MXPA97005153A - Aqueous composition fixing for hair quecontain copolymer grafted with silic - Google Patents

Abstract

The present invention relates to an aqueous hair setting composition, comprising: (a) from about 0.1% to about 15% by weight of a water-soluble cationic polymer hair fixative, the hair setting agent is a graft copolymer with silicone macromers which is derived by polymerization of: (1) from about 1% to about 20% by weight of silicone macromers; (ii) from about 5% to about 75% by weight of quaternizable nonionic monomers; and (iii) from about 90% by weight non-quaternizable and water-soluble nonionic monomers, wherein at least about 5% by weight of the monomers, calculated by the total polymer weight, are quaternized and the polymer has a main chain having a Tg of from about 30ø to about 140øC; and (b) from about 75% to about 99.9% by weight of ag

Description

AQUEOUS COMPOSITION FOR OIL HAIR CONTAINS COPOLYMER GRAFTED WITH SILICONE TECHNICAL FIELD The present invention relates to aqueous hair setting compositions containing silicone-grafted copolymers.

BACKGROUND OF THE INVENTION It is widely desired that the hair retain a particular design or style. There are many types of compositions for topical application to hair that are designed to obtain or achieve this benefit. These include mouses, gels, lotions, hair spray (aerosol and non-aerosol), rinses and hair shampoos. The hair fixative compositions can have many different types of ingredients, but generally have at least one type of ingredient in common - a hair adhesive agent of polymeric adhesive. Conventionally, hair fixative compositions use organic polymers as hair fixative agents, such as for example octylacrylamide / acrylates / butylaminoetyl methacrylate copolymer and methylvinyl ether / maleic anhydride copolymer ester. Although these polymers can provide good hair retention properties, unfortunately they have the additional effect of leaving hair feeling relatively stiff or stiff and brittle. More recently, it has been known to use copolymers grafted with silicone as agents for styling hair. These polymers contain silicone macromers attached to the polymer backbone, which improve the feel of hair against conventional hair fixative agents. More specifically, the hair feels softer to the touch and can be combed more easily after the use of the hair combing product with respect to the conventional polymers used for this purpose. Silicone grafted polymers suitable for hair care compositions are presented in, for example, US Pat. No. 5,061,481, Suzuki et al. Published on October 29, 1991, US Pat. No. 5,219,560, Suzuki et al. published on June 15, 1993, US Pat. No. 5,166,276, Hayama et al. published on November 24, 1992, U.S. Patent 5,106,609, to Bolich et al. published on April 21, 1992, U.S. Patent 5,100,658, to Bolich et al. published on March 31, 1992, U.S. Patent 5,100,657, to Ansher-Jackson et al. published on March 31, 1992, U.S. Patent 5,104,646, to Bolich et al. published on April 14, 1992, EPO 0 412 707, of Torgerson et al., granted on February 4, 1994, EPO 0 412 704, of Bolich et al., published on February 13, 1991, the EPO application 92918969.4, Peffly, filed August 18, 1992, EPO application 92918839.9, Hozshuh, et al., Filed August 18, 1992, and application EPO 92919224.3, filed August 18, 1992. The most common forms Commonly used hair setting compositions are the various forms of spray products, such as hair sprays, mouses and other spray products. Hair styling products typically have ethanol, water or ethane / water vehicles for the polymer hair fixative agent. However, it has gradually become increasingly desirable to market products that are characterized by aqueous vehicles, with few or no ethanol vehicles or other volatile organic vehicles. Unfortunately, it is difficult to formulate silicone-grafted copolymers having good retention properties for hair and low tackiness in aqueous vehicles, without the use of volatile organic solvents, such as, for example, ethanoi, cyclomethicone or others. In general, this is because the silicone portion of the polymer is very hydrophobic and, therefore, is not soluble in water and that polymer as a unit does not remain in water-soluble form. Copolymers grafted with cationic silicone that appear to be soluble in water have been specifically disclosed. In JP 04360812-A, published on December 14, 1992, of the Kao Corp., JP 04359913-A, published on December 14, 1992, of the Kao Corp. and JP 04359914-A, published on December 14, 1992. December 1992, by Kao Corp., for example, the use of silicone-grafted copolymers containing cationic monomers is presented. Although the polymers of these references can be soluble in water, they also tend to be relatively tacky and hydroscopic, due to the cationic monomer. U.S. Patent No. 5,166,276, Hayama et al., Issued November 24, 1992, and the EPO applications, EPO application 92918969.4, of Peffly, filed on August 18, 1992, the application EPO 92918839.9 of Hozshuh et al., filed August 18, 1992, and EPO application 929192245.3, filed August 18, 1992, disclose or disclose copolymers grafted with cationic silicone for use in hair care, but do not specifically disclose polymers having a good performance of hair retention, that have a soft touch and that are soluble in water, without the help of volatile organic solvents. It is an object of this invention to provide aqueous hair setting compositions containing silicone-grafted polymers as hair fixative agents, for improved hair feel, which are non-tacky and do not require the presence of volatile organic compounds to assist the solubilization of the polymer. A particular objective of this invention is to provide aqueous mouse compositions for hair containing silicone-grafted polymers as hair fixative agents, for an improved tactile sensation of the hair, which are not sticky and do not require the presence of organic compounds volatile to help the solubilization of the polymer. These and other objects and benefits as may be discussed or apparent may be obtained with the present invention, which is described below. In the present, all percentages are by weight of the compositions unless otherwise indicated. All proportions are weight proportions unless otherwise indicated. All percentages, proportions and levels of ingredients referred to herein are based on the actual amount of the ingredient and do not include solvents, fillers or other materials with which the ingredient can be combined as commercially available products, unless otherwise indicated thing. The invention herein may comprise, consist or consist essentially of the elements described herein, as well as of any of the preferred or optional ingredients also described herein.

SUMMARY OF THE INVENTION It has now been found that aqueous hair setting compositions containing water-soluble silicone-graft copolymers, such as hair setting agents that are essentially free of volatile organic solvents, can be provided using a quaternized silicone-grafted copolymer which it comprises a sufficient amount of silicone macromer to provide improved tactile sensation of the hair as compared to that of the silicone-free macromer-containing polymers. The polymers herein are derivatized by polymerization of a mixture of quaternizable nonionic monomers with non-quaternizable and non-ionic water-soluble monomers and, generally, also with silicone macromers, wherein a sufficient portion of the quaternizable monomers are quaternized in the polymer after polymerization, such that the polymer is soluble in water. In particular, the present invention provides an aqueous composition for fixing hair, comprising: (a) from about 0.1% to about 15% of a water-insoluble cationic polymeric hair-fixing agent, the hair-fixing agent is a copolymer grafted with silicone macromer derivative by polymerization of: (i) from about 1% to about 20% by weight of silicone macromer; (ii) from about 5% to about 75% by weight of quaternizable non-ionic monomers; and (iii) from about 5% to about 90% by weight nonionic, non-quaternizable and water soluble monomers; wherein at least about 5% by weight of the monomers, calculated by total weight of the copolymer, are quaternized and the copolymer has a chain P451 main having a Tg of from about 30 ° C to about 140 ° C; and (b) from about 75% to about 99.9% by weight of water.

DETAILED DESCRIPTION OF THE INVENTION Silicone-grafted copolymer The compositions herein comprise from about 0.1% to about 15% by weight of a hair-fixing, polymeric, cationic and water-soluble hair, preferably from about 0.5% to about 10%. %, more preferably from about 1% to about 8%. The hair setting agent is a silicone-grafted polymer (including mixtures of these polymers), which comprises silicone bonded or covalently bonded to the polymer backbone (ie, the silicone chains are grafted to the main chain) and, they are derived by the polymerization of a combination of non-ionic, non-quaternizable and water-soluble monomers and quaternizable non-ionic monomers. The silicone macromers will generally be incorporated into the polymer hair fixing agent by conducting the polymerization of the above two types of monomers also in the presence of a silicone macromer - i.e.

