MXPA97008097A - Topical composition of personal care containing copolymer grafted with silicone and blocked at the end with his styrene or alken - Google Patents

Abstract

Topical compositions for personal care containing aqueous or hydroalcoholic carriers and silicone-grafted copolymers with monomers containing acids, characterized in that it presents a hydrolysis substantially improved or eliminated from the silicone portion of the copolymer, these compositions are obtained by the selection of specific types of silicone macromers for incorporation into silicon-grafted copolymers. The silicone macromers are selected from the group consisting of end-terminated silicone macromers with alkenyl and end-styrene silicone macromers with styrene, and combinations thereof. The silicone macromers are polymerizable and ethylenically unsaturated monomers having an end-capped silicone group with styrene or alkenyl attached covalently to the ethylenically unsaturated portion of the monomer, by end blocking with styrene or alkene

Description

TOPICAL COMPOSITION OF PERSONAL CARE CONTAINING COPOLYMER GRAFTED WITH SILICONE AND BLOCKED AT THE END WITH A STYRENE OR ALOUENILO TECHNICAL FIELD The invention relates to topical personal care compositions containing silicone-grafted copolymers and an aqueous or hydroalcoholic carrier suitable for application to the skin or hair, wherein the silicone-grafted copolymer is soluble or dispersible in the continuous phase of the carrier BACKGROUND OF THE INVENTION The use of silicone-grafted copolymers in a wide variety of topical care compositions, for example hair care and skin care compositions, is widely known. These polymers are useful for their adhesive and film-forming properties, they can be used as additives in sprays for hair, foams and lotions, as well as for a wide variety of skin care products such as skin conditioning compositions. and cosmetic compositions, wherein their film-forming properties are used to soften the skin or as an auxiliary in administration to P497 the skin of another type of ingredients. One of the main benefits of silicone-grafted copolymers is that the silicone portions provide improved tactile properties relative to conventional polymers. For example, hair treated with these compositions retains its combed shape according to the wishes of the user, and still feels softer than hair combed with conventional hair styling polymers. Skin treated with polymers focused with silicone feels softer to the touch than that treated with conventional polymers. One of the most desired and least expensive ways to use silicone-grafted copolymers is to formulate them in aqueous or hydroalcoholic carriers, where the silicone-grafted copolymers are soluble or are stably distributed through the aqueous / hydroalcoholic phase. An alternate and also desired type of compositions provides silicone grafted copolymers solubilized in a non-aqueous solvent, for example cyclomethicone or hydrocarbon, which are emulsified in the form of droplets distributed through the aqueous carrier in hydroalcoholic. While this type of formulation is useful and desired for many types of products, it is more desirable and less expensive for many other products to use silicone-grafted copolymers that are P497 soluble or dispersed in a stable manner in non-emulsified forms and different from the drops, in the aqueous or hydroalcoholic carrier. One of the preferred types of silicone-grafted copolymers is used in aqueous topical compositions for personal care, especially for hair spray compositions, containing acrylic acid monomers and silicone macrosols blocked at the end by a methacryloxy propyl. It is greatly desired to use acrylic acid monomers since the acid group provides a high degree of polarity which allows the polymer to be soluble or dispersible in hydroalcoholic carriers or water. Other fairly polar monomers, such as cationic monomers, can provide similar solubility to polymers but tend to be more hydroscopic. This can result in the product becoming tacky during use, in particular during wet conditions. Unfortunately, it has been found that these silicone-grafted copolymers tend to hydrolyze in the aqueous or hydroalcoholic products at an undesirable high rate, resulting in the separation of the silicone portion from the rest of the polymer. Similar copolymers that contain the same type of silicone macromer but do not contain the acid monomers P-197 acrylic do not hydrolyze at these high rates. Thus, apparently the hydrolysis problem occurs surprisingly only when the polymer contains an acrylic acid or other acid-containing monomer. Hydrolysis is a matter of concern since a wide variety of products contain water as the co-solvent or primary solvent for hair styling polymers and other adhesive polymers for skin and hair care. It is a matter of particular importance in view of the current trend towards the development of products that have a high water content and lower levels of volatile organic compounds (known as VOCs). Of particular interest is the tendency to regulate the product to contain low levels of volatile organic compounds, for example, regulations that set a range between 55% and 80% are currently anticipated or already in force in many countries. of volatile organic compounds. Because this trend of topical personal care products with reduced levels of volatile organic compounds continues, formulas based on volatile organic compounds will be replaced in full and in part with aqueous and hydroalcoholic formulas. It is an object of this invention to provide topical hydroalcoholic compositions for personal care, containing silicone-grafted copolymers having improved stability as compared to hydrolysis. It is also an object of this invention to provide compositions as described above containing acrylic acid or other acid-containing monomers in the silicone-grafted copolymer, or which otherwise provide the product attributes found in these polymers. Another object of the invention is to provide compositions that comply with the above objects and that contain zero or relatively low levels of volatile organic compounds. These and other benefits of the present invention that will be immense to those skilled in the art will be attainable with the invention which will be described below. Unless otherwise indicated, all percentages are calculated based on the total weight of the composition and all proportions are calculated based on weight. Unless otherwise indicated, the ingredient amounts are given based on the active level and therefore do not include carriers or by-products that could have been included in the materials that are commercially or otherwise spread. The present invention comprise, consist of or consist essentially of any of the essential ingredients and various optional and / or preferred food ingredients described herein. The terms "soluble" and "insoluble" will refer to the solubility characteristics in particular ingredients of the composition, unless otherwise specifically indicated. All viscosities and solubilities are determined at 25 ° C, unless otherwise specifically indicated. Also, unless otherwise indicated, all percentages of the weight of the composition herein are given based on the total weight of the composition excluding any propellant that could possibly be incorporated into the product or contemplated in some other way.

SUMMARY OF THE INVENTION Topical personal care compositions containing aqueous or hydroalcoholic carriers and copolymers grafted with silicones, characterized by a substantially unexpected or eliminated hydrolysis of the silicone portion of the copolymer, can be maintained according to the present invention. It has been found that these compositions can be obtained by combining acid-containing monomers with the selection of specific types of macromers and silicones to be incorporated into the copolymer grafted with silicone. The silicone macromers of the present are selected from the group consisting of silicone macromers blocked at the end with alkenyl and silicone macromers blocked at the end with styrene, and combinations thereof. The silicone macromers are ethylenically saturated polymerizable monomers having a silicone subgroup desired at the end with styrene or with alkenyl, covalently bonded to the ethylenically unsaturated portion of the monomer, via the terminal block termination of styrene or alkenyl. The compositions herein can be used in a wide variety of topical applications for personal care, including hair care compressors, for skin care, are especially useful for hair care products are especially useful for products for hair styling, for example hair sprays, hair lotions, hair tonics, foams, hair rinses and shampoos, other useful applications of the specific product include skin care compositions, for example skin moisturizers and other skin conditioning compositions, sunscreens, sun tanning compositions, skin cleansing compositions, anti-acne compositions, topical analgesic compositions and other topical skin compositions containing drugs. Skin care compositions also include cosmetics. More specifically, the present invention provides topical personal care compositions containing silicone-grafted copolymers having improved resistance to hydrolysis, these compositions comprising: (a) from about 0.1% to about 50% by weight of the copolymer composition grafted with silicone containing: (i) from about 1% to about 99% by weight of the copolymer of acid-containing monomers, the acids of the acid-containing monomers are preferably selected from the group consisting of carboxylic acid and sulfonic acid , and combinations thereof; (ii) from about 1% to about 50% silicone macromers having the formula: X-CHj- (CH2) s-S1 (Ri) 3.pr-zm wherein: s is an integer from 0 to about 6; m is an integer from 1 to 3, R 2 is alkyl C -Co or alkylarylC, or n is integer from 0 to 4; X is an ethylenically unsaturated group of the formula: CH = C- I I R3 R4 wherein R 3 is -H or Ci-Cß alkyl, * R 4 is H or C 1 -C 5 alkyl; Z is R1 I RHSiOJr- R1 wherein each R is independently an alkyl, aryl or alkylaryl having from 1 to 10 carbon atoms, and r is an integer from about 4 to about 700, and combinations thereof; (iii) from about 0% to about 98% additional monomers and combinations thereof and (b) from about 1% to about 99.9% by weight of the composition of an aqueous or hydroalcoholic solvent of the silicone graft copolymer, applied to apply to hair > or to the skin, wherein the copolymer is soluble or dispersible in the solvent.

The present invention is described in more detail below in the Detailed Description of the Invention.

DETAILED DESCRIPTION OF THE INVENTION The topical hair care compositions of the present invention generally comprise: (a) from about 0.1% to about 50% by weight of the silicone-graft copolymers blocked at the end with styrene or with alkenyl of the present; preferably between about 0.2% to about 20%, more preferably between about 0.5% to about 15%, and still more preferably between about 1% to about 10%, and superlatively preferred between about 2% to about 8%; and (b) between about 1% to about 99.9% by weight of an aqueous or hydroalcoholic solvent for the silicone-grafted copolymer suitable for application to the skin or hair, preferably between about 50% to about 99.8%, as is preferably between about 60% to about 99.5%, still more preferably between about 70% to about 99%, and most preferably between about 80% to about 98%. The soluble silicone-dried copolymer or P4O7 dispersible in an aqueous or hydroalcoholic solvent. The topical personal care compositions herein are, by definition, suitable for topical application to the skin and hair. By "suitable for topical application to the skin or hair" is meant that the compositions are safe between topical application to the skin and hair when used in the manner for which they were designed and are effective to deliver the copolymers of the same to the skin or hair, so that the copolymer can provide the intended benefit.

Aqueous or hydroalcoholic solvent The aqueous or hydroalcoholic solvent for the copolymers of the present invention can be water or a combination of water and one or more C?-C6 monohydric alcohols, preferably C2-C3 alcohols, more preferably C2 alcohol (i.e. ethanol). The levels of aqueous or hydroalcoholic solvents are described above. By "hydroalcoholic" is meant any mixture of water and one or more alcohols containing at least about 0.5% by weight of solvent, of water. For hair care products, in general, for example hair sprays and foams, the compositions herein will generally comprise at least P497 less about 5% water, preferably at least about 10% water and more preferably at least about 20% water. In another aspect of this invention, the compositions herein are characterized by reduced levels of volatile organic compounds (VOC) and will comprise from about 40% to about 99.9% water and from 0% to about 80% monohydric alcohols, and preferably from 0% to about 55% monohydric alcohols. In a particularly preferred embodiment of aerosol hair removal compositions or in another form, the compositions will comprise from about 40% to about 75% water and from about 20% to about 55% monohydric alcohol, or from about 40% to about 95% water and about 0% to about 55% monohydric alcohol. In volatile organic compound compositions, the total level of these will preferably be no greater than about 80% by weight of the composition, including propellants, preferably not more than about 55%. For the purposes of this, VOCs are defined as any organic compound (including silicones) that either have a vapor pressure at 20 ° C of 0.1 mm Hg P497 or greater, or contain 12 or less carbon atoms. Conversely, organic compounds having a vapor pressure of less than 0.1 mm Hg under the same conditions or containing more than 12 carbon atoms are defined herein as non-volatile. The silicone-graft copolymers blocked at the styrene and alkenyl end of this invention are soluble or indispensable in the hydroalcoholic or aqueous solvent. This is an important contrast to the situation where the copolymer is not soluble or dispersible in the solvent, there being in this form a separate or discontinuous phase with respect to the solvent. Other solvents, co-solvents and solubilization aid may be incorporated into the compositions herein to assist in the solubilization of the copolymer without departing from the spirit or purpose of this invention. Examples of these ingredients include, without limitation, emulsifiers, surfactants and di- and trihydric alcohols.

In-End Copolymer with Silicone Blocked at the End with Styrene / Alkenyl The silicone-grafted copolymer (hereinafter sometimes simply referred to as the "copolymer") constitutes an essential component of the present invention.

P497 The term "copolymer", in the sense used herein, refers to polymers derived by polymerization of one or more different monomer species. The copolymers herein are made by the copolymerization of one or more types of monomers that transfer acids, one or more species of certain silicone macromers blocked at the end with styrene or alkenyl (or a mixture thereof) and, optionally, one or more types of monomers. For convenience, the copolymers of the present can sometimes refer to the fact that they are derived from monomers and macromers, it being understood that the copolymers are made by the copolymerization of these monomers and macromers. The term "monomer" in the sense used herein means ethylenically unsaturated compounds capable of polymerizing to form copolymers, in the manner defined herein. The term "macromer", in the sense in which it is used herein, will refer to a monomer characterized by having a polymeric substituent. The essential macromers of the present invention are silicone macromers, it being understood that the macromers have the silicone as a polymeric substituent. Also, the copolymers of the present can sometimes be said to comprise the monomers and macromers, it being understood that the copolymer comprises units corresponding to the macromers and P497 pre-polymerization monomers indicated.

