Note: Descriptions are shown in the official language in which they were submitted.
CA 02264769 1999-03-03W0 93/09507 PCT/US97/15549PERSONAL CARE COMPOSITIONSTEQHNIQAL FIELDThis is a continuation-in-part of application Serial No. 08/708,334, ï¬led on September 4,1996.The present invention relates to personal care compositions comprising a copolymer complexand a volatile, hydrophobic solvent component for solubilizing or dispersing the copolymer complex.The copolymcr complex is formed by complexing a fatty amine with a copolymer, wherein thecopolyrner comprises a hydrophobic monomer, a hydrophilic monomer such that at least 1%. byweight of the total copolymer. comprises hydrophilic monomers bearing acidic functional groups, andoptionally a hydrophobic macromonomer. These compositions provide improved delivery, depositionand retention to the hair and skin.BACKGRQUND OF THE INVENTIONThe rheological, holding, and ï¬lm-forming properties of polymers and copolymers havecontributed immensely to their usefulness in a wide variety of personal care compositions. Productscontaining polymers include hairsprays, shampoos, hair conditioners, skin creams and lotions, make-up products, antiperspirants and deodorants, shaving creams, topical drug compositions, sunscreenproducts, and the like. Consumers are constantly seeking products providing improved perfonnancebeneï¬ts.In their quest to improve upon current products and to create new products, scientists andforrnulators are continually seeking to develop new key ingredients for such products. Becausepolymers play such an important role in the formulation of many personal care products. a need existsfor new polymers having new and useful properties. In the hair care area, for example, style retentionis generally accomplished by application of either permanent chemical alteration products ortemporary styling products. A permanent chemical alteration product, which is commonly referred toas a "hair penn.â typically involves treating the hair with various sulfur-containing compounds inorder to break the disulï¬de bonds in the hair fibers, thereby enabling one to alter the shape andorientation of the hair ï¬bers. However, hair penn products have the disadvantage of being harsh anddamaging to the hair, and of being long-lasting and diï¬icult to reverse. Conversely, temporarystyling products generally do not break the chemical bonds in the hair ï¬bers. These temporary stylingproducts typically are in the form of gels. lotions, mousses, or sprays containing polymeric resins orgums for coating the hair ï¬bers and bonding them together. Many temporary styling products areinconvenient to use and have the disadvantage of not allowing one to readily restyle the hair alter theinitial application and styling is completed, without further application of additional product. ItCA 02264769 1999-03-03wo 98/09607 PCT/US97/155492would be preferable to deliver styling and hold beneï¬ts using rinse-off products such as conditionersand shampoos. These types of rinse-olf products, however. require styling agents that are substantiveto the hair and not readily removed during the rinsing process. Especially useful styling and holdagents for rinse-off compositions are hydrophobic polymeric materials. Such hydrophobic materials,however, may cause a buildup of an unsightly visible residue on the hair with repeated usage. Thisresidue can eventually completely surround the hair shaft and can be diï¬icult to remove with nomlalshampooing. Therefore, the need exists for improved compositions for providing temporary stylingand hold of human hair without the residue and negatives oï¬en associated with such compositions.Similarly, a need remains for ï¬lm-fanning skin compositions which are readily washed off by soapand water.It has surprisingly been found that hair care products comprising a copolymer complexcomprising a copolymer having at least one acid functional monomer and at least one fatty aminecomplexed with the acid functional monomer provide excellent temporary styling and hold beneï¬ts inaddition to improved "wash oï¬â characteristics. The copolymer complex of the present invention issoluble or dispersible in and readily deposited by hydrophobic solvent components, yet easily washedaway by aqueous surfactant solutions. These compositions can be made into any of a number ofconventional forms including, but not limited to, shampoos, conditioners, mousses, gels, lotions,sprays and the like.In addition to the afore-mentioned hair care benefits, it has been found that the copolymercomplex and volatile, hydrophobic solvent component of the present invention are also useful forincorporation into a wide variety of cosmetic and pharmaceutical compositions for topical applicationto the skin. These materials provide topical compositions which are more