MXPA98007662A - Compositions for hair care that leave little resi - Google Patents

Abstract

The present invention relates to hair care compositions that are removed by rinsing and that leave little residue on the hair after repeated use. These compositions have good styling retention or combing properties of the hair and have a natural, non-sticky feel to the hair. These compositions comprise a hydrophobic copolymer component and a suitable carrier for application to hair. The copolymer component further comprises a hydrophobic copolymer and a hydrophobic solvent volatile

Description

COMPOSITIONS FOR HAIR CARE THAT LEAVE LITTLE WASTE FIELD OF THE INVENTION The present invention relates to compositions for hair that are removed by rinsing and that leave little residue on the hair. These compositions have good styling retention properties and provide a natural non-sticky feel to the hair. These compositions comprise a hydrophobic copolymer component and a suitable carrier for application to hair. The copolymer component further comprises a hydrophobic copolymer and a volatile hydrophobic solvent.

BACKGROUND OF THE INVENTION The desire to have a hair that retains a particular style is widely maintained. Style retention is achieved in general by the application of either products. permanent chemical alteration or temporary stylization products. A permanent chemical alteration product, which is commonly referred to as a "hair permanent," typically comprises treating the hair with various sulfur-containing compounds in order to break the disulfide bonds in the hair fibers, thereby allowing the shape and orientation of the hair fibers are altered. However, permanent hair products have the disadvantage of being rough and damaging to the hair, and of persisting for a long time and being difficult to invest. Conversely, temporary styling products in general do not break the chemical bonds in the hair fibers. These temporary styling products are typically in the form of gels, lotions, foams or rubbers containing polymeric resins or gums to coat the hair fibers and bond them together. Many temporary styling products are inconvenient for use and have the disadvantage of not allowing the new style formation easily on the hair after the initial application and styling is finished, without the additional application of additional product. It would be preferable to provide stylization and retention benefits of the rinse products, such as conditioners and shampoos. These types of rinse products, however, require styling agents that are substantive to the hair and are not easily removed during the rinsing process. Styling and retention agents especially useful for rinsable or removable compositions are hydrophobic polymeric materials. However, these hydrophobic materials can cause the accumulation of an unpleasantly visible residue on the hair with repeated use. This residue can eventually completely surround the hair strand and can be difficult to remove without the normal shampooing process. Therefore, there is a need for improved rinse compositions to provide styling and temporary retention of human hair without the residue and the negative things frequently associated with these compositions. It has been surprisingly found in the present invention that hair care compositions that are removed by rinsing comprise certain hydrophobic copolymers that provide excellent styling preservative and temporary hair setting benefits, with a very little visible accumulation of residues in the hair. hair. These compositions may be made in any of the conventional forms of the rinse-off type, including, but not limited to, shampoos, conditioners, foams, gels, lotions, sprays and the like. . The compositions of the present invention provide those benefits without leaving the hair feeling stiff or stiff. The hair to which the compositions of the present invention are applied can be combed several times without requiring reapplication of the compositions.

P671 Hair care compositions containing various copolymers are well known in the prior art. Nevertheless, none of these references teaches or suggests compositions that have little visible residue in the hair. See, for example, U.S. Patent No. 3,208,911 to Oppliger, issued September 28, 1965, U.S. Patent No. 4,601,902, to Fridd et al., Issued July 22, 1986, U.S. Patent No. 4,654,161, to Kollmeier et al. , issued March 31, 1987, US Patent No. 5,106,609, Bolich hr. and collaborators, issued April 21, 1992, North American Patent No. 4,693,935 to Mazure, issued September 15, 1987, European Patent Application No. 412,704, to Bolich et al., published on February 2, 1991. The compositions of the present invention comprise a hydrophobic copolymer component and a carrier suitable for application to hair, wherein the hydrophobic copolymer component further comprises a hydrophobic copolymer and a volatile hydrophobic solvent. Therefore, it is an object of the present invention. providing rinsable or removable compositions that are useful for styling and retention of hair.

P671 It is another object of the present invention to provide compositions that are useful to provide a temporary retention and styling benefit for hair-J-o. It is another object of the present invention to provide compositions that do not leave a visible residue on the hair. It is another object of the present invention to provide methods for styling and retaining hair. These and other objects will become easily apparent from the detailed description that follows: SUMMARY OF THE INVENTION The present invention relates to hair care compositions that are rinsed off, comprising: (a) from about 0.25% to about 70% of a copolymer component, comprising: (i) from about 1.5% to about 70% by weight of the copolymer component, of a hydrophobic copolymer having a weight average molecular weight of from about 10,000 to about 5,000,000, the copolymer comprising a polymeric structure and hydrophobic polymeric side chains, grafted to the structure, wherein the weight percent of the copolymer in the rinsable or removable composition for hair care is from about 0.10% to about 7%; and (ii) from about 30% to about 98.5% of a volatile hydrophobic solvent having a boiling point at a C atmosphere of at least about 2225 °; Y (b) from about 30% to about 99. 75% of a suitable carrier for application to human hair, wherein the hair care composition that is removed by rinsing has a residue index on human hair of about 20 or greater. In additional embodiments, the present invention relates to methods for styling and retaining hair using these hair care compositions. Unless indicated otherwise, all percentages and ratios used herein are by weight of the total composition. All percentages by weight, unless otherwise indicated, are on an active weight basis. All measurements made are at 25 ° C, unless otherwise designated. The invention herein may comprise, consist of, or consist essentially of, the essential as well as optional components and components described herein.

DETAILED DESCRIPTION OF THE INVENTION The copolymers of the present invention comprise a hydrophobic copolymer component and a suitable carrier for application to hair, wherein the hydrophobic copolymer component further comprises a hydrophobic copolymer and a volatile hydrophobic solvent. The hydrophobic copolymers of the present invention can be described as graft copolymers. The term "graft copolymers" is familiar to an expert in polymer science, and is used herein to describe the copolymers that result from adding or "grafting" a polymeric (i.e., "graft") chemical portion onto another polymer portion commonly referred to as the "structure". The structure typically has a higher molecular weight than the grafts. In this way, graft copolymers can be described as polymers having side chains, polymeric, pendant, and as they are formed from the "graft" or incorporation of the polymeric side chains, on or in a polymer. The polymer to which they are incorporated - the grafts can be homopolymers or copolymers. The graft copolymers are derived from a variety of monomer qualities. The 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 resulting copolymer. The term "macromonomer" is a term familiar to a person 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 a type of monomer constitution block unit, of high molecular weight, which can be used in a polymerization reaction to form polymers with itself, with other monomers or with other macromonomers. The term "hydrophobic" is used in the present consistent. with its normal meaning of lack of affinity to water, while "hydrophilic" is used in -the present consistent with its normal meaning and having affinity to water. As used herein in relation to the monomer units and polymeric materials, including the macromonomers, copolymers and solvents for the copolymers, "hydrophobic" means substantially insoluble in water. In this regard "substantially insoluble in water" should refer to a material that is not soluble in distilled water (or equivalent), at 25 ° C, at a concentration of 0.2% by weight, and more preferably not soluble at 0.1 % in weigh. In contrast, "hydrophilic" means, substantially soluble in water. "Substantially soluble in water" should refer to a material that is soluble in distilled water (or equivalent), at 25 ° C, at a concentration of 0.2% by weight, and are preferably soluble at 1.0% by weight. The term "rinsable or removable", in contrast to the term "non-rinsing", is used herein to mean that the compositions of the present invention are used in a context in which the composition is finally rinsed from the hair or It is removed from it by washing, either after or during the application of the product. A "non-rinsing" product refers to a hair care composition that is applied to the hair and is not further subjected to a rinsing step. Non-limiting examples of the rinseable products of the present invention include conditioners and shampoos. The term "suitable for application to human hair" as used herein, means that P671 the compositions or components thereof described thus are suitable for use in contact with human hair and the scalp and skin, without toxicity, undue toxicity, incompatibility, instability, allergic response and the like. The definitions mentioned above must also apply to other materials so described herein, to the extent that any other definition with respect to these materials is consistent with those set forth above. The compositions of the present invention comprise the following essential components.

Copolymer Component The rinsing-off hair care compositions of the present invention comprise a copolymer component in an amount of from about 0.25% to about 70%, preferably from about 4% to about 30%, and more preferably from about 8% to about 18% by weight, based on the weight of the rinsable or removable composition for hair care. The copolymer component further comprises a hydrophobic copolymer and a volatile hydrophobic solvent for the hydrophobic copolymer.

P671 Hydrophobic Copolymer The copolymer component of the present invention comprises a hydrophobic copolymer in an amount of from about 1.5% to about 70%, preferably from about 5% to about 40% and more preferably from about 10% to about 25% by weight, based on the weight of the copolymer component. Based on the weight of the complete rinseable composition for hair care, the hydrophobic copolymer comprises from about 0.1% to about 7%, preferably from about 1% to about 4%, and most preferably from about 1.5% up to about 2.5% by weight. The copolymers of the present invention have a weight average molecular weight, in grams / moles, 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, processing, aesthetic characteristics, formulation compatibility, etc. The weight average molecular weight is generally less than about 5,000.00, more generally less than about 2,500,000, and typically less than about 1,500,000. Fit Preferred P671, the weighted average molecular weight is from 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 15,000,000, more preferably from about 125,000 to about 1,000,000. The copolymers of the present invention are formed from the copolymerization of randomly repeating monomer A units and macromonomer units B, preferably, wherein the monomer units A are selected from at least one monomer unit ethylenically unsaturated, polymerizable; and the macromonomer B units are selected from at least one hydrophobic macromonomer unit containing a polymer portion and a copolymerizable portion with the monomer units A, preferably an ethylenically unsaturated portion that is copolymerizable with the monomer units In 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 units of the macromonomer B. The polymer portion of the macromonomer B units forms the hydrophobic side chains of P671 copolymer. The monomer A units and the macromonomer B units can be selected from a variety of structure while the copolymer has the required properties and the molecular weight described herein. The copolymers are prepared by the combination of polymerization of monomers A and macromonomers B if they can be characterized by the weight percent of monomers and charged macromonomers in the reaction vessel in which the polymerization reaction is carried out. 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 the hydrophilic and hydrophobic monomers may vary as long as the graft copolymer is completely soluble in the hydrophobic solvent, volatile of the present. The solubility of the graft copolymer material, or. component thereof, in volatile hydrophobic solvents, is determined according to whether this material remains in solution is precipitated from the solution at 25 ° C. Graft copolymers that are soluble in volatile hydrophobic solvents of the present invention typically comprise from about 0% to P671 about 5% by weight of optional units of hydrophilic monomer. As will be clear to one skilled in the art and especially from the examples, the copolymer can have one or more hydrophobic side chains grafted onto the structure. In addition, the compositions of the present invention may include, in addition to the copolymer, corresponding copolymers that do not have hydrophobic side chains grafted to the structure. As is known in the art, synthetic graft copolymerization processes can produce a mixture of polymer molecules containing none, one or more of a hydrophobic side chain covalently linked and hanging from the polymer structure. From the knowledge of the numerical average number and molecular weight of the hydrophobic side chains in a polymer sample, the numerical average molecular weight of the polymer sample, it is possible to calculate the average number of hydrophobic side chains per polymer structure. The copolymer component of the present invention, when drying a film having 0.05% less of the volatile hydrophobic solvent has a Tg or Tm of at least about minus 20 ° C, more preferably at least about 25 ° C, so that the P671 copolymers are not unduly sticky or "adhesive" to the touch. As used herein, the abbreviation "Tg" refers to the glass transition temperature of the polymer structure and the abbreviation "Tm" refers to the crystalline melting point of the structure, if there is a transition for a polymer dice. Preferably, both the Tg and the Tm, if any, are above about -20 ° C, more preferably above about 25 ° C. The grafted copolymers must meet the following three criteria: (1) when the copolymer is dried the phases are separated into a discontinuous phase that includes the grafted polymeric side chain portion, and the continuous phase that includes the portions that do not have side chains . (2) the polymeric side chain portion is covalently bound to the portion of. structure; and (3) the number average molecular weight of the polymer side chain portion from about 5,000 to about 50,000.

