MXPA98007518A - Compositions of personal care containing copolymer of hydrophobo graft and solid volatil hidrof - Google Patents

Abstract

The present invention relates to personal care compositions, especially to hair care compositions, containing graft copolymers: hydrophobic, not silicone and a volatile, hydrophobic solvent for the copolymer. The solvent is selected from branched chain hydrocarbons, silicones and combinations thereof. This invention also relates to hair conditioners and hair styling products such as rinses, leave-on conditioners, and combination shampoo products for cleaning, styling and conditioning hair. The graft polymers must meet the following three criteria: (1) the graft portion is covalently bound to the polymeric structure portion, (2) the molecular weight of the graft portion is at least about 500, and (3) when used in a composition, such as a personal care composition for application to hair or skin, the polymeric structure portion must allow the graft polymer to be deposited on the proposed surface, such as the hair or skin. Preferred copolymers, when dried, are phase separated into a microfase including the graft portion and a microfase including the polymeric portion of the structure.

Description

COMPOSITIONS OF PERSONAL CARE CONTAINING COPOLYMER OF HYDROPHINIC GRAFT AND VOLATIL SOLVENT HYDROPHOBON TECHNICAL FIELD The present invention relates to personal care compositions, especially hair care compositions, containing a graft copolymer, hydrophobic and a volatile hydrophobic solvent, for the copolymer. Examples of the hair care compositions to which this invention refers are hair conditioners and hair styling agents that include rinses, non-rinsing conditioners, and combination shampoo products useful for cleaning, styling and conditioning the hair. hair.

BACKGROUND OF THE INVENTION The use of polymeric materials in hair care products is of increasing importance. In the area of hair care, polymers can be used for hair retention and fixation products, for hair conditioning products, and in shampoos. For example, the hair conditioner / styling rinse products typically comprise a hydrophobic polymer that is not removed after rinsing the hair. The polymer is P666 solubilizes in a suitable solvent that evaporates to leave the hair treated with the polymer. The solvent must be one in which the polymer is substantially soluble (i.e., the solvent is hydrophobic in general). A hair styling polymer should provide certain styling benefits. For example, the styling polymer should not leave the sensation and appearance of the hair. Also, the styling polymer must have sufficient adhesion without being unduly fragile, so that the hair can be re-stylized, for example, with tongs, and the new hairstyle is retained. Furthermore, the styling polymer must be able to be distributed from a shampoo matrix, that is, it must be deposited on the hair during the washing process and remain behind the hair fibers. Therefore, in the area of hair styling it is desirable to provide polymers that provide improved styling benefits and that can be distributed from a wide variety of dies, including rinses, non-rinsing compositions and shampoos. It is also desirable to provide hair styling compositions having improved hair performance (after application and drying of these compositions) at a particular level of hair conditioning or vice versa, P666 improved hair conditioning for a particular level of performance of hair feeling. It is well known that polymers can be modified by the incorporation or grafting of silicone. These polymers have hitherto been used in hair care compositions. See, for example, U.S. Patent No. 5,106,609, to R.E. Bolich Jr. et al., Issued on April 21, 1992; U.S. Patent No. 4,693,935, Mazurok, omitted on September 15, 1987; PCT Application No. US 94/08031, published February 16, 1995, and PCT Application No. US 94/09503, published March 02, 1995. Silicone graft polymers tend to have low surface energy and they provide unique aesthetic and formulation advantages, not usually obtained from non-silicone grafted polymers. However, for improved adhesion / retention of hair, conditioning, industrial hygiene, formulation, opportunities and / or economy, it is desirable to have alternative, non-silicone polymer based compositions that satisfy or approve the hair feeling properties provided. for materials based on silicone polymers. Hydrophobic graft copolymers, not silicone, are well known in the art, but have not been P666 used for personal care applications, such as hair care products. See, for example, Chemistry and Industry of acromonomers, Yuya Ya ashita (ED.), Huthig £ _ epf, New York, and macromolecular Design Concept and Practice, Munmaya K. Mishra (Ed.), Polymer Frontiers International, Inc. New York , 1994. Despite the advantages that non-polar graft copolymers can provide, these materials are generally difficult to formulate in solvents used in the personal care industry. However, it has been found in the present invention that the use of certain hydrophobic volatile solvents provides a highly desirable base for these compositions. The resulting compositions have good styling and conditioning performance and have a highly desirable hair feel, ie they do not leave the hair feeling unacceptably stiff. The graft copolymers of the present invention are hydrophobic, not silicone, materials that are relatively insoluble in water and / or alcohol and have certain thermomechanical properties. These characteristics make these copolymers quite useful for the formulation in hair care products. It is an object of the present invention P666 to provide new hair care compositions containing graft copolymers, non-polar, non-silicone. It is another object of the present invention to provide new hair care compositions that have improved styling and retention benefits. It is another object of the present invention to provide new hair care compositions that have improved conditioning benefits. These and other objects will become readily apparent from the detailed description that follows.

SUMMARY OF THE INVENTION The present invention relates to personal care compositions, preferably hair care compositions, comprising: (A) a graft copolymer having a polymeric structure and a hydrophobic, polymeric side chain grafted to the structure, The copolymer is formed from the copolymerization of randomly repeating monomer units A and units of macromonomer B, wherein the copolymer comprises: (i) from about 30% to about 95% by weight of monomer units A, wherein the monomer units A are copolymerizable monomer units with the macromonomer B units; (ii) from about 5% to about 70% by weight of the units of macromonomer B, wherein the units of macromonomer B are hydrophobic macromonomer units having a polymer portion and a portion copolymerizable with the monomer units A; wherein the monomer units A, in conjunction with the copolymerizable portions of the macromonomer B units, form the polymeric structure, wherein the polymeric portion of the units of the macromonomer B form the side chain (s) hydrophobic polymer (s); wherein the copolymer has a weight average molecular weight greater than about 10,000 and (B) a volatile, hydrophobic solvent for the copolymer suitable for application to the hair, the solvent that is selected from branched hydrocarbons, silicones and combinations thereof . The copolymer can exhibit at least two different Tg values, the first Ta corresponding to the structure having a value of at least about 25HC, preferably at least about 30SC; the second T. corresponding to the polymeric, hydrophobic side chains and having a value of less than about 10 ° C, preferably less than about 0 ° C. The present invention also relates to personal care compositions, preferably hair care compositions, comprising: (A) a graft copolymer having a polymeric structure and grafted to the structure, the copolymer formed from the copolymerization of units of randomly repeating monomer A, and units of macromonomer B wherein the monomer units A are at least one monomer unit copolymerizable with the macromonomer B units and are selected from the group consisting of acrylic acid esters, acid esters methacrylic; N-alkyl acrylamides; vinyl compounds, vinylidene compounds, unsaturated hydrocarbons (for example, olefins, including straight chain, branched chain and cycloaliphatic olefins, and ethylenically unsaturated, aromatic compounds); esters of alcohols of 1 to 18 carbon atoms of organic acids and anhydrides of organic acids; and combinations thereof; B is a copolymerizable macromonomer unit with a monomer unit A, corresponding to Formula (I) or (II): (- (C-r-i- E (II). where : "a" is an integer of approximately 50 or greater, and "b" is, on average, an integer of approximately 1 or greater; R1, R2, R3, R4 and R5 are, independently, H or straight or branched alkyl group of 1 to 5 carbon atoms; R6 = H or alkyl of 1 to 8 carbon atoms R7 = of 4 to 18 carbon atoms i and k are, independently, an integer of approximately 1 or greater; j and 1 are, independently, a whole number of P666 about 0 or greater; m is an integer from 10 to about 2000, preferably from 15 to 300, and more preferably from about 20 to about 250; and E and I are as defined herein, I preferably selected from the group consisting of hydrogen, straight or branched chain alkyl of 1 to 40 carbon atoms, benzyl, straight or branched chain alkyl of 2 to 40 carbon atoms, substituted with 1-phenyl, straight or branched chain alkyl of 2 to 40 carbon atoms, substituted with 1, 1-diphenyl, and mixtures thereof, and Y preferably an ethylenically unsaturated portion, copolymerizable with the unit of monomer A, selected from the group consisting of acrylamide, methacrylamide, vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl, 1-butenyl, 1-propenyl, isobutenyl, isoprenyl, cyclohexenyl, cyclopentenyl, and mixtures thereof; and (B) a volatile, hydrophobic solvent for the copolymer that is suitable for application to hair, the solvent that is selected from branched hydrocarbons, silicones and combinations thereof. The macromonomer B unit can be a P666 homopolymer, or a copolymeric macromonomer containing two or more units of randomly repeating monomer, different. In further embodiments, the present invention relates to methods for styling, retaining, and / or conditioning hair, which comprises applying the compositions of the present invention to hair. All percentages and ratios used herein are by weight of the total composition and all measurements are made at 252C, unless otherwise designed. The invention herein may comprise, consist of, or consist essentially of, the essential as well as optional ingredients and components described herein. All documents referred to herein, including all patents, patent applications and printed publications, are hereby incorporated by reference in their entirety in the description.

DETAILED DESCRIPTION OF THE INVENTION "Graft copolymers" is a term familiar to those skilled in the art in polymer science and is used herein to describe copolymers resulting from addition or "grafting", or a portion thereof. chemical, or polymeric (ie, "graft") over the other portion commonly referred to as the P666"structure". The structure typically has a higher molecular weight than the grafts. In this way, graft copolymers can be described as polymers having polymeric, pendant side chains, and as they are formed from the "graft" or the incorporation of the polymer side chains on or in a polymer. The polymer to which the grafts are incorporated may be homopolymers or copolymers, for example, random or block copolymers, linear. These copolymers are derived from a variety of monomer units. In this way, the graft copolymers of the present invention can be prepared from the copolymerization of monomer units and macromonomer units such that the macromonomer units are "grafted" or incorporated into the polymer formed from the units of monomer The term "macromonomer" is familiar to those skilled in the art in polymer science, and is used to describe a polymeric material that contains a polymerizable portion. In other words, a macromonomer is a macromolecular monomer, which is essentially of the high molecular weight type of monomer building block unit that can be used in a polymerization reaction to form polymers therewith, with other monomers, or with other macromonomers.

P666 The term "hydrophobic" is used in the. present with its normal meaning of lack of affinity for water; while "hydrophilic" is used in the present consistent with its normal meaning that it has an affinity for water. As used herein in relation to the monomer units, the polymeric materials "including the macromonomers and the graft copolymers", and the solvent for the graft copolymer, "hydrophobic" means substantially insoluble in water; "hydrophilic" means substantially water soluble In this regard, "substantially insoluble in water" should refer to a material that is not soluble in distilled water (or equivalent) at 25 SC, or a concentration of 0.2% by weight, and is preferably not soluble at 0.1% by weight (calculated on a weight basis of water plus material) These water-insoluble materials are typically non-polar.Similarly in this respect, "substantially water-soluble" should refer to a material that is soluble in distilled water (or equivalent), at 25 aC, at a concentration of 0.2 wt%, and are preferably soluble at 1.0 wt% The weighted average molecular weight for purposes of determining the solubil ad or substantial insolubility in water of a polymeric material should be approximately 10,000, although the solubility at higher molecular weight should be P666 also be indicative of solubility at about 10,000. "Soluble", "solubility", and the like, for the purpose herein, correspond to the maximum concentration of the monomer or polymer, as applicable, which may be dissolved in water or another solvent to form a solution that is substantially clear to the naked eye, as understood by those skilled in the art. The above-mentioned definitions should also apply to other materials thus described herein, to the extent that any other definition with respect to these materials is consistent with those cited above.

Graft Copolymers The hair care compositions of the present invention comprise a graft copolymer. In general, hair care compositions comprise from about 0.1% to about 25%, preferably from about 0.5% to about 20%, and more preferably from about 0.5% to about 10%, and more preferably from about 1% to about 5% of the graft copolymer, by weight of the total composition, although higher or lower amounts may be used depending on the application.

P666 The graft copolymers of the present invention are characterized by having a relatively high concentration, a polymer structure of high Tg with a hydrophobic polymeric side chain, of minor Ta, covalently attached to and pendant of the polymeric structure (the hydrophobic side chain is grafted to the polymer structure). This combination of polymer portions in a single copolymer provides the unique and useful properties of these materials. As will be clear to those skilled in the art and especially from the synthesis examples, the graft copolymer can have one or more hydrophobic side chains grafted to the structure. In addition, the compositions of the present invention may include, in addition to the graft copolymer, corresponding copolymers that do not have hydrophobic side chains grafted to the structure. (As is known in the art, the processes of graft copolymerization, synthesis, can produce a mixture of polymer molecules that do not contain, that contain one or that contain more than one hydrophobic side chain covalently attached to, and pendant from the polymer structure From the knowledge of the numerical average molecular weight and quantity of the hydrophobic side chains in a polymer sample, and the average molecular weight number of the polymer sample, it is possible to calculate the average number of polymer samples.