P451 monomers containing silicone. At least a portion of the quaternizable monomers are quaternized. The quaternization is conducted after the polymerization and conducted to a sufficient degree so that the polymer is soluble in water. By "water soluble" it is meant that that material is soluble in deionized water at 25 ° C at a concentration of 1.0%, preferably 2%, more preferably at least about 10%, and even more so preference to around 15%. The general solubility, although not necessarily, will be no greater than about 30%. By "soluble" with reference to the polymers in the compositions herein, what is meant is that a clear or translucent solution can be formed without the presence of other solvents other than water that impart said solubility. With respect to the silicone graft copolymers herein, the aqueous solutions thereof may be translucent, rather than clear, due to the presence of silicone macromer grafts that are not soluble in water. However, the polymeric non-silicone backbones of the polymers thereof have a sufficient water solubility, such that the polymer as a whole remains in clear or translucent solution. By "soluble in water" with respect to the monomers discussed in the P451 present, what is meant is that a homopolymer of the monomer having a number-average molecular weight of 10,000 would be soluble in water. The copolymers thereof can have any number average molecular weight of any level which is useful in providing the benefits of hair setting. Generally, the number average molecular weight will be at least about 10,000, usually at least about 30,000, preferably at least about 50,000. Generally, although not necessarily, the molecular weight will be less than about 1,000,000, preferably less than 750,000. The silicone macromer graft copolymers of the present will have a polymer backbone with a Tg of from about 30 ° C to about 140 ° C, preferably from about 40 ° C to about 120 ° C, more preferably, from about 40 ° C. ° C to approximately 100 ° C. Copolymers containing silicone macromers have an organic polymer backbone, preferably a vinyl backbone or other backbone based on the carbon derived from polymerizable ethylenically unsaturated monomers. The polymers herein are derived by P451 the polymerization of: from about 1% to about 20% by weight of silicone macromers, preferably from about 2% to about 15%, more preferably from about 5% to about 10%; from about 5% to about 75% by weight quaternizable nonionic monomers, preferably from about 5% to about 60%, more preferably from about 5% to about 40%; and, from about 5% to about 90% by weight non-quaternizable and water-soluble nonionic monomers, preferably from about 25% to about 70%, more preferably from about 30% to about 60%. The polymers herein will also comprise monomer units in the same ranges set forth above. At least about 5% by weight of the monomers, by weight of the copolymer, are quaternized, preferably from about 5% to about 75%, more preferably, from about 5% to about 60%, even more preferably from about 5% up to about 40%. Once quaternized, the quaternizable monomers of the present substantially improve the P451 water solubility of the graft copolymer with silicone monomer. In the quaternized form, these monomers tend to be hygroscopic (ie, they absorb water from the atmosphere) and reduce the Tg of the polymers that are incorporated therein, which can result in an undesirably tacky product. Nonionic, non-quaternizable and water-soluble monomers also aid in the solubility of the polymer, although because they are generally not polar as the quaternized monomers thereof, they have not been found to form soluble copolymers grafted with silicone macromer. However, these monomers tend to absorb less water from the atmosphere than the quaternized monomers, when incorporated into the final copolymer, thereby helping to reduce the stickiness of the polymer while allowing the polymer grafted with silicone macromer to remain soluble in water. When preparing the graft copolymer with silicone macromers, the polymerization is conducted with the quaternizable monomers in a non-quaternized non-ionic form. It has been found that this further facilitates the random polymerization of the monomers, the selection of suitable reaction solvents in which the monomers grafted with silicone monomer (i.e., to obtain solvents in which the monomers P451 quaternizable and non-quaternizable monomers are all soluble) and provide improved polymers and hair fixatives. The nonionic quaternizable monomers herein include quaternizable monomers having an amino and ethylenically unsaturated function, such as the amino-functional derivatives of styrene, acrylamides, methacrylamides, (meth) acrylate such as, for example, the C 1 Cs alkyl esters of acrylic acid and methacrylic acid. C-C alkylamines, especially C-amines, are preferred; L-C3. It is preferred to use tertiary amines (for example, trialkyl amines) although that does not necessarily mean that monoalkylamines, dialkylamines and other alkylamine derivatives are necessarily excluded. Particular preference is given to dimethyl amino C1-C3 alkyl amines. Examples of these monomers include: (i) p-dimethylaminomethyl styrene, p-dimethylaminoethyl styrene; (ii) dimethylaminomethyl acrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminomethyl methacrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide. The term "copolymer" refers to any P451 polymers comprising two or more types of monomers. As will be apparent to those skilled in the art, the copolymers herein will generally contain at least three types of monomers (ie "terpolymers") or more. The three types of monomers include non-ionic curable monomers, non-quaternizable nonionic monomers and silicone macromers. Quaternization of the amino groups can be effected by any suitable means known in the art. These include: (1) modification with an acid such as for example hydrochloric acid or lactic acid, (2) modification with a halogenated alkyl, such as for example methyl chloride, ethyl chloride, methyl bromide or ethyl iodide, ( 3) modification with a halogenated fatty acid ester, such as for example ethyl monochloroacetate or methyl onochloropropionate and, (4) modification with a dialkyl sulfate, such as, for example, dimethyl sulfate or diethyl sulfate. The use of the notation "(met)" which precede a chemical name, such as for example acrylate or acrylamide, is presented in this specification is intended to denote the methylated version as well as the non-methylated version of these species. The polymers of the present invention also include non-quaternizable, non-quaternizable and soluble monomers P451 in water. Examples of these monomers include acrylamides, methacrylamides, cinnamides, vinyl alcohols, vinyl pyrrolidones, vinyl oxazolidones and (meth) acrylates and derivatives thereof. Specific examples include acrylamide, methacrylamide, mono- and di-Ci-Cg, preferably alkyl (meth) acrylamides, such as for example dimethylacrylamide, dimethyl methacrylamide, isopropylacrylamide, t-butylacrylamide and isopropylmethacrylamide, diacetone acrylamide, diacetone methacrylamide, acrylglyc-amide, methacrylylglycinamide, vinyl alcohol, vinyl pyrrolidone, vinyl oxazolidone, vinylmethyloxazidone, and poly (ethylene glycol) phenyl ether (meth) acrylate (e.g., number average molecular weight from about 200 to about 400). Acrylamides, methacrylamides and cinnamides are preferred. Especially preferred are acrylamides and methacrylamides. Grafted to the backbone of the copolymers herein will be a plurality of silicone macromers having a weight average molecular weight of at least about 500, preferably from about 1,000 to about 100,000, more preferably from about 2,000 up to about approximately 50,000 even more preferred, from approximately 5,000 to P451 approximately 20,000. The silicone-grafted polymers are such that when formulated in the finished composition for hair care and dried, the polymer phase is separated into a discontinuous phase that includes the silicone macromer portion and a continuous phase that includes to the organic non-silicone main chain portion. The silicone macromer of the copolymers of the present invention is generally incorporated into the polymers by terpolymerization of the monomers containing silicone macromer with the non-ionic curable monomers and the non-quaternizable nonionic monomer. These monomers containing silicone macromer have the general formula: X (Y) nSi (R) 3.mZm wherein X is a vinyl group copolymerizable with the other monomers of the polymer; And it's a divalent binder group; R is a hydroxyl, a lower alkyl (eg, C! -C4), an aryl, an alkylamino, an alkaryl, a hydrogen or an alkoxy; Z is a polymeric monovalent siloxane moiety having a number average molecular weight of at least about 500 and depending on the organic polymer backbone described above, - n is 0 or 1; and m is an integer from 1 to 3. Of course, Z will essentially not be reactive under the polymerization conditions. He P451 silicone-containing monomer preferably has a weight average molecular weight of at least about 1,000, preferably from about 1,000 to about 100,000, more preferably from about 2,000 to about 50,000, even more preferably from about 5,000 to about 20,000. It preferably has the formula: wherein m is 1, 2 or 3 (preferably m = 1), • p is 0 or 1, preferably 0; R is alkyl or hydrogen; q is an integer from 1 to 6; X is R 2 is hydrogen or -COOH (preferably R 2 is hydrogen); R is hydrogen, methyl or -CH2COOH (preferably R3 is methyl), • Z is R4, R, R are independently alkyl, alkoxy, P451 alkylamino, aryl, alkaryl, hydrogen or hydroxyl (preferably alkyl, more preferably methyl); and r is an integer of at least about 5, preferably from about 10 to about 1500, (more preferably from about 25 to about 700), more preferably from about 70 to about 250. The monomers having silicone of the Polymers herein can be polymerized into a monomer form containing silicones. Alternatively, they can be polymerized in forms of their precursors that do not contain silicone and a silicone group can then be added. For example, monomers containing carboxylates, such as for example acrylic acid, can be polymerized and then reacted with the silicone-containing compound with a terminal epoxy group. The result, in general, will be a monomer containing silicones in the polymer having a structure equivalent to the formula X (Y) nSi (R) 3_mZm, written above and intended to be encompassed or included herein. Examples of the synthesis of copolymers containing silicone macromer are described in detail in US Pat. No. 4,693,935, Mazurek, published September 15, 1987, and P451 Patent of the United States of America 4,728,571, by Clemens et al. published on March 1, 1988, both are included herein as a reference and, also in U.S. Patent 5,061,481, to Suzuki et al. published on October 29, 1991, US Pat. No. 5,219,560, Suzuki et al. published on June 15, 1993, US Pat. No. 5,166,276, Hayama et al. published on November 24, 1992, U.S. Patent 5,106,609, to Bolich et al. published on April 21, 1992, U.S. Patent 5,100,658, to Bolich et al. published on March 31, 1992, U.S. Patent 5,100,657, to Ansher-Jackson et al. published on March 31, 1992, U.S. Patent 5,104,646, to Bolich et al. published on April 14, 1992, EPO 0 412 707, of Torgerson et al., granted on February 4, 1994, EPO 0 412 704, of Bolich et al., published on February 13, 1991, the EPO application 92918969.4, of Peffly, filed on August 18, 1992, the application EPO 92918839.9, of Hozshuh, et al., Filed on August 18, 1992, and the application EPO 92919224.3, filed on August 18, 1992, all these being they are incorporated herein by reference. The polymers of the present may also P451 contain nonionic monomers not soluble in water as optional ingredients, in such quantities that the polymer, as a whole, remains soluble in water. In general, it is preferred that the content of these optional monomers be not more than about 20% by weight of the copolymer, more preferably, not more than about 10%, even more preferably, of 0% and not more than about 5% . It is also preferred that the polymers are free of anionic monomers, which can interact with the cationic functionalities of the polymers and result in precipitation in the solution. If they are present, the anionic monomers should be limited to a low level, such as for example about 5% or less, preferably from 0% to not more than about 1%. Representative examples of nonionic monomers not soluble in water are esters of acrylic or methacrylic acid of C?-C18 alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1 -pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol , 3-methyl-1-pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3, 5-dimethyl-l-hexanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, P451 1-dodecanol, 1-hexadecanol, 1-oxadecanol and the like, the alcohols have from about 1-24 carbon atoms with the average number of carbon atoms of preferably about 4-18, more preferably, from about 4- 12; styrene, chlorostyrene, vinyl esters such as, for example, vinyl acetate, vinyl chloride; vinylidene chloride, acrylonitrile; alpha-methylstyrene, t-butylstyrene; butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; alkoxyalkyl (meth) acrylate, such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; and mixtures thereof. Other nonionic monomers include acrylate and methacrylate derivatives such as for example allyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, and oleyl methacrylate, acrylate and methacrylate, benzyl acrylate and methacrylate, tetrahydrofurfuryl acrylate and methacrylate. The polymers are synthesized by free radical polymerization methods, whose general principles are well understood. See, for example Odian, "Principals of Polymerization", 2nd edition, John Wiley & Sons, 1981, pp. 179-318. The desired monomers are all placed in a reactor, together with a sufficient amount of a polar mutual solvent, miscible in water, so that when the reaction is complete, the viscosity of the P451 reaction is reasonable. Suitable solvents include acetone, ethanol and tet ahydrofuran. Cyclic charges of monomers are from about 20% to about 50%. Undesirable terminators, especially oxygen, are removed as necessary. This is effected by evacuating or purging with an inert gas, such as, for example, argon or nitrogen. The indicator is introduced and the reaction is brought to the temperature necessary for the initiation to occur, assuming that thermal initiators are used. Alternatively, redox initiation or radiation may be used, as desired. The polymerization is allowed to proceed as long as it is necessary to achieve a high level of conversion, usually from a few hours to a few days. The solvent is then removed or removed, usually by evaporation or precipitation of the polymer by the addition of a non-solvent. The polymer is further purified, as necessary. After polymerization, the polymer can be quaternized to the desired degree by conventional quaternization reactions, such as those described above. By way of example, Polymers I, II, and III, which are described above, are synthesized in the following manner. There are many variations in these procedures that P451 are completely within the discretion of the chemist in charge of the synthesis (for example selection of the degassing method and seLection of the gas, selection of the type of initiator, extension of the conversion, loading of the reaction, etc. The selection of the initiator and the solvent is usually determined by the requirements of the particular monomers used, since the different monomers have different solubilities and different reactivities for a specific initiator Polymer I: place 30 parts of dimethylaminopropyl methacrylamide, 55 parts of isopropyl acrylamide and 15 parts of macromer of polydimethylsiloxane (PDMS) with a weighted molecular weight of 15,000 (15K) in a flask. Add enough acetone to produce a final concentration of 20% monomer. Add initiator, azobiisobutyronitrile (AIBN), at a level of 0.5% by weight relative to the amount of monomer. Evacuate the container and refill with nitrogen. Heat at 60 ° C and keep at this temperature for 20 hours while stirring. Finish the reaction by cooling to room temperature and removing the acetone by drying, pouring the reaction mixture into a tray coated with Teflon and placing it in a vacuum oven. For quaternization, place the polymer in a flask equipped with a magnetic stirrer. Add enough P451 amount of ethanol to produce a final polymer concentration of 20% by weight. Add 14.8 g of diethylsulfate per 50.0 g of polymer (or other desired stoichiometric amount, relative to the desired degree of quaternization) for 100% quaternization of the quaternizable monomer, drop by drop into the flask, continue stirring for two hours. Evaporate the ethanol to obtain the quaternized polymer. Polymer II: place 30 parts of dimethylaminopropylacrylamide, 55 parts of isopropylacrylamide and L5 parts of the PDMS macromer in a reaction vessel adapted with a temperature probe, a reflux condenser, an inlet port and an argon sprayer. Add enough acetone to bring the final concentration of the monomer to 20%. Spray with argon for 1 to 2 hours. While it is spraying, heat to 58 ° C in a water bath. Add initiator, azobiisobutyronitrile, at a level of 0.5% by weight relative to the weight of the monomer present. Maintain the temperature at 58 ° C and with a sufficient flow rate of argon to keep the solution mixed. Finish the reaction after 20 hours and purify in the same way as for Polymer I For quaternization, solubilize the polymer in enough ethanol to form a 20% solution P451 Bubble methyl chloride gas through the solution until the polymer initiates precipitation from the solution, for approximately 100% (theoretical) of the quaternization. Decant the solution and dry the polymer. Reduce the period of bubbling of methyl chloride for lower levels of quaternization. Polymer I?: Place 30 parts of dimethylaminoethylmethacrylate, 50 parts of isopropylacrylamide and 10 parts of the PDMS 15K macromer in a reaction vessel adapted with an argon spray, a temperature probe, a reflux condenser and an inlet port. Add enough acetone to bring the final concentration of the monomer to 20%. Start stirring and spray with argon for 1 hour. While it is spraying, heat to 58 ° C in a water bath. Add initiator, azobiisobutyronitrile, at a level of 1.0% by weight relative to the weight of the monomer present. Continue stirring and a slow spray of argon and maintain the reaction temperature at 58 ° C. Let it react for 20 hours. Finish the reaction and remove the solvent in the same way as with Polymer I. For quaternization, solubilize the polymer in enough ethanol to form a 20% solution. Bubble methyl chloride through the solution until the polymer initiates precipitation from the P45X solution, for approximately 100% (theoretical) quaternization. Decant the solution and dry the polymer. Reduce the period of bubbling of methyl chloride for lower levels of quaternization.