easily and unifonnly spreadupon the skin, which feel good upon the skin, and yet are highly substantive. Furthennore, thesecompositions are useful for providing occlusion to enhance the penetration of a wide variety ofcosmetic and pharmaceutical actives into the skin, or alternatively, through the skin for systemicdelivery.The compositions of the present invention comprise a copolymer complex and a volatile,hydrophobic solvent component stumble for application to the hair or skin. The copolymer complexcomprises a copolymer having at least one acid functional monomer and at least one fatty aminecomplexed with the acid functional monomer.It is therefore an object of the present invention to provide copolymer complexes havingimproved solubility or dispersibility characteristics. 4It is another object of the present invention to provide copolymer complexes that are solubleor dispersible in hydrophobic solvent components and yet are readily washed away by aqueoussurfactant solutions.It is another object of the present invention to provide personal care compositions in the formof hair care compositions having improved styling and/or hold properties and having improvedaesthetics.CA 02264769 1999-03-03wo 93/09507 PCT/US97/155493If is another object of the present invention to provide personal care compositions in the formof topical cosmetic and pharmaceutical compositions useful for delivering and retaining a widevariety of cosmetic materials and phamiaceutical actives to and/or through the skin.It is another object of the present invention to provide rinse off compositions useful forstyling and holding hair.It is another object of the present invention to provide methods for styling and holding thehair.It is another object of the present invention to provide methods for delivering and retainingto the skin cosmetic materials and pharmaceutical actives.These and other objects will become readily apparent from the detailed description whichfollows.§UMMARY QF THE INVENTIQNThe compositions of the present invention relate to personal care compositions, comprising:A.) a copolymer complex comprising:a.) a copolymer having a backbone formed from the copolymerization of repeatingA monomer and B monomer units wherein the backbone has optionally graï¬edto it hydrophobic C macromonomer units wherein the copolymer is prepared bythe polymerization combination of the following relative weight percentages ofthe A, B, and C units:i) from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units, wherein the A monomer units arecopolymerizable with the B monomer and C macromonomer units;ii) from about 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units, wherein the B monomer units arecopolymerizable with the A monomer and C macromonomer units andwherein at least about 1% by weight of the copolymer, of the B monomerunits, are selected from B monomer units having at least one acid functionalgroup; andiii) from 0 to about 50% by weight of the copolymer of one or more Cmacromonomer units wherein the C units are hydrophobic macromonomerunits, copolymerizable with the A monomer units and the B monomer units,the C macromonomer units having a number average molecular weight offrom about 1,500 to about 50,000; andb.) a complexing fatty amine wherein the fatty amine forms a complex with the acidfunctional group of the B monomer units;wherein the weight ratio of the copolymer to the fatty amine is from about 50:1 toabout 1:1;CA 02264769 1999-03-03wo 98/09607 PCT/US97/15549andB.) a volatile, hydrophobic solvent component for the copolymer complex having a boilingpoint at 1 atmosphere of about 260°C or less and a solubility parameter of about 8.5(cal/cm3)1/2 or lesswherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solventcomponent.In further embodiments, the present invention relates to a method of making a personal carecomposition, comprising the steps of:a.) preparing a copolymer having a backbone formed from the copolymerization ofrepeating A monomer and B monomer units wherein the backbone hasoptionally graï¬ed to it hydrophobic C macromonomer units wherein thecopolymer is prepared by the polymerization combination of the followingrelative weight percentages of the A. B, and C units:i) from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units, wherein the A monomer units arecopolymerivable with the B monomer and C macromonomer units;ii) from about 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units, wherein the B monomer units arecopolymerizable with the A monomer and C macromonomer units andwherein at least about 1% by weight of the copolymer, of the B monomerunits, are selected from B monomer units having at least one acid functionalgroup; andiii) from 0 to about 50% by weight of the copolymer of one or more Cmacromonomer units wherein the C units are hydrophobic