P6G6 hydrophobic side chains by polymer structure). T is a term well known in the art of polymer science used to describe the temperature at which a polymer or portion thereof undergoes a transition from a solid or brittle material to a rigid or rubber-like material. Vitreous transition temperatures can be measured using standard techniques that are well known to polymer scientists of skill in the art. Differential scanning calorimetry (also known as DSC) is a particularly useful technique for determining vitreous transitions. The vitreous transition phenomenon in polymers is described in Introduction to Polymer Science and Technology; An SPE Textbook; (eds H.S. Kaufman and J.J. Falcetta), (John Wiley &Sons: 1977). The Tg of the structure of the copolymers herein (ie, that part of the copolymer not containing the hydrophobic side chains) should be at least about 25 ° C. Preferably, this T is greater than about 30 aC, more preferably from about 30 eC to about 200 aC, still more preferably from about 30 aC to about 175 aC, and more preferably from about 35 aC to about 150 ci. The T of the hydrophobic side chains must be smaller than P666 about 10aC, preferably from about 02C to about -130aC, more preferably from about -20aC to about -125aC, more preferably from about -45aC to about -120aC. The aforementioned Tg of the structure polymer and the hydrophobic side chains can be determined in a thin film of the polymer formed only of the monomer units A or a thin film of the macromonomer B unit before the copolymerization with the monomer units? . The copolymers of the present invention can exhibit at least two intermixed, immiscible, distinct microphases. Without being limited by theory, it is believed that the hydrophobic side chains of the copolymers are closely associated with each other and thus exist substantially in a microfase, while the structure of the copolymer remains substantially in a separate microfase. It is believed that this phase separation property provides a specific orientation of the graft polymer which results in a desirable combination of touch sensation and film formation or adhesive benefits. The microphase separation properties of the graft copolymer can be determined by the following P666 method. The polymer is molded as a solid film of a solvent (i.e., a solvent that dissolves both the structure and the graft portions). This film is then sectioned and examined by transmission electron microscopy. The separation of the microphases is demonstrated by the observation of the inclusions in the continuous phase. These inclusions must be sized to match the size of the graft macromonomer chain (typically a few hundred nm or less) and the proper density to match the amount of the macromonomer present. This behavior is well documented in the literature for polymers with this structure (see, for example, SD Smith, Ph.D. Thesis, University of Virginia, 1987, and references cited therein, the thesis and references are incorporated by reference in the present) . One consequence of this phase immiscibility is that the graft copolymer can exhibit at least two different vitreous transition temperatures, or "T", specifically one Tg for the structure and one T for the hydrophobic side chains formed by the B macromonomers. In addition, when the graft copolymer exhibits at least two Tg and the ratio of the structure of the grafts is from about 50-80%, of the structure, 20-50% P666 by weight of the grafts, the hydrophobic grafts that tend to separate the microphases to form rubber domains within the structure matrix. Without intending to be limited by theory, he believes that these rubber domains act as energy dissipation sites and decrease the brittleness of the polymer film. These graft copolymers tend to have both a relatively high polymer extension / flexibility at break and an acceptable tensile strength. This dissipation of energy and its effects on the physical properties of the polymer are described in Mechanical Properties of Polymers and Composites, Second Edition, L.E., Nielsen and R.F. Landel; Marcel Dekker, Inc., New York 1994. The copolymers of the present invention have a weight average molecular weight (in grams / mol) of at least about 10,000. There is no upper limit for molecular weight except that it limits the applicability of the invention for practical reasons, such as viscosity, process, aesthetic characteristics, formulation compatibility, etc. The weight average molecular weight is generally less than about 5,000,000, more generally less than about 2,500,000, and typically less than about 1,500,000. Preferably, the weighted average molecular weight is from P666 about 10,000 to about 5,000,000, more preferably from about 75,000 to about 2,000,000, still more preferably from about 100,000 to about 1,000,000 more preferably from about 125,000 to about 1,000,000. The copolymers of the present invention are formed from the copolymerization of the units of macromonomer B and randomly repeating monomer A, preferably wherein the monomer units A are selected from at least one polymerizable ethylenically unsaturated monomer unit, and the units of the macromonomer B are selected from at least one hydrophobic macromonomer unit containing a polymer portion and a copolymerizable portion with the monomer A units, preferably an ethylenically unsaturated portion which is copolymerizable with the monomer A units. the preferred embodiments of these copolymers, the structure is formed from the polymerization of the monomer A units with the ethylenically unsaturated portion of the hydrophobic macromonomer B unit. The polymer portion of the units of the macromonomer B forms the hydrophobic side chains of the copolymer. The units of the monomer A and the units of the macromonomer B can be selected from P666 from a wide variety of structures as long as the copolymer has the required solubility, Tg, and molecular weight properties herein. The monomer units A and the hydrophobic macromonomer B units comprise or are derived from hydrophobic monomers and optionally a limited amount of hydrophilic monomers. The particular, relative amounts of hydrophilic and hydrophobic monomers may vary as long as the graft copolymer as a whole is soluble in the hydrophobic, volatile solvent herein. The solubility of the graft copolymer material (or the component thereof) in the volatile, hydrophobic solvents herein is determined according to whether this material can remain in solution or precipitate from the solution at 25aC at the concentration present in a composition. Dadaist. The graft copolymers which are soluble in these solvents typically comprise from about 50% to about 100% by weight, in hydrophobic monomers and from about 0% to 50% by weight of hydrophilic monomer units. By the selection and appropriate combination of the particular A monomer units and the B macromonomer units, and by choice of specific relative ratios of the units well within the capacity of the P666 skilled in the art, copolymers can be optimized for various physical properties such as solubility, Tg, and the like, and for compatibility with other ingredients commonly used in hair care applications.

Monomer units A Monomer unit A is selected from copolymerizable monomers, preferably ethylenically unsaturated monomers. Either an individual type of monomer A or combinations of two or more monomers A can be used. The monomers A are selected to meet the requirements of the copolymer. By "copolymerizable", as used herein, is meant a material that can be reacted with another material (e.g., monomer A and macromonomer B) in a polymerization reaction using one or more synthetic techniques, conventional, such as ionic, emulsion, dispersion, Ziegler-Narta, free radical, group transfer or gradual growth polymerization. In the present invention, monomers and macromonomers that are polymerizable using techniques initiated by free radicals, conventional, are preferred. The term "ethylenically unsaturated" is used herein to mean a material (including monomers A and P666 preferred B-macromonomers) containing at least one polymerizable carbon-carbon double bond) which can be mono-, di-, tri- or tetra-substituted). The units of monomer A and macromonomers B preferably consist of monomers which, when polymerized, form a saturated polymer. The monomer units A of the copolymers of the present invention may comprise from about 30% to about 95%, more preferably from about 35% to about 85%, and more preferably from about 50% to about 80%, by weight, of the copolymers. A wide variety of monomer units A can be used in the present invention, including mixtures of two of more monomers, while the T, molecular weight and solubility requirements of the graft copolymers are satisfied. Monomer units A include hydrophobic monomer units and optionally hydrophilic monomer units. In the polymeric structure it will preferably comprise from about 50% to about 100%, more preferably from about 60% to about 98%, more preferably from about 75% to about 95%, by weight of the polymer of hydrophobic monomer units , and from about 0% to about 50%, preferably from about 2% up to P666 about 40%, more preferably and from about 5% to about 25%, of hydrophilic monomer units. The non-limiting classes of monomers A useful herein include hydrophobic monomers selected from the group consisting of acrylic acid esters; esters of methacrylic acid; N-alkyl acrylamides; vinyl compounds, vinylidene compounds; unsaturated hydrocarbons (for example, olefins, including straight chain, branched chain and cycloaliphatic olefins, and ethylenically unsaturated, aromatic compounds); esters of alcohols of 1 to 18 carbon atoms of organic acids and anhydrides of organic acids; and combinations thereof. Representative examples of these hydrophobic monomers include esters of acrylic or methacrylic acid of alcohols of 1 to 18 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-l-butanol, 1-methyl-l-butanol, 3-methyl-l-butanol, 1-methyl-l-pentanol, 2-methyl-l- pentanol, 3-methyl-l-pentanol, t-butanol (2-methy1-2-propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl ~ 1-heptanol, 2-ethyl-1-hexanol, 3, 5-dimethyl-1-hexanol, 3, 5, 5-tri-methyl-1-hexanol, 1-decanol, 1-dodecanol, P666 1-hexadecanol, 1-octa-decanol, and the like, alcohols having from 1 to 18 carbon atoms with the number of carbon atoms which is preferably from about 1-12; dicyclopentenyl acrylate; 4-biphenyl acrylate, pentachlorophenyl acrylate; 3, 5-dimethyladamantyl acrylate; 3,5-dimethyladamantyl methacrylate, 4-methoxycarbonylphenyl methacrylate; trimethylsilyl methacrylate, styrene; esters substituted with alkyl including alpha-methylstyrene and t-butylstyrene; vinyl esters, including vinyl acetate, vinyl neononate, vinyl pivalate and vinyl propionite; vinyl chloride, vinylidene chloride, vinyltoluene; vinyl alkyl ethers, including isobutyl vinyl ether and s-butyl vinyl ether; butadiene; cyclohexadiene; bicycloheptadiene; 2,3-dicarboxylmethyl-1,6-hexadiene; ethylene; propylene; indene; norbonylene; β-pinene; a-pinene; and combinations thereof. Preferred hydrophobic monomers suitable for use as monomer A units including n-butyl methacrylate, isobutyl methacrylate; t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, indene, norbornylene, ß-pinene, a-pinene, vinyl pivalate, vinyl neonate, dicyclopentenyl acrylate, acrylate 4- biphenyl, P666 pentachlorophenyl acrylate, 3,5-dimethyladamantyl acrylate, 3,5-dimethyladamantyl methacrylate, 4-methoxycarbonylphenyl methacrylate, trimethylsilyl methacrylate, t-butyl styrene and combinations thereof. More preferably, the hydrophobic monomer is selected from t-butyl styrene, t-butyl acrylate, t-butyl methacrylate, and combinations thereof. The non-limiting classes of monomers A useful herein also include hydrophilic monomers selected from the group consisting of mono-, di- and polycarboxylic acids; (meth) acrylamides; (meth) acrylates; (meth) acrylate alcohols; organic acid anhydrides; esters of organic acid anhydrides; hydrophilic vinyl compounds; hydrophilic allyl compounds; hydrophilic imides; salts of any of these compounds; and combinations thereof. Representative examples of these hydrophilic monomers include acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, methacrylamide, Nt-butyl-acrylamide, maleic acid, maleic anhydride and their ester media, crotonic acid, itaconic acid, acrylamide, acrylate alcohols, P666 hydroxyethyl methacrylate, diallyldimethylammonium chloride, vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether), maleimides, vinyl pyridine, vinylimidazole, other heterocyclic vinyl compounds, polar, styrene sulfonate, alcohol, allyl, vinyl alcohol (such as that produced by hydrolysis) of vinyl acetate after polymerization), vinylcaprolactam, salts of any acids and amines listed above, and combinations thereof. Preferred hydrophilic monomers include acrylic acid, N, N-dimethyl acrylamide, dimethylaminoethyl methacrylate, quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, salts of acids and amines listed above and combinations thereof. The quaternized monomers can be quaternized either before or after copolymerization with other monomers of the graft copolymer. As used herein, monomers A are proposed to include monomers that are unsubstituted or substituted with one or more substituent groups. Exemplary substituent groups include, but are not limited to, alkyl, aryl, carboxyl, halo, and combinations thereof.