Acid-Containing Monomers The copolymers herein comprise from about 1% to about 99% by weight of the copolymer, of the acid-containing monomers. In general, the copolymers will preferably comprise between about 5% to about 90%, more preferably between about 10% to about 80%, and still more preferably between about 15% to about 75%. The particular level of the acid-containing monomer that is preferred for any specific understanding may vary depending on the type of formulation and the intended use, as well as the types and amounts of these monomers and macromers in the copolymer and the molecular weight of the copolymer. For hair spray and other hair care compositions, for example, the copolymer preferably comprises from about 5% to about 50%, by weight of copolymer, of the acid-containing monomer, more preferably of between about 10% at about 35%, and still more preferably between about 15% to about 25%. The monomers that contain acid preferably P497 will be selected from the monomers containing acid groups selected from the group consisting of carboxylic acids. and sulfonic acid, more preferably carboxylic acids. Other acid-containing monomers can also be used, including, without limitation, monomers containing phosphoric acid. Combinations of the above acid-containing monomer cycles may also be included. The acid-containing monomer units which are present in the final copolymer can be derived from the acid-containing starting monomers, which are polymerizable, or from polymerizable non-ionic monomers which are subsequently modified for polymerization into the acid functional groups. Within the term acid-containing monomers are the neutralized regions ie, salts of the monomers herein. The neutralization is discussed in more detail below. Examples of acid-containing monomers include: (i) carboxylic acid-containing monomers, including those corresponding to the formula: R R P497 wherein R5 and R6 are independently H or C -Ce alkyl, preferably H or methyl; R 7 is H, C -Ce alkyl or a carboxylic entity having up to about 12 carbon atoms, preferably H or methyl, or if R 7 is a carboxylic acid entity, preferably acrylic acid; and R is a carboxylic entity having up to about 12 carbon atoms. Specific examples of carboxylic acid-containing monomers include acrylic acid, methacrylic acid, maleic acid, middle ester of maleic acid, itaconic acid, fumaric acid, and protonic acid, medium esters of polybasic acid anhydride such as, for example, sulfuric anhydride, phthalic anhydride or the like, reacted with an acrylate containing hydroxyl group and / or a methacrylate such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and the like. (ii) monomers containing sulfonic acid such as styrenesulfonic acid and sulfoalkyl acrylate and sulfoalkyl methacrylates, preferably with Ci-Cß alkyl groups, more preferably C2 alkyl groups, such as sulfoethyl acrylate, sulfoethyl methacrylate and the like. (iii) monomers containing phosphoric acid, for example phosphoxyalkyl acrylates and methacrylates, Preference is given to C!-C6 oxyalkyl groups, more preferably C ox-C3 oxyalkyls. Specific examples include phosphoxyethyl acrylate, phosphoxyethyl methacrylate, phosphoxypropyl acrylate of 3-chloro-2-phospho-oxypropyl methacrylate and the like. Preferred acid-containing monomers are carboxylic acids and sulfonic acids. Most preferred are carboxylic acids. Examples of acid-containing monomers that are more preferred are acrylic acid, methacrylic acid and styrenesulfonic acid. Acid-containing monomers such as acrylic acid and methacrylic acid are especially preferred.

Silicone Macromers Blocked at the End with Styrene and Alkenyl The copolymers herein comprise between about 1% to about 50% by weight of the copolymer of silicone macromers blocked at the end with styrene, the silicone macromers blocked at the end with alkenyl or a combination thereof, preferably from about 2% to about 40%, more preferably from about 5% to about 40%, still more preferably from about 5% to about 25%.

P497 By end-blocked silicone macromer with "styrene" or "alkenyl" it is to be understood that the macromer contains a silicone ie a polymeric siloxane group or "polysiloxane" that is covalently linked to the monomer by a styrene or group group alkenyl, respectively. The silicone macromers blocked at the end with styrene that are preferred and the macromers blocked at the end with alkenyl that are preferred in the present invention have the following formulas, respectively: X-CH2- (CH2) s-Si (R1) 3-m-Zm wherein: s is an integer from 0 to about 6, preferably 0, 1 or 2, more preferably 0 or 1; m is an integer from 1 to 3, preferably 1; R 2 is a C 1 -C 10 alkyl or C 7 -C 10 alkylaryl, preferably C 1 -C 6 alkyl or C 7 -C 0 alkylaryl, more preferably alkyl, -02; n is an integer from 0 to 4, preferably 0 or 1, more preferably 0; X is an ethylenically unsaturated group P497 (before polymerization) of the formula: CH = C-? 3 R4 where R 3 is H or C 1 -C 6 alkyl; preferably H or C! -C2 alkyl, more preferably H; R 4 is H or C 1 -C 2 alkyl, preferably H or C 1 -C 2 alkyl, more preferably H or methyl; Z is: wherein: each R is independently an alkyl, aryl or alkylaryl having from 1 to 10 carbon atoms, preferably C 1 -Cg alkyl, more preferably C 1 -C 2, and still more preferably methyl; and r is an integer from about 4 to about 700, preferably from about 50 to about 500, more preferably from about 100 to about 300; and combinations thereof. For hair care compositions, for example hair sprays, it is more preferably about 150 to about 200. Preference is given to silicone macromers blocked at the end with styrene. The silicone portion of the macromer is preferably constituted at the para or meta positions of the aromatic ring in relation to X, more preferably in P497 the position for. If n is not 0, then the group or groups R 2 of preference are substituted in the target positions. The ortho positions preferably, although not necessarily, are not substituted. Silicone macromers blocked at the end with styrene and alkenyl and methods for making it are well known in the art. Refer, for example, to Holohan, George, Barrie, and Parker, "Monofunctional Polydimethylsiloxane Oligomers For Graft Copolymerization", Macromol. Chem. Phys. 195, 2965-2979 (1994), which disclose silicone macromers where s = 0 for macromer blocked at the end with styrene and where s = 0 or an integer of silicone macromers blocked at the end with alkenyl . Another disclosure that relates to the methods of making silicone macromers of the present may be found in the experimental section, below.

Additional Monomers The copolymers herein, in general, comprise from about 0% to about 98% by weight of the copolymer, of additional monomers other than the acid-containing monomers and the silicone macromers blocked at the end with styrene or alkylene which is describe before, preferably they comprise of P497 about 0% to about 80%, more preferably from 20% to about 70% of those additional monomers. For hair care compositions such as hair sprays, the copolymers preferably comprise from 40% to about 70% additional monomers. The use of additional monomers may be desired in particular to increase the Tg of the copolymer, as described in more detail below, is to adjust the solubility of the copolymer, depending on the particular types and levels of other copolymers and the type and amount of the solvents. aqueous or hydroalcoholic. When used in whole or in part for either or both of these purposes, the additional monomers will generally be used at a level of at least about 1% by weight of the copolymer and, generally, at least about 2% by weight of the copolymer. %, preferably at least about 5%, more preferably at least about 10%. A wide variety of additional monomers may be employed. These include nonionic monomers, cationic monomers and amphoteric monomers. The non-ionic monomers may be either high or low polarity monomers. The cationic monomers can be solubilized in the cationic state or can be polysteized as a non-ionic protector which is then quaternized or P497 is subsequently made cationically for polymerization. If the cationic monomers are those to be employed, it is preferred that the weight percentage of at least one of the monomers, whether cationic or acid-containing, is not greater than about 10%, preferably not more than about 5%. , to decrease the appearance of ionic interaction between the charged groups. Examples of non-ionic monomers of low polarity are: esters of acrylic and methacrylic acid of C 1 -C 4 alcohols, such as methanol, ethanol, allyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-methyl -l-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-methanol, 1-methyl-1-pentanoi, 2 -methyl-l-pentanol, 3-methyl-l-pentanol, t-butanol, cyclohexanol, 2-methyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol, 2 -methyl-1-hexanol, 3, 5-dimethyl-l-hexanol, 3,5,5-triethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol, oleyl alcohol, alcohol of isobornyl, tetrahydrofurfuryl alcohol and the like, the alcohols preferably have an average number of carbon atoms of between about 1-18, more preferably between about 1-12; styrene; alkylstyrene, preferably with C? -C alkyl & , for example t- P497 butyl styrene; chlorostyrene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl chloride, vinyl toluene; vinyl caprolactam; vinylidene chloride; acrylonitrile; alpha-alkylstyrene, preferably with Cx-Cg alkyl groups such as alpha-methylstyrene; 1,3-dialkene, such as butadiene and cyclohexadiene, ethylenically unsaturated hydrocarbons, preferably C al-Cs alkene, for example ethylene and propylene; alkoxyalkyl (meth) acrylates, preferably with C 1 -C 6 alkyl groups, such as methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate; and alkyl vinyl ethers, preferably alkyl vinyl ethers Ci-C ?, like methyl vinyl ether. Other non-ionic monomers of low polarity include: acrylate and methacrylate derivatives such as di-acrylates and di-methacrylates, for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butylene glycol di-methacrylate acrylate; and diacetone-acrylamine. As a sense used herein the term "(meth) acrylate" means that both acrylate and methacrylate are included. The required non-ionic monomers of low polarity include n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, t-butylacrylate, t-butyl methacrylate and mixtures thereof. Examples of high non-ionic monomers P497 polarity include: acrylamide; methacrylamide; N, N-dialkyl (meth) acrylamide, especially with C 1 -C 6 alkyls, preferably methyl, such as, for example, N, N-dimethylacrylamide; N-alkyl acrylamide, especially with C? -C alkyl & , such as, for example, N-t-butyl acrylamide and isopropylacrylamide; acrylate and methacrylate alcohols, especially C2-Cs (meth) acrylate alcohols, for example hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; vinyl pyrrolidone, allyl alcohol and vinyl alcohol (made by the hydrolyzation of vinyl acetate after polymerization). Cationic monomers include ethylenically unsaturated, quaternizable, amino-functional monomers, such as the amino functional derivatives of styrene, acrylamide, methacrylamide, (meth) acrylates such as C! -C5 alkyl esters of acrylic acid and methacrylic acid. Preferably, alkylamines are 0.05, especially C1-C3 amines. It is preferred to use tertiary amines (for example dialkylamine) although it is not necessarily understood that monoalkylamines, dialkylamines and other alkylamine derivatives should be excluded. Especially preferred are the C1-C3 alkylamines diethylamines. These monomers may be quaternized before or subsequent to the polymerization, preferably subsequent to the polymerization.

P497 Cationic monomers include: (i) monomers derived from acrylic acid or methacrylic acid, hereinafter collectively referred to as (meth) acrylic acid and quaternizable epihalohydrin products of a trialkylamine having 1 to 5 carbon atoms in alkyl such as, for example, (meth) acryloxypropyltrimethylammonium chloride and (meth) acryloxypropyltriethylammonium bromide; (ii) amino derivatives of (meth) acrylic acid or amino derivatives of (meth) acrylamide derived from (meth) acrylic acid or (meth) acrylamide and a dialkylalcanol amine having C 1 -C 4 alkyl groups, such as dimethylaminoethyl ( meth) acrylates, diethylethenoxy (meth) acrylate, dimethylaminopropyl (meth) acrylate or dimethylaminopropyl (meth) acrylamide; and (iii) derivatives of the products of group (ii) and above by (1) neutralization with an acid, for example hydrochloric acid or lactic acid; (2) modification with a halogenated alkyl, for example methyl chloride, ethyl chloride, methyl bromide or ethyl iodide; (3) modification with halogenated esters of fatty acid such as ethyl monochloroacetate or methyl onocloropropionate; and (4) modification with a dialkyl sulfate, for example dimethyl sulfate or diethyl sulfate. The specific examples of these monomers P497 include: (i) p-dimethylaminomethyl styrene, dimethylaminoethyl styrene; (ü) dimethylaminomethyl acrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminomethyl methacrylamide; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide. The cationic monomers also include amine derivatives of the allyl compounds, for example diallyldimethylammonium chloride and the like. As discussed above the cationic levels can be polymerized in cationic form or as an alternative they can also be polymerized in the form of their precursors, but which are modified to become cationic, for example, by means of a quaternization oil (for example ethyl monochloroacetate, dimethyl, etc). Examples of the amphoteric monomers include zwitterionized derivatives of the aforementioned amine derivatives of the (meth) acrylic acids or amine derivatives of the (meth) acrylamide such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide by halogenated salts of fatty acids such as potassium monochloroacetate, sodium monobromopropionate, aminomethylpropanol salt of acid P497 monochloroacetic, triethianolamine salts of monochloroacetic acid and the like; and amine derivatives of (meth) acrylic acid or (meth) acrylamide, as discussed above, modified with propanesulfone. These amphoteric monomers, like the aforementioned cationic monomers, can be polymerized in amphoteric form or, alternatively, they can also be polymerized in the form of their precursors, which are subsequently converted to the amphoteric state.

Copolymers Copolymers herein must have a weight average molecular weight of at least about 20,000, in order to provide effective adhesive or film-forming properties during application to hair or skin. There is no upper molecular weight limit other than limiting the applicability of the invention for practical issues, for example processing, aesthetic characteristics, ability to form a formulation, etc. In general, the weight average molecular weight will be less than about 10,000,000, more generally less than about 5,000,000, and preferably less than about 3,000,000. Preferably, the weight average molecular weight will be between about P497 50,000 and about 2,000,000, more preferably will be between about 75,000 about 1,000,000, still more preferably between about 100,000 and about 750, 000 Molecular weight can be determined by gel permeation chromatography by universal calibration with refractive index and differential viscometric detection using polystyrene standards or equivalents. Preferably, the polymer herein, when dried to form a film, has a Tg of at least about -20 ° C, preferably at least about 20 ° C, so that they are not excessively sticky or "chewy" " touch. Preferably, the Tg is between about 20 ° C and 120 ° C. In the sense used here, the abbreviation "Tg" refers to the vitreous transition temperature of a structure of a copolymer which does not contain silicone. Tg can be measured by techniques well known in the field such as differential scanning calorimetry (DSC) or dynamic mechanical analysis. The Tg can be controlled by varying the level and type of different monomers containing acid and additional monomers that are used. The methods for the preparation of silicone-grafted copolymers have been well known in the art.

P497 technique and have been published. The copolymers herein grafted with silicone can be made according to known processes subject to the additional requirements that the starting monomers be selected so that the final product is comprised of acid-containing monomers and blocked silicone macromers in the end with styrene, as already described. Examples of the process for making the silicone-grafted polymers are described in detail in U.S. Patent No. 4,693,935 to Mazurek, issued September 15, 1987 and U.S. Patent No. 4,728,571 to Clemens et al. ., issued March 1, 1988, both are incorporated herein by reference, also in U.S. Patent No. 5,061,481, to Suzuki et al., issued October 29, 1991, U.S. Pat. No. 5,219,560, Suzuki et al., Issued June 15, 1993, United States Patent No. 5,166,276, Hayama et al. Granted on November 24, 1992, U.S. Patent No. 5,106,609, issued by Bolich et al., Issued April 21, 1992, U.S. Patent No. 5,100,658, issued by Bolich et al., Issued the March 31, 1992, U.S. Patent No. 5,100,657, Ansher-Jackson et al., Issued March 31, 1992, U.S. Patent No. 5,104,646, to Bolich et al.