Aqueous vehicle. The compositions of the present invention comprise from about 75% to about 99.9% by weight of water, as a carrier for the silicone macromer graft copolymer, preferably between about 85% and 99%, and more preferably between about 90 % and 99%. The silicone polymer graft copolymer of the present invention is soluble in the aqueous carrier. In view of this solubility, it is not necessary to include in the composition organic solvents (including volatile solvents) such as ethanol, silicone fluids such as cyclomethicone or hydrocarbon solvents to aid in the solubilization of the copolymer. Accordingly, the compositions herein are essentially free of these solvents. By substantially free, it is understood that not more than about 10% by weight of the solvents, preferably not more than about 5%, more preferably not more than about 1% and more preferably zero percent.

P451 COMPOSITIONS FOR HAIR CARE The composition of the present invention may comprise a wide variety of additional ingredients for cosmetic purposes, therapeutic or rheology modification. The additional non-limiting ingredients are described below. The compositions of the present invention may be in liquid form of lotions, creams, gels etc. The vehicle may include gel vehicle materials or other rheology modifiers. These are particularly contemplated for use in products such as hair rinses, shampoos, creams and lotions. Gel vehicles can comprise two essential components: a lipid carrier material and a liquid cationic surfactant material. The cationic surfactant materials are described in detail below. The gel vehicles are generally described in the following documents, all are mentioned by reference: "The Self Body Action of the Mixed Emulsifier Sodium Dodecyl Sulfate / Cetyl Alcohol" 28 J. of colloid and Interface Science 82-91 (1968); Barry, et al., "The Self-Bodying Action of Alkyltrimethylammonium Bromides / Cetostearyl Alcohol Mixed Emulsifiers, Influence of Quaternary Chain Length", 35 J. of Colloid and Interface P451 Science 689-708 (1971); and Barry, et al., "Theology of Systems Containing Cetomacrol 1000 Cetostearyl Alcohol I. Self Bodying Action", 38 J. of Colloid and Interface Science 616-625 (1972). The vehicle may incorporate one or more lipid carrier materials, regardless of whether they also contain a cationic surfactant, which are essentially insoluble in water and contain hydrophobic and hydrophilic entities. The lipid carrier materials include naturally occurring or synthetic derived acids, acid derivatives, alcohols, esters, ethers, ketones and amides with carbon chains of between about 12 to about 22, preferably about 16 to about 18 carbon atoms. length. Fatty alcohols and fatty esters are preferred, fatty alcohols are particularly preferred. Preferred esters that are used herein include cetyl palmitate and glyceryl monostearate. Cetyl alcohol and stearyl alcohol are preferred as alcohols. A particularly preferred lipid vehicle is comprised of mixtures of cetyl alcohol and stearyl alcohol containing from about 55% to about 65% (by weight of the mixture) of cetyl alcohol.

P451 Lipid carrier materials among those that are useful for the present are exposed in Bailey's Industrial Oil and Fat Products. (3rd edition, D. Swern, ed .. 1979). which is mentioned here by reference. The fatty alcohols included among those useful herein are disclosed in the following documents, all mentioned herein by reference United States Patent No. 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent No. 4,165, 369, Watanave, et al., Issued August 21, 1979; U.S. Patent No. 4,269,824, Villamarin, et al., Issued May 26, 1981; British Specification 1,532,585, published November 15, 1978; and Fuku Shima, et al., "The Effect of Cetostearyl Alcohol in Cosmetic Emulsions", 98 Cosmetics & Toiletries 89-112 (1983). The fatty esters included among those useful herein are disclosed in the Patent of the States .United No. 3,341,465, Kaufman, et al., Issued September 12, 1976 (referred to herein by reference). If included in the compositions of the present invention, the lipid carrier materials are typically present in amounts of between about 0.1% to 10.0% of the composition, the cationic surfactant vehicle material is present between about 0.05% and 5.0% of the composition.