macromonomerunits, copolymerizable with the A monomer units and the B monomer units,the C macromonomer units having a number average molecular weight offrom about 1,500 to about 50,000; andb.) complexing the copolymer with a fatty amine wherein the weight ratio of thecopolymer to the fatty amine is from about 50:1 to about 1:1; andc.) dissolving or dispersing the copolymer complex in a volatile, hydrophobicsolvent component having a boiling point at 1 atmosphere of about 260°C or lessand a solubility parameter of about 8.5 (cal/cm3)â2 or less.In further embodiments, the present invention relates to a personal care composition whichprior to mixing, comprises:A.) a copolymer complex comprising: Ia.) a copolymer having a backbone formed from the copolymerization of repeatingA monomer and B monomer units wherein the backbone has optionally graï¬edto it hydrophobic C macromonomer units wherein the copolymer is prepared byCA 02264769 1999-03-03W0 93,o96o7 PCT/US97/155495the polymerization combination of the following relative weight percentages ofthe A, B, and C units:i) from about 10% to about 99% by weight of the copolymer of one or morehydrophobic A monomer units. wherein the A monomer units arecopolymerizable with the B monomer and C macromonomer units;ii) from about 1% to about 40% by weight of the copolymer of one or morehydrophilic B monomer units, wherein the B monomer units arecopolymerizable with the A monomer and C macromonomer units andwherein at least about 1% by weight of the copolymer, of the B monomerunits, are selected from B monomer units having at least one acid functionalgroup; andiii) from 0 to about 50% by weight of the copolymer of one or more Cmacromonomer units wherein the C units are hydrophobic macromonomerunits, copolymerizable with the A monomer units and the B monomer units,the C macromonomer units having a number average molecular weight offrom about 1,500 to about 50,000; andb.) a complexing fatty amine wherein the fatty amine fomis a complex with the acidfunctional B monomer unitswherein the weight ratio of the copolymer to the fatty amine is from about 50:1 toabout 1:1;andB.) a volatile, hydrophobic solvent component for the copolymer complex having a boilingpoint at 1 atmosphere of about 260°C or less and a solubility parameter of about 8.5(cal/cm3)â2 or lesswherein the copolymer complex is soluble or dispersible in the volatile, hydrophobic solventcomponentUnless otherwise indicated, all percentages and ratios used herein are by weight of the totalcomposition. All weight percentages, unless otherwise indicated, are on an actives weight basis. Allmeasurements made are at 25°C, unless otherwise designated. The invention hereof can comprise,consist of, or consist essentially of, the essential as well as optional ingredients and componentsdescribed herein.DETAILED DESCRIPTION OF THE INVENTIONEssential ComponentsThe compositions of the present invention comprise a copolymer complex and a volatile,hydrophobic solvent component suitable for application to the hair and skin, wherein the copolymercomplex comprises a copolymer complexed with a fatty amine.CA 02264769 1999-03-03wo 93/09507 PCT/US97/155496The copolymers of the present invention can include graft copolymers. The term "graï¬copolymers" is familiar to one of ordinary skill in polymer science and is used herein to describe thecopolymers which result by adding or "grafting" a polymeric chemical moiety (i.e. "graï¬s") ontoanother polymeric moiety commonly referred to as the "backbone". The backbone typically has ahigher molecular weight than the graï¬s. Thus, graï¬ copolymers can be described as polymers havingpendant polymeric side chains, and as being fonned from the "grafting" or incorporation of polymericside chains onto or into a polymer. The polymer to which the grafts are incorporated can behomopolymers or copolymers. The graï¬ copolymers are derived from a variety of monomer units.The copolymers of the present invention can be prepared from the copolymerization ofmonomer units and macromonomer units such that the macromonomer units are "grafted" orincorporated into the resulting copolymer. The term "macromonomer" is a term familiar to one ofordinary skill in polymer science, and is used to described a polymeric material containing apolymerizable moiety. In other words, a macromonomer is a macromolecular monomer, which isessentially a high molecular weight type of monomer building block unit which can be used in apolymerization reaction to form polymers with itself, with other monomers, or with othermacromonomers.The tenn "hydrophilic" is used herein consistent with its standard meaning of having affinityfor water, whereas "hydrophobic" is used herein consistent with its standard meaning of lackingaffinity for water. As used herein in relation to monomer units and