P497 al., Granted on April 14, 1992, EPO 0 412 707, of Torgerson et al., Granted on February 4, 1994, EPO 0 412 704, of Bolich et al., Published on February 13, 1991, the application EPO 92918969.4 of Peffly, filed on August 18, 1992, the application EPO 92918839.9 of Hozshuh, et al., Filed on August 18, 1992, and application EPO 92919224.3, filed on August 18, 1992, all of which are incorporated herein by reference. In general, the copolymers of the present invention can be made by free radical polymerization of the silicone macromers with acid-containing monomers and other monomers that can be employed. The general principles of polymerization methods for free radical are well known. Refer, for example, to Odian, "Principies of Polymerization" 2nd edition, John Wiley & sons, 1981, pp. 179-318. The desired monomers are all placed in a reactor together with a sufficient amount of a mutual solvent so that when the reaction is complete, the viscosity of the reaction is reasonable. Typical charges of the monomers range from about 20% to about 50%. Unwanted terminators, especially oxygen, are removed as required. This can be done by evacuation or by purging with an inert gas such as argon or nitrogen. The initiator is introduced and the reaction is P497 takes the temperature necessary for it to start, assuming that thermal initiators are used. Alternatively, the redox or radiation initiators may be used as desired. It is desired to proceed the polymerization as much as needed for a high degree of conversion, typically between a few hours to a few days. The solvent is then removed, usually by evaporation or precipitation of the copolymer by addition of a non-solvent. The polymer is subsequently purified, as required. The copolymers of the present invention will preferably be used in at least partially neutralized form. Neutralization can promote the solubility or dispersibility of the copolymer in the composition. In addition, the use of shape-neutralizing aids to remove the copolymer from the hair or from the skin, during cleaning with the shampoo, soap, detergent, or other cleaning products, is also used. In general it is preferred that from about 10% to 100%, more preferably from about 20% to about 90%, and still more preferably between about 40% to about 85% of the acid functionality is neutralized in the polymer. Any base, either organic or metallic, that is conventionally used can be used for neutralization. Metal hydroxides P497 alkaline and alkaline earth metals are suitable as neutralizers for use in silicone-grafted copolymers. The preferred neutralizing agents that are used in the hair spray compositions of the present invention are potassium hydroxide and sodium hydroxide. Examples of other suitable neutralizing agents that can be used include amines, especially aminoalcohols such as 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol (AEPD). 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB), onoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), mono-isopropanolamine (MIPA), diieopropanolamine ( DIPA), triieopropanolamine (TIPA) and dim dimethyl ester (DMS). Mixtures of amines and bases (metallic or organic) can also be used. The removal of unreacted silicone macromer, if any is present at undesirable high levels that could interfere with the performance of the product, can be done by any of the means known in the art. One method that can be used is the extraction of supercritical fluid, such as with supercritical carbon dioxide. Another method that is generally applied is membrane separation, carried out according to standard techniques in this field. A purification method that can be P497 particularly useful, for the copolymers herein is solvent extraction by a non-polar solvent. Suitable solvents include C3-Cβ hydrocarbons, preferably C5-C5 hydrocarbons, such as hexane. Before carrying out the extraction, the polymeric reaction product is precipitated from a reaction solvent (for example with water) and dried. The extraction solvent is preferably heated about or a little above the average Tg of the portion of the non-silicone-containing structure of the polysiloxane-grafted polymer of the adhesive agent. The temperature must be high enough so that the polymer softens, but not too high for it to set or cut. The extraction solvent and the reaction product can be mixed before or after the heating of the solvent. The extraction solvent and the polymer reaction product must be kept mixing and preferably in an excess of solvent, for a reasonable period of time to effect the removal of the soluble materials. This period will depend on the reflux temperature of the solvent, the Tg of the copolymer, the temperature at which the solvent is actually heated, the level of removal of the monomer that is to be reacted and the low viscosity material remaining after the polymerization, and the number of solvent extraction cycles that can be carried out.

P497 Typically, the solvent extraction periods will go from about every half hour to about every two hours, and more typically from about half an hour to about an hour. The solvent can be removed after each cycle by conventional means, for example decanting, filtering, etc. , with etching or distillation to remove the trace extraction solvent remaining in the product after the final extraction cycle. The analysis of the polymeric reaction product and the extracted materials, and the purified film-forming agent can be carried out by conventional techniques and analyzes known in the art. These include, for example, nuclear magnetic resonance (NMR), infrared molecular spectroscopy, gel permeation chromatography / size exclusion, liquid chromatography, gaees chromatography, atomic absorption and emission spectroscopy and wet methods such as titration.

Topical Compositions for Personal Care Under the present invention, a wide variety of topical personal care compositions are contemplated, including both hair care compositions and care compositions.

P497 of the skin. Hair care compositions include sprays for hair (aerosol and non-aerosol type), hair tonics, hair lotions, shampoos, hair rinse and foams. Skin care compositions include skin moisturizers and other skin conditioning compositions, sunscreens, sunless tanning compositions, skin cleansing compositions, anti-acne compositions, topical analgesic compositions and other applications. for topical skin that does not contain drugs, and the like. The skin care compositions also include cosmetics and fragrances, especially those intended for use in the facial area. Cosmetics include, for example: foundation for makeup; makeup for the eyes as a mascara for eyelashes and makeup for lips. Fragrances include perfumes, colognes and aftershave lotions. The topical personal care compositions of the present invention include products wherein the copolymer is used as an adhesive for styling the hair, for modifying the surface of the skin for skin conditioning purposes or for purposes of cosmetic appearance. The copolymer of the preend can also be used to facilitate the administration of a P497 active agent to hair or skin. The substantivity of the hair or of the skin can be improved for those ingredients which, as a result of the entrapment by the adhesive films formed by the polymers of the present invention, upon curing. Examples of these active ingredients include drugs, cosmetic actives (e.g. skin or hair conditioners, dyes and pigments for cosmetics, perfumes and fragrances, and the like), sunscreen actives (including eolar blocking physical assets such as dioxide of zinc or titanium, aeí as filtroe químicae that protect the skin or hair by selective absorption of UV-A and / or UV-B rays) and tanning agents without sun. The compositions herein can be formulated to include any of the chemically known ingredients for use in the. type of product desired, as well as other ingredients that can provide desirable benefits without unduly interfering with the function of the silicone-graft copolymers blocked at the end with styrene. A non-exclusive description of a variety of its ingredients for use in topical personal care compositions is provided below. Topical personal care compositions may contain a wide variety of materials P497 volatile, including, without limitation, the following: acetone, hydrocarbons (such as isobutane, hexane, decene), halogenated hydrocarbons (such as Freons), linalool, esters (such as ethyl acetate, dibutyl phthalate) and volatile silicon derivatives (especially siloxanes such as for example phenylmethylmethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, cyclomethicones such as octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane and polydimethyl siloxane, for example dimethicones having, for example, viscosity at 25 ° C of about 15 centipoisee or less) and mixtures of the miemoe. Volatile materials such as those commonly used in topical compositions, such as sprays, tonics, gels and foams. Topical aerosol personal care compositions, such as foams and spray aerosols for hair, can be used with any of the conventional propellants to administer the material. Examples of suitable propellants include materials such as trichlorofluoromethane, dichlorofluoromethane, difluoroethane, dimethyl ether, propane, N-butane or isobutane. The aerosol as well as spray products that do not employ aerosol may include a surfactant P497 to improve the spray quality. Examples of suitable surfactants include nonionic, cationic and anionic surfactants or mixtures thereof. Fluorosurfactants are also covered herein. Surfactants in particular are desired for spray products of the present invention, especially spray products such as hair spray, where the spray quality can affect the performance of the product since the compositions herein have relatively low levels of dew. Volatile organic compounds and relatively high levels of water. The relatively high water levels of the present invention could adversely affect the spray quality. If these surfactants are employed, they should preferably be used at a level of between about 0.01% to about 7.5% by weight of the total composition. The level of propellant can be adjusted as desired. In general from about 3% to about 30% by the total weight of the composition (weight with base including the propellant) of the foam compositions and from between about 15% to about 50% of the spray compositions for hair spray . The level of propellant in other products can vary widely, but in general it is between about 3% to about 70% by weight of the total composition.

P497 Suitable spray containers are well known in the field and include conventional non-aerosol type pump sprayers such as "atomizers", in the form of cans or cans having propellant, as already described, and also aerosol type containers pump that uses compressed air as a propellant. Pump-type aerosol containers are also disclosed, for example, in U.S. Patent No. 4,077,441, March 7, 1978, by Olofsson and in the 4,850,577, July 25, 1989, from TerStege, the doe's are incorporated here by reference, and also in U.S. Application Serial No. 07 / 839,648, Gosselin, Lun, Sojka, and Lefebvre, filed on February 21, 1992, "Consumer Product Package Incorporating A Spray Device Utilizing Large Diameter Bubbles ". Sprays for hair in pump-type aerosols use compressed air and are also currently marketed by The Procter & Gamble Company with the name VIDAL SASSOON AIRSPRAYR, sprays for hair. The compositions of the present invention can also be found in a wide variety of forms. For example in single-phase compositions as well as in emulsions wherein the silicone-grafted copolymer is present in the aqueous or hydroalcoholic phase of the emulsion. The emulsionee example include, ein P497 limitation, emulsions of oil in water, water in oil, water in oil in water and oil in water in silicone. The silicone-grafted copolymer of the present invention can be in an aqueous or hydroalcoholic phase of the composition. The compositions can cover a wide range of viscosities, preferably from about 1 cS to about 200,000 cS, at 25 ° C.

Additional Components A wide variety of additional components may be employed in topical co-positives for personal care of the present. Non-limitative examples include the following.

Pharmaceutical Assets The compositions of the present invention may comprise a safe and effective amount of a pharmaceutical active. The phrase "safe and effective amount" which in the sense used herein refers to an amount of an asset high enough to modify in a positive or positive manner the condition to be treated, but sufficiently low to avoid serious side effects (such as for example, a reasonable benefit / risk ratio), within the scope of medical judgment P497 reasonable. A safe and effective amount of the pharmaceutical active will vary with the specific asset, the ability of the composition to penetrate the active through the skin, the amount of the composition to be applied, the paular condition to be treated, the age and physical condition of the patient being treated, the severity of their condition, the duration of the treatment, the nature of the concurrent therapy and factors similar. The pharmaceutical actives that may be employed in the compositions of the present invention preferably comprise from about 0.1% to about 20% by weight of the compositions, more preferably from about 0.1% to about 10% and still more preferably from about 0.1% to approximately 5%. Mixtures of pharmaceutical active ingredients can also be used. Non-limiting examples of pharmaceutical actives may include the following: pharmaceutical actives useful in the composition of the present invention are anti-acne drugs, for example. Preferred anti-acne drugs that are used in the present composition include keratolytics such as salicylic acid, sulfur, lactic acid, glycolic acid, pyruvic acid, urea, resorcinol and N-acetylcysteine.; retinoid as retinoic acid and eus P497 derivatives (for example cis and trans); antibiotics and antimicrobials such as benzoyl peroxide, octopirox, erythromycin, zinc, tetracycline, triclosan, azelaic acid and its derivatives, phenoxyethanol and phenoxyproponol, ethyl acetate, clindamycin and meclocycline; eeboetata such as flavinoids; alpha and beta hydroxy acids and bile salts such as sulfate of eecirnol and its derivatives, deoxycholate and cholate. It is preferred to use ealicylic acid here. Pharmaceutical active agents useful in the compositions of the present invention include non-heteroloidal anti-inflammatory drugs (NSAIDS). The NSAIDS can be selected from the following category: propionic acid derivatives, acetic acid derivatives, fenamic acid derivatives; diphenylcarboxylic acid derivatives and oxicams. All of these NSAIDS are fully described in U.S. Patent No. 4,985,459 to Sunehine et al., Issued January 15, 1991, which is mentioned herein by reference. Most preferred are propionic NSAIDS including, without limitation, aspirin, acetaminophen, ibuprofen, benaproxen, flurbiprofen, fenoprofen, fenbuten, ketoprofen, indoprofen, pirprofen, carprofen, oxaprozin, pranoprofen, miroprofen, thioxaprofen, euprofen, alinoprofen, thiaprofenic acid, fluprofen and bucloxic acid. Anti-aging drugs are also useful P497 steroidal inflammatories among which ee include hydrocortizone and the like. The pharmaceutical actives useful in the compositions of the present invention include antipruritic drugs. Preferred antipruritic drugs for inclusion in the compositions of this invention are the pharmaceutically acceptable salts of metdilizine and trimeprazine. Pharmaceutically useful actives in the compositions of the present invention include anesthetic drugs. Preferred anesthetic drugs to be included in the compositions of the present invention are the pharmaceutically acceptable saltse of lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine, diclionine, hexylcaine, procaine, cocaine, ketamine, praoxin and phenol. Pharmaceutical actives useful in the compositions of this invention include antimicrobial drugs (antibacterial, antifungal, antiprotozoal and antiviral drugs). Preferred antimicrobial drugs for the compositions of this invention include pharmaceutically acceptable eleates of the b-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin, triclosan, deoxycycline, capriomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin, ethambutanol, metronidazole, P497 pentamidine, gentamicin, kanamycin, lineomycin, metacycline, etenanine, minocycline, neomycin, methylmycin, paromycin, esteptromycin, tobramycin, miconazole and manfadine. Preferred antimicrobial drugs for the compositions of the present invention include tetracycline hydrochloride, erythromycin estolate, erythromycin stearate (salt), amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate, chlorhexidine gluconate, chloroestidine hydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride, gentamicin eulfate, kanamycin sulfate, linomicin hydrochloride, methacycline hydrochloride, methenamine hippurate, methenimide mandelate, minocycline hydrochloride, neomycin, methylmycin sulfate, paronomycin sulfate, streptomycin sulfate, tobramycin sulfate, miconazole hydrochloride, amphibin hydrochloride, amanfadine sulfate, triclosan, octopirox, parachloromethaxyleneol, nystatin, tolnaftate and clotrimazole. A wide variety of alpha-hydroxy acid and beta-hydroxy can be used for pharmaceutical and cosmetic purposes on the skin, including anti-aging, reduced dryness, skin exfoliation and reduction in P497 the appearance of wrinkles and fine lines. These include salicylic acid, glycolic acid and lactic acid. Also useful here are sunscreen agents. A wide variety of sunscreen agents are described in U.S. Patent No. 5,087,445 to Haffey et al., Issued February 11, 1992; U.S. Patent No. 5,073,372 to Turner et al., issued December 17, 1991; U.S. Patent No. 5,073,371 to Turner et al., issued December 17, 1991; and Segarin, et al., in Chapter VIII, pages 189 and sub. , of Coemetics Science and Technology. all of which are mentioned here as a reference. Among the sunscreen agents included are those belonging to the group consisting of: 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl NN-dimethyl-p-aminobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-acid sulphonic, octocrylene, oxybenzone, homomenthyl ealicylate, octyl ealicylate, 4,4'-methoxy-t-butyldibenziolmethane, 4-isopropyl-dibenzoylmentane, 3-benzylidene camphor, 3- (4-methylbenzyl-den) camphor, titanium dioxide , zinc oxide, silica, iron oxide and mixtures thereof. In general, sunscreens may comprise from about 0.5% to about 20% of the compositions used herein. The exact amounts P497 will vary depending on the sunscreen that is selected and the Desired Solar Protection Factor (SPF). SPF is normally used as a measure of photoprotection of a sunscreen against erythema. Refer to Federal RegjLstrer, Vol. 43, No. 166, pp. 38206-38269, August 25, 1978, which is mentioned herein by reference. Also useful in the present invention are sunless tanning agents that include dihydroxyacetone, glyceraldehyde, indoles and their derivatives and emeasers. These tanning agents without sun can also be used in combination with sunscreen agents. Other useful actives include skin whitening agents (or agents that provide light) including, without limitation, hydroquinone, ascorbic acid, kojic acid and sodium metabisulfite. Other useful actives which are specialized for the compositions and hair care include anti-dandruff active such as zinc pyrithione, octopirox, selenium disulfide, sulfur, tars and the like. Zinc pyrithione and triclosan as well as other antibacterial agents can be used in antiperspirant compositions and deodorant compositions for use in the body, especially in the area under the arm.