P671 Without being limited by theory, it is believed that the phase separation property provides a specific orientation of the copolymer which results in a desired combination of feel to the touch, film formation or adhesive benefits, and the ability to dry quickly and easily. completely. The nature of the phase separation of the compositions of the present invention can be determined as follows. The copolymer is molded as a solid film of a solvent (i.e., the hydrophobic, volatile solvent of the present invention which dissolves the portions of both the structure and the graft side chains). This film is then sectioned and examined by transmission electron microscopy. Microphase separation is demonstrated by the observation of inclusions in the continuous phase. These inclusions must be sized to match the size of the side chains (typically, a few hundred nm or less) and the proper density to match the amount of the side chain present. This behavior is well documented in the literature for polymers with this structure (see, for example, SD Smith, Ph.D. Thesis, Univertisty of Virginia, 1987, and references cited herein, the thesis is incorporated by reference herein). ).

P671 The copolymers of the present invention are prepared by the polymerization combination of monomer A and macromonomer B. The copolymers can be synthesized by free radical polymerization of the monomers and macromonomer. The general principles of free radical polymerization methods are well understood. See, for example, Odian, "Principies of Polymerization", 3a. edition, John Wiley &; Sons, 1991, pp. 198-334. The desired monomer A and macromonomer B are all placed in a reactor, together with a sufficient amount of a mutual solvent, so that when the reaction is finished the viscosity of the reaction is reasonable. Unwanted terminators, especially oxygen, are removed as necessary. This is done by evacuating or purging with an inert gas, such as argon or nitrogen. The initiator is introduced and the reaction is set at the temperature necessary for the initiation to occur, assuming that thermal initiators are used. Alternatively, redox or radiation initiation can be used. . The polymerization is allowed to proceed as long as necessary to achieve a high level of conversion, typically from a few hours to a few days. Then, the solvent is removed, usually by evaporation or by precipitating the copolymer by the adhesion of a non-solvent. The copolymer can be purified P671 additionally, as necessary. As an alternative to a batch reaction, the copolymer can be made by a semi-continuous or continuous process. In the semi-continuous process, two or more additions of monomers or macromonomers are made during the polymerization reaction. This is advantageous when the polymer is made of several monomers that react during the polymerization at different speeds. The proportions of monomers added to the reaction at the separate points of addition can be adjusted by one skilled in the art, such that the polymers of the final product have a more uniform structure. In other words, the polymers of the final product will have a more consistent distribution of monomer content for each of the types of monomers charged to the reaction. Examples of related copolymers and how they are made are described in detail in U.S. Patent No. 4,693,935, Mazurek, issued September 15, 1987; U.S. Patent No. 4,728,571, Clemens et al., Issued March 1, 1988, both of which are incorporated herein by reference. Further grafted, silicone polymers are also described in EPO application 90307528.1, , published as Application for EPO 0 408 311 A2, on January 11, 1991, Hayama et al .; Patent P671 North American No. 5,061,481, issued October 29, 1991, Suzuki et al., US Patent No. 5,106,609, Bolich et al., Issued April 21, 1992, United States Patent No. 5,100,658, Bolich et al., Issued on March 31, March 1992, U.S. Patent No. 5,100,657, Ansher-Jackson et al., Issued March 31, 1992, U.S. Patent No. 5,104,646, Bolich et al., Issued April 14, 1992, U.S. Patent No. Serial No. 07 / 758,391, Bolich et al., Issued August 27, 1991, and US Patent No. 07 / 758,320, Torgerson et al., Issued August 27, 1991, all of which are incorporated by reference herein in their entirety. . The particular, relative amounts of monomers A and macromonomers B can vary as long as the structure of the copolymer is soluble in the hydrophobic, volatile solvent of the present and the grafted copolymer, of silicone, exhibits phase separation when dried. The copolymers are prepared by the polymerization combination of monomers A and macromonomers B. The copolymer composition is characterized by the amount of each monomer separated to the polymerization reaction vessel, or alternatively used in a process P671 continuous or semi-continuous. By the appropriate selection and combination of monomer units A and particular macromonomer B units, and by the choice of specific, relative ratios of the units, are well within the ability of the skilled person in the art, copolymers can be optimize for various physical properties and for compatibility with other ingredients commonly used in hair care applications.

Monomer A Units The hydrophobic copolymers of the present invention comprise monomer units A in an amount of from about 50% to about 85%, preferably from about 60% to about 85%, and most preferably from about 70% to about 80% by weight of the hydrophobic copolymer. The 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 P671 say a material that can be reacted with another material (e.g., monomer A and macromonomer B) in a polymerization reaction using one or more conventional synthesis techniques, such as ionic polymerization, in emulsion, by dispersion, Ziegler-Narta, free radical, by 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 indicate a material (including preferred monomers A and macromonomers B) containing at least one polymerizable carbon-carbon double bond) which may be mono-, di-, tri- or tetra-substituted). The units of monomer A and macromonomers B include hydrophobic monomer units and optionally hydrophilic monomer units. The non-limiting classes of monomers A useful herein include hydrophobic monomers selected from the. group consisting of esters of unsaturated carboxylic acid of alcohols having 1 to 18 carbon atoms, unsaturated alcohols (preferably having about 12 to about 30 carbon atoms), unsaturated hydrocarbons, aromatic hydrocarbons containing unsaturated alkyl groups, vinyl esters of P671 carboxylic acids, allylic ethers of carboxylic acids, allylic ethers, and mixtures 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, methoxyethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1- pentanol, 1-decanol, 2-ethylhexanol, cyclohexanol and the like; dicyclopentenyl acrylate; 4-biphenyl acrylate, pentachlorophenyl acrylate, 3,5-dimethyladamantyl acrylate, 4-methoxycarbonylphenyl methacrylate, methacrylate. of trimethylsilyl; styrenes such as methylstyrene, t-butylstyrene, isopropylstyrene; vinyl esters, such as vinyl acetate, vinyl neononate, vinyl pivalate and vinyl propionate; 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 mixtures thereof. Preferred hydrophobic monomers suitable for use as monomer A units include monomers selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate; t-butyl acrylate, t-butyl methacrylate, 2- methacrylate P671 ethylhexyl methacrylate, indene, norbornylene, ß-pinene-pinene, vinyl pivalate, vinyl neoato acrylate, dicyclopentenyl acrylate, 4-biphenyl acrylate, pentachlorophenyl acrylate, 3,5-dimethyladamantyl methacrylate 3, 5-dimethyladamantyl methacrylate, 4-methoxycarbonylphenyl methacrylate, trimethylsilyl, t-butyl styrene and mixtures thereof, more preferred are monomeric units selected from t-butyl styrene, t-butyl , t-butyl methacrylate, and mixtures thereof. As mentioned above, lower levels of hydrophilic monomers, ie, from about 0% to about 5%, based on the weight of the copolymer, may optionally be present in the copolymers of the present invention. Nonlimiting examples of the monomers include those selected from the group consisting of acrylic acid, methacrylic acid, N, N-dimethylacrylamide, dimethylaminoethyl methacrylate, methacrylamide, Nt-butyl acrylamide, maleiao acid, maleic anhydride, crotonic acid, itaconic acid, acrylamide, hydroxyethyl methacrylate, diallyl dimethyl ammonium chloride, vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, styrene sulfonate, allyl alcohol, and mixtures thereof chloride. Also useful herein are quaternized alkyl salts and derivatives of these P671 monomers, where applicable.