polymeric materials, includingthe macromonomers, copolymers, and solvents for the copolymers, "hydrophilic" means substantiallywater soluble. "Substantially water soluble" shall refer to a material that is soluble in distilled (orequivalent) water, at 25°C, at a concentration of 0.2% by weight, and are preferably soluble at 1.0%by weight. In contrast, "hydrophobic" means substantially water insoluble. In this regard,"substantially water insoluble" shall refer to a material that is not soluble in distilled (or equivalent)water, at 25°C, at a concentration of 0.2% by weight, and preferably not soluble at 0.1% by weight.The term âsolubleâ or "solubility" as used herein, means the capability of a substance to forma solution, i.e., either a true solution or a colloidal solution. A true solution being a uniformlydispersed mixture at the molecular or ionic level, of one or more substances (the solute) in one ormore substances (the solvent). These two parts of a solution are called phases. A colloidal dispersionis oï¬en called a solution. Since colloidal particles are larger than molecules it is strictly incorrect tocall such dispersions solutions; however this term is widely used in the literature. The term"dispersible" or "dispersibilityâ as used herein, means the capability of a substance to form adispersion, i.e., a two-phase system where one phase consists of finely divided particles (often in thecolloidal size range) distributed throughout a bulk substance, the particles being the disperse orinternal phase and the bulk substance the continuous or external phase.The tenn "rinse-off or wash oï¬â is used herein to mean that the compositions of the presentinvention are used in a context whereby the composition is ultimately rinsed or washed from the hairCA 02264769 1999-03-03wo 98/09607 PCT/US97/155497and/or skin either after or during the application of the product. Nonlimiting examples of rinse-oï¬'products of the present invention include hair conditioners. shampoos and soaps.The term "substantive" or "substantivity" as used herein, means the binding or retention of achemical or pharmaceutical active to the surface layer of the stratum comeum or to hair.The term "suitable for application to human hair and skin" as used herein, means that thecompositions or components thereof so described are suitable for use in contact with human hair andthe scalp and skin without undue toxicity, incompatibility, instability, allergic response, and the like.The aforementioned definitions shall also apply to other materials so described herein, to theextent any other deï¬nitions regarding such materials are consistent with those stated above.The compositions of the present invention comprise the following essential components.Copglmer complexThe hair and skin care compositions of the present invention comprise from about 0.25% toabout 30%, preferably from about 2% to about l5%, and more preferably from about 2% to about10%, by weight, based on the weight of the hair and skin care composition, of a copolymer complex.The copolymer complex comprises a copolymer having at least one acid functionalized monomercomplexed with a fatty amine. âl erThe copolymer complex of the present invention comprises from about 35% to about 99%,preferably from about 40% to about 90%, and more preferably from about 50% to about 70%, byweight, based on the weight of copolymer complex, of a copolymer. Based on the weight of theoverall hair and skin care composition, the copolymer comprises from about 0.1% to about 10%,preferably from about 1% to about 5%, and more preferably from about 1.5% to about 3.5%, byweight.The copolymer: of the present invention have a weight average molecular weight, ingrams/mole, of at least about 10,000. There is no upper limit for molecular weight except that whichlimits applicability of the invention for practical reasons, such as viscosity, processing, aestheticcharacteristics, formulation compatibility, etc. The weight average molecular weight is generally lessthan about 5,000,000, more generally less than about 2,500,000, and typically less than about1,500,000. Preferably, the weight average molecular weight is from about 10,000 to about 5,000,000,more preferably from about 50,000 to about 2,000,000, even more preferably from about 75,000 toabout 1,000,000, and most preferably from about 75,000 to about 500,000.The copolymers of the present invention are fonned from the copolymerization of randomlyrepeating A monomer units and B monomer units, preferably wherein the A monomers arepolymerizable, ethylenically unsaturated monomers selected to meet the requirements of thecopolymer. By "polymerizable." as used herein, is meant monomers that can be polymerized usingany conventional synthetic techniques. Monomers that are polymerizable using conventional freeradical initiated