P497 Conditioners The compositions of the present invention may comprise a wide variety of conditioning agents for the skin or hair. The conditioning agents are typically used at a level of between about 0.05% to about 20% by weight of the composition, preferably between about 0.01% to about 10% more preferably between about 0.05 to about 5%. The non-volatile agents, which are used herein, refer to those defined above. Conventional conditioning agents herein and especially useful for hair care and skin care compositions include non-volatile conditioning fluids such as hydrocarbons, silicone fluids, fatty esters and fatty alcohols as well as cationic materials. Conditioning fluids in general will have a viscosity of between about 3 million cS or less, preferably about 2 million cS or less, and more preferably about 1.5 cS or less. Conditioning fluids include liquids selected from the group consisting of hydrocarbon oils and fatty esters. Fatty esters include compounds characterized by having at least 10 carbon atoms and include esters with hydrocarbyl chains derived from fatty acids or alcoholee graeos, for example monoesters, polyhydric alcohol ester and di and tricarboxylic acid ester. The hydrocarbyl radicals of the fatty esters herein may also include functional groups or may be covalently linked to these other compatible functional groups such as amides and alkoxy (e.g. ethoxy or ether linkages), etc. ). The hydrocarbon oils include cyclic hydrocarbons, straight chain aliphatic hydrocarbons (saturated or unsaturated), branched chain aliphatic hydrocarbon (saturated and unsaturated). Straight chain hydrocarbon agents that preferably contain from 12 to 19 carbon atoms, although it does not necessarily mean that it is limited to this range. Branched chain hydrocarbon oils may contain and in fact typically contain a higher carbon atom number. Polymeric hydrocarbons of alkenyl monomers, such as C2-C6 alkenyl monomers, are also embraced herein. Specific examples of suitable materials include paraffin oil, mineral oil, saturated and unsaturated dodecane, saturated and unsaturated tridecane, saturated and unsaturated tetradecane, saturated and unsaturated pentadecane, saturated and unsaturated hexadecane and mixtures thereof. A preferred hydrocarbon polymer is polybutene, such as, for example, isobutylene and butene copolymer. A commercially available material of this type is polybutene L-14 from Amoco Chemical Co. (Chicago, Illinois, U.S.A.). The monocarboxylic acid esters herein include esters of alcohols and / or acids of the formula R'COOR, wherein the alkyl or alkenyl radicals and the sum of the carbon atoms in R 'and R are at least 10, preferably at least 20. Fatty esters include, for example, alkyl and alkenyl esters of the fatty acids having aliphatic chains with from about 10 to about 22, carboxylic acid ester and alkyl and alkenyl fatty alcohol having an aliphatic chain derived from alkyl and / or alkenyl alcohol with from about 10 to about 22 carbon atoms, and co-binating thereof. Examples include isopropyl isostearate, hexyl laurate, isohexyl laurate, isohexyl palmitate, isopropyl palmitate, decyl oleate, isodecyl oleate, hexadecyl stearate, decyl stearate, isopropyl isostearate, dihexyldecyl adipate, lauryl lactate, myristyl lactate, cetyl lactate, oleyl stearate, oleyl oleate, oleyl myristate, lauryl acetate, cetyl propionate and oleyl adipate. However, the monocarboxylic acid esters do not necessarily contain a chain with at least ten carbon atoms, as long as the total number of carbon atoms in the aliphatic chain is at least 10. Examples include adipate of diisopropyl, diipate diisohexyl and diisopropyl sebapate. The di and tri alkyl and alkenyl esters of the carboxylic acids can also be used. Examples include, for example, esters of C4-C8 dicarboxylic acids, such as esters of CJ-C22 (and preferably C6-C6) of succinic acid, glutaric acid, adipic acid, hexanoic acid, heptanoic acid and octanoic acid. Specific examples include isocetyl stearyol stearate, diisopropyl adipate and tristearyl citrate. The polyhydric alcohol esters include alkylene glycol esters, for example digraso acid and ethylene glycol mono fatty esters, diethylene glycol mono and digraso esters, polyethylene glycol mono and digraso esters, propylene glycol mono and digrae acid ester, monooleate of polypropylene glycol, polypropylene glycol monoetherate 2000, ethoxylated propylene glycol monostearate, esterree P497 glyceride mono and digraso acid, polyglycerol polyglass acid, ethoxylated glyceryl monostearate, 1,3-butylene glycol onostearate, 1,3-butylene glycol dieterate, polyoexethylene polyol fatty acid esters, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters, which were successfully used as polyhydric alcohol ethers. The glycerides include mono, di and triglycerides. More specifically they include glycerol mono, di and triesters and long chain carboxylic acids such as C 10 -C 22 carboxylic acids. A variety of these types of materials can be obtained from vegetable or animal fats or oils such as, for example, castor oil, safflower, cottonseed oil, corn oil, olive oil, cod liver oil, almond oil, avocado oil, palm oil, sesame oil, lanolin and soybean oil. Synthetic oils include triolein dilaurate and tristearyl glyceryl. The preferred glycerides are di and triglycerides. Especially triglycerides. Other fluid conditioning agents include fatty alcohols, preferably C10-C22 alcohols such as ethe- thyl and cetyl alcohols. Other conditioning agents more for the P497 hair and / or skin include urea, guanidine, aloe vera in any of its variety of forms (for example aloe vera gel), polyhydroxy alcohols such as sorbitol, glycerol, hexanothiol, propylene glycol, butylene glycol, hexylene glycol and the like; polyethylene glycol, sugars and starches, sugars and starch derivatives (for example alkoxylated glucose) hyaluronic acid, lactamide monoethanol amine; acetamide monoethanolamine and mixtures thereof.

Silicone Conditioning Agents As optional components of the present invention are the non-volatile silicone conditioning agents. The silicone conditioning agents that are used here preferably have an average viscosity of between about 1,000 to about 2,000,000 centistokes at 25 ° C, more preferably between about 10,000 to about 1,800,000, and still more preferably between about 100,000 and about 1,500,000. The viscosity of the silicone of the present can generally be measured by means of a glass capillary viscometer as established in Test Method Qow Corning Corporate CTM0004, July 20, 1970. The silicone conditioning agent is typically P497 will use in the compositions herein at levels of between about 0.05% to about 10% by weight of the composition, preferably between about 0.1% to about 10%, and more preferably between about 0.5% and about 8%, and still more preferably between about 0.5% and about 5%. Non-volatile and insoluble silicone conditioning agents which are suitable include polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes, polyether siloxane copolymers and mixtures thereof. Other insoluble non-volatile silicones can also be used. The silicones of the present can be silicone fluids or silicone gums. The term "silicone fluid" refers to flowable silicone materials that have a viscosity of less than 1,000,000 centistokes at 25 ° C. In general, the viscosity of the fluid will be between about 5 and 1,000,000 centistokes at 25 ° C, preferably between about 10 and about 100,000. The silicone gums are described in more detail below. The silicone fluids of the present include polyalkyl or polyaryl siloxanes with the following structural formula: P497 wherein R is alkyl or aryl, and x is an integer from about 1 to about 8,000, preferably from about 5 to about 8,000. "A" represents groups that block the ends of the silicone chains. The substituted alkyl or aryl groups on the siloxane chain (R) or on the end of the siloxane chains (A) can have any structure as long as the resulting silicones remain fluid at room temperature, are hydrophobic and are not irritating or toxic or harmful in any way when applied to hair, are compatible with other components of the composition, are chemically stable under normal conditions of use and storage and are capable of being deposited on the hair or condition it. Suitable groups A include methyl, methoxy, ethoxy, propoxy and aryloxy. The two groups R in the silicone atom can be present in the same form or be groups P497 different. Preferably, the two R groups represent the same group. Suitable R groups include methyl, ethyl, propyl, phenyl, methylphenyl and phenylmethyl. Preferred silicones are polydimethyl siloxane, polydiethylsiloxane and polymethylphenylsiloxane. Polymethylsiloxane is especially preferred. The non-volatile fluid of polyalkylenyloxane which can be used include, for example, polydimethylsiloxane. These siloxanes are available, for example, from the company General Electric Company in the Viecaeil product and the SF96 series and from Dow Corning in the Dow Corning 200 series. The polyalkylaryl siloxane fluids which may be employed also include, for example, polymethylphenyl siloxane. These siloxanes are available, for example, from the company General Electric Company as SF1075, methylphenyl fluid, or Dow Corning as the Cosmetic Grade Fluid 556. The polyether siloxane copolymers that may be employed include, for example, a polydimethylsiloxane, modified with polypropylene oxide (for example DC-1248) although ethylene oxide and mixtures of ethylene oxide with propylene oxide can also be employed. The level of ethylene oxide and propylene oxide must be sufficiently low to avoid solubility in water P497 and in the composition of the present. Other silicone materials that can be used in a special way in the silicone conditioning agents of the insoluble silicone rubber. The term "silicone rubber" in the sense in which it is used herein refers to polyorganosiloxane materials with a viscosity at 25 ° C greater than or equal to 1,000,000 centistokee. The eylicone gums are described by Petrarch and others, including United States Patent No. 4,152,416 by Spitzer et al., Issued May 1, 1979 and Noli, Walter, Chemistry and Techonology of Siliconee, New York; Academic Preee 1968. Silicon gums are also described in the General Electric SE 30, Se 33, SE 54 and SE 76 silicone rubber product specification sheet. All of these references described are incorporated herein by reference. The "silicone gums" will typically have a mass molecular weight greater than about 200,000, generally between about 200,000 and about 1,000,000. Specific examples include polydimethyl siloxane, (polydimethylsiloxane) copolymer (methylvinylsiloxane), poly (dimethylsiloxane) (diphenylsiloxane) copolymer (methylvinylsiloxane) and blend thereof.