Units Macromonomer B Hydrophobic copolymers of the present invention comprise units B macromonomer in an amount of from about 15% to about 50%, in preferably from about 15% to about 40%, more preferably from about 20% to 30% by weight of the copolymer. The macromonomer B units are hydrophobic macromonomer units copolymerizable with the monomers A, the B macromonomers that preferably have an ethylenically unsaturated moiety. Either an individual type of macromonomer B unit or combinations of two or more sample macromonomer units can be used herein. The macromonomers B are selected to meet the requirements of the copolymer. By "copolymerizable", as used herein, it is meant that macromonomers B can be selected with, or polymerized with, monomers A in a polymerization reaction using one or more conventional synthetic techniques, as described above. The macromonomers B that are useful herein contain a polymer portion and a portion P671 copolymerizable which is preferably an ethylenically unsaturated portion. Typically, preferred B-macromonomers are those that are capped at the end with the ethylenically unsaturated term. By "capped at the end" as used herein is meant the ethylenically unsaturated portion is at or near a terminal position of the macromonomer. The B macromonomers can be synthesized using a variety of normal synthesis procedures familiar to the polymer chemist skilled in the art. Additionally, these macromonomers can be synthesized by starting from commercially available polymers. Typically, the weight average molecular weight of the macromonomer B is from about 5,000 to about 50,000. Preferably, the units of macromonomer B are selected from the group consisting of polysiloxane macromonomers, polyethylene macromonomers and mixtures thereof. The polysiloxane B macromonomers are exemplified by the general formula: X (Y) nYes (R) 3.mZm wherein X is an ethylenically unsaturated group copolymerizable with monomers A, such as a vinyl group; P671 Y is a divalent linking group; R is a hydrogen, hydroxyl, lower alkyl (eg, 1 to 4 carbon atoms), aryl, alkaryl, alkoxy or alkylamino; Z is a polymeric monovalent siloxane portion having a number average molecular weight of at least about 15,000, is essentially unreactive under copolymerization conditions, and is pendant from the vinyl polymer structure described above; n is 0 or 1; and m is an integer from 1 to 3. The macromonomer B has a weight average molecular weight of from about 5000 to about 50,000, preferably from about 5,000 to about 30,000, more preferably from about 8,000 to about 25,000. Preferably, the macromonomer B has a formula selected from the following formulas: X-CHI- (CH2) s-Si (R ') 3.m-2m 01 0 II X-C-0- (CH2) q- (0) p-Si (Rl) 3_mZm In these structures, s is an integer from 0 to PS71 approximately 6, preferably 0, 1 or 2, more preferably 0 or 1; m is an integer from 1 to 3, preferably 1; p is 0 or 1; q is an integer from 2 to 6; Fl2 is alkyl of 1 to 10 carbon atoms or alkylaryl of 7 to 10 carbon atoms, preferably alkyl of 1 to 6 carbon atoms or alkylamino of 1 to 2 carbon atoms, more preferably alkyl of 1 to 2 carbon atoms; n is an integer from 0 to 4, preferably 0 or 1, more preferably 0; R is hydrogen, hydroxyl, lower alkyl, alkoxy, alkylamino, aryl, or alkaryl, preferably R is alkyl; X is CH = C- I I R3 R4 R 3 is hydrogen or -COOH-, preferably R 3 is hydrogen; R is hydrogen, methyl or CH 2 COOH, preferably R is methyl; Z is: R? I R5 - (- Si-O-) r; I R7 R, R and R are independently lower alkyl, alkoxy, alkylamino, aryl, alkaryl, hydrogen, or P671 c e -i hydroxyl, preferably, R, R and R are alkyls; and r is an integer from about 100 to about 350. More preferably. R, R, and R are methyl, p = 8, and q = 3. When the molecular weight of macromonomer B is less than or equal to about 13,000, and r is less than or equal to about 170, the weight percentage of monomer B charged to the spray reactor is preferably from about 25% to about 40%, most preferably 25% to about 30%. When the molecular weight of monomer B is greater than about 13,000, and r is greater than about 170, the weight percent of charged monomer C is preferably from about 15% to about 40%, most preferably 20% to about 30% . The polyalkylene macromonomers are exemplified by the general formula: [I] n- [W] mE wherein I. is an optionally present initiator (ie, n = 0 or 1), W is a hydrophobic monomer unit, I is an end cap group, and m is an integer from about 10 to about 2000. I is a portion of chemical primer, optionally present. Without being limited by any P671 theory, I can be derived from an initiator or chemical solvent used in the synthesis of the macromonomer B. The 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, carbanions of 1 to 20 carbon atoms, radicals of 1 to 20 carbon atoms, aliphatic alkoxy anions and aromatics of 1 to 20 atoms of carbon, ammonium ion, and substituted ammonium ions (eg, substituted with alkyl of 1 to 20 carbon atoms and alkoxy of 1 to 20 carbon atoms), and mixtures thereof. I can be derived from any useful solvent, non-limiting examples of which include water, methanol, ethanol, propanol, isopropanol, acetone, hexane, dichloromethane, chloroform, benzene, toluene and mixtures thereof. W is selected from one or more hydrophobic monomer units, the non-limiting classes of these monomers include acrylate esters of 1 to 18 carbon atoms, esters of (alkyl) acrylate of 1 to 18 carbon atoms, chain alkenes straight or branched from 2 to 30 carbon atoms, styrenes, vinyl ethers of 1 to 30 carbon atoms, straight or branched chain dienes of 4 to 30 carbon atoms, and mixtures thereof.

P671 Non-limiting examples of the W groups include those selected from the group consisting of n-butyl acrylate, dodecyl acrylate, ethyl acrylate, 2-ethylbutyl acrylate, n-heptyl acrylate, n-hexyl acrylate. , isobutyl acrylate, iso-decyl acrylate, iso-propyl acrylate, 3-methylbutyl acrylate, 2-methylpentyl acrylate, nonyl acrylate, octyl acrylate, 1-propyl acrylate, 2-ethylhexyl methacrylate , octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, n-decyl methacrylate, n-pentyl methacrylate, isobutylene, isoprene, 1,2-butadiene, 1,3-butadiene, 5-methyl-1 -hexene, 6-methyl-1-heptene, 4, 4-dimethyl-1-pentene, isobutyl vinyl ether, styrene, 2-methyl-styrene, 3-methylstyrene, 4-methyl-styrene, 2-t-butyl- styrene, 3-t-butyl styrene, 4-t-butyl styrene, and mixtures thereof. E is a copolymerizable portion or "end cap" group. Preferably, E is an ethylenically unsaturated moiety. It is most preferred when E is selected from the group consisting of vinyl, allyl, aryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1- butenyl, 1-propenyl, isobutenyl, cyclohexenyl, cycntenyl, and mixtures thereof. Even more preferred is when E is selected to Pd71 from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl and mixtures thereof. More preferred is when E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof. Non-limiting examples of the polysiloxane and polyalkylene macromonomer B units useful herein include those selected from the group consisting of polymers capped at the acryloyl, methacryloyl, or 3-, or 4-vinylbenzyl end of polydimethylsiloxane, polydiethyl siloxane , polyphenylmethylsiloxane, polyphenylethylsiloxane, poly (n-butyl acrylate), poly (dodecyl acrylate), poly (2-ethylhexyl acrylate), poly (2-ethylbutyl acrylate), poly (n-ethyl acrylate), poly ( n-heptyl acrylate), n-hexyl poly acrylate), poly (isobutyl acrylate), poly (iso-decyl acrylate, poly (iso-propyl acrylate), poly (3-methylbutyl acrylate), poly ( 2-methylpentyl acrylate), poly (nonyl acrylate), poly (octyl acrylate), poly (propyl methacrylate), poly (2-ethylhexyl methacrylate), poly (tridecyl methacrylate), poly (hexyl methacrylate) , poly (decyl methacrylate), poly (octyl methacrylate), poly (methacrylate) to P671 octadecyl), poly (dodecyl methacrylate), poly (n-pentyl methacrylate), poly (isobutylene), poly (isoprene), poly (1,2-hydrogenated butadiene, hydrogenated poly (1,4-butadiene), poly (isoprene) hydrogenated, poly (1,2-butadiene), poly (l-butene), poly (5-methyl-l-hexene), poly (6-methyl-1-heptene), poly (4, 4-dimethyl) -l-pentene), poly (isobutyl vinyl ether), poly [4-t-butyl-vinyl-benzyl-co-2-ethylehexyl] poly [2-ethylhexyl-acrylate-co-octyl acrylamide acrylate], poly [2-ethyl-vinyl-benzene-co-octyl methacrylate]] and mixtures thereof. Type B macromonomers of the "copolymer" containing two or more different randomly-repeating monomer units are useful, for example. Non-limiting examples of these types of macromonomer "copolymers" include poly [vinyl benzene-co (4-t-butyl vinyl benzene) (2,4-dimethyl-vinylbenzene)], poly [co (4-t-butyl- vinylbenzene) (2-ethylhexyl acrylate)], poly [co (2, 4-dimethyl-vinylbenecene) (2-ethylhexyl acrylate)], poly [co (2-ethylvinyl-benzene) (octylmethacrylate)], capped on the end with acryloyl, and simi 1.ir.

Preferred Polymers of the Present Invention The non-limiting examples of the preferred polymers of the present invention include those P671 selected from the group consisting of poly [(t-butylacrylate) -graft-poly (dimethylsiloxane)], poly [(4-t-tuitytirene) -graft-poly (dimethylsiloxane)], poly [poly-t-butylacrylate] ) -grafting-poly (isobutylene)], poly [poly- (4-t-butylstyrene) -graft-poly (isobutylene)], poly [(t-butylstyrene) -graft-poly (2'-ethylhexylmethacrylate)] poly [(4-t-butylacrylate-co-styrene) -graft- poly (isobutylene)] and mixtures thereof. More specific examples of copolymers of the present invention include the following, wherein the composition is given as a percentage by weight of each monomer used in the polymerization reaction (ie, the weight percentage of charged monomer and macromonomer). Poly [(t-butylacrylate) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 900,000, comprising about 75% t-butylacrylate and about 25% dimethylsiloxane macromonomer with a weight average molecular weight Approximately 11,000. Poly [(t-butylacrylate) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 900,000, comprising about 80% t-butyl acrylate, and about 20% dimethylsiloxane macromonomer with a molecular weight P671 weighted average of approximately 15,000. Poly [(t-butylstyrene) -graft-poly (dimethylsiloxane)] which has a weight average molecular weight of about 300,000, comprising about 70% t-butylstyrene, and about 30% dimethylsiloxane macromonomer with a molecular weight weighted average of approximately 20,000. Poly [(t-butyl acrylate-co-acrylic acid) -graft-polydimethylsiloxane acid]] having a weight average molecular weight of about 700,000, comprising about 67% butyl acrylate, and about 3% acrylic acid, and about 30% dimethylsiloxane macromonomer with a weight average molecular weight of about 11,000. Poly [(t-butylacrylate) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 1,000,000, comprising about 65% t-butyl acrylate, and about 35% dimethylsiloxane macromonomer with a molecular weight weighted average of approximately 30,000. Poly [(t-butylacrylate-co-2-ethylhexyl) -graft-poly (dimethylsiloxane)] ester having a weight average molecular weight of about 700,000, comprising about 70% t-butyl acrylate, about 5% methacrylate 2-ethylhexyl, and P671 about 25% dimethylsiloxane macromonomer with a weight average molecular weight of about 15, 000 Poly [t-butyl-acrylate-co-2-ethylhexylmethacrylate) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 700,000, comprising about 70% t-butyl styrene, and about 20% poly (2-ethylhexylmethacrylate) of dimethylsiloxane macromonomer with a weight average molecular weight of about 5000. Poly [(t-butylacrylate-co-styrene) -graft-poly (isobutylene) [having a weight average molecular weight of about 150,000, comprising about 60% t-butyl acrylate, and about 20% styrene, and about 20% polyisobutylene macromonomer of di-ethylsiloxane with a weight average molecular weight of about 10,000.

Hydrophobic, Volatile Solvent The copolymer component of the present invention comprises from about 30% to about 98.5%, preferably from about 60% to about 95%, and more preferably from about 75% to about 95%, based on to the weight of the component P671 copolymer, of a hydrophobic solvent, volatile for the hydrophobic copolymer. The term "volatile", as used herein, means that the solvent exhibits a significant vapor pressure at ambient conditions (e.g., an atmosphere of 25 ° C, as understood by those skilled in the art. The solvent has a boiling point at an atmosphere of about 225 ° C or less, preferably about 220 ° C or less, or more preferably about 215 ° C or less, and most preferably about 210 ° C or less. In addition, the boiling point of the solvent will generally be at least about 50 ° C, preferably at least about 90 ° C. The solvent should also be acceptable for topical application to hair and skin. , volatile, suitable, are selected from the group consisting of branched chain hydrocarbon, silicones, and mixtures thereof., Branched chain hydrocarbons, hydrophobic, preferred olfactants useful as the solvent herein contain from about 7 to about 14, more preferably from about 10 to about 13, and in the form P671 more preferably from about 11 to about 12 carbon atoms. Saturated hydrocarbons are preferred, although it is not proposed to describe unsaturated hydrocarbons. Examples of these preferred branched chain hydrocarbons include isoparaffins of the above chain sizes. Isoparaffins are commercially available from Exxon Chemical Co .; examples include Isopar E (isoparaffins of 8 to 9 carbon atoms), Isopar MR H and K (isoparaffins> of 11 to 12 carbon atoms), and Isopar MR (isoparaffins of 11 to 13 carbon atoms). Other suitable branched chain hydrocarbons are isodecane and isoundecane. Isodecane is preferred and commercially available from Presperse, Inc. (South Plainfield, NJ., USA) as Permethyl ™ 99A. Preferred silicones useful as the hydrophobic, volatile solvent herein include volatile siloxanes such as phenyl-pentamethyl-disiloxane, phenylethylpentamethyl disiloxane, hexamethyl-disiloxane, methoxy-propylheptamethyl-cyclotetrasiloxane, chloropropyl-pentamethyl-disiloxane, hydropropyl-pentamethyl-disiloxane. , octamethyl-cyclotetrasiloxane, decamethi-cyclopentasiloxane, and mixtures thereof. The most preferred among the silicones are cyclomethicones, examples of which include octamethyl cyclotetrasiloxane, and decamethyl.