Units of Hydrophobic B-Macromonomer P666 The hydrophobic macromonomer B units of the present invention are large, polymeric building blocks containing repeating structural units. Macromonomers B can be formed from the polymerization of smaller monomer units. The B macromonomers encompass a wide structural variety and are copolymerizable with the monomer units A. Without being intended to be limited by theory, the hydrophobic B macromonomer units are believed to contribute to the complete solubility properties of the copolymers. Either an individual type of B macromonomer or combinations of two or more B macromonomers can be used, while the Tg, solubility and molecular weight requirements of the copolymer are satisfied. Also, each macromonomer B can be constructed from two or more units of randomly repeating monomer, in which case the macromonomer will actually be considered a type of macromonomer copolymer. In any case, the B macromonomers are selected to meet the requirements of the graft copolymers. The hydrophobic macromonomers contain hydrophobic monomer units and optionally hydrophilic monomer units. • Hydrophobic B macromonomers comprise from about 5% to about 70%, more P666 preferred from about 15% to 65%, and more preferably from about 20% to about 50%, by weight of the copolymer. The macromonomers B that are useful herein contain a polymer portion and a copolymerizable portion, preferably an ethylenically unsaturated portion that can be copolymerized with the A units. Typically, the preferred B macromonomers are those that are end-marked with the ethylenically portion unsaturated By "capped at the end" as used herein is meant that the ethylenically unsaturated portion is or near a terminal position of the macromonomer. However, this definition of "end capped" is not intended to limit the macromonomer to only those macromonomers ending in the carbon-carbon double bond (whether it is mono-, di-, tri-, or tetra-substituted). The hydrophobic B macromonomers of the present invention can be synthesized using a variety of normal synthetic procedures familiar to the polymer chemistry of one skilled in the art. In addition, these macromonomers can be synthesized by starting from commercially available polymers. Typically, the average molecular weight. The weight of the macromonomer is at least approximately 500, preferably from P666 about 1000 to about 200,000, more preferably from 1500 to about 30,000, and most preferably from about 2000 to about 25,000. For example, hydrophobic B macromonomers can be synthesized by the polymerization (acid, base, free radical, or self-initiated) of one or more hydrophobic monomers and optionally hydrophilic monomers, to form a polymer that is subsequently reacted with, or "topped off". in extreme "with a copolymerizable structural unit A, preferably an ethylenically unsaturated portion. Alternatively, macromonomers B can be synthesized by starting with commercially available hydrophobic polymers that are "capped at the end" with the structural unit referred to herein as E. In yet another alternative, macromoromer B can be synthesized at the start of the unit E, and polymerizing the desired hydrophobic monomer units. It is to be understood that in this third alternative, the ethylenically unsaturated portion of unit E is not consumed in the synthesis but its integrity is preserved for the subsequent copolymerization of macromoromer B with units A. All synthesis alternatives are specifically illustrated already that any other suitable synthesis procedure can be used P666 for preparing the macromonomers B and the copolymers of the present invention. The macromonomer B is at least one hydrophobic macromonomer unit, copolymerizable with A, corresponding to Formula (I) or (II): (I) - (E , wherein: R1, R2, R3, R4 and R5 are, independently, H or straight or branched alkyl group of 1 to 5 carbon atoms; R6 = H or alkyl of 1 to 8 carbon atoms; R7 = from 4 to 18 carbon atoms; O II z- -C-O- P666 i and k are, independently, an integer of approximately 1 or greater; j and 1 are, independently, an integer of about 0 or greater; m is an integer from 10 to about 2000, preferably from 15 to 300, and more preferably from about 20 to about 250; and E and i are as defined herein, E is an ethylenically unsaturated "end cap" group which is copolymerizable with the monomer units A. Preferably, E is selected from the group consisting of acrylamide, methacrylamide, vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, isoprenyl, cyclohexenyl, cyclopentenyl, and combinations thereof. Even more preferred is when selected from the group of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, and combinations thereof. More preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3- P666 vinylbenzyl, 4-vinylbenzyl, and combinations thereof. I is a starter, chemical portion. Without being limited by theory, I can be derived from a chemical initiator or solvent used in the synthesis of the macromonomer B. Non-limiting examples of these initiators from which I can be derived include hydrogen ion, hydrogen radical , hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxide anion, carbocations of 1 to 20 carbon atoms, carboanions of 1 to 20 carbon atoms (eg, sec-carbanions, and 1, 1 -diphenyl-4-methylpentylcarbanion), radicals of 1 to 20 carbon atoms, aliphatic and aromatic alkoxy anions of 1 to 20 carbon atoms, ammonium ion, substituted ammonium ions (for example, substituted with alkyl of 1 at 20 carbon atoms and with alkoxy of 1 to 20 carbon atoms) and carbocations of 1 to 20 carbon atoms (eg, cumyl carbocation). I can be derived from any useful solvent, non-limiting examples of which include water, methanol, ethanol, propanol, isopropanol, acetone, hexane, dichloromethane, chloroform, benzene and toluene. Non-limiting examples of I include chemical moieties selected from the group consisting of hydrogen, straight or branched chain alkyl P666 of 2 to 40 carbon atoms substituted with 1-phenyl straight or branched chain alkyl of 2 to 40 carbon atoms, substituted with 1,1-diphenyl, and combinations thereof. More preferably, I is selected from the group consisting of 1,1-diphenyl-4-methylpentyl, sec-butyl, and cumyl. Most preferably I is sec-butyl or cumyl. R1, R2, R3, R4 and R5 are independently derived suitably from monomer units such as those described with reference to monomer units A. Preferred monomers are selected from the group consisting of straight or branched hydrocarbons , ethylenically unsaturated, and ethylenically unsaturated esters of acrylic acid and methacrylic acid. Preferred these monomers are hydrocarbons selected from isobutylene, butadiene, isoprene, 1-butene, 5-methyl-1-hexene, 6-methyl-1-heptene, 4, 4-dimethyl-1-pentene, etc., esters of acrylic acid and an alcohol selected from alcohol, n-butyl, dodecyl, 2-ethylhexyl, 2-ethylbutyl, n-ethyl, n-heptyl, n-hexyl, iso-butyl, iso-decyl, iso-propyl, -methylbutyl, 2-methylpentyl, nonyl, octyl, and propyl alcohol; and esters of methacrylic acid and an alcohol selected from dodecyl, 2-ethylhexyl, hexyl, decyl alcohol, P666 octadecyl, octyl, n-pentyl, and tridecyl alcohol. Non-limiting examples of these hydrophobic macromers include end-capped copolymers capped with acryloyl, methacryloyl, or 2-, 3-, or 4-vinylbenzyl, methacrylic or acrylic acid esters, such as poly (n-butyl acrylate), poly (dodecyl acrylate), poly (2-ethylhexyl acrylate), poly (2-ethylethylbutyl acrylate), poly (n-heptyl acrylate), poly (n-hexyl acrylate), poly (iso-butyl acrylate) ), poly (iso-decyl acrylate), poly (isopropyl acrylate), poly (3-methylbutyl acrylate), poly (2-methylpentyl acrylate), poly (nonyl acrylate) poly (heptyl acrylate), poly (2-ethylhexyl methacrylate), poly (tridecyl methacrylate), poly (n-pentyl methacrylate, poly (octyl methacrylate), poly (octadecyl methacrylate), poly (dodecyl methacrylate), poly (n-methacrylate) pentyl.) Other examples include end-capped polymers with methacryloyl, acryloyl, or 2-, 3-, or 4-vinylbenzyl, poly (is obutylene), poly (isoprene), hydrogenated poly (1, 2-butadiene), hydrogenated poly (1,4-butadiene), hydrogenated poly (isoprene), poly (1,2-butadiene), poly (1-butene), poly (5-methyl-1-hexene), poly (6-methyl-1-heptene), poly (4, 4-dimethyl-1-pentene), and poly (isobutyl) vinyl ether.

P666 Examples of these macromonomers include B-type "copolymer" macromonomers containing two or more units of randomly repeating monomer. Non-limiting examples of this type of "copolymer" of macromonomers include poly [4-t-butyl-vinyl-benzene-co-2-ethylhexyl-acrylate], end-capped with acryloyl, poly [2-ethylhexyl-acrylate- co-octyl acrylamide), poly [2-ethyl-vinyl-benzene-co-octylmethacrylate)], and the like. The end-capped hydrophobic macromonomers can be synthesized using standard synthetic methods comprising polymerization, usually under cationic or anionic initiation conditions, the appropriate monomer unit (eg, isobutylene, 1,3-butadiene, isoprene etc.) . A wide variety of initiation systems can be used, non-limiting examples of which include cationic initiators, such as cumyl acetate / TiCl 4, cumyl methyl ether / BCl; and anionic initiators such as n-butyllithium, sec-butyl lithium, t-butyl lithium, lithium ammonium hydride, sodium hydride, and the like. Non-limiting examples of these initiation systems are provided in Designed Polymers by Carbocationic Macromolecular Enqineerinq, Theory and Practice, J.P. Kennedy and B. Ivan, Chapter II, p. 5, Hanser Publisher, N.Y. (1991), and in Anionic Polymerization: Principies and Practice, Maurice P666 Morton, Chapter 2, p. 13, Academic Press, N.Y. (1983). In the case of cationic polymerization, once the desired degree of polymerization is completed, the polymer is isolated and optionally derivatized for the end capped polymer with vinylbenzyl, methacryloyl or acryloyl. A non-limiting example of n macromonomer synthesized by cationic polymerization is poly (isobutylene). In the case of anionic polymerization, once the desired degree of polymerization is achieved, an appropriate end-cap reagent is typically used to terminate the polymerization and cap off at the end to the macromonomer. Non-limiting examples of these endcapping reagents include 2-vinylbenzyl chloride, 3-vinylbenzyl chloride, 4-vinylbenzyl chloride, and the like. Alternatively, the end cap can be achieved by reacting the polymer reaction mixture with an equivalent of ethylene oxide to terminate the polymer with a -CH2CH2-0- portion, followed by the reaction with a cap reagent in the end such as an unsaturated acid halide.

Preferred Polymers of the Present Invention Particularly preferred polymers for use in the present invention include the following ( P666 per hundred by weight below refer to the amount of reactants added in the polymerization reaction, not necessarily the amount in the finished polymer): (i) Poly [poly (tertiary butyl acrylate) -graft-poly (isobutylene) macromonomer ] (80/20 p / p); weighted average molecular weight of the total graft copolymer of 100,000; weight average molecular weight of the macromonomer of 5000. (ii) Poly [poly (4-tert-butylstyrene) -injertopoly (isobutylene) macromonomer] (70/30 w / w); weighted average molecular weight of the total graft copolymer of 150,000; Weighted average molecular weight of the macromonomer of 3000. (iii) Poly [(4-tert-butylstyrene) -graft-poly (2-ethylhexyl macromonomer] (80/20 w / w), weighted average molecular weight of the total graft copolymer of 150,000, weighted average molecular weight of the macromonomer of 10,000 (iv) Poly [(tert-butylacrylate-co-styrene) -graft-poly (isobutylene)] (60/20/20 w / w / w), weighted average molecular weight of the total graft copolymer of 100,000, weight average molecular weight of the macromonomer of 5000.

Synthesis of Graft Copolymers Graft copolymers can be made by P666 the copolymerization of free radicals of the monomers A with the macromonomers B. It is not proposed to necessarily exclude from this invention any of the polymers made by means of another polymerization of free radicals, as long as the product has the desired physical properties. The copolymers herein are formed from randomly repeating monomer A units, and macromonomer B units. The general principles of free radical polymerization methods are well understood. See for example, Odian, "Principies of Polimerization", 2a. edition, John Wiley & SONS, 1981, PP. 179-318. The desired monomers and macromonomers are all placed in a vector, together with a sufficient amount of a mutual solvent so that when the reaction is finished the viscosity of the reaction is reasonable. Typical monomer and macromonomer fillers are from about 10% to about 50%, on a weight basis. Unwanted terminators, especially oxygen, can be removed as needed. This is done by evacuation or purging with an inert gas, such as argon or nitrogen. The initiator is introduced and the reaction is brought to the temperature necessary for the initiation to occur, assuming that the thermal initiators are used. Non-limiting examples of suitable primers P666 include those selected from the group consisting of azo initiators, peroxide initiators, redox initiators, and photochemical initiators. The polymerization is allowed to proceed as long as it is necessary for a high level of conversion to be achieved, typically from a few hours to a few days. Then, the solvent is removed, usually by evaporation or by precipitating the copolymer by the addition of a non-solvent. The copolymer can be further purified, as necessary using a variety of techniques including filtration, extrusion, membrane separation, gel permeation chromatography, and the like. There are numerous variations in these procedures that are entirely at the discretion of the synthetic chemical (eg choice of degassing and gas method, choice of type of initiator, degree of conversion, reaction charge, etc.). The choice of initiator and solvent are often terminated by the requirements of the particular monomers and the macromonomer used, because different monomers and macromonomers have different solubilities and different reactivities to a specific initiator. The copolymers of the present invention can also be synthesized by first preparing an intermediate, reactive polymer from the monomer units P666 A, followed by additional polymerization of the intermediate copolymer, resulting, with suitable monomers to form the hydrophobic side chains. The analysis of the reaction product of the graft copolymer and the extracted materials and the purified graft copolymer can be carried out by the techniques conventional in the art. These include, for example, nuclear magnetic resonance (NMR), infrared molecular spectroscopy, gel permeation chromatography / size extrusion, membrane osmometry, and atomic absorption and emission spectroscopy.