P497 Cationic Polymer Hair Conditioning Agents The compositions of this invention may also comprise cationic polymer conditioning agents. The polymeric cationic conditioning agents of the present will generally be employed at levels of from about 0.05% to about 5%, preferably from about 0.1% to about 4%, more preferably from about 0.2% to about 3% by weight of the shampoo composition. The cationic conditioning polymers are preferably soluble in water. By "water-soluble" cationic organic polymer is meant a polymer that is sufficiently soluble in water to form a substantially clear solution with the naked eye at a concentration of 0.1% in water (distilled or equivalent) at 25 ° C. Preferably, the polymer is sufficiently soluble to form a substantially clear solution at a concentration of 0.5%, more preferably at a concentration of 1.0%. The cationic polymers herein will generally have a weight-average or weight-average molecular weight of at least about 5,000 and typically at least about 10,000, and up to about 10 million. Preferably, the molecular weight will be between P497 approximately 10,000 and approximately 2 million. Cationic polymers in general can be characterized as having cationic nitrogen containing entities such as quaternary ammonium or cationic amino entities or mixtures of the miemoe. Any anionic counterion can be used for the cationic polymer and provided that the water solubility criteria are met. Suitable counterions include halides (for example Cl-, Br-, I-, or F-, and preferably Cl-, Br-, or I-), sulfate and methylisulfate. Others can also be used since this list is not exclusive. The entities containing cationic nitrogen will be present, in general, as a substituent or a fraction of the total monomer of the cationic hair conditioning polymers. In this form, the cationic polymer may comprise copolymers, terpolymers, etc. of monomeric units substituted with cationic amino or quaternary ammonium and other non-cationic units referred to herein as separating monomer units. These polymers are known in the art and a wide variety of them is found in CTFA Cosmetic Ingredient Dictionary, 3rd edition, edited by Estrin, Crosley, and Haynes, (The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, DC, 1982). Suitable cationic polymers include, P497 example, copolymers of vinyl monomers having functions of quaternary ammonium or cationic amine with water-soluble separating monomers, for example acrylamide, methacrylamide, alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamides, alkyl acrylate, alkyl methacrylate, vinyl caprolactone and vinyl pyrrolidone. Substituted monomers with alkyl and dialkyl preferably have C?-C7 alkyl groups, more preferably CJ-C3 alkyl groups. Other suitable spacer monomers include vinyl esters, vinyl alcohol (made by hydrolysis of polyvinyl acetate), maleic anhydride, propylene glycol, and ethylene glycol. The cationic amines can be primary, secondary or tertiary aminae depending on the particular species and the pH of the shampoo. In general, secondary and tertiary amines, especially tertiary amines, are preferred. The amino-substituted vinyl monomers can be polymerized in the form of amines, and optionally can subsequently be converted to ammonium by a quaternization reaction. The amines can also be quaternized in a manner similar to the formation of the polymer. For example, the tertiary amine operae may be quaternized by reaction with a salt of the formula R'X, where R 'is a chain alkyl P497 cuts, preferably alkyl C_-C? , more preferably alkyl C \ -C_. , and X is an anion that forms a water soluble salt with quaternized ammonium. Suitable cationic monomers of the amino and quaternary ammonium type include, for example, vinyl compounds substituted with dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate, monoalkylaminoalkyl methacrylate, trialkyl methacryloxyalkyl ammonium salt, trialkyl acryloxyalkyl ammonium salt, quaternary diallyl ammonium salt and vinyl ammonium-quaternary monomers having cyclic rings containing cationic nitrogen such as for example pyridinium, 1-idazolium and quaternized pyrrolidone, for example, alkyl vinyl imidazolium, alkyl vinyl pyridinium, alkyl vinyl pyrrolidone. The alkyl functions of these monomers are preferably lower alkyl such as C 1 -C 6 alkyl, more preferably C 1 and C 2 alkyl. Substituted amine vinyl monomers which are suitable for the present include dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylamide, and dialkylaminoalkyl methacrylamide, wherein the alkyl groups are preferably C? -C hydrocarbyls, more preferably alkyl. -03.

P497 The cationic polymers herein may comprise mixtures of monomer units derived from compatible spacer monomers and / or substituted monomers such as quaternary ammonium and / or amino. Suitable polymers cationic type hair conditioners include, for example, copolymers of l-vinyl-2-pyrrolidone and l-vinyl-3-methylinidazolium (for example chloride salt) (in industry these are mentioned in Cosmetic, Toiletry, and Fragrance Association, "CTFA" as Polyquaternium-16), such as those obtained commercially from BASF Wyandotte Corp. (Parsippany, NJ, USA); with the name LUVIQUAT, trademark (for example LUVIQUAT FC 370); copolymers of l-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (in the industry known to the CTFA as Polyquaternium-11) as are commercially available from Gaf Corporation (Wayne, NJ USA) under the trade name GAFQUAT (for example GAFQUAT 755N) ); polymers containing cationic diallyl quaternary ammonium, for example homopolymer of dimethyldiallylammonium chloride and copolymers of acrylamide and dimethyldiallylammonium chloride, which in industry (CTFA) are known as Polyquaternium 6 and Polyquaternium 7, respectively; and amino acid esters of aminoalkyl esters of homo and unsaturated carboxylic acid copolymers having from 3 to 5 carbon atoms as P497 describes in U.S. Patent No. 4,009,256, which is mentioned herein by reference. Other cationic polymers that can be employed include polysaccharide polymers such as cationic cellulose derivatives and cationic starch derivatives. The polysaccharide polymeric cationic materials suitable for the present invention include that of the formula: R 1 I A-0 (RN -R 3 -X ") R 2 wherein: A is an anhydroglucose residual group such as, for example, an anhydrous glucose residue of starch or cellulose, R is an alkylene oxyalkylene, polyoxyalkylene or hydroxyalkylene or a combination thereof: R 1, R 2 and R 3 are independently alkyl, aryl, alkylaryl, arylalkyl, oxyalkyl or alkoxyaryl groups, each group containing up to 15% carbon and the total number of carbon atoms of each cationic entity (i.e. the sum of the carbon atoms in R 1, R 2 and R 3) is preferably at least about 20 or less and X is an anionic counterion, as It was previously described.

P497 Cationic cellulose is obtained from Amerchol Corp. (Edison, NJ, USA) in its series of polymers JR R and LRR, as hydroxyethylcellulose salts that are reacted with epoxides substituted with trimethylammonium, which in industry are known (CTFA) as Polyquaternium 10. Another type of cellulose cationic includes the polymeric quaternary ammonium salts of the hydroxyethylcellulose which are reacted with substituted epoxide with lauryl dimethylammon, which in the industry are known (CTFA) Polyquaternium 24. These materials are obtained from Amerchol Corp. (Edison, NJ, USA) with the trademark Polymer LM-200. Other cationic polymers that may be employed include cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride which is commercially available from Celanese Corp. in its Jaguar series). Other materials include cellulose esters containing quaternary nitrogen for example that described in U.S. Patent No. 3,962,418, which is mentioned herein by reference) and etherified cellulose copolymers and esterified starch (e.g., that described in US Pat. U.S. Patent No. 3,958,581, incorporated herein by reference).

P497 Cationic surfactant conditioning agents The cationic surfactants useful herein as conditioning agents include quaternary ammonium salts or salts of fatty amines. Preferred quaternary ammonium salts are trialkyldimethylammonium chloride, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long chain fatty acids. Representative examples of quaternary ammonium eleate include dimethyl ammonium dichloride chloride, dimethyl ammonium methyl diiso sulfate, dihexyl dimethyl ammonium chloride, and di (hydrogenated tallow) ammonium chloride. Other quaternary ammonium salts useful herein are di-cationic such as ammonium propane propane dichloride. The quaternary imidazolium salts are also useful herein. Examples of these materials are imidesolium salts containing C12-22 alkyl groups such as 1-methyl-l- [(stearyrolamide) -ethyl] -2-heptadecyl-4, 5-dihydroimidazolium chloride, l-methyl chloride, l- [(Palmitoyloaraid) -ethyl] -2-octadecyl-4,5-dihydroimidazolium and 1-methyl-l- [(seboamide) -ethyl-2-tallow imidazolium methyl sulfate. Also useful herein are the salts of fatty amines. Examples of these compounds include ethethylamide hydrochloride, eoyamide hydrochloride, and ethethylamine format. The conditioning agent P497 useful are disclosed in U.S. Patent No. 4,387,090 to Bolich, issued June 7, 1983 and incorporated herein by reference. The cationic surfactant conditioning agents are generally employed at a level between about 0.1% to about 5% by weight of the composition.

Surfactants The eurfactants are optional ingredients of the composition of the invention, when present, the surfactant typically comprises between about 0.05% to about 50% of the composition. Surfactants are especially useful for cleaning compositions such as cleansing compositions of the skin and shampoos, and can be used for a wide variety of other purposes in these and other types of compositions herein. Exemplary uses include emulsifiers, solubilizers of other ingredients and conditioners (particularly cationic surfactants). For a shampoo and other cleaning compositions, the level of surfactant preferably ranges from about 5% to about 30%, more preferably from 12% to about 35% of the composition. For conditioners, the preferred level of surfactants is P497 between about 0.05 to about 5%. Surfactants useful in compositions of the present invention include anionic, nonionic, cationic, and amphoteric surfactants. A wide variety of these useful agents are disclosed in U.S. Patent No. 5,151,209 to McCall et al., Issued September 29, 1992; in U.S. Patent No. 5,151,210 to Steuri et al., issued September 29, 1992; and in U.S. Patent No. 5,120,532 to Wells et al., issued June 9, 1992, all of which are mentioned by reference. Useful anionic detergents herein include alkyl and alkyl ether sulfates. These materials specifically have the respective formulas: ROSO3M and RO (C2H4?) XS? 3M, wherein R ee alkyl or alkenyl of between about 10 to about 20 carbon atoms, x is 1 to 10 and M is a water soluble cation , ammonium, sodium, potassium and triethanolamine. Another suitable class of anionic surfactants are the water soluble salts of the reaction products of the organic sulfuric acid of the general formula: R1-S03-M wherein R1 is selected from the group consisting of a saturated, chain aliphatic hydrocarbon radical straight or branched, which has about 8 to P497 about 24, preferably about 12 to about 18 carbon atoms; and M is a cation, the important examples are the salts of an organic sulfuric acid reaction product of a hydrocarbon of the methane series, including iso, neo and n-paraffins, having from about 8 to about 24 carbon atoms , preferably from about 12 to about 18 carbon atoms and a sulfonating agent, for example S03, H2SO4, fuming sulfuric acid, obtained according to known eulfonation methods, including bleaching and hydrolysis. Preferred are the N-paraffins C12_? E sulphonated ammonium and alkali metal. Other examples of synthetic anionic surfactants which fall within the scope of the terms of the present invention are the reaction products of fatty acid esterified with isethionic acid and neutralized with sodium hydroxide wherein, for example, the fatty acids are derived from the coconut; Sodium or potassium salts of the fatty acid amides of the required methyl where the fatty acids, for example, are derived from coconut oil. Other synthetic anionic surfactants of this variety are set forth in U.S. Patent Nos. 2,486,921; 2,486,922; and 2,396,278. Still other synthetic anionic surfactants include the class designated as succinamates. This class P497 includes surfactant agents such as sodium N-octadecyleulfoeuccinamide, N- (1,2-dicarboxyethyl) -N-octacylsulfosuccinamate tetrasodium; diamide ether of the sulfoeuccinic acid of eodium; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of the sulfur-succinic acid of eodium. Other suitable anionic surfactants that are employed herein are olefin sulfonates having from about 12 to 24 carbon atoms. The term "olefin sulfonates" in the sense used herein refers to compounds that can be produced by sulfonation of α-olefins by means of non-complexed sulfur trioxide, followed by neutralization of the acid reaction mixture under conditions such that any Sulfone that has been formed in the reaction is hydrolyzed to give the corresponding hydroxy alkane sulphonate. The α-olefins from which the olefin sulfonates are derived are mono-olefins having from about 12 to 24 carbon atoms, preferably from about 14 to 16 carbon atoms. Another class of anionic organic surfactants are the β-alkyloxy alkane sulfonates. These compounds have the formula: P497 wherein R ^ is a straight-chain alkyl group having from about 6 to 20 carbon atoms, R2 is a lower-chain alkyl group having from about 1 (preferred) to about 3 carbon atoms, and M is a water soluble cation, as described below. Many additional synthetic non-soap anionic surfactants are described in McCutcheon's, Detergents and Emulsifiere, 1984 Annual. published by Allured Publishing Corporation, which is mentioned here by reference. Also in U.S. Patent No. 3,929,678, Laughlin et al., Issued December 30, 1975, many other anionic surfactants as well as other types of surfactants are disclosed, and are incorporated herein by reference. Soaps can also be used as anionic surfactants. The nonionic surfactants can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or aromatic alkyl. Examples of these classes of nonionic surfactants are: 1. Those derived from the ethylene oxide condemnation with the product resulting from the reaction of propylene oxide and ethylene diamine.