P451 The use of nonionic cellulose ethers and water-soluble gums for the thickening compositions is also contemplated. Refer, for example, to U.S. Patent No. 4,557,928, Glover, issued December 10, 1985, which discloses a hair conditioner comprising a suspension system consisting of one of: glucan gum, guar gum and hydroxymethyl cellulose; and U.S. Patent No. 4,581,230, Grollier et al., issued April 8, 1986, which discloses cosmetic compositions for treating hair, comprising as thickening agents hydroxyethylcellulose or water-soluble vegetable thickeners, such as guar gum. , each one mentioned by reference. The cellulose ethers are relatively low molecular weight but are capable of producing highly viscous aqueous solutions in practical concentrations. These materials are nonionic cellulose ethers having a sufficient degree of nonionic substitution, selected from the group consisting of methyl, hydroxyethyl and hydroxypropyl, to make them soluble in water and which are further substituted with a hydrocarbon radical having from about 10 to 24 carbon atoms in an amount between about 0.2 weight percent, and the amount that makes the cellulose ether soluble in water at less than 1 weight%. He P451 cellulose ether to be modified is preferably one of low to medium molecular weight, ie less than about 800,000 and preferably between about 20,000 and 70,000 (about 75 to 2,500 D.P.). Water-soluble nonionic cellulose ethers are the preferred polymers that can be employed in hair care compositions. Commercially available and widely used nonionic cellulose ethers include methyl cellulose, hydroxy propyl methyl cellulose, hydroxyethyl cellulose, hydroxyproyl cellulose and ethyl hydroxyethyl cellulose. Other carrier ingredients that are used in the compositions of the present invention, especially for hair rinses, include combinations of polymer materials hydrophobically modified with surfactants, such as quaternary ammonium compounds. (as diphe- dimethyl ammonium chloride). These vehicles are described in detail in the following patents: U.S. Patent No. 5,106,609, issued Apr. 21, 1992 to Bolich et al., U.S. Patent No. 5,100,658, issued March 31, 1992 Bolich et al., U.S. Patent No. 5,104,646, issued April 14, 1992 by Bolich et al. , and United States Patent No. 5,100,657, granted on December 31, P451 March 1992 by Ansher-Jackson et al. , all mentioned here by reference. These systems provide a rheology similar to that of a gel without necessarily being gels in the technical sense. By "Water-soluble, non-ionic, hydrophobically modified polymer" is meant a water-soluble nonionic polymer that has been modified by substitution with a sufficient amount of hydrophobic groups to render the polymer less soluble in water. By "soluble water" it is understood that it is the polymer or the salt thereof, which constitutes the polymeric structure of the thickener that must be sufficiently soluble, so that it forms a substantially clear solution when dissolved in water at a level of 1% in weight of the solution, at 25 ° C. Therefore, the polymer structure of the primary thickener can essentially be that of any water-soluble polymer. The hydrophobic groups can be C8 to C22 alkyl groups, aryl alkyl, alkyl aryl and mixtures thereof. The degree of hydrophobic substitution of the polymer structure should range from about 0.10% to about 1.0%, depending on the particular polymer structure. More generally, the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is between about 10: 1 to about 1000: 1.

P451 The nonionic water soluble cellulose ethers are preferred for use as the polymeric substrate of these hydrophobically modified polymers. Thus, for example, there are hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose and methyl hydroxyethyl cellulose, which can all be modified. The amount of the nonionic substituent such as methyl, hydroxyethyl or hydroxypropyl is shown to be non-critical, as long as there is sufficient amount to ensure that the ether is soluble in water. The long chain alkyl modifier can be attached to the cellulose ether substrate via an ether, ester or urethane linkage. The ether bond is preferred. A commercially available material that meets these requirements is NATROSOL PLUS Grade 4430, which is hydrophobically modified hydroxyethylcellulose available from Aqualon Company, Wilmington, Delaware. This material has a C16 alkyl substitution of from about 0.5% to about 0.9% by weight. The molar substitution of hydroxyethyl for this material ranges from approximately 2.8 to approximately 3.2. The average molecular weight for water soluble cellulose before modification is about 300,000.

P451 Other material of this type is sold under the trade name NATROSOL PLUS CS Grade D-67, by Aqualon Company, Wilmington, Delaware. This material has a Cig alkyl substitution ranging from about 0.50% to about 0.95%, by weight. The molar substitution of hydroxyethyl for this material ranges from about 2.3 to about 3.3. The average molecular weight for water soluble cellulose before modification is about 700,000. Examples of water-soluble polymers include hydroxyethylcellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, dextrans, for example purified crude Dextran Grade 2P which is obtained from D & amp;; Or Chemicals, plant exudates such as acacia, gati and tragacanth, algae extracts such as sodium alginate, propylene glycol alginate, sodium carrageenan, cationic polymers such as Ucare JR-polymer (a cationic modified hydroxyethylcellulose available from Union Carbide) natural polysaccharides such as guar gum, locust bean gum and xanthan gum. When these systems are used to thicken the compositions herein, preferably from about 0.3% to about 5.0% are used, P451 more preferably between about 0.4% and 3.0% of the hydrophobically modified nonionic polymer, with from about 0.3% to about 5.0%, preferably from about 0.4% to about 3.0% of the water-soluble polymeric material. An alternative secondary thickener material for the hydrophobically modified nonionic polymer is a water soluble surfactant having a molecular weight of less than about 20,000. By "water-soluble surfactant" are meant surfactant materials which form substantially clear isotropic solutions when dissolved in water at a percentage of 0.2 percent by weight, at 25 ° C. Practically? any water-soluble surfactant material that meets these requirements will work for the present invention, including the following exemplary materials: cetyl betaine, ammonium lauryl sulfate, ammonium laureth sulfate, cetyl trimethyl ammonium chloride, and mixtures thereof. When these systems are used to thicken the compositions herein, in general from about 0.1% to about 10.0%, preferably from about 0.2% to 5.0%, of the hydrophobically modified nonionic water-soluble polymer is used, with about 0.02. % to approximately 0.30%, of P451 preferably from about 0.05% to about 0.30%, more preferably from about 0.05% to about 0.20% of the water-soluble surfactant. The level of water-soluble surfactant is kept low since the higher levels of water-soluble surfactant interfere with the hydrophobically modified hydroxyethyl cellulose thickener and produce compositions with much less desirable rheologies. When the hydrophobically modified polymer ee combines it is a water-insoluble surfactant having a molecular weight of less than about 20,000 by "water-insoluble surfactant" are meant surfactant materials that do not form substantially clear isotropic solutions when dissolved in water at more than 0.2 percent by weight, at 25 ° C. Virtually any water-insoluble surfactant material that meets these requirements will work in the present invention, however, water insoluble cationic surfactant materials are preferred. The cationic surfactants are described further below. The following non-exclusive surfactant materials are suitable: stearamide diethanolamine (stearamide DEA), cocoamide methanolamine (cocoaamine MEA), dimethyl stearamine oxide, glyceryl monooleate, sucrose stearate, stearam PEG-2, ethers P451 polyethylene glycol fatty alcohols such as Ceteth-2 of the formula CH3- (CH3) 14-CH2 - (OCH2CH2) n-0H, where n has an average value of 2 (commercially available under the trade name Brij 56 of ICI Americas), glycerol stearate citrate, hydrogenated tallow dimethylammonium chloride, polyoxyethylene, polyoxypropylene block polymers such as Poloxamer 181, of the formula: H0- (CH2-CH2-0)? (CH-CH2-0)? (CH2- CH20) zH; wherein on average x = 3, y = 30 and z = 3 (commercially available from BASF Wyandotte under the tradename Pluronic L-61), hydrogenated tallow dimethyl betaine and hydrogenated tallow amide DEA. When these systems are used to thicken the compositions herein, from about 0.1% to about 10.0%, preferably from about 0.2% to about 5.0%, of hydrophobically modified hydroxyethyl cellulose are used, with from about 0.2% to about 10.0 %, preferably from about 0.0% to about 3.0%, more preferably from about 0.05% to about 2.0% of the water-insoluble surfactant. It is also contemplated to use a suspending agent to thicken the compositions and / or suspend the polymer / resin / solvent phase. Suitable suspending agents are long chain acyl derivatives, oxides of P451 long chain amine and mixtures thereof, wherein these suspending agents are present in the shampoo compositions in crystalline form. A variety of these suspending agents are described in the reissue of U.S. Patent No. 34,584 to Grote et al. granted on April 12, 1994. Ethylene glycol distearate is especially preferred. Also included among the long chain acyl derivatives useful as suspending agents are N, N-di (hydrogenated) amido benzoic acid Cg-C22 (preferably Ci2-C22 'more preferably, or the soluble salts (eg the salts K, Na) thereof, particularly the N, N-tallow di (hydrogenated) amide benzoic acid commercially available from Stepan Company (Northfield, Ill., USA) Surfactants are optional ingredients in the compositions of the invention, when they are present, the surfactant typically comprises from about 0.05% to about 50% of the composition.The useful surfactants present in the compositions of the present invention include anionic, nonionic, cationic and amphoteric surfactants.For a shampoo, the level of preference is between about 5% to about 30%, more preferably between about 10% to about 25% of the composition. For conditioners, the level p surfactant ratio ranges from about 0.1% to about 3%. Foams are particularly preferred compositions of the present invention. The foams will, in general, comprise a foaming agent such as amine oxide, especially C10-C22 alkyl amine oxides, preferably i2-C18, a surfactant, especially an amphoteric surfactant such as a betaine or a combination thereof. These foaming agents will generally be used at a level of between about 0.05% to about 3%, preferably from about 0.1% to about 2%. Anionic detergents useful herein, particularly for shampoo compositions, include alkyl and alkyl ether sulphates. These materials typically have the respective formulas R0S03M and RO (C2H40) xS03M, wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium , potassium and triethanolamine. Another suitable class of anionic surfactants are the water soluble salts of the reaction products of organic sulfuric acid of the general formula: R! -S03-M P451 wherein Rx is selected from the group consisting of straight or branched chain, radial saturated aliphatic hydrocarbon having from about 8 to about 24, preferably about 12 to about 18 carbon atoms, - and M is a cation. Important examples are the salts of a reaction product of organic sulfuric acid of a hydrocarbon of the methane series, which includes iso-, neo-, and n-paraffins, having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms and a sulfonate agent, for example, S03, H2S04, sulfuric acid fumerant, obtained according to the known methods of sulfonation, including leaching and hydrolysis. Preferred are C12-? Β n-paraffins sulfonated with ammonium and alkanyl metal. Additional examples * of anionic synthetic surfactants remaining within the terms of the present invention are the reaction products of the sterile fatty acids ested with isethionic acid and neutralized with sodium hydroxide, where for example, the fatty acids ee are derived of coconut oil, - sodium and potassium salts of methyl tauride fatty acid amides, where the fatty acids, for example, are derived from coconut oil. Other synthetic anionic surfactants from P451 this variety are set forth in U.S. Patents Nos. 2,486,921; 2,486,922; and 2,396,278. Still other synthetic anionic surfactants include the class designated as succinamates. This class includes surfactant agents such as disodium N-octadecylsulfosuccinamate; N- (1, 2-dicarboxyethyl) -N-octadecylsulfosuccinamate of tetrasodium, -diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid, - dioctyl esters of sodium sulfosuccinic acid. Other suitable anionic surfactants useful herein are olefin sulfonates having from about 12 to about 24 carbon atoms. The term "olfein sulfonates" in the form used herein means compounds that can be produced by the sulfonation of alpha-olefins, by means of non-complexed sulfur trioxide, followed by neutralization of the acidic reaction mixture under conditions such that either of the sulfones that have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkane sulphonates. The alpha-olefins from which the olefin sulfonates are derived are monoolefin having from about 12 to about 24 carbon atoms, preferably about 14 to about 16 carbon atoms.