P671 cyclopentasiloxane, which is commonly referred to cyclomethicone D4 and D5, respectively. Carrier The rinsable or removable hair care compositions of the present invention also comprise a carrier, or a mixture of these carriers, which are suitable for hair application. The carriers are present from about 30% to about 99.75%, preferably from about 70% to about 96%, more preferably from about 82% to about 92% of the composition. As used herein, the phrase "suitable for application to hair" means that the wearer does not damage or negatively affect the aesthetics of the hair or cause skin irritation.

Hair Conditioner Where hair care compositions are conditioner compositions, the carrier may comprise gel vehicle materials. This gel vehicle comprises two essential components: a lipid carrier material and a cationic surfactant carrier material material. The cationic surfactant materials are described in detail P671 later. Gel-like vehicles are generally described in the following documents, all incorporated by reference herein: Barry, "The Self-Bodying Actoin of the Mixed Emulsifier Sodium Dodecyl Sulfate / Cetyl Alcohol," 28 J. Of Colloid and Interface Science 82- 91 (1968); Barry, et al, "The Self-Bodying Action of Alkyltrimethylammonium Bromides / Cetostearyl Alcohol Mixed Emulsifiers; Influence of Quaternary Chain Length", 35 J_ ^ Of Collopid and Interface Science 689-708 (1971); and Barry, et al., "Rheology of Systems containing Cetomacrogol 1000 - Cetostearyl Alcohol, I. Self bodying Action", 38 J. Of Colloid and Interface Science 616-625 (1972). Gel vehicles can incorporate one or more lipid carrier materials that are essentially insoluble in water, and contain hydrophobic and hydrophilic portions. The lipid carrier materials include naturally occurring or synthetically derived acids, acid derivatives, alcohols, esters, ethers, ketones and amine with carbon chains from about 12 to about 22, preferably from about 16 to about 18, carbon atoms of length. Fatty alcohols and fatty esters are preferred. Fatty alcohols are particularly preferred.

P671 Lipid carrier materials among those useful herein are described in Bailey's Industrial Oil and Fat Products, (3rd edition, D. Swern, ed., 1979), incorporated by reference herein. Fatty alcohols included among those useful herein are described in the following documents, which are incorporated by reference herein. U.S. Patent No. 3,155,591 to Hilfer, issued November 3, 1964; U.S. Patent No. 4,165,369, Watanabe et al., Issued August 21, 1979; U.S. Patent No. 4,269,824, to Villamarin et al., Issued May 26, 1981; British Specification 1,532,585, published November 15, 1978; and Fujushima et al. "The Effect of Cetostearyl Alcohol in Cosmetic Emulsions", 98 Cosmetics & Toiletries 89-112 (1983). The fatty esters included among those useful for example are described in U.S. Patent No. 3,341,465, Kaufman, et al., Issued September 12, 1976 (incorporated herein by reference). If included in the compositions of the present invention, a lipid carrier material is present from about 0.1% to about 10.0%, preferably from 0.1% to about 5%, of the composition; the vehicle material of surfactant Cationic P671 is present from about 0.05% to about 5.0%, preferably from 0.1% to about 3%, of the composition. Preferred esters for use herein include cetyl palmitate and glyceryl monostearate. Cetyl alcohol and stearyl alcohol are preferred alcohols. A particularly preferred lipid carrier material is composed of a mixture of cetyl alcohol and stearyl alcohol containing from about 55% to about 65% (by weight of the mixture) of cetyl alcohol. Preferred carriers for use in the compositions of the present invention include combinations of hydroxyethyl cellulose materials, hydrophobically modified with thickeners (such as xanthan gum), particular surfactants, quaternary ammonium compounds (such as tallow dimethyl ammonium) these vehicles are described in detail in U.S. Patent No. 5,100,658, issued to Bolich, R. .E., and collaborators on March 31, 1992; U.S. Patent No. 5,104,646, issued to Bolich, R. E., and collaborators on April 14, .1992; U.S. Patent No. 5,106,609, issued to Bolich, R. E. and collaborators on April 21, 1992, all incorporated herein by reference.

P671 Ampus Where hair care compositions are shampoo compositions, the carrier may include a surfactant material. The surfactant materials for the shampoo carriers of the invention comprise from about 5% to about 50%, preferably from about 10% to about 30%, more preferably from about 12% to about 25% of the composition. The anionic, synthetic detergents, useful herein, particularly for shampoo compositions, include alkyl ether and alkyl sulfates. These materials have the respective formulas ROS03M and RO (C2H40) xS03M, wherein R is alkyl or alkenyl from about 10 to about 20 ac4, x is from 1 to 10, and M is a water soluble cation such as ammonium, sodium, potassium, and triethanolamine. The alkyl ether sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. Preferably, R has from about 12 to about 18 carbon atoms both in the alkyl ether sulfates and in the P671 alkyl. The alcohols can be derived from fats, for example, coconut oil or tallow or can be synthetic. Lauryl alcohol and straight chain alcohols and derivatives from coconut oil are referred to herein. The alcohols are reacted with about 10, especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species, which have, for example, an average of 3 moles of ethylene oxide per mole of alcohol, if sulfate and neutralize. Specific examples of the alkyl ether sulfates that can be used in the present invention are triethylene glycol, alkyl, coconut, sodium sulfate; triethylene glycol ether sulphate, tallow alkyl, sodium; and tallow-alkyl, sodium, hexoxyethylene sulfate. Highly preferred alkyl ether sulfates are those which comprise a mixture of individual compounds, the mixture having an average alkyl chain length of from about 12 to about 16 carbon atoms and an average degree of stoxylation of about 1 to about 4 moles of ethylene oxide. This mixture also comprises from about 0 to about 20% by weight of compounds of 12 to 13 carbon atoms; from about 60 to about 100% by weight of P671 compounds of 14, 15 and 16 carbon atoms, from about 0 to about 20% by weight of compounds of 17, 18 and 19 carbon atoms; from about 3 to about 30% by weight of compounds having an ethoxylation degree of 0; and from about 45 to about 90% by weight of compound having an ethoxylation degree of from about 2 to about 4; from about 10 to about 25% by weight of compounds having an ethoxylation degree of from about 4 to about 8; and from about 0.1 to about 15% by weight of compounds having an ethoxylation degree of more than about 8. Another suitable class of anionic surfactants are the water-soluble salts of the reaction products of sulfuric acid, organic, from the General Formula: R1-S03-M wherein R is chosen from the group consisting of a straight or branched chain saturated, aliphatic hydrocarbon radical having from about 8 to about 24, preferably from about 12 to about 18, P671 carbon; and n is a cation. The important agents are the salts of a reaction product of sulfuric acid, an organic hydrocarbon of the methane series, which includes the iso-, neo-, ineso- and n-paraffins having from about 8 to about 24 carbon atoms, preferably from about 12 to about 18 carbon atoms, and a sulfonation agent, for example, S03, H2SO ", oil, obtained according to known sulfonation methods, including bleaching or hydrolysis. The sulfonated n-paraffins of 12 to 18 carbon atoms are preferred. with ammonium and alkali metal. Further examples of synthetic, anionic surfactants, which come within the terms of the present invention are the reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, where, for example, the fatty acids are derived from from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other synthetic, anionic surfactants of this variety are disclosed in U.S. Patent No. 2,486,921; 2,486,922 and 2,396,278. Still other synthetic surfactants, P671 anionic, include the class designated as succina atos. This class includes surface active surfactants such as disodium N-octadecylsulfosuccinamate; N- (1,2-dicarboxyethyl) -N-octadecylsulfosuccinamate tetrasodium; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sulfosuccinic acid. Other suitable anionic 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 alpha-olefins by means of unconverted sulfur trioxide, followed by neutralization of the reaction mixture under conditions such that any sultone that has been formed in the reaction is hydrolysed to give the corresponding hydroxy-alkane sulfonates. Sulfur trioxide may be liquid or gaseous and usually, but not necessarily, diluted by inert diluents, for example, by S02 liquids, chlorinated hydrocarbons, etc., when used in the liquid form, or by air, nitrogen, gas S02 , when used in the gaseous form. The alpha-olefins from which the olefin sulfonates are derived are mono-olefins which P671 have from about 12 to about 24 carbon atoms, preferably from about 14 to about 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosine. In addition to the true alkene sulphonates and a portion of the hydroxy alkane sulfonates, the olefin sulfonates may contain minor amounts of other materials, such as alkene disulfonates, depending on the reaction conditions, proportion of the reactants, the nature of the the starting olefins and the impurities in the side reactions and the olefin raw material during the sulphonation process. A specific alpha-olefin sulfonate mixture of the above type is more fully described in U.S. Patent No. 3, 332, 880, to Pflaumer and Kessler, issued July 25, 1967, incorporated herein by reference. Another class of organic, anionic surfactants are the b-alkyloxy alkane sulphonates. These compounds have the general formula: P671 0R2 H I í Rl - c - c - so3M I I H H where RL is a straight chain alkyl group having from about 6 to about 20 carbon atoms, R2 is a lower alkyl group having from about 1 (preferred) to about 3 carbon atoms, and M is a water soluble cation as described herein. Specific examples of the b-alkyloxy alkane-1-sulfonates, or alternatively 2-alkyloxy-alkane-1-sulfonates, having low sensitivity to hardness (calcium ion) useful herein include: potassium b-methoxidecane sulphonate, Sodium 2-methoxytridenesulfonate, potassium 2-ethoxytetradecylsulphonate, sodium 2-isopropoxyhexadecylsulphonate, lithium 2-t-butoxytetradecyl sulfonate, sodium b-methoxyoctadecylsulphonate, and ammonium bn-propoxydecylsulphonate. Many anionic, synthetic, non-soap surfactants are described in McCutcheon's, Detergents and Emulsifiers, 1984 Annual, published by Allured Publishing Corporation, which is incorporated herein by reference. Also, the Patent North American No. 3, 929,678, by Laughlin et al., P671 issued December 30, 1975, describes many other anionic surfactants as well as other types and is incorporated herein by reference.