Solvent for the Graft Copolymer The compositions of the present invention comprise a hydrophobic, volatile liquid which is a solvent for the graft copolymers of the present invention. Suitable solvents were selected from the branched chain, volatile, hydrophobic, silicone hydrocarbons and combinations thereof. In general, the present compositions will comprise from about 0.1% to about 75%, preferably from about 0.2% to about 25%, and more preferably from about 0.5% to about 15% of the solvent. The weight ratio of P666 linear copolymer solvent is generally from about 1: 100 to about 5: 1, preferably from about 1:10 to about 1: 1, more preferably from about 1: 8 to about 2: 3. The volatile, hydrophobic solvent exhibits a significant vapor portion at ambient conditions (eg, 1 atmosphere, 25 aC), as understood by those skilled in the art. As used herein, the term "volatile" refers to solvents having a boiling point at an atmosphere of 260 aC or less, preferably 250 aC or less, more preferably 230 aC or less, in the most preferred 225 aC or less. In addition, the boiling point of the volatile, hydrophobic solvent will generally be at least about 50%, preferably at least about 100%. The term "non-volatile" on the other hand, should refer to solvents that have a boiling point to an atmosphere of more than 260SC. The solvent should also be acceptable for topical application to hair and skin (ie, no undue irritation, sensitization or other reactions are induced by the solvent). The graft copolymer is soluble in the volatile, hydrophobic solvent in the present compositions. In general, the copolymer must be soluble P666 at 25 aC at a concentration of 0.1% by weight the solvent, preferably at 1%, more preferably at 5%, more preferably at 15%. However, the hydrophobic, volatile solvent is soluble in aqueous carriers of the composition. This is determined in the absence of the copolymer, or other emulsifying agents and can be easily verified by observing whether the solvent and the aqueous carrier form separate phases after being mixed together at room temperature (as seen without increase). The preferred, preferred, hydrophobic branched chain hydrocarbons useful as the solvent herein contain from about 10 to about 16, more preferably from about 12 to about 16, more preferably from about 12 to about 14 carbon atoms. carbon. (For example, branched chain hydrocarbons, preferred, include branched chain hydrocarbons of 10 to 16 carbon atoms, branched chain hydrocarbons of 11 to 14 carbon atoms, and branched chain hydrocarbons of 12 carbon atoms). Natural hydrocarbons were preferred, although it is not proposed to exclude unsaturated hydrocarbons. Examples of these preferred branched chain hydrocarbons include isoparaffins of the P666 previous chain sizes. Isoparaffins are commercially available from Exxon Chemical Co .; examples include Isopar ™ H and K (isoparaffins of 11 to 12 carbon atoms), and Isopar "* (isoparaffins of 11 to 13 carbon atoms.) Other suitable branched chain hydrocarbons are isodecane and isohexadecane. Isododecane and are commercially available from Preperse, Inc. (South Plainfield, NJ, USA) as Permethyl ™ 99 A. Preferred silicones useful as the volatile, hydrophobic solvent herein include volatile, hydrophobic siloxanes (such as phenyl-pentamyl). disiloxane, phenylethyl-pentamethyl-disiloxane, hexamethyl-disiloxane, methoxypropyl-heptamethyl-cyclotetrasiloxane, chloropropyl-pentamethyl-disiloxane, hydroxypropyl-pentamethyl-disiloxane, cyclomethicones, including octamethyl-cyclotetrasiloxane and decamethyl-cyclopentasiloxane), and mixtures thereof. Preferred are cyclomethicones, more preferably octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane.

Hair Care Compositions The compositions of the present invention also comprise a suitable hair care matrix or carrier for distributing the graft copolymer and the hair P666 volatile, hydrophobic solvent, to the hair. Any suitable carrier can be used to distribute the hydrocarbon copolymer / solvent to the hair. The carrier may comprise a volatile liquid that is water or is otherwise soluble in water, or a mixture thereof and to which the volatile solvent of the copolymer is not soluble. In general, the compositions will comprise from about 50% to about 92.3%, preferably from about 70% to about 29%, more preferably from about 85% to about 98%, of the hair care matrix or matrix. The carrier liquid herein can include water or other hydrophilic fluids, and combinations thereof. Carrier fluids suitable for use in the present invention, in addition to water, include lower alcohols (alcohols of 1 to 4 carbon atoms, preferably alcohols of 2 to 4 carbon atoms such as ethanol and isopropanol) and mixtures of lower alcohols. Preferred solvents include water, ethanol and mixtures thereof. Especially preferred is water. Preferred compositions are in the form of a discontinuous phase of dispersed droplets, or particles of the copolymers and the volatile, hydrophobic solvent, P666 distributed throughout the length of the carrier. The carrier also comprises a variety of components, such as other active ingredients, rheology modifiers such as thickeners, gelation agents, etc. The compositions of the present invention may be in the form of liquids, lotions, creams, gels, etc. The carrier may include gel vehicle materials or other rheology modifiers. These are particularly contemplated for use in products such as rinses, shampoos, foams and creams and hair lotions. Gel vehicles can comprise two essential components: a liquid carrier material and a surfactant vehicle material. Gel agents are generally described in the following documents: "The Self-Bodying Action of the Mixed Emulsifier Sodium Dodecyl Sulfate / Cetyl Alcohol", 28 J. de 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. de Colloid and Interface Science 689-608 (1971); and Barry, et al. "Rheology of Systems Containing Cetomacrogol 1000 - Cetostearyl Alcohol, I. Self Bodying Action", 38 J. de Colloid and Interface Science 616-625 (1972).

P666 The carrier may incorporate one or more lipid carrier materials that are essentially insoluble in water, and that contain hydrophobic and hydrophilic moieties. The lipid carrier materials include naturally occurring or synthetically derived acids, acid derivatives, alcohols, esters, ethers, ketones and amides. With carbon chains from about 12 to about 22, preferably from about 16 to about 18 carbon atoms in length. Fatty esters and fatty alcohols are preferred, fatty alcohols are particularly preferred. Preferred esters for use herein include cetyl palmitate and glyceryl monostearate. Cetyl alcohol and stearyl alcohol are the preferred alcohols. A particularly preferred lipid carrier material is comprised in the mixture of cetyl alcohol and sterile alcohol containing from about 55% to about 65% (by weight of the mixture) of the cetyl alcohol. The lipid carrier materials among those useful herein are described in Bailey's Industrial Oil and Fat Products, (3rd edition, D. Swern, ed., 1979). The fatty alcohols included among those useful herein are described in the following documents: P666 North American Patent No. 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent No. 4,165,369, Watanabe et al., Issued August 21, 979; U.S. Patent No. 4,269,824, Villamarin et al., Issued May 26, 1981, British Specification No. 1,532,585, published November 15, 1978; and Fuku Shi a et al., "The Effect of Cetostearyl Alcohol in Cosmetic Emulsions", 98 Cosmetics & toiletries 89-112 (1983). Fatty esters included among those useful herein are described in U.S. Patent No. 3,341,465, Kaufman, et al. Issued September 12, 1976. If compositions are included in the present invention, the lipid carrier material is typically present. from about 0.1% to about 10 5 of the composition; the cationic surfactant vehicle material is present from about 0.05% to about 5.0% of the composition. The cationic surfactant materials are suitable for the use of gel vehicles, and include, but are not limited to, those described in detail below. The compositions herein may also contain a lipid vehicle without the inclusion of a cationic surfactant. The use of non-ionic cellulose ethers and P666 water-soluble gums for thickener compositions is also contemplated. See, for example, U.S. Patent No. 4,557,928, Glover, issued December 10, 1985, which teaches a hair conditioner comprising a suspension system consisting of a glucan gum, guar gum, and hydroxyethylcellulose; and U.S. Patent No. 4,581,230, Grollier et al., issued April 8, 1986, which teach cosmetic compositions for treating hair comprising as thickening agents, hydroxymethylcellulose, or water soluble vegetable thickeners, such as guar gum. Water-soluble, non-ionic cellulose ethers are preferred polymers that can be employed in hair care compositions. The cellulose esters are of relatively low molecular weight, but are capable of producing highly viscous aqueous solutions in practical concentrations. These materials are nonionic cellulose esters having a sufficient degree of nonionic substitution selected from the group consisting of methyl, hydroxyl, and hydroxypropyl to make them soluble in water and which are further substituted with a hydrocarbon radical having from about 10 to about 24 carbon atoms in an amount between P666 about 0.2 weight percent and the amount returning to the cellulose ether less than 1%, by weight, soluble in water. The cellulose ether to be modified is preferably one of low to medium molecular weight; that is, less than about 800,000 and preferably between about 0,000 and 700,000 (about 75 to 2500 D.P.). Commercially available nonionic cellulose ethers widely used include methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and ethyl hydroxyethyl cellulose. Other carrier ingredients for use in the compositions of the present invention, especially for hair rinses, included in combinations of one or more polymeric, water-soluble, non-ionic materials, which have been hydrophobically modified (hereinafter referred to in a manner alternative as "water-soluble polymer, non-ionic, hydrophobically modified"), with one or more surfactants, such as quaternary ammonium compounds (such as ditallowdimethylammonium chloride) these vehicles are described in detail in the following patents: US Patent No. 5,106,6909, issued April 21, 1992 to Bolich et al., US Patent No. 5,100,658, issued March 31, 1992 to Bolich et al., P666 North American Patent No. 5,104,646, issued April 14, 1992 to Bolich et al., And US Patent No. 5,100,657, issued March 31, 1992 to Ansher-Jackson et al. These systems provide a gel-like rheology without necessarily being gels in the technical sense. When these systems are used to express the present compositions, preferably from about 0.3% to about 5.0%, more preferably from about 0.4% to about 3.0% of the water-soluble, non-ionic, hydrophobically modified polymer is used, with from about 0.3% to about 5.0%, preferably from about 0.4% to about 3.0%, a thickener, polymeric, water soluble material, as described herein. By "water-soluble, non-ionic, hydrophobically modified polymer" is meant a water-soluble, non-ionic polymer that has been modified by substitution with a sufficient amount of hydrophobic groups to render the polymer less soluble in water. By "water soluble" it is meant that the polymer or salt thereof, which constitutes the polymer structure of the thickener, must be sufficiently soluble such that it forms a substantially clear solution when dissolved in P666 water at a level of 1%, by weight of the solution, at 25 SC. The structure of the water-soluble, non-ionic, hydrophobically modified polymer can be essentially any water-soluble polymer. Examples of the water-soluble polymers useful for forming the water-soluble, non-ionic, hydrophobically modified polymer include hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol, polyvinyl pyrrolidone, dextrans, for example. , Grade 2P crude purified dextran, available from D &O Chemical, plant exudates such as acacia ghatti, and tragacanth, seaweed extracts, such as sodium alginate, propylene glycol alginate, carrageenan sodium, cationic polymers such as JR. Ucare polymer (a hydroxyethylcellulose, cationic, modified, available from Union Carbide), natural polysaccharide materials, such as guar gum, acacia seed gum, and santane gum. Water-soluble, non-ionic cellulose ethers are preferred to be used as the polymer substrate of these hydrophobically modified polymers. Thus, for example, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxy ethyl cellulose, and methyl hydroxyethyl cellulose can be modified. The amount of P666 nonionic substituent such as methyl, hydroxyethyl or hydroxypropyl teaches that it is not critical as long as there is a sufficient amount to ensure that the ether is soluble in water. Hydrophobic groups which the water-soluble, non-ionic polymer can modify can be alkyl of 8 to 22 carbon atoms, aryl-alkyl, alkylaryl groups, and mixtures thereof. One or more hydrophobic groups can be attached to the cellulose ether substrate via an ether, ester or urethane linkage. The ether link is preferred. The degree of hydrophobic substitution in the polymer structure should be 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 from about 10: 1 to about 1000: 1. A commercially available, water-soluble, non-ionic, hydrophobically modified polymeric material that meets the above requirements is NATROSOL PLUS Grade 430 hydrophobically modified hydroxyethylcellulose available from Aqualon Company, Wilmington, Delaware. This material has an alkyl substitution of 16 carbon atoms from about 0.5% to about 0.9% by weight. The molar substitution of hydroxyethyl for this P666 material is from about 2.8 to about 3.2. The average molecular weight for water soluble cellulose, before modification is about 300,000. Other material of this type is sold under the trademark NATROSOL PLUS CS Grade D-67, by Aqualon Company, Wilmington, Delaware. This material has an alkyl substitution of 16 carbon atoms from about 0.50% to about 0.95%. The molar hydroxyethyl substitution for this material is from about 2.3 to about 3.3. The average molecular weight for water soluble cellulose before modification is about 700,000. The water-soluble, non-ionic, hydrophobically modified polymer can be used in combination with water-soluble or water-insoluble surfactants. In this regard, "water soluble surfactant" means surfactant materials that form isotropic, substantially clear solutions, when dissolved in water at 0.2 wt% at 25 aC. The water soluble surfactant preferably has a molecular weight of less than about 20,000. Essentially any water-soluble surfactant material that meets these requirements P666 will work in the present invention. However, the following materials have been found to be particularly preferred: cetyl betaine, ammonium lauryl sulfate, ammonium laureth sulfate, cetyltrimethylammonium chloride, and mixtures thereof. When these systems are used to express the present compositions, from about 0.1% to about 10.0%, preferably from about 0.2% to about 5.0%, of the water-soluble, non-ionic, hydrophobically modified polymer, it is generally used with about 0.02% to about 0.30%, 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 the water-soluble surfactant is maintained below because high levels of the water-soluble surfactant interfere with the hydrophobically modified hydroxyethyl cellulose thickener and produce compositions with much less desirable rheologies. By "water-insoluble surfactant" for use in these systems is meant surfactant materials which do not form substantially clear isotropic solutions when dissolved in water of more than 0.2% by weight at 25 aC. The insoluble surfactant P666 in water preferably has a molecular weight of less than about 20,000. Essentially any water-insoluble surfactant material that meets these requirements will work in the present invention, however, cationic, water-insoluble surfactants are preferred. The cationic surfactants are described below. The following non-exclusive materials are suitable: stearamide-diethanolamine (stearamide DEA), cocoamide-methanolamine (cocoamide MEA), dimethyl-stearamide oxide, glyceryl monooleate, sucrose stearate, PEG-2 stearamine, polyethylene glycol ethers of fatty alcohols, such as Cetheth-2 of the formula CH, - (CH 2) u-CH 2 (OCH 2 CH 2) 8-OH, wherein n has an average value of 2 (commercially available under the Brij brand 56 from ICI Americas), glyceol citrate stearate, tallow dimethyl ammonium dihydrogen chloride, polyoxyethylene, polyoxypropylene block copolymers, such as poloxamer 181, of the formula: where on average x = 3, y = 30 and z = 3 (commercially available from BASF Wyandotte under the trademark P666 Pluronic L-61), hydrogenated tallow-dimethyl-betaine, and hydrogenated DEA tallow-amide. When these systems are used to express the present compositions, generally from about 0.1% to about 10.0%, preferably from about 0.2% to about 5.0% of the nonionic polymer is used., hydrophobically modified, with from about 0.02% to about 10.0%, more preferably from about 0.05%, to about 3.0%, more preferably from about 0.05% to about 2.0%, of the water-insoluble surfactant. The cationic surfactants useful in the compositions of the present invention, including the gel vehicle systems as well as the hydrophobically modified nonionic polymer systems, include those containing hydrophilic portions of quaternary ammonium or amino, which are positively charged when dissolve in the aqueous composition of the present invention. Cationic surfactants among those useful herein are described in more detail below. It is also contemplated to use a dispersion or suspension agent to express the compositions and / or to disperse the phase of the hydrocarbon solvent.