P451 Another class of anionic organic surfactants are beta-alkyloxy alkane sulfonates. Composite phases have the following formula: 0R2 H I I R «- C - C- SO3M I I HH wherein R is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R 2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms and M is a cation soluble in water as described here. Many additional synthetic non-soap anionic surfactants are described in McCutcheon's Detergents and Emulsifiers, 1984 Annual published by Allured Publishing Corporation, which is mentioned here by reference. Also, U.S. Patent No. 3,929,678, Laughlin et al. issued December 30, 1975, discloses many other anionic surfactants as well as other types of surfactants and are mentioned herein by reference. The soaps can also be used as anionic surfactants. Nonionic surfactants can be broadly defined as compounds produced by the condensation of alkylene oxide groups (by nature P451 hydrophilic) with an organic hydrophobic compound, which may be of an alkyl aromatic or aliphatic nature. Examples of the classes of nonionic surfactants are: 1. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine products. 2. The condensation product of aliphatic alcohols having from about 8 to about 18 carbon atoms, either straight or branched chain, with ethylene oxide, for example a condensate of coconut alcohol and ethylene oxide having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction has from about 10 to about 14 carbon atoms. 3. The long chain tertiary amine oxides as those corresponding to the following general formula: R1R2R3 > Wherein R 1 contains an alkyl, alkenyl or monohydroxyalkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide entities and from 0 to about 1 glyceryl entity, and R 2 and R 3 contains about 1 to about 3 carbon atoms and from 0 to P451 about 1 hydroxy group, for example methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals (the arrow in the formula is conventional representation of a semi-polar bond 4. Long chain tertiary phosphine oxides corresponding to the following general formula: RR'Rp> 0 wherein R contains an alkyl, alkenyl or monohydroxyalkyl ranging from about 8 to about 18 long chain carbon atoms, from 0 to about 10 ethylene oxide entities and from 0 to about 1 glyceryl entity, and R 'and R "are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms The date of the formula is a conventional representation of a semipolar bond 5. The long chain dialkyl sulfoxide contains a hydroxyalkyl or alkyl radical of short chain ranging from about 1 to about 3 carbon atoms (usually methyl) and a long hydrophobic chain including alkyl, alkenyl, hydroxy alkyl or alkyl keto, containing from about 8 to about 20 carbon atoms, from about 0 to about about 10 ethylene oxide entities and from about 0 to about 1 glyceryl entity.

Examples include: octadecyl methyl sulfoxide, 2-cetotridecyl methyl sulfoxide, 3,6,9-trixaoctadecyl 2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, oleyl 3-hydroxypropyl sulfoxide, tetra decyl methyl sulfoxide, 3-methoxytridecyl methylsulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methylsulfoxide. Cationic surfactants useful in the compositions of the present invention, particularly the conditioning compositions, contain amino or quaternary ammonium hydrophilic entities that are positively charged when dissolved in the aqueous composition of the present invention. Cationic surfactants among those useful herein are disclosed in the following documents, all of which are incorporated by reference: M.C. Publishing Co. , McCutcheon 's, Detergents &; Emulsifiere, (North American Edition (1979), Sch artz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; United States Patent No. 3,155,591, Hilfer, granted on November 3. of 1964; U.S. Patent No. 3,929,678, Laughlin, et al., issued December 3, 1975; U.S. Patent No. 3,959,461 to Bailey, et al., issued June 7, 1983. include in the compositions of the present invention, the cationic surfactant in general is present between about 0.05% and about 5. Among the cationic quaternary ammonium surfactant materials useful herein are those of the general formula: wherein R1-R4 are independently an aliphatic group of from about 1 to about 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkyl aryl group having from about 12 to 22 carbon atoms, - and X is a selected anion of halogen, acetatable phosphate, nitrate and alkyl eulfate radicals. The aliphatic groups may contain, in addition to the carbon and hydrogen atoms, ether linkages and other groups such as amino groups. Aliphatic long chain groups, for example those of about 12 carbon or higher, may be saturated or unsaturated. Other quaternary ammonium salts useful herein are the diuaternary ammonium salts, such as those of tallow propane diammonium dichloride. The quaternary ammonium salts include dialkyldimethyl-ammonium chlorides, wherein the alkyl groups have from about 12 to about 22 carbon atoms and are derived from long chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids which they give quaternary products wherein R and R2 have predominantly from 16 to 18 carbon atoms). Examples of quaternary ammonium salts useful in the present invention include ditallowdimethyl ammonium chloride, ditallowdimethyl ammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dimocosyl dimethyl chloride ammonium, didocoeyl dimethyl amino chloride, di acetate (hydrogenated tallow) dimethyl ammonium, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, dipropyl ammonium diphosphate phosphate, di-dimethyl ammonium nitrate, di (coconut alkyl) dimethyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride. Dimethyl ammonium dichloride chloride, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl chloride, and cetyl trimethyl ammonium chloride are the preferred quaternary ammonium salts useful herein. Di- (saturated or unsaturated tallow) dimethyl ammonium chloride is a particularly preferred ammonium chloride salt. Salts of primary, secondary and tertiary fatty amines are also useful as cationic surfactant materials. The alkyl groups of these amines have P451 preferably from about 12 to about 22 carbon atoms and may be substituted or unsubstituted. These amines useful herein include propyl dimethyl amine estelamide, diethyl amino ethyl stearamide, dimethyl stearamide, dimethyl amine, soyamine, myristyl amine, tridecylamine, ethyl stearylamine, N-sebopropane diamine, ethoxylated stearylamine (5 moles of ethylene oxide) dihydroxy ethyl stearylamine and arachidylbehenylamine. Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. These salts include stearyl amine, hydrochloride, soyamine chloride, stearylamine format, N-sebopropane diamine dichloride and stearamidopropyl dimethylamine citrate. The cationic amine surfactants included among the tools for the present invention are set forth in U.S. Patent No. 4,275,055, Nachtigal, et al., Issued June 23, 1981, which is mentioned herein by reference. Amphoteric surfactants include those which can be extensively described as derivatives of the aliphatic, phosphonium and eulphonium quaternary ammonium compounds, wherein the aliphatic radicals can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to P451 about 18 carbon atoms and one contains an anionic water solubilizing group, for example carboxy, sulfonate, sulfate, phosphate or foefonate. A general formula of these compounds is: (R3) x wherein R 2 contains an alkyl, alkenyl or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide entities and from 0 to about 1 glyceryl entity; Y is selected from the group consisting of nitrogen, phosphorus and sulfur atoms, - R3 is an alkyl or monohydroxyalkyl group containing from 1 to about 4 carbon atoms, - X is 1 when Y is a carbon atom. sulfur and 2 when Y is a nitrogen or phosphorus atom; R is an alkylene or hydroxyalkylene of about 1 to about 4 carbon atoms and Z is a radical that is selected from the group consisting of the carboxylate, sulfonate, sulfate, phosphonate and phosphate groups. Other amphoteric groups such as betaine are useful in the present invention. Examples of useful betaines herein include higher alkyl betaines such as coconut dimethyl carboxymethyl betaine, lauryl dimethyl P451 carboxymethyl betaine, lauryl dimethyl alpha carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis- (2-hydroxyethyl) carboxymethyl betaine, stearyl bis- (2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine and lauryl bis- (2- hydroxypropyl) alpha-carboxyethyl betaine. The sulfobetaines may be represented by coconut dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis (2-hydroxyethyl) sulfopropyl betaine and sejemant, - the aminobetaines and amidosulfobetaines, where the radical RCONH (CH2) 3 binds to the betaine nitrogen atom and are useful for the present invention. Other examples of amphoteric surfactants that may be used in the compositions of the present invention are those which are broadly described as derivatives of amines to the secondary and tertiary ifatics, wherein the aliphatic radical may be straight or branched chain, and wherein one of the Aliphatic substituents contain from about 8 to about 18 carbon atoms and one contains a water, anionic, solubilizing group, for example, carboxy, sulfonate, sulfate, phosphate or phosphonate. Examples of the compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino propane sulfonate, N-alkyltaurinae as prepared by the reaction of dodecylamine with sodium tetraethionate, according to the teachings of US Pat. No. 2,658,072, higher N-alkyl aspartic acids as those produced according to the teachings of US Pat. No. 2,438,091 and the products sold under the trade name "Miranol" and described in U.S. Patent No. 2,528,378.