Rinseable or removable compositions in general Nonionic surfactants, which are preferably used in combination with an anionic surfactant, amphoteric or zwitterionic, can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with a hydrophobic, organic compound, which may be aliphatic or aromatic alkyl. Examples of these preferred classes of nonionic surfactants are: 1. The polyethylene oxide condensates of alkyl phenols, for example, the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12. carbon atoms in either a straight chain or branched chain configuration, with alkylene oxide, the ethylene oxide being present in amounts equal to about 10 to about 60 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in these compounds can be derived from polymerized propylene, isobutylene, octane, or nonane, P671 example way. 2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine products which can be varied in the composition depending on the balance between the hydrophobic and hydrophilic elements that is desired. Compounds containing from about 40 to about 80% ethylene polyoxide by weight and having a molecular weight from about 5,000 to about 11.00 resulting from the reaction of ethylene oxide groups with a hydrophobic base constitute the product of reaction of ethylenediamine and excess propylene oxide, the base having a molecular weight of the order of about 2,500 to about 3,000, is satisfactory. 3. 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 by, for example, a condensate of ethylene oxide with 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.

P671 4. the long chain tertiary amine oxides correspond to the following general formula: R? R2R3N > 0 Where Rx is an alkyl, alkenyl or monohydroxyalkyl radical, of from about 8 to about 18 carbon atoms, from 0 to about 10 portions of ethylene oxide, and from 0 to 1 glyceryl portion, and R2 and R3 contains from about 1 to about about 3 carbon atoms and from 0 to about 1 hydroxy group, for example methyl, ethyl, propyl, hydroxyethyl, or hydroxypropyl radicals. The arrow in the formula is a conventional representation of a semipolar link. Examples of amine oxides suitable for use in this invention include dimethyl dodecylamine oxide, oleyl di (2-hydroxyethyl) amine oxide, dimethyloctylamine oxide, dimethyl-decylamine oxide, dimethyl tatradecylamine oxide, 3-oxide, 6,9-trioxoheptadecyldietylamine, di (2-hydroxyethyl) -tetradecylamine oxide, 2-dodecoxyethyldimethylamine oxide, 3-dodecoxy-2-hydroxypropyl (3-hydroxypropyl) amine oxide, dimethylhexadecylamine oxide. 5. The long chain tertiary phosphine oxides corresponding to the following general formula: P671 RR "R '* P -> O Where R contains an alkyl, alkenyl or monohydroxyalkyl radical ranging from about 8 to about 18 carbon atoms in the chain length, from 0 to about 10 portions of ethylene oxide and of about 1 portion of glyceryl and R 'and R'1 are each alkyl or monohydroxyalkyl groups containing from about 1 to about 3 carbon atoms. The arrow in the formula is a conventional representation of a semipolar link. Examples of suitable phosphine oxides are: dodecyldimethylphosphine oxide, tetradecyldimethylphosphine oxide, tetradecylmethylethylphosphine oxide, 3,6,9-trioxaoctadecyldimethylphosphine oxide, acetyldimethylphosphine oxide, 3-dodecoxy-2-hydroxypropyldi (2-hydroxyethyl) phosphine oxide. , stearyldimethylphosphine oxide, cetylethylpropylphosphine oxide, oleyldiethylphosphine oxide, dodecyldiethylphosphine oxide, tetradecyldiethylphosphine oxide, dodecyldipropylphosphine oxide, dodecyl di (hydroxymethyl) phosphine oxide, dodecyl (2-hydroxyethyl) phosphine oxide, tetradecylmethyl-2-hydroxypropylphosphine oxide , oleyldimethylphosphine oxide, 2-hydroxydedecyldimethylphosphine oxide.

P671 6. The long chain dialkyl sulfoxides containing a short chain alkyl or hydroxyalkyl radical of from about 1 to about 3 carbon atoms (usually methyl) and a long hydrophobic chain including alkyl, alkenyl, hydroxyalkyl or alkyl keto radicals, which contains from about 8 to about 20 carbon atoms, from 0 to about 10 portions of ethylene oxide and from or up to about 1 portion of glyceryl. Examples include: octadecyl-methyl sulfoxide, 2-cetotridecylmethyl sulfoxide, 3, 6, 9-trioctadecyl-2-hydroxyethyl sulfoxide, dodecyl-methyl sulfoxide, oleyl-3-hydroxypropyl sulfoxide, tetradecyl-methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecylbutylmethyl sulfoxide. The cationic surfactants useful in the compositions of the present invention, particularly the conditioner compositions, contain hydrophilic, quaternary ammonium or amino moieties, 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, all incorporated by reference herein: M.C. Publishing P671 Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent No. 3,155,591, Hilfer, issued November 3, 1964; U.S. Patent No. 3,929,678, Laughlin, et al., Issued December 30, 1975; U.S. Patent No. 3,959,461, to Bailey, et al., Issued May 25, 1976; and U.S. Patent No. 4,387,090, to Bolich, Jr., issued June 07, 1983. If included in the compositions of the present invention, the cationic surfactant is present from about 0.05% to about 5%. Among the cationic surfactant materials, which contains quaternary ammonium, useful herein are those of the general formula: R., R R » wherein Rx-R,) are independently an aliphatic group of about 1 to about 22 carbon atoms, or an aromatic, alkoxy, polyoxyalkylene, alkylamino, hydroxyalkyl, aryl, or alkylaryl group having P671 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. The ammonium, quaternary salts useful in the present have the formula: R2 R4 ++ I I Rl - N - (CH2) 3 - N - R6 2X I I R3 R wherein R1 is an aliphatic group having from about 16 to about 18 carbon atoms, R2, R3, R, R5, and R6 are selected from hydrogen and alkyl having from 1 to 4 carbon atoms, and X is an ion selected from halogen, acetate, phosphate, nitrate and alkyl sulfate radicals. These quaternary ammonium salts include tallow-propane-diammonium dichloride. Preferred quaternary ammonium salts include dialkyldimethyl ammonium chloride, wherein the alkyl groups have from about 12 to about 22 carbon atoms and are derived from P671 of long chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids produce quaternary compounds wherein Rj and R2 have predominantly 16 to 18 carbon atoms). Examples of quaternary ammonium salts useful in the present invention include ditallowdimethyl ammonium chloride, ditallow dimethyl ammonium methylsulfate, dihexadecyl dimethyl ammonium chloride, di (hydrogenated tallow) dimethyl chloride, dioctadecyl dimethyl chloride -ammonium, diethylsilyl-dimethyl-ammonium chloride, didocosyl-dimethyl-ammonium chloride, di (hydrogenated tallow) -di-ethyl-ammonium acetate, dihexadecyl-dimethyl-ammonium chloride, dihexadecyl-dimethyl-ammonium acetate, diphyo dipropyl ammonium, di-dimethyl-ammonium nitrate, di (co-butyl alkyl) -dimethyl-ammonium chloride, and stearyl-dimethyl-benzyl-ammonium chloride. Dichloromethyl ammonium chloride, dicetyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and cetyl trimethyl ammonium chloride are the preferred quaternary ammonium salts useful herein. The di- (hydrogenated tallow) dimethyl ammonium chloride is a quaternary ammonium salt, particularly preferred. Salts of primary, secondary and tertiary amines, fats, are also preferred cationic surfactants. The alkyl groups of these amines preferably have from about 12 up to P671 about 22 carbon atoms and can be substituted or unsubstituted. Secondary and tertiary amines are preferred, tertiary amines are particularly preferred. These amines, useful in the present invention, include stearamide-propyl-dimethyl-amine, diethylamino-ethyl-stearamine, dimethyl-stearamine, dimethyl-stearamine, dimethyl-soyamine, soyamine, myristyl-amine, tridecylamine, ethyl-stearylamine, N-sebopropane-diamine, ethoxylated stearylamine (5 moles of E.O.), dihydroxy-diethyl-stearylamine, and arachidylbehenylamine. Suitable amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate, alkyl sulfate salts. These salts include stearylamine hydrochloride, soyamine chloride, silylamine formate, N-sebopropane-diamine dichloride, and stearamidopropyl-dimethylamine citrate. The cationic amine surfactants included among those useful in the present invention are described in U.S. Patent No. 4,275,055, to Nachtigal, et al., Issued June 23, 1981, incorporated by reference herein. Zwitterionic surfactants useful in shampoos as well as conditioners are exemplified by those which can be broadly described as derivatives of ammonium, phosphonium and quaternary sulfonium compounds, Aliphatic PS71, 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 an anionic group of solubilization in water, for example, carboxy , sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is: R2 - Y (+) -.-- .. cH2 - R --Z ' wherein R2 contains an alkyl, alkenyl, or hydroxy-alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 portions of ethylene oxide and from 0 to about 1 portion of glyceryl; And it is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; R3 is an alkyl or monohydroxyalkyl group containing from 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, P671 and phosphate. Examples of these surfactants include: 4- [N, N-di (2-hydroxyethyl) -N-octadecylammonium] -butane-1-carboxylate; 5- [S, 3-hydroxypropyl-Shexadecylsulfonium] -3-hydroxypentane-1-sulfate; 3- [P, P-diethyl-P-3, 6, 9-trioxatetradexocylphosphonium] -2-hydroxy-propane-1-phosphate; 3- [N, N-dipropyl-N-3-dodecoxy-2-hydroxypropylammonio] -propane-1-phosphonate; 3- (N, N-dimethyl-N-hexadecylammonium) propane-1-sulfonate; 3- (N, N-dimethyl-N-hexadecylammonium) -2-hydroxypropane-1-sulfonate; 4- [N, N-di (2-hydroxyethyl) -N- (2-hydroxydedecyl) ammonium] -butane-1-carboxylate; 3- [S-ethyl-S- (3-dodecoxy-2-hydroxypropyl) sulfonium] -propanol-phosphate; 3- [P, P-dimethyl-P-dodecylphosphonium] propane-1-phosphonate; and 5- [N, N-di (3-hydroxypropyl) -N-hexadecylammonium] -2-hydroxy-pentane-1-sulfate. Other zwitterionics such as betaines are also useful in the present invention. Examples of betaines useful herein include the higher alkyl betaines, such as coco-dimethyl-carboxymethyl-betaine, lauryl-dimethyl-carboxymethyl-betaine, lauryl-dimethyl- P671 alphacarboxyethyl bean, ceti1-dimethyl-1-carboxymethyl-betaine, lauryl-bis- (2-hydroxyethyl) -carboxymethyl-betaine, stearyl-bis- (2-hydroxypropyl) -carboxymethyl-betaine, oleyl-dimethyl-gamma-carboxypropyl- betaine, and lauryl-bis- (2-hydroxypropyl) alpha-carboxyethyl-betaine. The sulfobetaines can be represented by coco-dimethyl-sulfopropyl-betaine, stearyl-dimethyl-s-l-phopropyl-betaine, lauryl-dimethylsulfoethyl-betaine, lauryl-bis- (2-hydroxyethyl) -sulfopropylbetaine and the like; amidobetaines and amidosulfobetaines, wherein the radical RCONH (CH2) 3 is attached to the nitrogen atom of betaine are also useful in this invention. Examples of amphoteric surfactants that can be used in the compositions of the present invention are those which are broadly described as derivatives of the secondary and tertiary amines, aliphatic, and in which the aliphatic radical can be straight or branched chain and in wherein one of the aliphatic substituents contains from about 87 to about 18 carbon atoms and one contains a water, anionic, solubilization group, for example, carboxy, sulfonate, sulfate, phosphate or phosphonate. Examples of compounds that fall within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, N-alkyl taurines such P671 as prepared by reacting dodecylamine with sodium isethionate according to the teaching of US Patent No. 2,658,072 N-higher alkyl aspartic acids such as those produced in accordance with the teaching of US Patent No. 2,438,091, and the products sold under the trademark "Miranol" and described in US Patent No. 2, 528,378. The surfactants mentioned above can be used alone or in combination in the hair care compositions of the present invention. The alkyl sulfates,. the ethoxylated alkyl sulfates, and mixtures thereof are preferred for use herein. The hair care compositions herein may contain a variety of other optional components suitable for rendering those compositions more cosmetically or aesthetically acceptable or to provide them with an additional benefit of utility. These optional, conventional ingredients are well known to those skilled in the art, for example, pearlescent aids, such as ethylene glycol distearate.; preservatives, such as benzyl alcohol, methylparaben, propylparaben, and imidazolidinyl urea; thickener and viscosity modifiers, such as diethyl amide of a long chain fatty acid (e.g., PEG 3 P671 lauric diethanolamide), cocomonoethanol amide, dimethicone copolyols, guar gum, methylcellulose, starches and starch derivatives; fatty alcohols, such as cetearyl alcohol; sodium chloride; sodium sulfate; polyvinyl alcohol; ethyl alcohol; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, and sodium carbonate; coloring agents, such as any of the dyes FC &C or D &C; hair oxidation agents (bleaching) such as hydrogen peroxide, perborate and persulfate salts; hair thinning agents such as thioglocolates; perfumes; sequestering agents, such as disodium ethyldiamine tatracetate; and copolymer palminating agents, such as glycerin and propylene glycol. These optional ingredients generally use individually at levels from about 0.01% to about 10.0%, preferably from about 0.05% to about 5.0% of the composition.