P497 2. The condensation product of aliphatic alcohols having approximately 8 to 18 carbon atoms, either straight or branched chain, with ethylene oxide, for example a condensate of ethylene oxide and coconut alcohol, having about 10 to 30 mole of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction has from about 10 to about 14 carbon atoms. 3. Long chain tertiary amine oxides such as those corresponding to the following general formula: R1R2R3N > Wherein R ^ contains an alkyl, alkenyl or monohydroxyalkyl radical of between about 8 and 18 carbon atoms, from 0 to about 10 ethylene oxide entities and from 0 to about 1 glyceryl entity, and R2 and R3 contain from about 1 to 3 carbon atoms and from about 0 to 1 hydroxy group, for example methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl (the arrow of the formula is a conventional representation of a semipolar bond). 4. The long chain tertiary phosphine oxides corresponding to the following general formula: RR.R "P> 0 wherein R contains an alkyl, alkenyl or P497 monohydroxyalkyl ranging from about 8 to 18 carbon atoms in its chain length, from 8 to about 10 ethylene oxide entities and from 0 to 1 glyceryl entity, and R 'and R "are each alkyl or monohydroxyalkyl contains about 1 to 3 carbon atoms The arrow in the formula is a conventional representation of a semipolar bond 5. Long chain dialkyl sulfides containing a short chain alkyl or hydroxyalkyl radical of between about 1 to 3 carbon atoms carbon (usually methyl) and a long chain hydrophobic chain including alkyl, alkenyl, hydroxyalkyl or ketoalkyl containing from about 8 to 20 carbon atoms, from 0 to about 10 ethylene oxide entities and from 0 to about 1 glyceryl Examples include: octadecylmethylsulfoxide, 2-cetotridecylmethyl-sulphoxide, 3,6,9-trioxaoctadecyl 2-hydroxyethyleulfoxide, dodecylmethyl-sulfoxide, oleyl 3-hydroxypropylsulfoxide, tetradecylmethylsulfoxide, 3-methoxytridecylmethylsulfoxide, 3-hydroxytridecylmethylsulfoxide, 3-hydroxy-4-dodecoxybutylmethylsulfoxide. 6. N-polyhydroxy fatty acid amidae, such as, for example, polyhydroxyhydrocarbyl C9-C19 fatty acid amides having polyhydroxy function with at least three hydroxy groups, preferably derivatives P497 sugar reducers such as glucose, fructose, maltose, lactose and the like. Surfactants of this type are disclosed in U.S. Patent No. 2,965,576 to E. R. Wileon, issued December 20, 1960 and referred to herein by reference. Cationic surfactants useful in compositions of this invention, particularly conditioning compositions, contain hydrophilic ammonium or quaternary ammonium entities that are positively charged when dissolved in the aqueous composition of the present invention. Cationic surfactants between those useful herein are disclosed in the following document, and all are incorporated by reference: M.C. Publishing Co., McCutcheon's, Deterqents & Emulsifiers, (North American edition 1979); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology. New York: Interscience Publishere, 1949; U.S. Patent 3,155,591 to Hilfer issued November 3, 1964; U.S. Patent No. 3,929,678 to Laughlin, et al., Issued December 30, 1975; U.S. Patent No. 3,959,461 to Bailey, et al., Issued May 25, 1976 and U.S. Patent No. 4,387,090 to Bolich, Jr., issued June 7, 1983. If they are included in the composition of the present invention, the cationic eurfactantee are P4 «7 present in general between about 0.05% to 5%. Among the useful cationic surfactant-containing quaternary ammonium surfactants of the present are those of the general formula: X "K-l R wherein R1-R4 are independently an aliphatic group of between about 1 and 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having from about 12 to 22 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate and alkyl sulfate. The aliphatic groups may contain, in addition to the carbon and hydrogen atoms, ether linkages and other groups such as amino groups. Long chain aliphatic groups, for example those of 12 carbon atoms or greater, may be saturated or unsaturated. Other quaternary ammonium salts useful herein are the diquaternary ammonium saltse such as eebo propane diamonium dichloride. The quaternary ammonium salts include dialkyldimethylammonium chlorides, wherein the alkyl group has P497 from about 12 to about 22 carbon atoms and are derived from long chain fatty acids, such as hydrogenated tallow fatty acid (tallow fatty acids that give quaternary compounds where R ^ and R2 have predominantly 16 to 18 atoms of carbon). Examples of quaternary ammonium salts useful in the present invention include ditallowdimethylammonium chloride, ditallowdimethylammonium sulfate, dihexadecyldimethylammonium chloride, di (hydrogenated tallow) dimethylammonium chloride, dioctadecyldimethylammonium chloride, didocosyldimethylammonium chloride, didocosyldimethylammonium chloride, di (hydrogenated eebo) dimethylammonium, dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium acetate, dierebo dipropylammonium phosphate, dimethyl ammonium dihydrate, di (cocoalkyl) dimethylammonium chloride and stearyl dimethylbenzylammonium chloride. Dimethylammonium dichloride chloride, dicetyl dimethyl ammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltrimethylammonium chloride are preferred as useful quaternary ammonium salts herein. The di (saturated or unsaturated tallow) dimethylammonium chloride is the particularly preferred quaternary ammonium salt. Salts of primary, secondary and tertiary fatty amines are also useful as materials P4 ° 7 cationic surfactants. The alkyl groups of these amines preferably have between about 12 and 22 carbon atoms and can be substituted or unsubstituted. These useful amines in the present include propylene dimethylamine, diethylaminoethyl stearamide, dimethyl stearamide, dimethyl amine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N-sebopropane diamine, ethoxylated stearylamine (5 moles of ethylene oxide), dihydroxyethyl stearylamine and arachidylbehenylamine. These amine salts include the halogen, acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts. These salts include stearylamine hydrochloride, soyamine chloride, ethyl acetate format, N-eebopropane diamine dichloride and stearamido propyl dimethylamine citrate. The cationic amine surfactants included among those useful in the present invention are disclosed in U.S. Patent No. 4,275,055 to Nachtigal et al., Issued June 23, 1981 and which is mentioned herein by reference. Amphoteric surfactants include those which can be broadly described as aliphatic, phosphonium and sulfonium quaternary ammonium derivatives, wherein the aliphatic radicals can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms P497 and one contains an anionic solubilizing group in water, for example carboxy, sulfonate, sulfate, phosphate or phosphonate. The general formula of these compounds is: wherein R2 contains an alkyl, alkenyl or hydroxyalkyl of between about 8 and 18 carbon atoms, from 0 to about 10 ethylene oxide entities and from 0 to about 1 glyceryl entity; 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 alkylene or hydroxyalkylene of about 1 and 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups. Other amphoteric compounds such as betaines are also useful in this invention. Examples of useful betaines of the present include higher alkyl betaine such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethyl alpha carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, lauryl bis- (2-hydroxyethyl) carboxymethylbetaine, stearyl bis- (2- P497 hydroxypropyl) carboxymethylbetaine, oleyldimethyl-gamma-carboxypropylbetaine and lauryl bis- (2-hydroxypropyl) alpha-carboxyethylbetaine. The sulfobetaine may be represented by cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, lauryl bis- (2-hydroxyethyl) sulfopropylbetaine and the like; amidobetaines and amidosulfobetaines wherein the radical RCONH (CH2) 3 is bonded to the nitrogen atom of betaine, are also useful for the invention. Other examples of amphoteric surfactants which may be employed in the compositions of the invention are those which are broadly described as derivatives of aliphatic, secondary and tertiary amines wherein the aliphatic radical may be straight or branched chain and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, for example carboxy, sulfonate, sulfate, phosphate or phosphonate. Examples of the compounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate, N-alkyl taurines such as that which is prepared by reacting dodecylamine with sodium isethionate according to the teachings of the Patent. of the United States No. 2,658,072, a-tartaric acids of N-alkyl P497 superior as those produced according to the teachings of U.S. Patent No. 2,438,091, and products sold under the trade name "Miranol" and described in U.S. Patent No. 2,528,378.

Thickening Agents __ of Suspension The compositions of this invention may comprise a wide variety of rheology modifiers as thickening agents and / or suepeneion agents. The example ingredients of this type are described below. The compositions may include gel vehicle materials. These are particularly useful for use in products such as hair rinses, creams and lotions. The gel vehicles can comprise two essential components: a lipid carrier material and a cationic surfactant vehicle material. The cationic surfactant materials are described in greater detail below. Gel vehicles in general are described in the following documents, all of which are mentioned here by reference: Barry, "The Self Body Action of the Mixed Emulsifier Sodium Dodecyl Sulfate / Cetyl Alcohol", 28 J. of Colloid and Interface Science 82 -91 P497 (1968); Barry, et al., "The Self-Bodying Action of Alkyltrimethylammonium Bro ides / Cetostearyl Alcohol Mixed Emulsifiers; Influence of Quaternary Chain Length", 35 J. of Colloid and Interface Science 689-708 (1971); and Barry, et al., "Rheology of Syeteme Containing Cetomacrogol 1000 -Cetostearyl Alcohol, I. Self Bodying Action", 38 J. of Colloid and Interface Science 616-625 (1972). The carrier can incorporate one or more lipid carrier materials, regardless of whether they also contain cationic surfactant, which are essentially insoluble in water and contain hydrophobic and hydrophilic entities. The lipid carrier materials include eectic or natural acid derivatives, derivatives of acids, alcohols, esters, ethers, ketones and amides with carbon chains of between about 12 and 22, preferably between about 16 and 18 carbon atoms in length . Fatty alcohols and fatty esters are preferred; fatty alcohols are particularly preferred. Preferred esters that are used herein include cetylpalmitate and glyceryl onostearate. Cetyl alcohol and stearyl alcohol are the preferred alcohols. A particularly preferred lipid carrier material is comprised of a mixture of cetyl alcohol and stearyl alcohol containing P4a7 about 55% to about 65% (by weight of the mixture) of the cetyl alcohol. If included in the compositions of the invention, the lipid carrier material is typically present between about 0.1% and about 10.0% of the composition.; the cationic surfactant vehicle material is present between about 0.05% and 5.0% of the composition. The use of non-ionic cellulose ethers and water-soluble gums for the composition of eepesants is also contemplated. Refer, for example, to U.S. Patent No. 4,557,928 to Glovr, issued December 10, 1985, which discloses a hair conditioner comprising a seventh suspeneion consisting of a glucan gum, guar gum and hydroxyethylcellulose; and U.S. Patent No. 4,581,230 to Grollier et al., issued April 8, 1986, which discloses cosmetic compositions for treating hair, comprising hydroxyethylcellulose thickening agents or water soluble thickeners of vegetable type such as guar gum, each mentioned here by reference. Cellulose ethers useful for producing viscosate compositions include those having a high degree of selected non-ionic energetic constituents.

P497 of the group consisting of methyl, hydroxyethyl and hydroxypropyl to make them soluble in water and which are further substituted with a hydrocarbon radical having from about 10 to 24 carbon atoms, in an amount between about 0.2 weight percent and the amount that causes the cellulose ether to be less than 1% by weight soluble in water. The cellulose ether to be modified is preferably one of medium to low molecular weight, ie less than 800,000 and preferably between 20,000 and 700,000 (about 75 to 2500 degree of polymerization). Water-soluble nonionic cellulose ethers are preferred polymers that can be used in hair care compositions. Commercially used and non-ionic cellulose ethers that can be widely used include methylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose and ethylhydroxyethylcellulose. Other thickening agents which are used in the compositions of the invention are especially hair rinses, and include combinations of polymeric materials hydrophobically modified with surfactants such as quaternary ammonium compounds (such as ditallowdimethylammonium chloride). These vehicles are described in detail in the following Patents: Patent de loe Eetadoe P 07 U.S. No. 5,106,609 issued April 21, 1992 to Bolich et al., U.S. Patent No. 5,100,658 issued March 31, 1992 to Bolich et al., U.S. Patent No. 5,104,646, issued to April 14, 1992 to Bolich et al., And United States Patent No. 5,100,657 issued March 31, 1992 to Ansher-Jackson et al., All of which are mentioned herein by reference. By the term "hydrophobically modified water-soluble nonionic polymer" is meant a water-soluble nonionic polymer that has been modified by substitution with a sufficient amount of hydrophobic groups to render the polymer less soluble in water. By "water soluble" it is meant that the polymer or salt thereof, which constitutes the polymer structure of the spreader, can be e? Erently soluble so that a substantially clear solution is formed upon dissolving in water at a level of 1% by weight of the solution, at 25 ° C. Therefore, the polymer structure of the primary thickener can be essentially any water-soluble polymer. The hydrophobic groups may be C8 to C22 alkyl, arylalkyl, alkylaryl, and mixtures thereof. The degree of hydrophobic substitution of the polymer structure should be between about 0.10% and 1.0% depending on the particular structure of the polymer. In more form In general, the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is between about 10: 1 to 1000: 1. Water-soluble non-ionic cellulose ethers are preferred as a polymer substrate of hydrophobically modified polymers. Thus, for example, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose and methylhydroxyethylcellulose can be used. It is also contemplated to use a suspending agent to thicken the compositions and / or to suspend the insoluble ingredients of the compositions. Suitable suspending agents are long chain acyl derivatives, long chain amine oxides and mixtures thereof, wherein the suspeneion agents are present in the shampoo compositions in crystalline form. A variety of this euspension agent is described in the republication of United States Patent 34,584 of Grote et al., Issued April 12, 1994. Ethylene glycol distearate is especially preferred. The long-chain acid derivatives useful as suspending agents are also included N, N-di (hydrogenated) C8-C22 amido (preferably C ^ 2-c22 'more preferably C16-C18) benzoic or the soluble salt P407 (for example K, Na ealee) of the same, particularly the N, N-di (hydrogenated tallow) amidobenzoic acid sold by Stepan Company (Northfield, Illinoie, USA). Another useful component is in the compositions for thickeners or for suspending agents of insoluble ingredients of the present is a crosslinked polymeric carboxylic thickener. Eetoe polymer and crosslinked contain one or more monomers derived from acrylic acid, substituted acrylic acids and salts and esters of these acrylic acids and substituted acrylic acids, wherein the crosslinking agent contains doe or more carbon-carbon double bonds and is derived from a polyhydric alcohol. Examples of commercially available carboxylic acid polymers include Carbomers, which are homopolymers of acrylic acid crosslinked with alkyl ethers of sucrose or pentaerythritol. Carbomers are obtained as Carbopol® 900 series from B.F. Goodrich. Examples of commercially available copolymers also include copolymers of C ^ or -30 alkyl acrylates with one or more monomers of acrylic acid, methacrylic acid or one of their short chain esters (ie C? _4 alcohol), wherein The crosslinking agent is an allyl ether of sucrose or pentaerythritol. These copolymers P "are known as crosslinked polymers of acrylate / alkyl acrylate C10-30 and are commercially available under the name of Carbopol® 1342, Pemulen TR-1 and Pemulen TR-2, from BF Goodrich When used, the compositions of the present invention they will generally comprise between about 0.01% and 2%, more preferably between about 0.05% and 1%, and more preferably between about 0.10% and 0.75% polymeric carboxylic acid thickeners.Some other espeeantes include: low pH espeeantee agents such as polyacrylamide, which are obtained under the name Sepigel from Seppic Corporation, and cross-linked quaternary methyl dimethylaminomethacrylate which is obtained as Saleare SC95 from Allied Colloids.