Conditioning agents for hair with silicone base. An optional component of the present invention is a non-volatile silicone conditioning agent. The silicone-based hair conditioning agent to be used herein will preferably have an average viscosity of from about 1,000 to about 2,000,000 centistokes at 25 ° C, more preferably from about 10,000 to about 1,800,000 and still more preferably from 100,000 to approximately 1,500,000. The viscosity of the silicones herein may, in general, be measured by means of a glass capillary viscometer as set forth in the test method of Dow Corning Corporate Test Method CTM0004, July 20, 1970.

The silicone-based hair conditioning agent will typically be employed with the shampoo compositions herein, at levels ranging from about 0.05% to about 10% by weight of the composition, preferably from about 0.1% to about 10%. , more preferably from about 0.5% and about 8%, more preferably from about 0.5% and about 5%. Non-volatile insoluble silicone fluids which are suitable include polyalkyl siloxane, polyaryl eyloxanes, polyalkylaryl siloxane, polyether siloxane copolymers and mixtures thereof. Other non-volatile and insoluble silicone fluids having hair conditioning properties can also be used. The term "non-volatile" in the sense used herein refers to the fact that the silicone material exhibits a very low vapor pressure or not significant to environmental conditions, as understood by those skilled in the art. In general, this means no more than 0.2 mm Hg at one atmosphere and 25 ° C. The term "silicone fluid" refers to silicone materials that can flow and have a viscosity of less than 1,000,000 centistokes at 25 ° C. In general, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25 ° C, preferably between about 10 to about 100, 00. The silicone fluids herein include polyalkyl or polyarylsiloxanes with the following structure: wherein R is alkyl or aryl, and x is an integer of about 1 to about 8,000, preferably about 5 to about 8,000 may be used. "A" represents groups that block the ends of silicone chains. The substituted alkyl or aryl groups in the siloxane chain (R) or the ends of the siloxane chain (A) can have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic, are not irritating, toxic or harmful when applied to the hair, are compatible with other components of the composition, are chemically stable under normal conditions of storage and use, and are capable of being deposited in the hair and conditioned. Suitable groups A include methyl, methoxy, ethoxy, propoxy and aryloxy. The two R groups on the silicone atom can represent the same or different groups. From P451 preference, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenyl ethyl. Preferred silicones are polydimethyl siloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Particular preference is given to polydimethylsiloxane. Non-volatile polyalkylsiloxane fluids that may be used include, for example, polydimethylsiloxanes. These siloxanes are available, for example from General Electric Company in their series Viscaeil and SF 96, or from Dow Corning in the USA Dow Corning 200. The polyalkylaryl siloxane fluids that can be used also include, for example, polymethylphenylsiloxanes. These siloxanoes are available, for example from General Electric Company as SF 1075 methyl phenyl fluid or from Dow Corning as Cosmetic Grade Fluid 556. The polyether siloxane copolymthat can be employed, include, for example, polypropylene oxide modified with polypropylene oxide (by example, Dow Corning DC-124B) although ethylene oxide or mixture of ethylene oxide and propylene oxide can also be used. The level of ethylene oxide and propylene oxide should P451 be sufficiently low to avoid solubility in water and in the composition of the present. Another silicone material that can be especially useful in silicone conditioning agents is insoluble silicone rubber. The term "silicone gum" which is used herein, refto polyorganosiloxane materials having a viscosity at 25 ° C, greater than or equal to 1,000,000 centistokee. The silicone gums are described by Petrarch and othincluding U.S. Patent No. 4,152,416, to Spitzer et al. granted on May 1, 1979 and Noli, Walter, Chemistry and Technology of Silicones, New York: Academic Press 1968. Silicone gums are also described as for example in the General Electric SE 30 Silicone Rubber Product specification sheets. , SE 33, SE 54 and SE 76. All of these edicted references are mentioned here for reference. The "silicone gums" will typically have a molecular weight greater than 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethylsiloxane, (polydimethylsiloxane) copolymer (methylvinylsiloxane), poly (dimethylsiloxane) copolymer (diphenyl siloxane) (methylvinylsiloxane) and mixtures thereof.

P451 Cationic polymer-based hair conditioning agent The compositions of the present invention can also comprise a water-soluble cationic organic polymer hair conditioning agent. The polymeric cationic conditioning agent of the present will generally be at levels of from about 0.05% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3% by weight of the shampoo composition. By "water-soluble" cationic organic polymer is meant a polymer that is sufficiently soluble in water to form a substantially clear solution to the naked eye, at a concentration of 0.1% in water (distilled or equivalent) at 25 ° C. Preferably, the polymer will be sufficiently soluble to form a substantially clear solution at a concentration of 0.5%, more preferably a concentration of 1.0%. The cationic organic polymers useful in the hair conditioning agent herein are organic polymers which can provide hair conditioning benefits and which are soluble in the shampoo composition. Any cationic polymer that can provide these benefits can be used. HE P451 also use here the term "polymer" which will include materials either made by polymerization of one type of nomomer or made by polymerization of one type of monomer or made by two (ie, copolymer) or more types of monomers. The cationic polymers of the present will generally have a weighted molecular weight of at least 5,000, typically of at least 10,000 and less than about 10 million. Preferably, the molecular weight is between 130,000 and 2 million approximately. The cationic polymers will have nitrogen containing cationic entities such as quaternary ammonium or cationic amino entities, or a mixture thereof. Any anionic counterion can be used for cationic polymers as long as the water solubility criteria are met. Suitable counterions include halides (for example Cl-, Br-, I-, or F-, preferably Cl-, Br-, or I-), sulfate and methyl sulfate. Others can also be used, since this list is not exclusive. The cationic nitrogen-containing entity will generally be present as a substituent, or a fraction of the total monomer units of the cationic hair conditioning polymers. In this way, the cationic polymer may comprise copolymers, P451 terpolymers, etc. of monomeric units of quaternary ammonium or subetitides with cationic amino and other non-cationic units referred to herein as monomeric separating units. These polymers are known in the art and a variety of them are found in the CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, toiletry, and Fragrance Aesociation, Inc., Washington, DC, 1982). Suitable cationic polymers include, for example, copolymers of vinyl monomers having quaternary ammonium or cationic amine functionalities with water-soluble separating monomers, such as acrylamide, methacrylamide, alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The alkyl and dialkyl substituted monomers preferably have C 1 C alkyl groups, more preferably C 1 -C 3 alkyl groups. Other spacing monomers include vinyl esters, vinyl alcohols (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol. The cationic amines can be primary, secondary or tertiary amines, depending on the particular species and the pH of the shampoo. In general, P451 secondary and tertiary amines, especially tertiary amines, are preferred. The amine-substituted vinyl monomers can be polymerized in the amine form, and then optionally converted to the ammonium by a quaternization reaction. The amines can similarly be quaternized subsequent to the formation of the polymer. For example, the tertiary amine functionalities can be quaternized by reaction with a salt of the formula R'X wherein R 1 is a short chain alkyl, preferably a C -Cv alkyl, more preferably a C 1 -C 3 alkyl and X is an anion that forms a salt soluble in water with quaternized ammonium. Suitable monomers of cationic amino and quaternized ammonium include, for example, vinyl compound substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts and quaternary vinyl ammonium monomers having cationic, cyclic, nitrogen-containing rings, such as pyridinium, imidazolium and quaternized pyrrolidone, for example, alkyl vinyl imidazolium salts, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone. The alkyl portions of these monomers are preferably lower alkyl such as C -C3 alkyl, more preferably Ci and C2 alkyl. Suitable substituted amine-substituted vinyl monomers herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkylacrylamide and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably Cx-Cv hydrocarbyls, more preferably CX-C3 alkyls. The cationic polymers herein may comprise mixtures of thin monomer units of amino and / or quaternary ammonium substituted monomers and / or compatible spacer monomers. Suitable cationic hair polymers or conditioners include, for example: copolymer of l-vinyl-2-pyrrolidone and l-vinyl-3-methylimidazolium (for example, the chloride) (referred to in the industry by Cosmetic, Toiletry, and Fragrance Association, "CTFA", as Poliquaternium-16), those commercially obtained by BASF Wyandotte Corp., (Parsippany, NJ, USA) with the trade name LUVIQUAT (ie LUVIQUAT FC 370), - copolymer of l-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (in the industry referred by the CTFA, Polyquaternium-11) such as those P451 commercially available from Gaf Corporation (Wayne, NJ USA) under the trademark GAFQUART (for example GAFQUART 755N), cationic diallyl polymers containing quaternary ammonium including, for example, copolymers and homopolymers of dimethyl dealylammonium chloride of acrylamides and dimethyl tiallyl ammonium chloride, which in the industry are referred to as (CTFA) Poliquaternium 6 and Poliquaternium 7, respectively and salts of mineral acids of the aminoalkyl esters and homo and copolymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms. carbon, as described in U.S. Patent No. 4,009,256, which is mentioned herein by reference. Other cationic polymers that may be employed include polysaccharide polymers, such as cationic cellulose derivatives and cationic starch derivatives. Polymeric cationic polymeric materials suitable for use herein include those of the formula: wherein: A is a residual group of anhydroglicoea, such as, for example, anhydrous starch or cellulose residual group.