Plasticizers The plasticization of the copolymers of the present invention can dramatically impede the removal capacity of the copolymers with normal washing with shampoo. If it is limited by theory, it is believed P671 that the plasticization of the copolymer softens the polymer film in the hair; thus decreasing the stress to the cohesion rupture and increasing the tension to the cohesion break of the polymer. This in turn results in the billing of the polymer film during shampooing instead of the breaking of the adhesive bond to the hair. This results in incomplete removal of the copolymer and eventual accumulation of the residue in the hair. The compositions of the present invention are limited in the amount of materials that act as copolymer plasticizers. In the preferred embodiments, the compositions of the present invention should be substantially free of plasticizing materials, that is, they should contain less than about 2%, preferably less than about 1%, and preferably less than about 0.5% in weight, of plasticizing materials. The plasticizing materials are in general relatively non-volatile organic liquids compatible with the copolymer component. By "non-volatile" it is meant that the boiling point of the liquids is greater than or equal to about 260 ° C. A non-limiting list of example materials that can act as plasticizers of the copolymers of the present invention P671 include diisobutyl adipate, acetyl-tri-n-butyl citrate, di (2-ethyl-hexyl) azelate, 2-ethyl-hexyl-diphenyl phosphate, diisoctyl isophthalate, isooctyl-benzyl phthalate, butyl stearate , tri-2-ethyl-hexyl trimellitate, N-octyl neopentanoate, diisostearyl malate, colloidal fumed silica (such as Cab-O-Sil®, sold by Cabot Corp.) and more perfume materials. pH The pH of the present compositions should be between about 3 and about 9, preferably between about 4 and about 8.

Method of Use The hair care compositions of the present invention are used in conventional manners to provide the styling and retention benefits of the present invention. This method of use depends on the type of composition used but generally comprises the application of an effective amount of product to the hair, which is preferably wet or soaked. The products are subsequently rinsed off the hair before drying and styling. The methods of the present invention comprise the application of an effective amount of the compositions P671 of the present invention to hair. By "effective amount" is meant an amount sufficient to provide the desired styling and retention benefits of the hair, considering the length and texture of the hair, the type of product used, and the style and retention desired. Typical amounts are in general from about 0.5 g to about 50 g of the product.

WASTE INDEX The rinsing-off hair care compositions, which are described herein, have a hair residue index of about 20 or more, preferably about 35 or more, and more preferably of approximately 50 or more. The hair residue index of the compositions of the present invention can be measured by different in vitro techniques. For example, a preferred method is one in which the compositions are evaluated on human hair tufts, in repeated cycles that comprise the steps of shampooing the hair with a surfactant solution, treating the hair lock with the composition that is Remove by rinsing to be evaluated, rinse the hair and dry the hair. The P671 portion of hair is evaluated for the presence of waste after a defined number of cycles. For example, to determine the residue index, it is particularly useful to visually examine the hair lock to determine the presence of visible waste after finishing a multiple of five treatment cycles, ie, after 5, 10, 15, 20, 25 , and 30 cycles, and so on, until the point is achieved Visual end desired. The residue index is defined here as the number of treatment cycles in increments of 5 units, after which a visible residue is first visually observed on the hair. As already mentioned, the compositions of the present invention do not leave a visible residue on the hair locks, ie they do not exhibit a visible residue until after approximately 20 or more cycles. In other words, these compositions have a residue index of about 20 or more. More preferred are compositions that do not exhibit a visible residue until after approximately 35 or more cycles, in other words, these compositions have a residue index of about 35 or more. Still more preferred are compositions that do not exhibit a visible residue until after about 50 or more cycles, in other words, these compositions have a residue index of about 50 or more. Even though there is no upper limit for the residue index, it is recognized that the higher the index, the better the performance of the composition, as it does not leave a visible residue on the hair. In the present invention, the preferred method for measuring the residue index is as follows. Residue index measurements are made on strands of human hair that have been placed in the shape of a horse's tail, ie the hair is held firmly at one end. The lock that contains 20 grams of virgin, fine, dark brown hair that has a general length of approximately 8 inches, is the one used. These tufts contain hair fibers having an overall length of about 8 inches and an average hair fiber diameter of about 40 to about 70 microns. The average diameter of the hair fiber is determined by making measurements on at least 10 hair fibers in the sample of the hair. The diameter of the hair fiber can be verified using a micrometer or the standard microscopic techniques familiar to those with expertise in the field of cosmetics science. By "virgin hair" it is understood that the hair has not been subjected to chemical treatments such as discoloration or P671 permanent. The hair lock can be examined by standard electron microscopy techniques to evaluate hair quality, ie the condition of the hair cuticles can be examined. It has been found convenient to evaluate the residue index of a composition that is removed by rinsing in several strands of hair. The strands of hair are moistened with a water jet, with water at a temperature of 100 ° F and at a flow rate of about 1 gallon per minute. It is preferred to use gloves (eg surgeon's latex gloves) when handling hair to avoid contaminating hair samples with skin oils and other materials. Using a syringe, 1 cc of hair is applied to a surfactant solution which has the following composition in percentage by weight, and the hair is worked for approximately 15 seconds.

Surfactant solution for the residue index method Ingredient. Percent by weight Distilled water 78% Laureth-3 ammonium sulfate 13% Ammonium lauryl sulfate 9% with an average of about 3 ethylene oxide molecules incorporated per molecule (or alternatively 3 moles of ethylene oxide per mole of surfactant) .

The lock of hair is then rinsed with water (100 ° F, one gallon / minute) for 15 seconds, during which the lock of hair is gently pressed 3 times while running the fingers along the length of the hair. lock. Excess water is squeezed out of the hair. Using a syringe, the strand is then treated with 6 cc of the composition to be evaluated, which is removed by rinsing, work is done on the hair for approximately 15 seconds. The lock of hair is then rinsed with water (100 ° F, 1 gallon / minute) for about 15 seconds where the lock of hair is gently squeezed 12 times while running the fingers along the length of the lock. Excess water is squeezed out of the hair. The lock of the hair is then hung until it dries in a chamber having an air temperature of about 100 ° F, where the air flow is decreased to avoid entangling the tufts, for about 60 minutes. These steps of washing with surfactant, rinsing, treatment with the rinsing, rinsing, and air-drying composition constitute a cycle. After 5 of these cycles, the lock of the hair is examined visually while the P671 fingers, without a glove, are made to run through the strand to determine if there is residue of visible composition on the strands of hair. The residue must be such that it surrounds the hair fibers. The presence of these surrounding residues can be verified using an augmentation technique available to anyone with expertise in this field. If no visible surrounding residues are observed, additional groups of 5 wash cycles are repeated with surfactant, rinsed, treatment with the composition that is rinsed off, rinsed, and air dried, until visible surrounding residues are observed. Once the presence of a surrounding residue is established, the lock of hair is subjected to two vigorous washes with 1 cc of surfactant solution as described above, each followed by a 15 second rinse (100 ° F water, 1 gallon). / minute). If the residue remains after these two additional washes with surfactant, the composition that is removed by rinsing is defined with a residue index corresponding to the number of cycles completed before the two additional washes with surfactant. If no visible residue is observed after two additional washes with surfactant, additional groups of 5 cycles of treatment are performed on other substrates of the hair lock until a visible residue is observed.

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

EXAMPLE 1 AND 2 The following synthesis procedure is an example of the methods useful for synthesizing the copolymers of the present invention.

EXAMPLE 1 Synthesis of ppli (4-t-butyl styrene) -grafting- [poly (isobutylene) A. Synthesis of end-capped polyisobutylene macromonomer with acryloyl. Prepare a solution of 100 grams (0.024 mol) of polyisobutylene polymer capped at the end with P671 hydroxyl (PIB-OH) having a weight-average molecular weight of 4.172 g / mol by the conventional, latent, carbocationic polymerization of isobutylene (for example, as described in G. Kaszas, Poly. Bull., 20 , 413 (1989) Add a two-fold molar excess (4.84 g, 0.048 mol) of triethylamine to the solution, add this solution dropwise to a solution of acryloyl chloride (4.35 g, 0.048 mol) in methylene chloride. dry (100 g) at 0 ° C. 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.

B ^ Synthesis by batch of the copolymer. Place 5 parts of acrylic acid, 75 parts of t-butyl acrylate, and 20 parts of the polyisobutylene macromonomer (10,000 PM) from experiment IA in a flask. Add enough tetrahydrofuran as the reaction solvent to produce a final monomer concentration of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen or argon. Add the initiator, (2, 2'-azobisisobutyronitrile) to a level appropriate for the desired molecular weight. Typically, this is in the range of 0.5% to 1.0% by weight relative to the amount of monomer. Heat at 60 ° C and maintain this temperature for 48 hours while stirring. Finish the reaction on cooling to room temperature. The polymer is purified by complete drying of the reaction solvent in an oven.