techniques are preferred. The term "ethylenically unsaturated" is used herein tomean monomers that contain at least one polymerizable carbon-carbon double bond (which can beCA 02264769 1999-03-03wo 93/09607 PCT/US97/155498mono-, di-, tnâ-, or tetra-substituted). The B monomer units are hydrophilic monomers which arecopolymerizable with A and selected from polar monomers, preferably having a Tg or a Tm aboveabout -20°C, and wherein at least 1%, by weight of the copolymer, of the hydrophilic B monomer isselected from hydrophilic B monomers having at least one acid functional group. The A monomerand B monomer units fonn what is termed the backbone of the polymer and can be selected from awide variety of structures as long as the copolymer has the required properties and meets themolecular weight and other requirements described herein. The copolymers of the present inventionmay optionally incorporate C macromonomer units. The C macromonomer units are selected from atleast one hydrophobic rnacromonomer unit which contains a polymeric portion and a moietycopolymerizable with the A monomer and the B monomer. The C rnacromonomer units formhydrophobic side chains on the copolymer.The copolymers are prepared by the polymerization combination of A and B monomers andcan be characterized by the weight percent of the monomers charged to the reaction vessel in whichthe polymerization reaction is run. C macromonomers may be optionally incorporated into thepolymerization reaction.As will be clear to one skilled in the art and especially from the Examples, the copolymermay have one or more hydrophobic side chains grafted to the backbone. As known in the an,synthetic graï¬ copolymerization processes may produce a mixture of polymer molecules containingno, one, or more than one hydrophobic side chains covalently bonded to and pendant from thepolymeric backbone. From knowledge of the amount and number average molecular weight ofhydrophobic side chains in a polymer sample, and the number average molecular weight of thepolymer sample, it is possible to calculate the average number of hydrophobic side chains per polymerbackbone.The copolymer complex of the present invention, when dried to a film having 0.5% or less ofthe volatile hydrophobic solvent component, have a Tg or Tm of at least about -20°C, more preferablyat least about 20°C, so that the copolymers are not unduly sticky, or "tacky" to the touch. As usedherein, the abbreviation "Tg" refers to the glass transition temperature of the backbone of thepolymer, and the abbreviation "Tm" refers to the crystalline melting point of the backbone, if such atransition exists for a given polymer. Preferably, both the Tg and the Tm, if any, are above about -20°C, more preferably above about 20°C.The graï¬ed copolymers should satisfy the following criteria:(1) the polymeric side chain portion is covalently bonded to the backbone portion; and(2) the number average molecular weight of the polymeric side chain portion is from about1,500 to about 50,000.The copolymers of the present invention are prepared by the polymerization combination ofA monomers and B monomers. C macromonomers may optionally be incorporated into thepolymerization process. The copolymers can be synthesized by free radical polymerization of themonomers and macromonomers. The general principles of free radical polymerization methods areCA 02264769 1999-03-03wo 98/09607 PCT/US97/155499well understood. gg, for example, Odian, "Principles of Polymerization", 3rd edition, John Wiley &Sons. 1991, pp. 198-334. The desired monomers and macromonomers are all placed in a reactor,along with a suï¬icient amount of a mutual solvent so that when the reaction is complete the viscosityof the reaction is reasonable. Undesired terminators, especially oxygen, are removed as needed. Thisis done by evacuation or by purging with an inert gas, such as argon or nitrogen. The initiator isintroduced and the reaction brought to the temperature needed for initiation to occur, assumingthermal initiators are used. Alternatively, redox or radiation initiation can be used. Thepolymerization is allowed to proceed as long as needed for a high level of conversion to be achieved,typically from a few hours to a few days. The solvent is then removed, usually by evaporation or byprecipitating the copolymer by addition of a nonsolvent. The copolymer can be further purified, asdesired.As an alternative to a batch reaction, the copolymer can be made by a semi-continuous orcontinuous process. In the semi-continuous process, two or more additions of monomers ormacromonomers are made during the polymerization reaction. This is advantageous when thecopolymer is made of several monomers which react during the polymerization at different rates.The proportions of monomers added to the reaction at the separate