms in the nucleus, one atom of R. R or R is a radical of the formula: which may also be oxygen;  
 (II) (C H -O) (CH JH-O (-C H 0) (C H R CH l 2 R3 l R1 in which: wherein the resin defined by the formula I above con- (1 is a whole number 2 or 3; tains the quaternary group: b is a whole number 2 or 3; v c&#39; is a whole number 1 to 4; g&#39;g ifi&#39; m is a number from O to 10; CH n is a whole number from 0 to 3; 2 p is a whole number from 0 to 10; R in: 1... R X q is zero or 1; 3 I 1 R7 R is H or COOMe group in which Me is H, Na, K or R NH4 2 X is a salt forming anion; 40  
 in the average of about 0.l to 3 quaternary groups per v is a number equal to the valence of X; anhydroglucose unit,  
 R R and R are alkyl, aryl, aralkyl, alkaryl, cycloal- 4 t f n kyl. alkoxyalkyl or alkoxyaryl in which the alkyl l r Said grooming a a y moieties have up to 6 carbon atoms; the aryl moi- UNITED STATES PATENT OFFICE EERTIFIEATE 0F CRECTION Patent No. 3 876 760 Dated April 3 1975 Ara Nersesian et al. Inventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 10 Example 1, line 51, &#34;43&#34; should read 43.13  
 Table 2 Example 10 item 2, &#34;2.15&#34; should read 92.15  
 Column 13, Example 37 item 2 &#34;O 0&#34; should read 50 .0  
 item 3, &#34;6.2&#34; should read 46 2 Column 14 Example 46,  
 item 5 &#34;O .0&#34; should read 50. 0 item 6, &#34;3.4&#34; should read 43.4 I  
 Signed and sealed this 15th day of July 1975.  
 (SEAL) Attest:  
  C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks UNITED STATES PATENT OFFICE QETIHQATE ()F CRECTION Patent No. 3,876,760 Dated April s, 1975 Ara Nersesian et al. lnventor(s) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 10 Example 1, line 51, &#34;43&#34; should read 43.13  
 Table 2 Example 10 item 2, &#34;2 .15&#34; should read 92 .15  
 Column 13 Example 37 item 2 &#34;0 .0&#34; should read 50 .0  
 item 3, 6. 2&#34; should read 46 2 Column 14, Example 46,  
 item 5 &#34;0.0&#34; should read 50. 0 item 6, &#34;3.4&#34; should read 43.4  
 Signed and sealed this 15th day of July 1975.  
 (SEAL) Attest C. MARSHALL DANN RUTH C. I- ASON Commissioner of Patents Attesting Officer and Trademarks