P666 branched, copolymer in the carrier. Suitable suspending agents are long chain acyl derivatives, long chain amine oxides, and mixtures thereof, wherein these suspending or dispersing agents are present in the shampoo compositions in crystalline form. A variety of these suspension agents are described in US Patent No. 4,741,855, to Grote et al., Issued May 3, 1988. Especially preferred is ethylene glycol distearate. Also included among the long chain acyl derivatives useful as suspending agents are N, N-di (hydrogenated) C8_C22 (preferably C12-C22, more preferably C16Clß) to ido-benzoic acid, or the soluble salt (eg example, salts of K, Na) thereof, particularly NN-di (hydrogenated) tallow-amido-benzoic acid commercially sold by Stepan Company (Northfiled, Illinois, USA).

Surfactants Surfactants are optional ingredients in the compositions of the invention, particularly shampoo and conditioner compositions. When present, the surfactant typically comprises from about 0.05% to about 50% of the composition. For a shampoo, the P666 level is preferably from about 10% to about 30%, more preferably from about 12% to about 25%, of the composition. For conditioners, the preferred level of the surfactant is from about 0.2% to about 3%. Surfactants useful in the compositions of the present invention include surfactants, anionic, nonionic, cationic, and antireeric agents. The synthetic anionic detergents useful herein, particularly for shampoo compositions, include alkyl sulfates and alkyl ether sulphates. These materials typically have the respective formulas ROSO.M and RO (C2H40) xS03M, wherein R is alkyl or alkenyl from about 10 to about 20 carbon atoms, x is from 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 organic, sulfuric acid reaction products of the general formula: l ^ - SO, - M wherein R. is selected from the group consisting of aliphatic, saturated, chain hydrocarbon radical P666 straight or branched, having from about 8 to about 24, preferably from about 12 to about 18, carbon atoms; and M is a cation. Important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including 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 sulfonating agent. For example, S03, H2S04, oleum, obtained according to known sulfonating methods, including bleaching and hydrolysis. Preferred are n-paraffins of 12 to 18 carbon atoms, sulfonated with ammonium and alkali metal. Further examples of the synthetic, anionic surfactants, which is within the terms of the present invention are the reaction products of the esterified fatty acids, isethionic acid and neutralized with double sodium hydroxide, for example, the fatty acids are derive from coconut acid; sodium or potassium salts of the methyl-tauride fatty acid amides in which the fatty acids, for example, are derived from coconut oil. Other synthetic, anionic surfactants of this type are exposed P666 variety, in U.S. Patent 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 surface active agents such as sodium N-octadecylsulfosuccinamate.; N- (1,2-dicarboxylethyl) -N-octadecylsulfosuccinamate tetrasodium; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; diethyl esters of sodium sulfosuccinic acid. Other suitable surfactants, usable herein, are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds that can be produced by the sulfonation of α-olefins by means of non-complex sulfur trioxide, followed by neutralization of the acid reaction mixture under conditions such that any sultone that has been formed in the reaction is hydrolysed to give the corresponding hydroxy-alkane sulphonates. The α-olefins from which the olefin sulfonates are derived are mono-olefins having from about 2 to about 24 carbon atoms, preferably from about 14 to about 16 carbon atoms. Other class P666 of organic, anionic surfactants are the β-alkyloxy alkane sulfonates. These compounds have the following formula: where R x 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 water-soluble cation as described later herein. Many additional anionic, synthetic, non-soap surfactants are described in McCutcheon's Detergents and Emulsifiers, 1984 Annual, published by Allured Publishing Corporation. Also, U.S. Patent No. 3,929,678, Laughlin et al., Issued December 30, 1975, discloses many other types of anionic surfactants as well as other types. Nonionic agents, which are preferably used in combination with an anionic, amphoteric or zwitterionic surfactant, can be broadly defined as compounds produced by condensation P666 of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. Examples of the preferred 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, in either the straight or branched chain configuration, with ethylene oxide, for example, a condensate of ethylene oxide of coconut alcohol , having from about 10 to about 30 moles of ethylene oxide per mole of coconut alcohol, the fraction of coconut alcohol having from about 10 to about 14 carbon atoms. 3. The long chain tertiary amine oxides such as those corresponding to the following general formula: R.R2R3N > Or wherein Rx contains an alkyl, alkenyl or monohydroxy-alkyl radical, from about 8 to about 18 carbon atoms, from 0 to P666 about 10 portions of ethylene oxide, and from about 0 to about 1 portion of glyceryl, and R2 and R3 contain from about 1 to about 3 carbon atoms and from 0 to about a hydroxy group, for example, methyl, ethyl radicals , propyl, hydroxyethyl, or hydroxypropyl (the arrow in the formula is a conventional representation of a semipolar junction). 4. Long chain tertiary phosphine oxides corresponding to the following general formula: RR'R '' P > Or wherein R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in the length of a chain, from 0 to about 10 portions of ethylene oxide from 0 to about 1 portion of glyceryl, and R 'and R "are each alkyl or monohydroxyalkyl groups containing from about 2 to about 3 carbon atoms. The arrow in the formula is a conventional representation of a semipolar union. 5. Long chain dialkyl sulfides containing a short chain alkyl or hydroxyalkyl radical from about 1 to about 3 P666 carbon atoms (usually methyl) and a long hydrophobe including alkyl, alkenyl, hydroxyalkyl, or keto-alkyl radicals containing from about 8 to about 20 carbon atoms, from 0 to about 10 portions of ethylene oxide and from 0 up to about 1% glyceryl. Examples include: octadecyl methyl sulfoxide; 2-cetotridecyl-methyl sulfoxide, 3, 6, 9-trixaoctadecyl-2-hydroxyethyl sulfoxide, dodecyl methyl sulfoxide, dodecyl methyl sulfoxide, oyl-e-hydroxyuipropyl sulfoxide, tetra-decyl-methyl sulfoxide, 3-methoxytridecyl-methyl sulfoxide, 3-hydroxytridecyl-methyl sulfoxide, 3-hydroxy-5-dodecoxybutyl-methyl sulfoxide. The cationic agents useful in the compositions of the present invention, particularly, the conditioner compositions, include those hydrophilic portions of quaternary ammonium or amino, which are positively charged when dissolved in the aqueous composition of the present invention. Cationic surfactants among those useful herein are described in the following documents: M.C.

Publishing Co., MeCuteheon's, Deterqents & Emulsifiers (North American edition 1979); Schwartz and collaborators, Surface Active Agents, Their Chemistrv and Technology, New YORK: Interscience Publishers, 1949; Patent P666 North American No. 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent No. 3,929,678, to Laughlin, et al., Issued December 30, 1975; U.S. Patent No. 3,959,461, to Bailey, et al., Issued May 25, 12976; and U.S. Patent No. 4,387,090, to Bolich, JR. , issued June 7, 1983. If the compositions of the present invention are included, the cationic surfactant is present from about 0.05% to about 5%. Among the cationic quaternary ammonium surfactant materials useful herein are those of the general formula: wherein R ^ ^ are independently an aliphatic group of from about 1 to about 20 carbon atoms, or an aromatic, alkoxy, polyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group, having from about 2 to about 22 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate, and alkyl sulfate radicals. The aliphatic groups may contain, in addition to the carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. Longer chain aliphatic groups, for example, those of about 12 carbon atoms, or higher, may be saturated and unsaturated. Other quaternary ammonium salts useful herein are the diquaternary ammonium salts, such as tallow-propane-diammonium dichloride. The quaternary ammonium salts include the dialkyldimethyl-ammonium chlorides, wherein the alkyl groups have from about 12 to about 20 carbon atoms and are derived from long chain fatty acids, such as hydrogenated fatty acid-tallow acid (and the acids sebum-fatty produce quaternary compounds where Rx or R2 have predominantly 26 to 18 carbon atoms). Examples of quaternary ammonium salts useful in the present invention include ditallowdimethyl ammonium chloride, ditallowdimethylammonium methylsulfate, dihexadecyl dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, dienoxyol dimethyl ammonium chloride, didocosyl dimethyl ammonium chloride, di (tallowhydrogenated) dimethyl ammonium acetate, dihexadecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium acetate, diphosphonyl ammonium phosphate, design nitrate P666 dimethyl-ammonium, di (co-conjokatural) -dimethylammonium chloride, and stearyl-dimethyl-benzyl-ammonium chloride. Ditallow dimethyl ammonium chloride, dicetyl dimethyl ammonium chloride, stearyl dimethylbenzyl ammonium chloride, and cetyl trimethyl ammonium chloride are the quaternary ammonium salts useful herein. The di- (sebosaturated or unsaturated) -dimethyl ammonium chloride is a quaternary ammonium salt, especially preferred. The salts of primary, secondary and tertiary fatty amines are also suitable surfactant, cationic materials. The alkyl groups of the amines preferably have from about 2 to about 22 carbon atoms and can be substituted or unsubstituted. These amines, useful herein, include stearamide-propyl-dimethylamine, diethyl-amino-ethyl-stearamide, dimethy1-stearamine, dimethylaminoamine, soyamine, myristyl-amine, tridecyl-a, ethyl-stearylamine, N- sebopropane-diamine, ethoxylated stearylamine (5 moles of EO), dihydroxy-ethyl-stearyl amine, 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 formate, N-sebopropane-diamine dichloride, and stearamidopropyl-dimethylamine citrate. Amine, cationic surfactants, and included among those useful in the present invention are described in US Patent No. 4,275,055, Nachtigal et al., Issued June 23, 1981. Zwitterionic surfactants, useful in shampoos as well as conditioners, are exemplified by those which can be broadly described as derivatives of ammonium, phosphonium and aliphatic quaternary sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains a water, anionic, solubilization group, for example, carboxy, sulfonate, sulfate, phosphate or phosphonate. A general formula for these compounds is: wherein R2 contains an alkyl, alkenyl, or hydroxy-alkyl radical, from about 8 to about 18 carbon atoms, from 0 to about 10 portions of ethylene oxide, and from 0 to about 1 glyceryl portion; And it is selected from the group consisting of atoms of P666 nitrogen, phosphorus and sulfur; R3 is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R 4 is an alkylene or hydroxyalkylene of about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups. Other zwitterionics such as betaines are also useful in the present invention. Examples of betaines useful herein include the higher alkyl betaines, such as coconut dimethyl-carboxymethyl-betaine, lauryl-dimethyl-carboxymethyl-betaine, lauryl-dimethyl-alpha-carboxyethyl-betaine, cetyl-dimethyl-carboxymethyl-betaine , lauryl-bis- (w-hydroxyethyl) -carboxymethyl-betaine, stearyl-bis- (2-hydroxypropyl) -carboxymethyl-betaine, oleyl-dimethyl-gamma-carboxypropyl-betaine, and lauryl-bis (2-hydroxypropyl) alpha- carboxyethyl betaine. The sulfobetaines can be presented by coconut dimethyl-sulpropyl betaine, stearyl-dimethyl-sulfopropyl-betaine, lauryl-dimethyl-1-sulfoethyl-betaine, lauryl-bis- (2-hydroxyethyl) -sulfopropyl-betaine and the like; amidobetaines and amidosulfobetaines, wherein the radical RCONH (CH2) 3 binds to the hydrogen atom of betaine are also useful in this invention.