P451 R is an alkylene oxyalkylene, polyoxyalkylene or hydroxyalkylene, or combinations thereof, R 1, R 2 and R 3 are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl groups, each group contains up to 18 carbon atoms and the total number of carbon atoms for each cationic entity (ie the sum of carbon atoms in R 1, R2 and R) is preferably about 20 less, and X is an anionic counterion as already described. Cationic cellulose is obtained from Amerchol Corp. (edison, NJ, USA) in its Polymer JR and LR series of polymers, such as hydroxyethyl cellulose salts that react with epoxide substituted with trimethylammonium, which in industry (CTFA) are referred to as Polyquaternium 10. Other type of cellulose cationic includes the polymeric quaternary ammonium salts of the hydroxyethylcellulose reacted with ammonium substituted lauryl dimethyl epoxide, referred to in the industry (CTFA) as Polyquaternium 24. These materials are obtained from Amerchol Corp. (Edison, NJ, USA) under the trade name Polymer. LM-200. Other cationic polymers that may be employed include cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride (commercially available from Celanese Corp., in its Jaguar series). Other materials include cellulose ethers that contain P451 quaternary nitrogen (for example as referred to in U.S. Patent 3,962,418 which is mentioned herein by reference) and copolymers of etherified cellulose and starch (e.g., as obtained in U.S. Patent No. 3,958,581, which is incorporated herein by reference). mention here by reference).

Organic Oil Conditioning Agents The compositions of the present invention may also comprise an organic, water-insoluble, non-volatile oil, as a conditioning agent for hair. The oily hair conditioner liquid can add shine and luster to the hair. The conditioning oil is typically present in the compositions at a level between about 0.05% and 5% by weight of the composition, preferably between about 0.2% and 3%, more preferably between about 0.5% and 1%. By "non-volatile" it is meant that the oily material exhibits a low or non-significant vapor pressure at ambient conditions (e.g., an atmosphere, 25 ° C), as understood in the art. The non-volatile oily materials preferably obtain a boiling point at ambient pressure of about 250 ° C or higher.

P451"Insoluble in water" means that the oily liquid is not soluble in water (deethylated or equivalent) at concentrations of 0.1%, at 25 ° C. The conditioner oil of the present will generally have a viscosity of about 3 million is or less, preferably about 2 million is or less, more preferably about 1.5 million is or less. The conditioning oils herein are liquid selected from the group consisting of hydrocarbon oils and fatty esters. The fatty esters of the present invention are characterized by having at least 10 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, for example monoesters, polyhydric alcohol esters and di and tricarboxylic acid esters. The hydrocarbyl radicals of the fatty esters of the present invention may also include, or have covalently attached to it, other compatible functionalities, such as amides and alkoxy entities (for example ethoxy or ether bonds, etc.). The hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), branched chain aliphatic hydrocarbons (saturated or unsaturated). The straight chain hydrocarbon agents will preferably contain P451 about 12 to about 19 carbon atoms although it does not necessarily mean that the hydrocarbons are limited to this range. Branched chain hydrocarbon oils may contain, and typically contain, greater numbers of carbon atoms. Also included are polymeric hydrocarbons of alkenyl monomers, such as, for example, C2-Cg alkenyl monomers. These polymers may be branched straight chain polymers. Straight chain polymers will typically be of a shorter length, having a number of carbon atoms as described for straight chain hydrocarbons in general. The branched chain polymers can have a substantially higher chain length. The number average molecular weight of these materials can vary widely, but typically is up to about 500, preferably between about 200 and 400 and more preferably between about 300 and 350. Specific examples of suitable materials include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane saturated and unsaturated pentadecane, saturated and unsaturated hexadecane and mixtures thereof. The branched chain isomers of these compounds, as well as the higher chain length hydrocarbons P451 can also be used. Exemplary branched chain isomers are highly branched saturated and unsaturated alkanes such as permethyl substituted isomers, for example the isomers substituted with permethyl of hexadecane and eicosane, such as for example 2, 2, 4, 4, 6, 6, 8 , 8-dimethyl-10-methylundecane and 2,2,4,4,6,6-dimethyl-8-methyl-nonane, sold by Permethyl Corporation. A preferred hydrocarbon polymer is polybutene as a copolymer of isobutylene and butene. A commercially available material is the L-14 polybutene type from Amoco Chemical Co. (Chicago, Illinois, U.S.A.). The monocarboxylic acid esters herein include esters of alcohols and acids of the formula R'COOR, wherein the alkyl or alkenyl radicals and the sum of carbon atoms in R 'and R is at least 10, preferably at least 20. Fatty esters include, for example, alkyl and alkenyl esters of fatty acids having aliphatic chains with from about 10 to about 22 carbon atoms and carboxylic acid esters of alkyl and alkenyl alcohol having a aliphatic chain derived from alkyl and / or alkenyl alcohol with from about 10 to about 22 carbon atoms, and combinations thereof. Examples include isopropyl, isostearate, hexylurea, P451 isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyl decyl aditate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetilpropionato and oleil adipato. The monocarboxylic acid ester does not necessarily have to contain at least one chain with at least 10 carbon atoms, as long as the total number of carbon atoms of the aliphatic chain is at least 10. Examples include isopropyl adipate , diisoethyl adipate, and diisopropyl sebacate. The di and tri-alkyl and alkenyl esters of the carboxylic acids can also be used. This includes, for example, C4 ~ C8 carboxylic acid esters, such as C1-C22 esters (preferably Cx-Cg) of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic acid and octanoic acid. Specific examples include isocetyl stearate stearate, diisoproyl adipate and trietearyl citrate. The esters of polymeric alcohols include alkylene glycol ester, for example ethylene glycol mono and digrase esters, diethylene glycol mono and digraso acid esters, mono and digraso acid esters of P451 polyethylene glycol, mono and digraso acid esters of propylene glycol, propylene glycol monooleate, polypropylene glycol 2000 monoetherate, ethoxylated propylene glycol monoetherate, glyceryl mono and digraso acid ethers, polyglycerol polyglycerol esters, glyceryl ethoxylated monostearate, monoetherate of 1,3-butylene glycol, 1,3-butylene glycol distearate, fatty acid esters of polyoxyethylene polyol, sorbitan fatty acid ester and fatty acid esters of sorbitan and polyoxyethylene, are satisfactory as a polyhydric alcohol ester used at the moment. Glycerides include, mono, di and triglycerides. More specifically, they include the mono-di, and triestere of glycerol and the long-chain carboxylic acids such as the carboxylic acids C1 () - C22- A variety of these types of materials can be obtained from vegetable and animal oils and fats, such as curing oil, safflower oil, cottonseed oil, corn oil, liver and cod oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oils include trioleyl and tristearyl glyceryl dilaurate. Preferred glycerides are di and triglycerides, triglycerides are especially preferred. The compositions herein may contain P451 a variety of other optional components suitable for these compositions to be acceptable in cosmetic or aesthetic sense or to provide them with benefits of additional uses, for example, medicinal benefits. These conventional optional ingredients are well known to those skilled in the art, for example, solar filters, medicaments, (eg anti-bacterial, anti-inflammatory, anti-acne active, etc.), colors and dyes, perfumes, adjuvants pearlized as ethylene glycol distearate; preservatives, such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinyl urea; thickeners and viscosity modifiers such as diethanolamine of a long-chain fatty acid (eg diethanol lauric amide PEG 3), cocomonoethanol amide, dimethicone copolyols, guar gum, methyl cellulose, starches and starch derivatives, - fatty alcohols as alcohol cetearyl; sodium chloride; sodium eulfate, - polyvinyl alcohol; ethyl alcohol, pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts in general such as acetate acetate and sodium chloride; coloring agents as are any of the dyes FD &C or D &C; hair oxidants (bleaches, such as hydrogen peroxide, perborate and P451 persulfate salee; hair reducing agents such as thioglycollates; perfume, sequestering agents such as disodium ethylenediamine tetraacetate; polymeric plasticizing agents such as glycerin, disobutilty adipate, butyl stearate, and propylene glycol. These optional ingredients are generally used individually at levels ranging from about 0.01 to about 10.0%, preferably from about 0.05% to about 5.0% of the composition. The pH of the compositions herein are generally between about 3 and 9, preferably between about 4 and 8. The compositions of the present invention can be dispensed from containers that are of the aerosol or spray pump type. These dispensers, ie recipients, are well known to those of ordinary skill in the art and are commercially obtained from a variety of manufacturers, including American National Can Corp. and Continental Can Corp. When the spray compositions are dispensing from a pressurized aerosol container a propellant consisting of one or more of the conventionally known aerosol propellants can be used to drive the compositions. A suitable propellant that is used in general is the liquefiable gas that P451 is conventionally used for aerosol containers. Suitable propellants which are used are volatile hydrocarbon propellants which may include liquefied lower hydrocarbons of 3 to 4 carbon atoms such as propane, butane and isobutane. Other suitable propellants are hydrofluorocarbon such as 1,2-difluoroethane (Hydrofluorocarbon 152A), supplied by Dy DuPont 152A. Other examples of propellants are dimethyl ether, nitrogen, carbon dioxide, nitrous oxide and atmospheric gas. The aerosol propellants can be mixed with the compositions herein or they can be contained in a separate phase or compartment of an aerosol container. The amount of propellant to be mixed is governed by the normal factors known in the aerosol art. The levels of the required ingredients and other optional ingredients of the composition described above are based on the total weight of the ingredients of the hair care composition and do not include the aeroeol propellants. In general, for liquefiable propellants, the propellant level is from about 3% to about 60% of the composition (hair care compositions and aerosol propellant) of preferably about 3%; P451 to about 50% by weight of the total composition. Alternatively, the aerosol dispensers used can be used when the propellant is removed from contact with the spray composition to the hair, such as a double-compartment can of the type sold under the trade name SEPRO of American National Can Corp. Other suitable aerosol dispensers are characterized by the propellant which is compressed air and can be filled in the dispenser by means of a pump or equivalent device, before use. These dispensers are described in U.S. Patent No. 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25, 1989, TerStege, both mentioned herein by reference and the Application of the United States of America No. of Series 07 / 839,648, Gosselin et al., filed on February 21, 1992, and which is also mentioned by reference. Suitable compressed air aerosol containers that are used are currently marketed by Procter & Gamble Company with the trade name VIDAL SASSOON AIRSPRAYR, dew for hair. Conventional non-aerosol pump spray dispensers, ie atomizers, can also be used.