Emulsifiers The compositions herein may contain different emulsifiers. These emulsifiers are useful for emulsifying the various carrier components of the composition herein and are not required to solubilize or disperse the polymers of the invention. Suitable emulsifiers can include any of a wide variety of nonionic, cationic, anionic and zwitterionic surfactants as mentioned above and as P497 reveals in the literature in general. Refer, for example, to McCutcheon's, Detergents and Emulsifiers, North American Edition (1986), published by Allured Publishing Corporation; U.S. Patent No. 5,011,681 to Ciotti et al., Issued April 30, 1991; U.S. Patent No. 4,421,769 to Dixon et al., Issued December 20, 1983 and U.S. Patent No. 3,755,560 to Dickert et al., Issued August 28, 1973. Suitable emulsifiers also include esters of glycerin, propylene glycol ether, polyethylene glycol fatty acid esters, polypropylene glycol fatty acid ester, sorbitol esters, sorbitan anhydride esters, carboxylic acid copolymers, glucose esters and ethers, ethoxylated ethers, ethoxylated alcohols, alkyl phosphates, polyoxyethylene phosphate ether graeoe, fatty acid amides, acyl lactylate, soap and mixtures thereof. Suitable emulsifiers also include, without limitation, polyethylene glycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, methylglucose ether distearate PPG-2, Ceteth-10, Polysorbate 80, cetyl phosphate, cetyl phosphate potassium, diethanolamine cetylphosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate and P497 mixtures thereof. The emulsifiers can be used individually or with a mixture of two or more and can comprise between about 0.1% and 10%, more preferably between about 1% and 7%, and more preferably between about 1% and 5% of the compositions of the present invention.

Other components . The compositions herein may contain a variety of additional optional components suitable for rendering the compositions cosmetically and aesthetically acceptable and for improving storage stability and efficiency or for providing them with additional benefits of use. These conventional optional ingredients are known to those with expertise in this field and eon, for example, colors and dyes, perfumes, aperient aids such as ethylene glycol distearate, preservatives such as benzyl alcohol, methylparaben, propylparaben and imidazolidinyl urea; thickeners and viscosity modifiers such as diethanolamide of a long-chain fatty acid (for example lactic phenolamide PEG 3), cocomonoethanolamide, guar gum, methylcellulose, starch derivatives and starches, fatty alcohols such as cetearyl alcohol; sodium chloride; sodium sulfate; polyvinyl alcohol; 497 ethyl alcohol; pH adjusting agents such as citric acid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; salts in general such as potassium acetate and sodium chloride, coloring agents like any of the dyes FD &C or D &C; perfumes; sequestering agents such as sodium ethylenediaminetetraacetate, polymeric plasticizing agents such as glycerin, diisobutyl adipate, butyl stearate and propylene glycol; vitamins and derivatives thereof (such as, for example, ascorbic acid, vitamin E, tocopherol acetate, retinoic acid, retinol, retinoids and the like; agents for skin perception, astringents, skin softening agents, skin healing agents) and the like, non-limiting examples of these aesthetic components include panthenol and derivatives (for example ethylpantenol), pantothenic acid and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl-lactate, witch hazel distillate, allantoin , bisabalol, dipotassium glycyrrhizinate and similae); polymers to assist the film-forming properties and the ebutantey of the composition (for example a copolymer of eicosene and vinylpyrrolidone, an example of which is obtained from GAF Chemical Corporation as Ganex® V-220); preservatives to maintain the antimicrobial integrity of the PI97 compositions, skin penetration aids such as DMSO, l-dodecylazacycloheptan-2-a (available from Azone de Upjohn Co.); and similar. These optional ingredients are generally used individually at levels between about 0.01% and 10.0%, preferably between about 0.05% and 5.0% of the composition.

Methods for Employing Topical Skin Care Compositions The compositions of this invention are used in conventional ways to provide the desired desired benefits of the product to styling hair, preserving, cleaning and conditioning hair and the like for hair care compositions. and the benefits such as wetting, sun protection, anti-acne properties, anti-wrinkle, artificial tanning, analgesic properties and other coeméticoe and pharmaceutical benefits for skin care compositions. These methods of use depend on the type of composition used but generally involve the application of an effective amount of the product to the skin or hair, which is subsequently rinsed from the skin or hair (as in the case of shampoos and some products). conditioners) or is left to remain in the hair (as in the case of sprays, foams or gel products) N "'or is left to remain on the skin (as in the case of skin care compositions.) By" effective amount "is meant an amount sufficient to provide the desired benefit, preferably gel products, Foam and hair rinses are applied to wet or damp hair before it is combed and combed., the hair is dried and combed in the normal way according to the user. Sprays for hair are typically applied to dry hair after it has dried and combed. Lae compoeicionee for skin care, topical, cosmetic and pharmaceutical types are applied to the skin by rubbing. The following examples further illustrate the preferred embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and are not intended to be limiting of the invention since many variations are possible without departing from the spirit and scope of the invention.

EXPERIMENTS The macrosomers of eicicone I and II and polymer I, II and III can be synthesized according to the following procedures. There are many variations of these procedures that are completely at the discretion of the P497 chemical expert in eynteeis (for example selection of degassing method and gas, selection of type of initiator, degree of conversion, reaction load, etc.). The selection of initiator and solvent are usually determined by the requirements of the particular monomers that are used, since the different monomers have different solubilities and different reactivities towards a specific initiator.

Synthesis of l- (Dimethylchlorosilyl) -2- (p-styryl) ethane end block In a three-necked round bottom flask equipped with a magnetic stirrer, a thermometer and an addition funnel, a solution of divinylbenzene ( 50.Og, 0.384 moles) and dimethylsilane chlorine (11.113 g, 0.128 moles) in dry tetrahydrofuran (THF) (200 mL). To this solution, a solution of chloroplatinic acid (0.150 g in 20 mL THF) is added dropwise. The reaction is highly exothermic since a slow addition of chloroplatinic acid is necessary. After the addition of the platinic acid, the reaction is allowed to continue for a further hour with stirring. This solution (10.64 M) is used to prepare silicone macromer I with styrene end block, as described below. Silicone Macromers I and II: A flask of P497 Round bottom which is stirred with a magnetic stirrer, a hexamethylcyclotrisiloxane monomer solution (150 g) is prepared in dry cyclohexane (150 g). The initiator of sec-butyl lithium (0.0125 mol) is added dropwise. The reaction mixture is allowed to stir for 10 minutes. This is followed by the addition of THF (150 g) to the reaction mixture. The solution is stirred overnight, followed by heating at 50 degrees C for 5 hours. The end block (0.025 moles) is then added slowly to the solution. The silicone macromer I is prepared with the end blocking of 1- (dimethylchloro-ethyl) -2- (p-eethyryl) ethane, as prepared above. The end blocking eXolution of the anterior synthesis of end block is added dropwise. The silicone macromer II is made with a chlorodimethylstyryl silane end block, which can be prepared as described and shown in Holohan, George, Barrie, and Parker, "Monofunctional Polydimethylsiloxane Oligomere For Graft Copolymerization", Macromol. Chem. Phye. 195, 2965-2979 (1994). The end blocking of this synthesis is added dropwise to the solution. Alternatively, the end block can be solubilized in THF and then added dropwise. The macromer is recovered by precipitation of the final solution in ethanol. Polymer I: Place 20 parts of acrylic acid, P497 63 parts of t-butylacrylate and 17 parts of polydimethylsiloxane macromer blocked at the end with styrene (Silicone Macromer I) in a flask. Add enough acetone or ethyl acetate (preferably acetone) as the reaction solvent to produce a final monomer concentration of 25%. Add initiator, azobisisobutyronitrile, at a level of 0.5% by weight in relation to the amount of monomer. Purge the oxygen flask by inserting a line of argon gas below the liquid surface and allowing the argon to bubble in the reaction solvent for approximately 15 minutes. Heat at 60 ° C and maintain this temperature for 48 hours while stirring. Finish the reaction by cooling to room temperature and drying to remove the reaction solvent by pouring the reaction mixture into a Teflon-coated tray and placing it in a vacuum oven. Polymer II: Place 20 parts of acrylic acid, 63 parts of t-butylacrylate and 17 parts of polydimethylsiloxane macromer blocked at the end with ethene (Silicone Macromer II) in a flask. Add enough ethyl acetate or "acetone (preferably acetone) as the reaction solvent to produce a final monomer concentration of 25% Add initiator, azobisisobutyronitrile, at a level of 0.5% by weight relative to the amount of the monomer. he P497 oxygen flask by inserting a gas line through argon below the liquid surface and allowing the argon to bubble to the reaction solvent for approximately 15 minutes. Heat at 60 ° C and maintain this temperature for 48 hours while stirring. Finish the reaction by cooling to room temperature and removing the reaction solvent by drying by pouring the reaction mixture into a Teflon-coated tray and placing it in a vacuum oven. Polymer III: Place 20 parts of acrylic acid, 30 parts of N-isopropylacrylamide, 35 parts of t-butylacrylate and 15 parts of polydimethylsiloxane macromer blocked at the end with styrene (Silicone Macromer I) in a flask. Add enough ethyl acetate or acetone (preferably acetone) as the reaction solvent to produce a final monomer concentration of 25%. Add initiator, azobisisobutyronitrile, at a level of 0.5% by weight relative to the amount of monomer. Purge the oxygen flask by inserting a line of argon gas below the liquid surface and allow the argon to bubble into the reaction solvent for approximately 15 minutes. Heat at 60 ° C and maintain this temperature for 48 hours while stirring. Finish the reaction by cooling to room temperature and drying the reaction solvent to P497 pour the reaction mixture into a tray coated with Teflon and placing it in a vacuum oven.

EXAMPLES The following examples further describe and demonstrate the embodiments of the invention that are within the scope thereof. The examples are only intended to illustrate the invention and not to limit it since many variations of it are possible without departing from the spirit and scope thereof. In the following formulas, ethanol is anhydrous unless otherwise indicated.

EXAMPLES l A 4 The following is an example composition of foam of the present invention. Component (% p) 1 2 3 4 Polymer III 3.00 3.00 3.00 3.00 Lauramina-oxide 0.10 0.10 0.00 0.10 Coca idopropylbetaine 1.33 1.33 0.30 1.33 Propylene glycol 0.20 0.10 0.10 0.10 Perfume 0.10 0.10 0.05 0.10 Disodium EDTA Dihydrate 0.10 0.10 0.10 0.10 Phenoxyethanol 0.25 0.25 0.25 0.25 Methylparaben 0.15 0.15 0.15 0.15 Polyquaternium-4! 0.00 0.00 0.00 0.20 Chloride of 0.00 0.00 0.20 0.00 stearyltrimethylammonium Solution KOH (45% active) 0.80 0.80 1.00 0.90 Deionized Water c.b.p. c.b.p. c.b.p. c.b.p. 1Celquat L200, National Starch and Chemical Corp.

(Bridgewater, NJ, USA, diallyldimethylammonium chloride copolymer and hydroxyethylcellulose) The composition is made by mixing the silicone-grafted copolymer in the water with the KOH solution, and then adding the remaining ingredients, except for the perfume, by stirring, heating, and heating. 40 ° C - 60 ° C with stirring, and stirring for an additional period of about eight hours while allowing the composition to cool to room temperature and then mixing in the perfume. The product can then be packaged in a conventional aerosol container or in an aerosol spray container.

EXAMPLES 5 TO 8 Below are several examples of reduced VOC hair spray compositions of the present invention. Component (% p) 5 6 7 8 Polymers I or II 4.50 3.50 4.00 3.00 Deionized water 5.00 3.00 18.00 17.00 Isododecano 1.50 0.00 0.00 0.00 KOH solution (45% active) 0.90 0.65 0.00 0.75 NaOH solution (30% active) 0.00 0.00 1.00 0.00 Triethyl citrate 0.20 0.40 0.00 0.10 Perfume 0.10 0.25 0.05 0.10 Propylene glycol 0.05 0.00 0.00 0.10 N-Butane (Propellant) 7.50 6.00 0.00 0.00 HFC 152A (Propellant) 15.00 17.00 0.00 0.00 Dibutyl Adipate 0.00 0.00 1.30 0.00 Ethanol SDA 40 c.b.p. C.b.p. c.b.p. C.b.p.

The compositions are made by adding the ethanol to a mixing vessel followed first by the addition of the remainder of the non-propellant ingredients, sequentially in the order shown above, and followed by vigorous stirring for two or three hours. The composition of Example 5 and Example 6 is added to conventional aerosol containers in the typical manner and charged with propellants. The composition of the Example is added to conventional spray cans without aerosol.

EXAMPLE 9 The following is a representative shampoo composition of the present invention. Component% in Weight Laureth ammonium sulfate 5.00 Cocamido propylbetaine 6.00 Polymer III 4.00 Solution NaOH (30% active) 0.10 Distearate PEG 150 2.00 Glydant1 0.38 aminomethylpropanol 0.40 Perfume 1.00 Deionized water c.b.

Commercial preservative obtained from Glyco, Inc. The shampoo is prepared by combining the ammonium laureth sulfate and the silicone-grafted copolymer (Polymer III) and heated at 70 ° C for about 1/2 hour with mixing. The quenching ingredients are added and mixed in half an hour more. The batch is cooled to room temperature. The pH is adjusted to 6.5 by the addition of citric acid or sodium hydroxide, if necessary.

EXAMPLE 10 The following is a rinse composition for conditioning hair type and for hair styling, representative of the present invention. Component% in Weight Polymer III 3,. 00 NaOH solution (30% active) 0,. 90 Premix Silicone Rubber Silicone GE SE761 0. . 50 Decamethyl cyclopentasiloxane 4. , 00 Main mixture Cetil hydroxyethylcellulose2 0.60 Carob bean gum 1.50 Disodium salt of EDTA 0.15 DTDMAC 0.65 Glydant3 0.40 Deionized water c.b.p. 1 It is obtained commercially from General Electric, P497 2Polysurf by Aqualon Co. 3 Commercial preservative obtained from Glyco, Inc. The Silicone Premix is mixed separately by conventional means. The main mixture is prepared by adding all the ingredients and heating at 95 ° C for 1/2 hour with stirring, as the batch is cooled to approximately 60 ° C, the Silicone Premix, the silicone-infected copolymer (Polymer III) and the NaOH solution is added to the main mixture with stirring and the batch is cooled to room temperature.