C. Semi-continuous synthesis of the copolymer Place 5 parts of acrylic acid, 75 parts of t-butyl acrylate, and 20 parts of the polyisobutylene macromonomer (10,000 PM) from experiment IA in a flask. Add 300 parts of tetrahydrofuran as the reaction solvent to produce a final monomer concentration of 20%. Purge the vessel with an inert atmosphere, for example, nitrogen or argon. Add the initiator, (2, 2 * -azobisisobutyronitrile) as in experiment IB. Heat to 60 ° C and maintain this temperature. After the polymerization of these monomers has continued for about 15 minutes to about 1 hour, for example, about 30 minutes, add a second charge of monomer of 20 parts of acrylic acid 60 parts of t-butyl acrylate, to give a charge total monomer end of about 40% by weight. Keep at room temperature for 48 hours. Finish the reaction on cooling to room temperature. The polymer is purified at P671 completely dry the reaction solvent in an oven.

EXAMPLE 2 Synthesis of Poly [(t-butyl acrylate) -graft-polydimethylsiloxane)] Place 75 parts of t-butyl acrylate and 25 parts of polydimethylsiloxane macromonomer (11,000 PM) (commercially available from 3M, St. Paul, MN) in a flask. Add enough ethyl acetate as the reaction solvent to produce a final monomer concentration of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen or argon. Add the initiator (2,2'-azobisisobutyronitrile) to a level appropriate for the desired molecular weight. Typically, this is in the range of about 0.25% to about 1.0% by weight relative to the amount of monomer. Heat at 60 ° C and maintain this temperature for 48 hours while stirring. Finish the reaction on cooling to room temperature. The polymer is purified by, complete drying of the solvent in an oven. By varying the monomers and macromonomers used, the general procedures given above in Examples 1 and 2 are used to prepare other macromonomers and copolymers of the present invention.

P671 EXAMPLES 3-11 The hair care composition illustrated in Examples 3-11 is useful for application to hair to provide a styling and retention benefit. These compositions have a residue index of about 20 or more. The following Table 1 defines the non-limiting examples of copolymers that can be used in the hair care compositions shown in Examples 3-11. Each of Examples 3-10 is illustrated with the # 1 copolymer, however, any of the other copolymers of Table 1, or any other copolymer of the present invention may be employed. In Table 1, the relative weight percentages of the monomers and macromonomers are given.

TABLE 1 # 1 Poly [(t-butyl acrylate) -graft-poly (dimethyljsiloxane)] copolymer having a weight average molecular weight of about 900,000, comprising about 75% t-butylacrylate and about 25% dimethylsiloxane macromonomer with a Weighted average molecular weight of approximately 11,000.

P671 Copolymer # 2 Poly [(t-butyl acrylate) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 900,000, comprising about 80% t-butylacrylate and about 20% dimethylsiloxane macromonomer with a weighted average molecular weight of approximately 15,000.

Copolymer # 3 Poly [(t-butylstyrene) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 300,000, comprising about 70% of t-butylstyrene and about 30% of dimethylsiloxane macromonomer with a molecular weight weighted average of approximately 20,000.

Copolymer # 4 poly [(t-butyl acrylate-co-acrylic acid) -graft-poly (dimethylsiloxane)] having a weight average molecular weight of about 700,000, comprising about 67% t-butylacrylate, about 3% of acrylic acid, and about 30% di-ethylsiloxane macromonomer with a weight average molecular weight of about 11,000. # 5 Poly [(t-butyl acrylate) -graft-poly (dimethylsiloxane)] copolymer having a weight average molecular weight of about 1,000,000, comprising P671 about 65% t-butylacrylate and about 35% dimethylsiloxane macromonomer with a weight average molecular weight of about 30,000.

Copolymer # 6 poly [(t-butylacrylate-co-2-ethylhexyl) -graft-poly (dimethylsiloxane)] copolymer having a weight average molecular weight of about 700,000, comprising about 70% t-butylacrylate, about 5% of 2-ethylhexyl methacrylate, and about 25% dimethylsiloxane macromonomer with a weight average molecular weight of about 15,000.

Copolymer # 7 poly [(t-butylstyrene) -graft-poly (2-ethylhexylmethacrylate)] having a weight average molecular weight of about 150,000, comprising about 80% t-butylstyrene and about 20% poly (2) macromonomer -ethylhexylmethacrylate) with a weighted average molecular weight of about 5,000.

Copolymer # 8 poly [(t-butylacrylate-co-styrene) -graft-poly (isobutylene)] having a weight average molecular weight of about 150,000, comprising about 60% t-butylacrylate, about 20% styrene and about 20% of macromonomer of P671 polyisobutylene with a weight average molecular weight of about 10,000.

EXAMPLE 3 The following is a rinseable composition of hair conditioner, representative of the present invention. Ingredient% by weight Water c.b. for 100 Hydroxyethylcellulose Hydrophobically 0.25 Modified Stearalkonium Chloride 0.87 Cetyl Alcohol 1.85 Stearyl Alcohol 0.21 Stearamidopropyl Dimethylamine 0.50 Dimethicone Gum (CF1213) 2.33 Methylchloroisothiaolinone (y) 0.03 Methylisothiazolinone Perfume 0.33 Copolymer # 1 2.00 Trimethylsiloy-isilicate 0.21 Cyclomethicone 11.30 Available as Polysurf 67 from Aqualon Chemical Company. 2 Commercially available from General Electric. These compositions are prepared by dissolving copolymer # 1 in cyclomethicone D4 (solvent). The rubber of P671 dimethicone added to this solution. The other components (except for methylchloroisothiazolinone and methylisothiazolinone and the perfume) are mixed in a separate container at a sufficiently high temperature (80 ° C) to melt the solids. The polymer / solvent mixture and the dimethicone gum are separately added to the other components after they have cooled to at least 45 ° C. Finally, the methylchloroisothiazolinone (y) methylisothiazolinone, and the perfume, and the product are added. It is cooled to room temperature.

EXAMPLE 4 The following is a hair conditioner composition, representative of the present invention. Ingredient% by weight Water C.S. for 100 Hydroxyethylcellulose 0.50% Hydrogenated Distebodimethyl Ammonium Chloride 0.85% Cetyl Alcohol 0.90% Stearyl Alcohol 0.81% Ceteareth-20 0.50% Estearamidopropyl Dimethylamine 0.22% Dimethicone Gum (CF1213) 2 1.33% Methylchloroisothiaolinone (y) 0.03 • Methylisothiazolinone PG71 Perfume 0.33% Copolymer # 1 2.50% Mix [90/10] of Cyclomethicone D / 4D5 11.30% 1 commercially available from General Electric. This product is prepared by dissolving the # 1 copolymer in the mixture of cyclomethicone D4 / D5 (solvent) The other components (except methylchloroisothiazolinone (y) methylisothiazolinone and perfume) are mixed in a separate container at a sufficiently high temperature (80 ° C)) to melt the solids. The polymer / solvent mixture and the dimethicone gum are separately added to the other components after they have been cooled to at least 45 ° C. Finally, the methylchloroisothiazolinone (y) methylisothiazolinone and the perfume are added, and the product It is cooled to room temperature.

EXAMPLE 5 The following is a hair shampoo composition representative of the present invention. Ingredient% by weight C.S. for 100 Water Lauryl ammonium sulfate 3.14% Lauteth ammonium sulfate 13.56% Cetyl alcohol 0.45% P671 Stearyl Alcohol 0.19% Coconut Monoetanol Amide 3.00% Ethylene Glycol Distearate 2.00% Tricetylmethyl Ammonium Chloride 0.50% Methylchloroisothiaolinone (y) 0.03 Methylisothiazolinone Perfume 0.20% Copolymer # 1 4.00% Isododecane 7.40% This product is prepared by dissolving the # 1 copolymer in isododecane (solvent). The other components are mixed in a separate vessel at a temperature high enough to melt the solids. The polymer / solvent mixture is added to the other components with mixing after they have cooled.

EXAMPLE 6 The following is a hair shampoo composition representative of the present invention. Ingredient% by weight C.S. for 100 Water Cocoamidopropyl Betaine 8.30% Lauryl Ammonium Sulfate 2.12% Laureth Ammonium Sulfate 6.35% 'Monoethanol Coconut Amide 1.50% P671 Hydroxypropylmethylcellulose 0.25% Ethylene glycol distearate 1., 50% Tricetylmethyl ammonium chloride 0.50% Methylchloroisothiaolinone (y) 0..03 Methisothiazolinone Perfume 0., 20% Copolymer # 1 3. 00% Isododecane 10.00% This product is prepares by dissolving copolymer # 1 in isododecane. The other components are mixed in a separate vessel at a temperature high enough to melt the solids. The polymer / solvent solution is added to the other components after they have cooled.

EXAMPLE 7 The following is a rinseable gel hair styling composition representative of the present invention. Ingredient% by weight Polymer-solvent mixture Copolymer # 1 1.25% Isoparaffins1 of C11-C12 3.75% Water Premix 43.00% P671 Hydrogenated disodium chloride 1.00% Main mix Water 50.00% Carbomer 0.75% Pantenol 0.05% Perfume 0.20% 1 Available as Isoparh H from Exxon Chemical. 2 Available as Carbopol 940 from B.F. Goodrich. This composition is prepared by dissolving copolymer number 1 in the isoparaffins of 11 to 12 carbon atoms. The hydrogenated di-tallowonium chloride is mixed with water at 80 ° C. The polymer / solvent mixture is then added at a high or low temperature to the mixture of di-tallow-dimonium chloride. The resulting mixture is added with mixing to the remaining ingredients which are first mixed together in a separate vessel.

EXAMPLE 8 The following is a rinseable hair spray gel composition representative of the present invention. Ingredient% by weight C.S. for 100%, Water P671 Sertrimony Chloride 0.10% Hydrogenated Disodium Chloride 0.90% Panthenol 0.05% Perfume 0.20% Copolymer # 1 1.00% Hexamethyl-disiloxane 3.00% This composition is prepared by dissolving the # 1 copolymer in hexamethyldisiloxane. The other ingredients are mixed in a separate vessel at a high enough temperature, about 70 ° C to melt the solids. The polymer / solvent solution is added to the other components at a high or low temperature.

EXAMPLE 9 The following is a rinse composition of hair feel representative of the present invention. Ingredient,% by weight Premix A Water 4.98% Disodbodimony Chloride 1.43% Dimethicone rubber (CF1213) 1 2.33% Amodimethicone 0.10% P671 Premix B Water 9.97% 0.30% esteralconium chloride Pantenol DL 0.225% Ether-ethyl-pantil 0.025% Main mix Water '67.49% hydrophobically modified hydroxyethylcellulose 1.23% 0.25% xanthan gum Citric acid 0.02% Sodium citrate 0.09% Cetyl alcohol 0.12% Stearyl alcohol 0.08% Polymer-solvent mixture Copolymer # 1 1.75% Blend of [70/30] of cyclomethicone D4 / D5 8.54% Trimethylsiloxysilicate (SS4230) 1 0.21% Preservatives and fragrance Methylchloroisothiazolinone (and) Methylisothiazolinone 0.03 Benzyl alcohol 0.50% Perfume 0.33% Commercially available from GE.