P666 Examples of amphoteric surfactants that can be used in the compositions of the present invention are those which are broadly described as derivatives of secondary and tertiary aliphatic amines, in which the aliphatic radical can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water solubilizing group, for example, carboxy, sulfate, phosphate, or phosphonate. Examples of the compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylamino-dparopane sulfonate, N-alkyl taurines, such as one prepared by reacting dodecylamine with sodium isethionate in accordance with teachings of U.S. Patent No. 2,658,072, N-higher alkyl aspartic acids, such as those produced in accordance with the teachings of U.S. Patent No. 2,658,072, and the products sold under the trademark "Miranol", and described in U.S. Patent No. 2, 528, 378.

Silicone Hair Conditioning Agent An optional component of the present invention is a conditioning agent, of silicone, not Volatile P666, which is not soluble in the aqueous or water-soluble phase, of compositions wherein the carrier is water-based or other base in water-soluble solvents. The silicone hair conditioning agent for use herein will preferably have an average viscosity of from about 1,000 to about 20,000,000 centistokes to 25BC, more preferably from about 10,000 to about 10,000,000, more preferably from about 100,000 to about 5,000,000 . The viscosity of the silicones herein can generally be measured by means of a glass capillary viscometer as set forth in the CTM0004 test method of Dow Corning Crporate Test Method, July 20, 1970. The hair conditioning agent silicone will typically be used in the shampoo compositions herein at levels from about 0.05% to about 10% by weight of the composition, preferably from about 0.01% to about 10%, more preferably from about 0.5% to about about 8%, more preferably from about 0.5% to about 5%. Suitable non-volatile silicone fluids include polyalkyl siloxanes, polyarylsiloxanes, P666 polyalkylarylsiloxanes, polyether-siloxane copolymers and mixtures thereof. Other silicone fluids, non-volatile, insoluble, which have hair conditioning properties, can also be used. The term "non-volatile" as used herein may mean that the silicone material exhibits a very low or no significant vapor pressure at ambient conditions, as understood by those skilled in the art. The term "silicone fluid" should mean fluid silicone materials that have a viscosity of less than 1,000,000 centistokes at 25aC. 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 100,000. The silicone fluids herein also include polyalkyl or polyarylsiloxanes with the following structure: wherein R is alkyl or aryl, and x is an integer from about 1 to about 8,000, preferably from about 5 to about P666 about 8,000"A" represents groups blocking the ends of the silicone chains. The substituted alkyl or aryl groups on the siloxane chain (R) or on the ends of the siloxane chains (A) can have any structure while the remaining silicones remain fluid at room temperature, are hydrophobic, are not toxic irritants or otherwise dangerous when applied to the hair, they are compatible with the other components of the composition, are chemically stable under normal use and storage conditions and are capable of being deposited in and conditioning the hair. Suitable groups A include methyl, methoxy, ethoxy, propoxy, and aryloxy, the two R groups of the silicone atom may represent the same or different groups. Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Preferred silicones are polydimethylsiloxane, polydiethylsiloxane, and polymethylphenylsiloxane. Polydimethylsiloxane is especially preferred. The non-volatile polyalkylsiloxane fluids that can be used include, for example, polydimethylsiloxane. These siloxaà ± os are available, for example, from General Electric in their Viscasil series. " P666 and SF 96 and from Dow Corning in their Dow Corning 200 series. The polyalkylaryl siloxane fluids that can be used also include, for example, polymethylphenylsiloxane. These siloxanes are available, for example, from the General Electric Company as the SF 1075 methyl phenyl fluid or from Dow Corning as the Cosmetic Grade Fluid 556. The polyether siloxane copolymers that may be used include, for example, a modified polydimethylsiloxane. with polypropylene oxide (e.g., Dow Corning DC-1248) although oxyethylene or mixtures of oxyethylene and propylene oxide can also be used. The level of ethylene oxide and propylene oxide should be sufficiently low to prevent solubility in water and the composition herein. Another silicone material that can be especially useful in silicone conditioning agents is insoluble silicone rubber. The term "silicone gum" as used herein means polyorganosiloxane materials having a viscosity at 25 aC of more than or equal to 1,000,000 centistokes. Silicone gums are described from the back and others including US Pat. No. 4,152,416, Spitzer et al., Issued May 1, 1979 and Noli, Walter, Ciemistry and Technology of Silicones, New York; Academic P666 PRESS 1968. Silicon gums are also described in General Electric Silicone Rubber Product Data Sheets SE 30, SE 33, SE 54 and SE 76. "Silicone gums" will typically have a mass molecular weight in excess of about 200,000, generally between about 200,000 and approximately 1,000,000. Specific examples include polydimethylsiloxane copolymer, (polydimethylsiloxane) (methylvinylsiloxane), copolymer of poly (dimethylsiloxane) (diphenylsiloxane) ((methylvinylsiloxane) and mixtures thereof.

Hair Conditioning Agents of the Cationic Polymer The compositions of the present invention may also comprise a water-soluble, cationic, organic polymer conditioning agent for hair. The cationic, polymeric conditioning agent herein will generally be present at levels from about 0.05% to about 5% more preferably from about 0.1% to about 4%, more preferably and from about 0.2% to about about 2% by weight, of the shampoo composition. By "water-soluble" cationic organic polymer, which means that it is a polymer that is sufficiently soluble in water to form a solution P666 substantially clear to the naked eye at a concentration of 0.1% in water (distilled or equivalent) at 25 aC. Preferably, the polymer will be sufficiently soluble to form a substantially clear solution at a concentration of 0.05%, more preferably at a 1.0% concentration. The cationic organic polymers useful in the hair conditioning agent herein are organic polymers which can provide conditioning benefits to hair and which are soluble in the shampoo composition. Any of the cationic polymers that can comprise these benefits can be used. As used herein, the term "polymer" should include materials either made by polymerization of one type of monomer or made by two or more types (ie, copolymers) of monomers). The cationic polymers herein will generally have a weight average molecular weight that is at least about 5,000, typically at least about 10,000, and is at least about 10,000,000. Preferably, the molecular weight is from about 100,000, to about 2,000,000. The cationic polymers will have cationic, nitrogen containing portions, such as quaternary ammonium or cationic amino moieties, or mixtures of the P666 same. The cationic charge density is preferably at least about 0.9 meq / gram, more preferably at least about 1.0 meq / gram, even more preferably at least about 1.0 meq / gram, even more preferably at least about 1.1 meq / gram. / gram, more preferably at least about 1.2 meq / gram. The cationic charge density is preferably not greater than about 4 meq / gram, more preferably not more than about 2.0 meq / gram, more preferably not more than about 2.0 meq / gram. The cationic charge density of the cationic polymer can be determined according to the Kjeldahl method. Those skilled in the art will recognize that the charge density of the amino-containing polymers may vary depending on the pH and the isoelectric point of the amino groups. The charge density should be within the limits prior to the proposed use pH, which will generally be from about pH 3 to about pH 9, more generally from about pH 4 to pH 8. Any of the anionic cations can be used. for cationic polymers while meeting the water solubility criteria. Suitable counterions include halides (e.g., Cl-, P66G Br-, I-, or F-, preferably Cl-, Br-, or I-) sulfate, and methylsulfate. You can also use others, since this list is not exclusive. The portion containing cationic nitrogen will generally be present as a substit in a fraction of the total monomer units of the cationic hair conditioning polymers. In this way, the cationic polymer may comprise copolymers, terpolymers, etc., of the monomer units substituted with cationic amine or quaternary ammonium., and other non-cationic units referred to herein as spacer monomer units. These polymers are known in the art, and a wide variety can be found in CTFA Cosmetic Ingredient Dictionary, 3a. edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1982). Suitable cationic polymers include, for example, copolymers of vinyl monomers having functionalities of quaternary ammonium or cationic amine with water-separating monomers, such as acrylamide, methacrylamide, alkyl- or dialkyl-acrylamides, alkyl- and dialkyl-methacrylamides, acrylate of alkyl, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone. The monomers substituted with alkyl and dialkyl have P666 preferably alkyl groups of 1 to 7 carbon atoms, more preferably alkyl groups of 1 to 3 carbon atoms. Other suitable spacing monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol and ethylene glycol. Cationic amines can be primary, secondary or tertiary, depending on the particular species and the pH of the shampoo. In general, 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 ammonium by a quaternization reaction. The amines subsequent to polymer formation can similarly be quaternized. For example, the tertiary amine functionalities can be quaternized by the reaction with a salt of the formula R'X, where R 'is a short chain alkyl, preferably an alkyl of 1 to 7 carbon atoms, in the form more preferably an alkyl of 1 to 3 carbon atoms, and X is an anion which forms a water-soluble salt with the quaternized ammonium. Suitable quaternary ammonium and ammonionic monomers include, for example, P666 vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, diallyl quaternary ammonium salts, and quaternary ammonium monomers of vinyl having nitrogen-containing, cationic, cyclic 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 alkyls of 1 to 3 carbon atoms, preferably alkyls of 1 to 2 carbon atoms. Suitable amine substituted vinyl monomers for use herein include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably hydrocarbyls of 1 to 7 carbon atoms, more preferably alkyls of 1 to 3 carbon atoms. The cationic polymers herein may comprise mixtures of monomer units derived from compatible spacer monomers and / or substituted monomers P666 with quaternary ammonium and / or amine. Suitable hair conditioning polymers, cationic, include, for example, polymers of l-vinyl-2-pyrrolidone and salt of 12-vinyl-3-methylimidazolium (for example, chloride salt) (referred to in the industry by cosmetic , Toiletry, and Fragrance Association, "CTFA" as poly-16-temper), such as those commercially available from BASF Wyandotte Corp. (Parsippany, NJ, USA); under the LUVIQUAT trademark (for example, LUVIQUAT FC 370); copolymers of l-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (referred to in the industry by CTFA as Polyquaternium-11), such as those commercially available from ISP Corporation (Wayne, NH, USA; polymers containing diallyl ammonium, quaternary ammonium, cationics, including, for example, homopolymer of dimethyldiallylammonium chloride and copolymers of acrylamide and dimethyldiallylammonium chlorides, preferred in the industry (CTFA) as Polyquaternium 6 and Polyquaternium 7, respectively, and mineral acid salts of homo-acrylic esters of homo - and co-polymers of unsaturated carboxylic acids having from 3 to 5 carbon atoms, as described in US Patent No. 4,009,256 Other cationic polymers that may be used include polysaccharide polymers, such as derivatives P666 cationic cellulose and cationic starch derivatives. The cationic polysaccharide polymer materials, suitable for use herein include those of the formula: wherein A is a residual group of anhydroglucose, such as an anhydroglucose residue of starch or cellulose, R is an alkylene-oxyalkylene, polyoxyalkylene or hydroxyalkylene group, or a combination thereof. R1, R2, and R3 are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl, or alkoxyaryl groups, each group containing from about 18 carbon atoms, and the total number of carbon atoms for each cationic portion (i.e., the sum of carbon atoms in R1, R2 and R3, which is preferably close to 20 or less, and X is an anionic counterion, As previously described, cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in its series Polymer JRR and LRR of P666 polymer, such as salts of hydroxyethyl cellulose reacted with epoxide substituted with trimethyl ammonium, referred to in the industry (CTFA) as Polyquaternium 10. Another type of cationic cellulose includes the quaternary ammonium salts, polymeric, of hydroxyethylcellulose reacted with epoxide substituted with lauryl dimethyl ammonium, referred to in the industry (CTFA) as Polyquaternium 24. These materials are available from Amerchol Corp. (Edison, NH, USA) under the trademark Polymero LM-200. Other cationic polymers that may be used include guar gum, cationic derivatives, such as guar hydroxypropyltrimonium chloride (commercially available from Celanese Corp. in its Jaguar series.) Other materials include quaternary nitrogen containing cellulose ethers (e.g. , as described, in US Patent No. 3,962,418), and copolymers of etherified cellulose and starch (for example, as described in US Patent No. 3,958,581).