EXAMPLE 11 Dew composition for reduced hair in VOC prepared according to the following components. Ingredients A B C D Water c.b.p. 100 c.b.p. 100 c.b.p. 100 c.b.p. 100 Ethanol 54.0 54.0 54.0 54.0 Polymer I, II or III 4.0 3.0 4.0 3.0 KOH solution (45% 0.80 0.60 1.00 0.75 active) Dioctyl phthalate 0.40 0.10 Fragrance 0.05 0.2 These products are prepared by first dissolving the polymer in the ethanol with stirring. The remaining ingredients are added with stirring. The resulting hair spray compositions can then be packaged in a non-aerosol spray pump container.

P497 Alternatively, the compositions can be combined with conventional propellants and packaged in an aerosol spray container.

EXAMPLE 12 Foam compositions which are prepared according to the following components using conventional mixing techniques. Ingredients% in Weight A B C Water c.b.p. 100 c.b.p. 100 c.b.p. 100 Polymer III 3.00 2.50 3.50 NaOH solution (30% 0.80 0.50 0.90 active) Lauramide DEA 0.33 0.33 0.33 Methyl Oleyl Taurate of 1.67 1.67 1.67 Sodium DMDM Hydantoin 0.78 0.78 0.78 EDTA from Disodium.

Isostearyl alcohol 0.10 0.10 0.10 polyoxyalkylated1 Fragrance 0.10 0.10 0.10 Propellant2 7.0 7.0 7.0 These products are prepared by first dissolving the polymer in water with agitation. The remaining ingredients, except the propellant, are then added with stirring. The resulting foam concentrate can then be combined with conventional propellant (eg Propellant A462) and packed in a spray container P497 in spray. These foams are useful for applying to the hair in order to provide benefits in combing and preserving hair. 1 Aerosurf 66-E10. 2 Obtained as a mixture of 82.46% isobutane, 16.57% propane and 0.001% butane.

EXAMPLE 13 Hair tonic compositions are prepared from the following components using conventional mixing techniques. Ingredients% in Weight A B C Ethanol (190 degrees c.b.p. 100 c.b.p. 100 c.b.p. 100 Proof) Polymer I, II or III 0.75 1.00 1.25 Aminomethyl Propanol 0.15 0.18 0.22 Fragrance 0.10 0.20 0.30 These products are prepared by dissolving polymer in the ethanol with stirring and then adding the fragrance and any color. These hair tonics are useful to apply to the hair to provide ease of combing and hairstyle conservation.

EXAMPLE 14 A shampoo composition is prepared P497 conditioner and hair styling facilitator from the following components using conventional mixing techniques. Ingredients% in Weight Agent to Facilitate the Hairstyle Polymer III 3.00 Solution NaOH (30% active) 0.20 Premix Silicone Rubber 0.50 Dimethicone, 350 cs fluid 0.50 Main Mix Water c.b.p. 100 Ammonium Lauryl Sulfate 11.00 Cocamide MEA 2.00 Ethylene Glycol Dieterate 1.00 Xanthan Gum 1.20 Methylchloroisothiazolinone (y) Methylisothiazolinone 0.04 Citrus at a pH of 4.5, as required The main mixture is prepared by first dissolving the xanthan gum in the water with conventional mixing. The rest of the ingredients of the main mixture are added and the main mixture is heated to 150 ° F with stirring for 1/2 hour. The hair styling agent and the premix are then added sequentially in about 10 minutes of agitation between additions, and the entire mixture is stirred while the batch is cooled to room temperature. For sizes of P497 various particles, the premix and the styling agent can be added at different times using high shear mixing or normal agitation, or both.

EXAMPLE 15 Anti-Acne Composition. An anti-acne composition is made by combining the following components and using conventional mixing technology. Ingredient% in Weight Water c.b.p. 100 Salicylic Acid 2.00 Polymer I, II or III 2.00 Ethanol (SDA 40) 40.00 Aminomethyl Propanol 0.40 EXAMPLE 16 A topical analgesic composition is made by combining the following ingredients using conventional mixing techniques. Ingredient% in Weight Water, Purified c.b.p. 100 Ibuprofen 2.00 Polymer III 2.00 Aminomethyl Propanol 0.45 Ethanol (SDA 40) 20.00 P49! EXAMPLE 17 A sunless tanning composition is made by combining the following ingredients and using conventional mixing techniques. Ingredients% in Weight Phase A Water c.b.p. 100 Polymer III 2.00 NaOH solution (30% active) 0.70 Carbomer 9341 0.20 Carbomer 9802 0.15 Acrylic acid copolymer3 0.15 Phase B PPG-20 Methylgluous ether distearate 2.00 Tocopheryl acetate 1.20 Mineral oil 2.00 Stearyl alcohol 1.00 Shea Butter 1.00 Alcohol of Cetyl 1.00 Ceteareth-20 2.50 Ceteth-2 1.00 Ceteth-10 1.00 Faee C DEA-Cetyl Phosphate 0.75 Phase D Dihydroxyacetone 3.00 Phase E Butylene glycol 2.00 P4 «7 Hydantoin DMDM (y) Butylcarbamate 0.25 Iodopropynyl Phase F Fragrance 1.00 Cyclomethicone 2.00 In a suitable container disperse the ingredients of Phase A in water and with heating at 78-85 C. In a separate container combine the ingredients of Fae B and ee heat to 85-90 C until they melt. Subsequently, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirred until it dissolves.

This mixture is then added to Phase A to form the emulsion. The emulsion is cooled to 40-45 C with continuous mixing. Subsequently, in a separate vessel the hydroxyacetone is dissolved in water and the resulting solution is mixed with the emulsion. In another container, the ingredients of Phase E are heated with mixing at 40-45 C until a clear solution is formed and subsequently this solution is added to the emulsion. Finally the ingredients of Phase F are added to the solution with the help of mixing, and then cooled to 30-35 C and then at room temperature. This solution is useful for topical application to the skin in order to provide an artificial tan. 1 Obtained as Carbopol R934 from B.F. Goodrich. 2 Obtained as Carbopol R980 from B.F. Goodrich.

P497 Obtained as Permulen TRl from B.F. Goodrich, EXAMPLE 18 Sunscreen Composition An oil-in-water emulsion is prepared by combining the following components and using conventional mixing techniques. Ingredients% Weight Phase A Water QS100 Carbomer 954 0.24 Carbomer 1342 0.16 Polymer III 1.75 NaOH (30%) 0.70 Disodium EDTA 0.05 Phase B Isoaraquilyl neopentanoate 3 2.00 4 Copolymer of PVP Eicosene 2.00 Octyl methoxycinnamate 7.50 Octocrylene 4.00 Oxybenzene 1.00 Titanium dioxide 2.00 cetyl palmitate 0.75 steraroxytriethylsilane (and) alcohol stearyl 0.50 glyceryl tribehenate 0.75 dimethicone 1.00 tocopheryl acetate 0.10 DEA-cetyl phosphate 0.20 F497 Phase C Water 2.00 Triethanolamine 99% 0.60 Faee D Water 2.00 Butylene glycol 2.00 DMDM hydantoin (y) Iodopropynyl butylcarbamate 0.25 dL Panthenol 1.00 Fae E Cyclomethicone 1.00 1 Available as Carbopol 954 from B.F. Goodrich 2 Available as Carbopol 1342 from B.F. Goodrich 3 Available as Elefac 1-205 from Bernal Chemical. 4 Available as Ganex V-220 from GAF Corporation 5 Available as DC 580 Wax from Dow Corning. 6 Available as Synchroax HRC from Croda. 7 Available from Lonza Glydant Plus. In a suitable container, the following ones of Phase A are dispersed in the water and heated to 75-85 ° C. In a separate vessel combine the ingredients of Phase B (except DEA-cetyl phosphate) and heat to 85-90 ° C until melted. The DEA-cetyl phosphate is then added to the liquid phase B and stirred until dissolved. This mixture is then added to Phase A to form the emulsion. The ingredients of Phase C are combined until they are P497 dissolve and then add to the emulsion. The invention is then cooled to 40-45 ° C with continuous mixing. In another vessel, the ingredients of Phase D are heated by mixing at 40-45 ° C until a clear solution is formed and this solution is then added to the emulsion. Finally, the emulsion is cooled to 35 ° C and the ingredient of Phase E is added and mixed. This emulsion is useful for topical application to the skin in order to provide protection against damaging effects of ultraviolet radiation.

EXAMPLE 19 Facial Moisturizer A facial emulsion composition is prepared which remains on the skin, combining the following components and using conventional mixing techniques. Ingredients% by weight Water QS100 Polymer III 1.00 Solution NaOH (30% active) 0.40 Glycerin 3.00 Cetyl Palmitate 3.00 Cetyl Alcohol 1.26 Quaternium-22 1.00 Glyceryl Stearate Monohydroxy 0.74 Dimethicone 0.60 P497 Stearic Acid 0.55 Octyldodecyl myristate 0.20 Carbomero 1342 0.125 EDTA of Tetrasodio 0.10 DMDM Idantoin and Iodopropynyl butyl 0.10 carbamate Carbomer 951 0.075 P497

Claims (10)

1. CLAIMS: 1. A topical personal care composition containing silicone-grafted copolymer having improved resistance to hydrolysis, the composition is suitable for topical application to the skin or hair and comprises: (a) between about 0.1% to about 50%, by weight of composition, of the silicone-grafted copolymer containing: (i) from about 1% to about 99% by weight of the copolymer, of acid-containing monomers; (ii) from about 1% to about 50% by weight of the copolymer, of a silicone macromer blocked at the end with styrene or blocked at the end with alkenyl, having the formulas, respectively: 3 ^? - Zm X-CB - (CH2) s-S¡ (R) 3.m-Zm wherein: s is an integer from 0 to about 6; m P497 is an integer from 1 to 3, R2 is C 1 -C 7 alkyl, or 7-C 10 alkylaryl is an integer from 0 to 4; X is an ethylenically unsaturated group of the formula: CH = C- I I R3 R < wherein R 3 is -H or C -C6 alkyl; R4 is H or alkyl C! -C6; Z is Rl RMS¡O) r- R1 wherein each R independently is an alkyl, aryl or alkylaryl having from 1 to 10 carbon atoms, and r is an integer from about 4 to about 700, and combinations thereof; (iii) from about 0% to about 98% additional monomers and combinations thereof; and (b) from about 1% to about 99.9% by weight of the composition of an aqueous or hydroalcoholic solvent of the silicone-grafted copolymer, suitable for applying to the skin or hair, wherein the copolymer is soluble or diesable in said solvent.
2. 2. A composition according to claim 1, P497 wherein the silicone macromer is the silicone macromer blocked at the end with styrene, n is 0 and the ~ (CH2) s-Si (R) 3-m-Zm of the eicicone macromer is substituted in the position for relation to X, where s ee from 0 to 2, m is 1, n ee 0, R 3 is H, R 4 is H or CH 3, R 1 is an alkyl, preferably where R is methyl and r is from 50 to 500
3. 3. A composition according to any of the preceding claims, wherein the copolymer comprises from 1% to 50% by weight of the copolymer, of additional monomers, the additional monomers are nonionic, cationic, amphoteric or a combination thereof, preferably wherein the additional monomers are nonionic monomers that are selected from the group consisting of: acrylic and methacrylic acid ester of C? -C24 alcohols; styrene; rent us; chlorine styrene; vinyl esters; vinyl chloride, vinyl toluene; vinyl caprolactam; vinylidene chloride; acrylonitrile, alpha-alkyl styrene; 1, 3-dialquenoe, ethylenically monounsaturated hydrocarbon; Alkoxyalkyl (meth) acrylate, alkyl vinyl ether; di-acrylates and di-methacrylates; acrylamide; methacrylamide; diacetone acrylamide, N-N-dialkyl (meth) acrylamides; N-alkyl (meth) acrylamide; acrylate and methacrylate alcohols; vinyl pyrrolidone; allyl alcohol; vinyl alcohol and combinations thereof. P4 7
4. 4. A composition according to any of the preceding claims, wherein the acid-containing monomers are selected from the group consisting of carboxylic acids and sulfonic acids.
5. 5. A composition according to any of the preceding claims, wherein the acid-containing monomers are carboxylic acids.
6. 6. A composition according to any of the preceding claims, wherein the carboxylic acid monomers are selected from the group consisting of those corresponding to the formula: R5 R6 wherein R 5 and R 6 are independently H or Ci-Cg alkyl, R 7 is H, Ci-C alkyl or a carboxylic entity having 0 up to 12 carbon atoms; and R is a carboxylic entity having up to 12 carbon atoms; and mix of loe miemoe.
7. A composition according to any one of the preceding claims, wherein the copolymer comprises: (i) from 5% to 90% by weight of the copolymer, of acid-containing monomers; (ii) from 2% to 40% by weight of the copolymer, P497 silicone macromers; (iii) from 0% to 70% by weight of the copolymer, of additional monomers.
8. A composition according to any one of the preceding claims, wherein the copolymer comprises: (i) from 10% to 75% by weight of the copolymer, of acid-containing monomers; (ii) from 5% to 40% by weight of the copolymer of silicone macromers; (iii) from 5% to 70% by weight of the copolymer, of additional monomers.
9. 9. A composition according to any of the preceding claims, wherein the copolymer comprises: (i) from 15% to 50% by weight of the copolymer, of acid-containing monomers; (ii) from 5% to 25% by weight of the copolymer, of monomers derived from the silicone monomer; , (iii) from 40% to 70% by weight of the copolymer, of the additional monomers.
10. 10. A hair spray product comprising the composition of any one of the preceding claims, placed in an aerosol spray or spray-free container. P497