P671 Available from Aqualon Chemical Company as Polysurf 67. The polymer / solvent mixture is prepared by dissolving copolymer # 1 in the mixture of cyclomethicone D4 / D5 (solvent) and trimethylsiloxysilicate is added. Premixes A and B are prepared separately by combining the indicated ingredients at 70 ° C. Separately, the main mix is also prepared by mixing the indicated ingredients. Premix A is placed through a colloid mill and cooled to 38 ° C. The polymer / solvent mixture, the methylchloroisothiazolinone (and) the methylisothiazolinone and the perfume are added to the main mixture which is ground and cooled to 38 ° C. C. Then, premixes A and B are added. Then, the benzyl alcohol is added.

EXAMPLE 10 The following is a rinse hair styling composition representative of the present invention. Ingredient % by weight Premix A Water 4.67% Di-tallow-dimonium chloride (Varisoft 470) 1.00% Dimethicone rubber (15% in cyclomethicone D5) 1.00% Amodimethicone 0.40% P671 Premix B Water 9.36% Stearalkonium Chloride 0.15% D, L-panthenol 0.225% Ether-ethyl-pantil 0.025% Main mix Water 63.53% hydrophobically modified hydroxyethylcellulose 1.00% Xanthan gum 0.10% Citric acid 0.02% Sodium citrate 0.09% Cetyl alcohol 0.60% Stearyl alcohol 0.40% Polymer-solvent mixture Copolymer # 1 2.50% Blend of [70/30] of cyclomethicone D4 / D5 14.17% Methylchloroisothiazolinone (y) Methylisothiazolinone 0.03 Perfume 0.33% Benzyl Alcohol 0.50% This composition is prepared by dissolving the # 1 copolymer in the mixture of cyclomethicone D4 / D5 (solvent). Premixes A and B were prepared separately by combining the indicated ingredients at 70 ° C.

PG71 Separately, the main mix is also prepared by mixing the indicated ingredients. Premix A is placed through a colloid mill and cooled to 38 ° C. The polymer / solvent mixture, the methylchloroisothiazolinone (and) the methylisothiazolinone, and the perfume are added to the main mixture which is milled and cooled to 38 ° C. Then, premixes A and B are added. Then, benzyl alcohol is added.

EXAMPLE 11 The following is a rinse composition of hair styling foam representative of the present invention. Ingredient% by weight Water C.S. for 100% Seborrimony Chloride 0.10% Hydrogenated Disodbondimony Chloride 0.90% Lauramine Oxide 0.20% Panthenol 0.05% Perfume, 0.20% Copolymer # 1 1.00% Hexamethyldisiloxane 3.00% Isobutane 7.00% This composition is prepared by dissolving the # 1 copolymer in hexamethyldisiloxane (solvent ). The P671 other components (except isobutane) are mixed in a separate container at a sufficiently high temperature (70 ° C) to melt the solids. The polymer / solvent solution is added to the other components after they have cooled. Then, aluminum aerosol cans are filled with 95 parts of this batch, equipped with a valve that is held in position, and finally filled with 5 parts of isobutane.

P671

Claims (1)

CLAIMS: 1. A hair care composition that is rinsed off, comprising: (a) from about 0.25% to about 70% of a copolymer component, comprising: (i) about 1.5% to about 70% by weight of the copolymer component, of a hydrophobic copolymer having a weight average molecular weight of between about 10,000 to about 5,000,000, the copolymer comprises a polymeric structure and hydrophobic polymeric side chains grafted to the structure, wherein the weight percent of the copolymer in the hair care composition that is removed by rinsing is from about 0.10% to about 7%; and (ii) from about 30% to about 98.5% of a volatile hydrophobic solvent having a boiling point at an atmosphere of about 225 ° C or less; and (b) from about 30% to about 99.75% of a suitable carrier to be applied to the hair, wherein the hair care composition that is removed by rinsing has a hair residence index of about 20 or greater. P671 2. A rinsing-off hair care composition according to claim 1, wherein the composition has a hair residue index of about 50 or greater. 3. A rinsing-off hair care composition according to claim 1, wherein the hydrophobically grafted copolymer is formed from the copolymerization of randomly repeating monomer units A and units of macromonomer B, wherein the copolymer comprises: ( a) from about 50% to about 85% of the monomer units A, wherein the monomer units A are monomer units copolymerizable with the macromonomer B units; and (b) from about 15% to about 50% by weight of the units of macromonomer B, wherein the units of macromonomer B are hydrophobic macromonomer units having a polymeric portion and a copolymerizable entity with the monomer units A. A composition according to claim 3, wherein the monomer units A are ethylenically unsaturated monomer units and the units of macromonomer B are units having a polymeric portion and an ethylenically unsaturated entity. 5. A composition according to claim 4, P671 wherein the monomer units A comprise hydrophobic monomers selected from the group consisting of esters of unsaturated carboxylic acid of C1-C18 alcohols, unsaturated alcohols, unsaturated hydrocarbons, aromatic hydrocarbons containing unsaturated alkyl groups, vinyl esters of carboxylic acids, vinyl ethers, allyl esters of carboxylic acids, aryl ethers and mixtures thereof. 6. A composition according to claim 5, wherein the monomer units A comprise hydrophobic monomers selected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, indene, norbornylene, ß-pinene, α-pinene, vinyl pivalate, vinyl neononanoate, dicyclopentenyl 1 acrylate, 4-biphenyl acrylate, pentachlorophenyl acrylate, 3,5-dimethyladandyl acrylate, 3,5-dimethyladanedyl methacrylate, 4-methoxycarbonylphenyl methacrylate , trimethylsilyl methacrylate, t-butyl styrene and mixtures thereof. 7. according to claim 5, wherein the macromonomers B have a weight average molecular weight of from about 5,000 to about 50,000 and are selected from the group consisting of polysiloxane macromonomers, polyalkylene macromonomers and mixtures P671 of them. 8. A composition according to claim 7, wherein the silicone macromonomers correspond to the formula: X (Y) nSi (R) 3.m (Z) m wherein X is a vinyl group copolymerizable with the monomer units A and the units of macromonomer B, Y is a divalent linking group, R is selected from the group consisting of hydrogen, alkyl, alkoxy, aryl and mixtures thereof, Z is a monovalent siloxane polymer entity having a number average molecular weight of at least about 1500, n is 0 or 1 and m is an integer from 1 to 3. 9. A composition according to claim 7, wherein the polyalkylene macromonomers correspond to the formula, [I] n- [W] mE wherein I is a initiating entity, n is an integer of 0 or 1, W is a hydrophobic monomer unit, E is an end cap group, and m is an integer of about 10 to about 2,000. P671 10. A composition according to claim 9, wherein I is selected from the group consisting of initiators derived from hydrogen ion, hydrogen radical, hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxide anion, C1-C20 carbocations, C1-C20 carbanions, C 1 -C 20 carbon radicals, C 1 -C 20 aliphatic alkoxy anions, C 1 -C 20 aromatic alkoxy anions, ammonium ions, C 1 -C 20 alkyl substituted ammonium ions, C 1 -C 20 alkoxy substituted ammonium ions, and mixtures thereof; W is selected from the group consisting of n-butyl acrylate, dodecyl acrylate, ethyl acrylate, 2-ethylbutyl acrylate, n-heptyl acrylate, n-hexylacrylate, iso-butyl acrylate, iso-decyl acrylate, iso-propyl acrylate, 3- methylbutyl acrylate, 2-methylpentyl acrylate, nonyl acrylate, octyl acrylate, 1-propyl acrylate, 2-ethylhexyl methylacrylate, octyl methacrylate, n-dodecyl methacrylate, n-octadecyl methacrylate, n-decyl methacrylate, n-pentyl methacrylate, isobutylene, isoprene , 1,2-butadiene, 1,3-butadiene, 5-methyl-1-hexene, 6-methyl-1-heptane, 4,4-dimethyl-1-petent, iso-butyl vinyl ether, styrene, methyl styrene, 3-methylstyrene, 4-methylstyrene, 2-t-butyl styrene, and mixtures thereof; and E is selected from the group consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vi? ilbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, P671 isobutenyl and mixtures thereof. 11. A composition according to claim 7, wherein the units of macromonomer B are selected from the group consisting of acryloyl, methacryloyl, or polymers capped with 2-, 3-, or 4-vinylbenzyl being the polymers of polydimethylsiloxane, polydiethylsiloxane, polyphenylmethylsiloxane , polyphenylethylsiloxane, poly (n-butylacrylate), poly (dodecyl acrylate), poly (2-ethylhexyl acrylate), poly (2-ethylbutyl acrylate), poly (n-ethyl acrylate), poly (n-heptyl acrylate), poly ( n-hexyl acrylate), poly (iso-butyl acrylate, poly (iso-decylacrylate), poly (isopropyl 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 (n-pentyl methacrylate), poly (isobutylene), poly (isoprene), poly (1,2-butadiene or) hydrogenated, hydrogenated poly (1,4-butadiene), poly (hydrogenated isoprene, poly (1,2-butadiene), poly (1-butene), poly (5-methyl-1-hexene), poly (6) methyl-l-heptene), poly (4,4-dimethyl-1-pentene), poly (iso-butyl vinyl ether), poly [4-t-butyl vinyl benzene-co-2-ethylhexyl acrylate], poly [ 2-ethylhexyl acrylate-co-octyl acrylamide), poly [2-ethyl vinyl benzene-co- P671 octyl methacrylate)], and mixtures thereof. A composition according to claim 1, wherein the hydrophobic copolymer is selected from the group consisting of poly [(-butylacrylate) -graft-poly (dimethylsiloxane)], poly [(4-t-butylstyrene) -graft-poly ( di ethylsiloxane)], poly [poly-t-butylacrylate) -graft-poly (isobutylene)], poly [(-butylacrylate) -graft-poly (dimethylsiloxane); polyisobutylene)]; poly [4-t-butylstyrene) -graft-poly (dimethylsiloxane); polyisobutylene)]; poly [poly (4-t-butylesterino-graft-poly (isobutylene)], poly [(t-butylstyrene-graft-poly (2-ethylhexyl methacrylate)], poly [(4-t-butylacrylate-co-styrene) - graft-poly (isobutylene)] and mixtures thereof 13. A composition according to claim 12, wherein the hydrophobic volatile solvent is selected from the group consisting of C7-C14 branched carbides, cyclomethicones and mixtures thereof. A composition according to claim 1, in the form of a conditioner wherein the carrier comprises from about 0.1% to about 10.0% of a lipid material based on the weight of the composition that is removed by rinsing, and from about 0.05% to about 5% by weight of the composition, of a cationic surfactant. P671 15. A composition according to claim 14, wherein the cationic surfactant is a quaternary ammonium surfactant. 16. A composition according to claim 15, wherein the lipid material is selected from the group consisting of cetyl alcohol, stearyl alcohol, cetyl palmitate, glyceryl monostearate and mixtures thereof. 17. A composition according to claim 1, in the form of a shampoo wherein the composition further comprises from about 10% to about 30% by weight of the total composition of one or more of the surfactants. 18. A composition according to claim 17, wherein the surfactant is selected from the group consisting of alkyl sulfates, ethoxylated alkyl sulphates and mixtures thereof. 19. A method for styling the hair comprising applying thereto an effective amount of a composition according to claim 1. 20. A method for fixing the hair comprising applying thereto an effective amount of a composition according to claim

1. P671