Organic Oils Conditioning Agents The compositions of the present invention may also comprise an organic oil, insoluble in water, non-volatile, as a conditioning agent for the hair. Oily liquid, hair conditioning can add shine and luster to hair. He P666 conditioning oil is typically present in the compositions at a level from about 0.05% to about 5% by weight of the composition, preferably from about 0.2% to about 3%, most preferably from about 0.5% to about 1 %. By "volatile" it is meant that the oily liquid exhibits a very low or non-significant pressure and vapor at ambient conditions (eg, an atmosphere, 25aC, as understood in the art.) The non-volatile oily materials preferably have a point boiling at room temperature of about 260aC or above.For "insoluble in water" it is meant that the oily liquid is not soluble in water (distilled or equivalent) at a concentration of 0.1%, at 25 aC. of the present will generally have a viscosity of about 3 million cs or less, preferably 2 million is or less, preferably about 1.5 million cs or less.The conditioning oils herein are liquids selected from the group consisting of oil of hydrocarbons and fatty esters The fatty esters of the present are characterized to have at least 10 P666 carbon atoms, and include esters with hydrocarbyl chains derived from fatty acids or alcohols, for example, monoesters, polyhydric alcohol esters, and di- and tri-carboxylic acid esters. The hydrocarbyl radicals of the fatty esters of the present invention may also include or have covalently bound to these other compatible functionalities, such as amides and alkoxide moieties (e.g., ethoxy or ether bonds, etc.). Hydrocarbon oils include cyclic hydrocarbons, straight-chain aliphatic hydrocarbons (saturated or unsaturated), and aliphatic, branched-chain hydrocarbons (saturated or unsaturated). The straight chain hydrocarbon oils will preferably contain more than 16 carbon atoms. Also encompassed herein are the polymeric hydrocarbons of the alkenyl monomers, such as alkenyl monomers of 2 to 6 carbon atoms. These polymers can be straight or branched chain polymers. Straight chain polymers will typically be relatively short in length, having a total of carbon atoms as described above for straight chain hydrocarbons in general. The branched chain polymers can have a substantially larger chain length. He P666 number average molecular weight of these materials can vary widely, but will typically be at least about 400, preferably at least about 500, more preferably at least about 600. Specific examples of suitable materials include paraffin oil, mineral oil , and mixtures thereof. The branched-chain isomers of these compounds, as well as chain-length hydrocarbons, may also be used. Branched chain isomers, for example, are alkanes, unsaturated or saturated, highly branched, such as the isomers substituted with permethyl, for example, isomers substituted with permethyl of eicosane, such as 2, 2, 4, 4, 6, 6 , 8, 8-10nonylmethylundecane, sold by Permethyl Corporation. A preferred hydrocarbon polymer is polybutene, such as the copolymer of isobutylene and butene. A commercially available material of this type is L-14 polybutene from Amoco Chemical Co. (Chicago, Illinois, U.S.A.). The monocarboxylic acid esters herein include esters of alcohols and / or acids of the formula R'COOR, wherein the alkyl or alkenyl radicals and the sum of the carbon atoms in R 'and R are only at least 10, preferably at least 20. Fatty esters include, for example, esters P666 of alkyl or alkenyl of fatty acids having aliphatic chains with from about 10 to about 22 carbon atoms, and carboxyl acid esters of alkyl and alkenyl fatty alcohol having an aliphatic chain derived from allyl and / or alkenyl alcohol with about 10 to about 22 carbon atoms, and combinations thereof. Examples include isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate , myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate, and oleyl adipate. However, the necessary monocarboxylic acid esters do not necessarily contain at least one chain with at least 10 carbon atoms, while the total number of carbon atoms of the aliphatic chain is at least 10. Examples include diisopropyl adipate , diisohexyl alipate, and diisopropyl sebacate. The Di- and tri-alkyl and alkenyl esters of carboxylic acids can also be used. These include, for example, esters of dicarboxylic acids of P666 4 to 8 carbon atoms such as esters of 1 to 22 carbon atoms (preferably 1 to 6 carbon atoms) of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic acid, octanoic acid. Specific examples include isocetyl stearyol stearate, diisopropyl adipate, and tristearyl citrate. The polyhydric alcohol esters include alkylene glycol esters, for example, esters of mono- and di-fatty acids, of diethylene glycol, esters of diethylene glycol raono- and di-fatty acids, esters of mono- and di-fatty acids of polyethylene glycol, esters of mono- and di-fatty acids, polypropylene glycol, polypropylene glycol monooleate, polypropylene glycol monostearate 2000, ethoxylated propylene glycol monostearate, esters of mono- and di-fatty acids, of glyceryl, esters of polyglycerol polyglyceryl acids, glyceryl monostearate ethoxylated, 1,3-butylene glycol monostearate, 1,3-butylene glycol diistearate, esters of polyoxyethylene polyol fatty acids. fatty acid esters of sorbitan, and esters of polyoxyethylene sorbitol fatty acids are polyhydric alcohol esters satisfactory for use herein. The glycerides include mono-, di-, and triglycerides. More specifically, included are the mono-, di-, and tri-esters of glycerol and the acids P66G long chain carboxylic acids, such as carboxylic acids of 10 to 22 carbon atoms. A variety of these types of materials can be obtained from vegetable and animal fats, and oil, such as castor oil, sunflower oil, cottonseed oil, corn oil, olive oil, cod liver oil, oil of almonds, avocado oil, palm oil, sesame oil, lanolin oil and soy. Synthetic oils include triolein dilaurate and tri-glycerides. The preferred glycerides are di- and triglycerides. Triglycerides are especially preferred. The compositions herein may contain a variety of other optional components suitable for rendering these compositions more cosmetically or aesthetically acceptable or for providing them with additional useful benefits, for example, medicinal benefits. These optional, conventional ingredients are well known to those skilled in the art, for example, sun blockers, medicaments, for example, antibacterial, anti-inflammatory, anti-acne, etc.), colors and dyes, perfumes, pearlescent aids, such as ethylene glycol distearate; preservatives, such as benzyl alcohol, methylparaben, propylparaben and imidazolidinylurea; thickeners and modifiers P666 viscosity, such as a diethanolamide of a long chain fatty acid (eg, lauric diethanolamide PEG 3), cocomonoethanolamide, dimethicone-polyols, guar gum, methyl cellulose, starches, and starch derivatives; fatty starches, such as stearyl alcohol; sodium chloride; sodium sulfate; polyvinyl alcohol; ethyl alcohol; pH adjusting agents, such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts, in general, such as potassium acetate and sodium chloride; coloring agents, such as any of the dyes FD &C and D &C; hair oxidation agents (bleaches), such as hydrogen peroxide, perborate and persulfate salts; hair reduction agents, such as thioglycollates; perfumes; sequestering agents, such as ethylene diamine tetraacetate-sodic; and polymer plasticizing agents, such as glycerin, diisobutyl adipate, butyl stearate, and propylene glycol. These optional ingredients are generally used individually at levels from about 0.01% to about 10.0%, preferably from about 0.05% to about 5.0% of the composition. The pH of the present compositions will generally be between about 3 and about 9, preferably between about 4 and about P666 8. 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 formulation and mixing techniques. Methods for making various types of cosmetic compositions are more specifically described in the following examples.

Method of Use of Hair Care Compositions Hair care compositions are used in conventional ways to provide the desired benefit, appropriate to the product, such as hair styling, retention, cleaning, conditioning and the like, for care compositions. hair related. These methods of use depend on the type of composition used, but generally include the application of an effective amount of the product to the hair, which can then be rinsed from the hair (as in the case of shampoos and some conditioning products) or allowed to remain in the hair. hair (as in the case sprayed, foams or gel products) By "effective amount" is meant an amount sufficient to provide the desired benefit.Preferably, the rinse, foam and gel products P666 for hair is applied to damp or soaked hair before drying and styling hair. After those compositions are applied to the hair, the hair is dried and stylized in the usual ways of the user. Hair sprays are typically applied to dry hair after it has been cleaned and styled already. The following examples further illustrate the preferred embodiments within the scope of the present invention. The examples are given only for the purposes of illustration and are not to be construed as limitations of the present invention since many variations of the invention are possible without departing from their spirit and scope.

EXAMPLES The following examples further describe and demonstrate embodiments with the scope of the present invention. The examples are given solely for the purpose of illustration and should not be construed as limitations of the present invention, since many variations thereof are possible without departing from their spirit and scope of the invention. The ingredients are identified by the chemical name or CTFA name.

P666 EXAMPLE 1 Synthesis of Polyisobutylene Macromonomer Topped with Acryloyl Prepare the hydroxyl end capped polyisobutylene polymer (PIB-OH) having a weight average molecular weight of about 4.172 g / mol by conventional, latent, carbocationic polymerization of isobutylene (e.g., as described in G. Kaszas, Poly, Bull., 20, 413 (1989) .Prepared a solution of 100 grams (0.024 mol) of (PIB-OH) in 300 grams of dry methylene chloride.Add a two-fold molar excess (4.84 g, 0.48 mol) of triethylamine to the solution.

Add this solution dropwise to a solution of acryloyl chloride (4.35 g, 0.048 mol) in dry methylene chloride (100 g) at 0aC. Stir for about 12 hours at room temperature, filter the mixture and evaporate the excess of triethylamine and methylene chloride to obtain the end-capped polyisobutylene macromonomer with acryloyl.

EXAMPLE 2 (i) Synthesis of poly (tert-butyl-acrylate) -graft-Poly [isobutylene] macromonomer] (80/20 w / w); Weighted average molecular weight of total graft copolymer of P666 100,000; 5000-macronomer. To a solution of 20.0 grams of the poly (isobutylene) macromonomer topped with the acryloyl end of Example 1, and 80 grams of tert-butyl acrylate in 500 ml of tetrahydrofuran, add 0.5 grams of azoisobutrionitiro initiator ( AIBN). Reflux the resulting solution for about 20 hours, then rapidly quench the reaction by the addition of about 5 mL of methanol. Pour the solution into a Teflon crucible and evaporate the tetrahydrofuran at room temperature under a fume hood. Redissolve the resulting polymer film in THF and precipitate in water. Dry the resulting polymer in a vacuum oven. Alternatively, by varying the monomers and macromonomers used, this general procedure is used to prepare other copolymers of the present invention: (ii) Poly (4-tert-butyl styrene) -graft- [poly (isobutylene) macromonomer] (70/30 w / w); weighted average molecular weight of total polymer of 150,000; weight-molecular weight of macromonomer of 3000. (iii) Poly (4-tert-butyl styrene) -graft- [poly (2-ethylexyl methacrylate) macromonomer] (80/20 w / w); weighted average molecular weight of total polymer of 150,000; weighted average molecular weight of macromonomer of 10,000. (iv) Poly (tert-butyl acrylate-co-styrene) -grafting- P666 Tpoli (isobutylene) macromonomer] (60/20/20 w / w / w); weighted average molecular weight of total polymer of 100,000; weighted average molecular weight of macromonomer of 5000.

EXAMPLES 3-5 The following rinse compositions are styling / hair conditioning are representative of the present invention.

Composition 3 4 5 Premix of conditioner% by weight% by weight% by weight Water c. s c. s c. s Citric acid 0.02 0.02 0.02 Sodium Critrate 0.09 0.02 0.10 Cetyl alcohol 0.12 0.12 0.12 Stearyl alcohol 0.08 0.08 0.08 Natrosol plus CS Grade D-671 1.02 1.00 0.99 Xanthan gum 0.25 0.25 0.25 Styling polymer premix Copolymer of the graft of the example 2 (i) 1.75 1.75 1.75 Permethyl 99A 8.54 8.54 8.54 Trimethylsiloxysilicate 0.11 0.11 0 Katon cG 0.03 0.03 0.03 P666 Perfume 0.33 0.33 0.33 Silicone premix Water DRO 9.48 9.48 8.57 Adopt 47O4 0.70 0.60 0.93 Adopt 4715 0.05 0.15 0.07 Demethyl cyclopentasiloxane / polydimethexosiloxane3 gum 1.67 1.67 2.33 (Dow Corning Q2-8220) 0.10 0.10 0.10 Surface-active agent premix Water DRO 5.70 5.70 5.70 Stearalkonium Chloride 0.30 0.30 0.30 ^ hydrophilic modified hydrophobic cellulose Aquacon Corp. 2 Xantan gum easily dispersible. 3Goma SE-76 available from General Electric. 4 Dimethyl ammonium dichloride chloride, Sherex Chemical Co. , 75% aqueous solution. 5 Trimethyl ammonium tallow chloride, Sherex Chemical Co., 50% aqueous solution. Prepare the silicone premix by combining and mixing (in a separate container) water, Adogen 470 Adogen 471 to 852C. Cool to 71 ° C and add the silicone gums / decamethylcyclopentasiloxane solution and P666 amodimethicone; Mix until homogeneous. Cool to 38 ° C, while using the homogenizer (such as Tekmar). Prepare the premix of surfactant by combining and mixing (in a separate container) water and stearalkonium chloride at 38 ° C. Prepare the premix of conditioner by combining and mixing (in a separate container) the DRO water heated to 71 ° C, add to the citric acid, sodium citrate, cetyl alcohol, stearyl alcohol and Natrosol plus CS grade D-67, and mix until homogeneous.