P451 As with all compositions, the present invention should not contain components that unduly interfere with the performance of the compositions. The hair care compositions of the present invention can be made using conventional formulations and conventional mixing techniques. In general, the silicone-grafted copolymer can be mixed with water before, subsequent to the addition of additional ingredients. The compositions are preferably heated to about 40 ° C-60 ° C with stirring and then allowed to cool for about 6 to 8 hours at room temperature with stirring.

Method of using the hair care compositions The hair care compositions of the present invention are used in conventional manner to provide the desired desired benefit of the product, such as hair styling, fixing, cleaning, conditioning and the like for the hair care compositions. hair care compositions. These methods of use depend on the type of composition used but, in general, involve the application of an effective amount of the product to the P451 hair, which can then be rinsed from the hair (as in the case of shampoos and some conditioning products) or left to remain on the hair (as in the case of sprays, foams or gel products). By "effective amount" is meant an amount sufficient to provide the desired benefit. Preferably, the hair rinse, foam or gel is applied to wet or damp hair before drying and combing it. After these compositions are applied to the hair, the hair is dried and combed in the normal manner of the wearer. Hair sprays are typically applied to dry hair after it has dried and combed. The compositions herein may also be used for topical application to the skin and in cosmetic compositions and for topical hair care, and the uses thereof do not necessarily mean that they are excluded from the claims, unless otherwise stated. . The following examples are further illustrated in preferred embodiments within the scope of the present invention. The examples are given solely for the purpose of illustrating the invention and should not be construed as limitations of the present invention, since it is possible to make many variations without departing from the spirit and scope thereof.

P451 EXAMPLES 1 TO 4. The exemplary foam compositions of the present invention are shown below. Component (% by weight) 1 2 3 4 Grafted copolymer with 3.00 3.00 3.00 3.00 silicone Lauramine oxide 0.10 0.10 0.00 0.10 Cocamidopropyl betaine 1.33 1.33 0.30 1.33 Propylene glycol 0.20 0.10 0.10 0.10 Perfume 0.10 0.10 0.05 0.10 Disodium EDTA - dihydrate 0.10 0.10 0.10 0.10 Phenoxyethanol 0.25 0.25 0.25 0.25 Methyl paraben 0.15 0.15 0.15 0.15 Poliquaternium - 4 2 0.00 0.00 0.00 0.20 Chloride of 0.00 0.00 0.20 0.00 stearyltrimethylammonium Deionized water c.b.p c.b.p c.b.p c.b.p polymer I, II or III, described above 2 Celquat L200, National Starch and Chemical Corpo. (Bridgewater, NJ. USA, hydroxyethylcellulose copolymer and diallyldimethyl ammonium chloride The composition is prepared by mixing the silicone-grafted copolymer with water in agitation, sequentially adding the rest of the ingredients, with the exception of the perfume, heating at 40 ° C-60 ° C with stirring and P451 is stirred for about eight hours while the composition is allowed to cool to room temperature and the perfume is then mixed. The product can then be packaged in a conventional spray or non-aerosol mouse spray.

EXAMPLES 5-8 Below are several exemplary compositions of the hair spray of the present invention. Component (% by weight) 5 6 7 8 Copolymer grafted with silicone 5.00 5.00 5.00 5.00 Perfume 0.10 0.10 0.10 0.10 Deionized water c.b.p. c.b.p. c.b.p. c.b.p. Compositions are prepared by mixing the graft copolymer with silicone in water, heating with stirring at 40 ° C-60 ° C and cooling to room temperature, stirring for about 8 hours while allowing the composition to cool.

EXAMPLE 9 The following is a representative shampoo composition of the present invention.

P451 Component Weight in% Ammonium Laureth Sulfate 5.00 Cocamino propyl betaine 6.00 Copolymer grafted with silicone I, II, III 2.00 PEG 150 distearate 2.00 Glydant1 0.38 Perfume 1.00 Deionized water c.b.p. Conservatively commercially available from Glyco, Inc.

The shampoo is prepared by combining the ammonium laureth sulfate (usually supplied as a 2% solution in water) and the silicone-grafted copolymer, and heating the ethanol 70 ° C for about 1/2 hour and mixing. The reeto of the ingredients are added and mixed for an additional 1/2 hours. The batch is then cooled to room temperature. The pH of the composition is adjusted to 6.5 by the addition of citric acid or sodium hydroxide, if necessary.

EXAMPLE 10 The following is a stylized rinse composition representative of the present invention.

P451 Component Weight in% Copolymer grafted with silicone I, II, III 3.00 Premix Rubber silicone GE SE761 0.50 Decamethyl cyclopentasiloxane 4.00 Main mixture Hydroxyethylcellulose cetyl 2 0,. 60 Carob bean gum 0. 50 EDTA, disodium salt 0. . 15 DTDMAC 0. . 65 Glydant3 0. . 40 Deionized water c. b. p. Obtainable in commercial form from General Electric 2 Polisurf de Aqualon Co. Conservative commercially available from Glyco Inc.

The premix is mixed separately by conventional means. The main mixture is prepared by adding all the ingredients and heating at 95 ° C for half an hour with stirring. As the batch cools to about 60 ° C, the premix and the silicone-grafted copolymer are added to the main mixture with agitation and the batch is cooled to room temperature.

P451

Claims (9)

1. CLAIMS; f 1. An aqueous hair setting composición7, comprising: (a) from 0.1% to 15% by weight of a hair setting agent, polymeric, cationic and soluble in water, the hair setting agent is a grafted copolymer silicone macromer derived by the polymerization of: (i) from 1% to 20% by weight of silicone macromers; (ii) from 5% to 75% by weight of quaternizable nonionic monomers; and (iii) from 5% to 90% by weight of non-quaternizable and water-soluble nonionic monomers, - wherein the copolymer has a degree of quaternization of at least 5% by weight, of the monomers, calculated by the total weight of the copolymer, are quaternized and the copolymer has a backbone having a Tg of from 30 ° C to 140 ° C; and (b) from 75% to 99.9% by weight of water. An aqueous hair setting composition according to claim 1, wherein the composition is essentially free of volatile organic solvents and, wherein the polymer has an average molecular weight of
2. P451 number from approximately 10,000 to 1,000,000.
3. 3. An aqueous hair setting composition according to any of the preceding claims, wherein the monomers of point (a) (ii) are selected from the group consisting of ethylenically unsaturated amino functional monomers of acrylamide, methacrylamide, alkyl acrylates ^^ 4, C 1 -C 4 alkyl methacrylates, styrene and combinations thereof, preferably, the monomers are selected from the group consisting of tertiary alkyl amines C] _-C.
4. 4. An aqueous hair setting composition according to any of the preceding claims, wherein the monomers of (a) (iii) are selected from the group consisting of acrylamide, methacrylamide, mono- and di-alkyl acrylamides Ci-Cg, mono- and di-alkyl methacrylamide Cx-C, cinnamides and combinations thereof, preferably the monomers are selected from the group consisting of acrylamide, methacrylamide, mono- and di-alkylacrylamides C? -C6, mono- and di-alkyl methacrylamides Ci-Cg, cinnamides and combinations thereof and, more preferably, wherein the monomers are selected from the group consisting of mono- and di-alkylacrylamides C;, _C2, acrylamide, methacrylamide, mono- and di- C1-C3 methacrylamides and combinations of the miemos.
5. 5. An aqueous composition to fix the hair P4S1 according to any of the preceding claims, which further comprises 0.05% to 3% by weight of a foaming agent.
6. 6. An aqueous hair setting composition according to any of the preceding claims, dispensed in an aerosol container, whereby the composition foams wdispensed.
7. 7. An aqueous composition for fixing the hair according to any of the preceding claims, comprising from 2% to 15% of the monomer containing silicone macromer, from 5 to 60% of the quaternizable monomer and from 25% to 70% of the non-monomer quaternizable and non-ionic.
8. 8. An aqueous composition for fixing the hair according to any of the preceding claims, comprising from 5% to 10% of the monomer containing silicone macromer, from 5 to 40% of the quaternizable monomer and from 30% to 60% of the monomer not quaternizable and non-ionic.
9. 9. An aqueous hair setting composition according to any of the preceding claims, wherein the copolymer is soluble in 10% deionized water at 25 ° C. P451