Add the xanthan gum and mix until homogeneous. Prepare the styling polymer premix by combining and mixing (in a separate container) the graft copolymer, permethyl 99A, and trimethylsiloxysilicate until homogeneous. Combine and mix the styling polymer premix, Katon CG and perfume until homogeneous. Disperse the mixture further with an in-line homogenizer (such as homogenizer in Tekmar) and then cool the mixture to 38 ° C. Finish the conditioner by adding the premix of conditioner, the silicone pre-mix and the premix of surfactant at 38 ° C. Mix until homogenous, and then cool the composition to 25a C. Apply the compositions defined in Examples 3-5 to the hair in the conventional manner to P666 provide effective conditioning and styling / retention benefits of the hair without leaving the hair feeling sticky / hard.

EXAMPLE 6 Polymer premix with added drying aid. Prepare the next polymer premix using conventional mixing techniques. Ingredients% by weight Graft copolymer of example 2 (ii) 16.83 Permethyl 99A 83.17 Trimethylsiloxysilicate 1.00 Prepare the polymer premix by adding the graft copolymer to Permethyl 99A while mixing. Heat 80-842 C in a covered container, keep mixing. Cool to 23-272 C and add trimethylsiloxysilicate while mixing.

EXAMPLE 7 Premix of polymer with the aid of added drying. Prepare the next polymer premix using the conventional mixing techniques. Ingredients% by weight Graft copolymer of example 2 (iv) 15.00 Isododecane 83.50 P666 Polydimethylsiloxane 1.50 (Dow Corning, Dow Corning 200 fluid (20 csk)) Prepare the polymer premix by adding the graft copolymer to the isododecane while mixing. Heat 80-842 C in a covered container, keep mixing. Cool to 23-27 C and add trimethylsiloxysilicate while mixing.

EXAMPLE 8 Hair Conditioner Prepare a hair conditioner composition for rinsing the following components using conventional mixing techniques.

Ingredient% by weight ___ __. Premix of styling agent Premix of copolymer of example 71 10.00 10.00 Silicone premix Silicone rubber, GE SE762 0.30 0.30 Octamethyl-cyclotetrasiloxane 1.70 1.70 Main mixture Water QS100 QS100 Cetyl Alcohol 1.00 Quaternium 183 0.85 0.85 P666 Stearyl alcohol 0.70 Hydroxyethyl-cellulose 0.50 Cetyl-hydroxy-ethyl-cellulose4 1.25 Ceteareth-20 0. 35 Fragrance 0. 200 . twenty Dimethicone-copolyol 0 20 Citric acid 0. 13 0. 13 Methyleloroisothiazolinone (y) 0. 04 0. 04 Methylisothiazolinone Sodium chloride 0.01 0.01 Xanthan gum 0.20 Prepare the conditioner by first mixing all the ingredients of the main mix, heating approximately 60 aC with mixing. Cool the mixture to about 45 aC with colloid grinding (Example A) or mixing (Example B). At this temperature, add the two premixtures separately with moderate agitation. Allow the resulting conditioner to cool to room temperature. Alternatively, the conditioner compositions are prepared with the polymer premixes of example 2 (ii) and 2 (iii). 2Commercially available from General Electric. 3 Dimethyl-Di (hydrogenated tallow) -ammonium chloride.

P666 4 Commercially available as Polisur D-67 from Aqualon.

EXAMPLE 9 Shampoo Composition Prepare a shampoo composition from the following components using conventional mixing techniques. Ingredients% by weight Styling agent Polymer premix of example 7 15.00 Silicone premix Silicone rubber 0.50 Dimethicone, 350 cs fluid 0.50 Main mixture Water 'C.S. 100.00 ammonium lauryl sulfate 11.00 cocamide MEA 2.00 ethylene glycol distearate 1.00 Xanthan gum 1.20 Methylchloroisothiazolinone (y) Methylisothiazolinone 0.04 Citric acid at pH 4.5 as necessary.

Prepare the main mix by first dissolving the xanthan gum in the water with conventional mixing.

P666 Add the ingredients of the remaining main mixture and heat the mixture to 150 ° F with stirring for 1/2 hour. Add the styling agent and the silicone premix sequentially with approximately 10 minutes of agitation between the additions. Add the entire mixture while the batch is cooled to room temperature. For a varied particle size, the styling agent and the silicone premix are added at different times using either either a high cut (high speed disperser) or normal agitation mix, or both. Use shampoo for hair cleaning and to provide a stabilizing benefit. While the particular embodiments of the present invention have been described, it will be obvious to those skilled in the art that various changes and modifications to the invention can be made without departing from the spirit and scope of the invention. It is proposed to cover, in the appended claims, all modifications, which are within the scope of the present invention.

P666

Claims (22)

1. CLAIMS t 1. A hair care composition, comprising: (A) a graft copolymer having a polymeric structure and a hydrophobic polymeric side chain grafted to the structure, the copolymer being formed from the copolymerization of monomer units A, randomly repeating and at least one unit of macromonomer B, wherein the copolymers comprise: (i) from about 30% to about 95% by weight of the monomer units A, wherein the units of monomer A are units of monomer copolymerizable with the units of macromonomer B; and (ii) from about 5% to about 70% by weight of the units of macromonomer B, wherein the units of macromonomer B are hydrophobic macromonomer units having a polymer portion and a portion copolymerizable with the monomer units A; and wherein the monomer units A, in conjunction with the copolymerizable portions of the macromonomer units B, form the structure, the T that corresponds to the structure that has a value of at least about P666 25aC; wherein the polymeric portion of the macromonomer B unit forms the hydrophobic side chain, the Tg corresponding to the side chain having at least a value of less than about 10aC; wherein the copolymer has a weight average molecular weight greater than about 10,000; (B) a volatile, hydrophobic solvent for the copolymer, the solvent is selected from the group consisting of branched hydrocarbons, silicones and combinations thereof.
2. 2. A composition according to claim 1, wherein the monomer units A are ethylenically unsaturated monomer units, and the macromonomer units B are units having a polymer portion and an ethylenically unsaturated portion which is copolymerizable with the monomer units A
3. 3. A composition according to claim 2, wherein the monomer units A comprise hydrophobic monomers selected from the group consisting of acrylic acid esters; esters of methacrylic acid; N-alkyl acrylamide; vinyl compounds, vinylidene compounds, unsaturated hydrocarbons; esters of alcohol of 1 to 18 carbon atoms of organic acids and organic acid anhydrides; and combinations of P666 same.
4. 4. A composition according to claim 3, wherein the monomer units A comprise hydrophobic monomers selected from the group consisting of: acrylic or methacrylic acid esters of alcohols of 1 to 18 carbon atoms, dicyclopentyl acrylate, acrylate 4-biphenyl, pentachlorophenyl acrylate, 3,5-dimethyladamantyl acrylate, 3,5-dimethyladamantyl methacrylate, 4-methoxycarbonyl methacrylate, trimethylsilyl methacrylate, styrene, alpha-methylstyrene, p-butylstyrene, vinyl acetate, neononanoate vinyl, vinyl pivalate, vinyl propionate, vinyl chloride, vinylidene chloride, vinyl toluene, isobutyl vinyl ether, s-butyl vinyl ether, butadiene, cyclohexadiene, bicycloheptadiene, 2,3-dicarboxylmethyl-1, 6- hexadiene, ethylene, propylene, indene, norbornylene, β-pinene, α-pinene, and combinations thereof.
5. A composition according to claim 4, wherein the monomer A units comprise hydrophobic monomers selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, methacrylate 2-ethylhexyl, methyl methacrylate, indene, norbornylene, ß-pinene, α-pinene, vinyl pivalate, neononanoate P666 vinyl, cyclopentyl acrylate, 4-biphenyl acrylate, pentachlorophenyl acrylate, 3,5-dimethyladamantyl acrylate, 3,5-dimethyladamantyl methacrylate, 4-methoxycarbonylphenyl methacrylate, trimethylsilyl methacrylate, t-butyl styrene and combinations thereof .
6. 6. A composition according to claim 5, wherein the monomer units A comprise hydrophobic monomers selected from the group consisting of t-butyl styrene, t-butyl acrylate, t-butyl methacrylate, and combinations thereof.
7. A composition according to claim 4, wherein the monomer units A further comprise hydrophobic monomers selected from the group consisting of mono- and poly-carboxylic acids, organic, unsaturated, (meth) acrylamides, (meth) acrylates, (meth) acrylate alcohols, organic acid anhydrides, esters of organic acid anhydrides, hydrophilic vinyl compounds, hydrophilic allyl compounds, hydrophilic imides, salts of the above compounds, and combinations thereof.
8. 8. A composition according to claim 2, wherein the macromonomer B units are of the Formula (I) or (II): P666 wherein R1, R2, R3, R4 and R5 are, independently, H or straight or branched alkyl group of 1 to 5 carbon atoms; R6 = H or alkyl of 1 to 8 carbon atoms R7 = of 4 to 18 carbon atoms i and k are, independently, an integer of approximately 1 or greater; j and 1 are, independently, an integer of about 0 or greater; m is an integer from 10 to about 2000; E is an end finishing group, ethnically P666 unsaturated, copolymerizable with monomer units A, selected from the group consisting of acrylamide, methacrylamide, vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl, 2-vinylbenzoyl, -vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, isoprenyl, cyclohexenyl, cyclopentenyl, and combinations thereof; and I is a chemical starter portion.
9. The composition according to claim 8, wherein E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl , 1-propenyl, isobutenyl, and combinations thereof.
10. The composition according to claim 9, wherein E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and combinations thereof.
11. The composition according to claim 10, wherein the units of macromonomer B selected from the group consisting of acryloyl, methacryloyl, or end-capped polymers with 2-, 3- or 4-vinylbenzyl of: esters of methacrylic acid or acrylic, P666 poly (alkene), poly (alkene) hydrogenated, poly (ethervinyl), poly (vinylbenzene), and combinations thereof.
12. The composition according to claim 8, wherein the units of macromonomer B are selected from the group consisting of end-capped polymers with acryloyl, methacryloyl, or 2-, 3- or 4-vinylbenzyl of: poly (butyl n-acrylate), poly (dodecyl acrylate), poly (2-ethylhexyl acrylate), poly (2-ethylbutyl acrylate), poly (n-ethyl acrylate), poly (heptyl n-acrylate) , poly (hexyl n-acrylate), poly (butyl iso-acrylate), poly (decyl iso-acrylate), poly (propyl iso-acrylate), poly (3-methylbutyl acrylate), poly (2-) methylpentyl acrylate), poly (nonyl acrylate), poly (octyl acrylate), poly (propyl acrylate), poly (2-ethylhexyl methacrylate), poly (tridecyl methacrylate), poly (hexyl methacrylate), poly (decyl methacrylate), poly (octyl methacrylate), poly (octadecyl methacrylate), poly (dodecyl methacrylate), poly (pentyl n-methacrylate), poly (isobutylene), poly (isoprene), poly (1) , 2-butadiene) hydrogenated, poly (1,4-hydrogenated butadiene, poly (hydrogenated isoprene, poly (1,2-butadiene), poly (1-butene), poly (5-methyl-1-hexene), poly ( 6-methyl-1-heptene), poly (4, 4-dimethyl-l-pentene), poly (iso-butyl-vinyl-ether, poly [4-t-butyl-vinyl-benzene-co-2- P666 ethylhexyl acrylate], poly [2-ethylhexyl-acrylate-co-octyloacrylamide), poly [2-ethyl-vinyl-benzene-co-octyl-methacrylate], and combinations thereof.
13. 13. A composition according to claim 1, wherein the graft copolymer is selected from the group consisting of poly [poly (tert-butylacrylate) -graft-poly (isobutylene) macromonomer], poly [poly (4-ter- butyl styrene) -graft-poly (isobutylene) macromonomer], poly [(4-tert-butylstyrene) -graft-poly (2-ethylhexyl methacrylate) macromonomer], poly [(tert-butylacrylate-co-styrene-graft-poly (isobutylene )], and combinations thereof
14. 14. A composition according to claim 1, wherein the solvent is selected from the group consisting of branched chain hydrocarbons consisting of 10 to 16 carbon atoms and combinations thereof.
15. 15. A composition according to claim 14, wherein the solvent is selected from the group consisting of branched chain hydrocarbons containing 12 to 16 carbon atoms and combinations thereof
16. 16. A composition according to claim 15, where The solvent comprises isododecane.
17. 17. A composition according to claim 1, P666 where the solvent is a silicone.
18. 18. A composition according to claim 1, comprising from about 0.1% to about 25% of the copolymer and from about 0.1% to about 75% of the solvent.
19. 19. A composition according to claim 1, wherein the copolymer exhibits at least two different T-values, one of the Tg corresponding to the hydrophobic polymeric side chains and having a value of less than about 10 BC, another of the Tg which they correspond to the structure that have a value of at least 25 BC.
20. The composition according to claim 1, further comprising an aqueous carrier for the graft copolymer and the solvent.
21. 21. A method for styling the hair, comprising applying an effective amount of the composition of claim 1 to the hair.
22. 22. A method for conditioning the hair comprising applying an effective amount of the composition of claim 1 to the hair. P666