points of addition can be adjustedby one of ordinary skill in the art such that the polymers of the ï¬nal product have a more uniformstructure. In other words. the polymers of the ï¬nal product will have a more consistent monomercontent distribution for each of the monomer types charged to the reaction.Examples of related copolymers and how they are made are described in detail in U.S. Patent4,693,935, Mazurek, issued September 15, 1987, U.S. Patent 4,728,571, Clemens eta1., issued March1, 1988, both of which are incorporated herein by reference. Additional graï¬ed polymers are alsodisclosed in U.S. Patents 5,166,276 and 5,480,634, Hayama, et al., issued November 24, 1992 andJanuary 2, 1996, respectively; U.S. Patent 5,061,481, Suzuki et al., issued October 29, 1991; U.S.Patent 5,106,609, Bolich et al., issued April 21, 1992; U.S. Patent 5,100,658, Bolich et al., issuedMarch 31, 1992; U.S. Patent 5,100,657, Ansher-Jackson, et al., issued March 31, 1992; and U.S.Patent 5,104,646, Bolich et al., issued April 14, 1992, all of which are incorporated by referenceherein in their entirety.The copolymer composition is characterized by the amount of each monomer charged to thepolymerization reaction vessel, or altematively used in a continuous or semi-continuous process.By appropriate selection and combination of the panicular monomer units andmacromonomer units, and by the choice of specific relative ratios of the units well within the ability ofone of ordinary skill in the art, the copolymers can be optimized for various physical properties andfor compatibility with other ingredients commonly used in hair care applications.A Monomer QnitsThe copolymers of the present invention comprise from about 10% to about 99%, preferablyfrom about 40% to about 80%, and more preferably from about 50% to about 70%, by weight of thehydrophobic copolymer, of A monomer units.CA 02264769 1999-03-03wo 93/09507 PCT/US97I1554910The A monomer unit is selected from copolymerizable hydrophobic monomers or mixturesthereof, preferably ethylenically unsaturated monomers. Either a single type of A monomer unit orcombinations of two or more A monomer units can be utilized. The A monomers are selected to meetthe requirements of the copolymer. Preferably, the A units are soluble or dispersible in the volatile,hydrophobic solvent component. By "copolymerizable", as used herein, is meant that the A monomercan be reacted with or polymerized with the B monomers or C macromonomers in a polymerizationreaction using one or more conventional synthetic techniques, such as ionic, emulsion, dispersion,Ziegler-Natta, free radical, group transfer or step growth polymerization. In the present invention,monomers and macromonomers that are copolymerizable using conventional free radical initiatedtechniques are preferred. The term "ethylenically unsaturatedâ is used herein to mean a material thatcontains at least one polyrnerizable carbon-carbon double bond, which can be mono-, di-, tri- or tetra-substituted.Nonlimiting classes of A hydrophobic monomers useful herein include monomers selectedfrom the group consisting of unsaturated carboxylic acid esters of Cl-C18 alcohols, unsaturatedalcohols (preferably having about l2 to about 30 carbons), unsaturated hydrocarbons, aromatichydrocarbons containing unsaturated alkyl groups, vinyl esters of carboxylic acids, vinyl ethers, allylesters of carboyxlic acids, allyl ethers, and mixtures thereof.Representative examples of hydrophobic monomers include acrylic or methacrylic acid estersof C1-C13 alcohols such as methanol, ethanol, methoxy ethanol, l-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 1-decanol, 2-ethylhexanol, cyclohexanol, and the like; dicyclopentenyl acrylate;4-biphenyl acrylate, pentachlorophenyl acrylate; 3,5-dimethyladamantyl acrylate; 4-methoxycarbonylphenyl methacrylate, trimethylsilyl methacrylate; styrenes such as methyl styrene; I-butyl styrene, isopropyl sytrene; vinyl esters, such as vinyl acetate, vinyl neononanoate, vinylpivalate; and vinyl propionate; vinyl chloride; vinyl toluene; alkyl vinyl ethers, including isobutylvinyl ether and s-butyl vinyl ether; allyl chloride, allyl acetate, 1,2-butadiene; 1,3-buatdiene, 1,3-hexadiene, 1,3-cyclohexadiene; bicycloheptadiene; 2,3-dicarboxylmethyh1,6-hexadiene; ethylene;propylene; isoprene; 1-butene, 2-butene, isobutylene, indene; norbomylene; B-pinene; or-pinene; andmixtures thereof.Preferred hydrophobic monomers suitable for use as the A monomer units include monomersselected from the group consisting of n-butyl methacrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methyl methacrylate, r-butyl styrene and mixturesthereof. More preferred are monomer units selected from the group consisting of t-butyl styrene, (-butyl acrylate, I-butyl methacrylate, 2-ethylhexyl methacrylate and mixtures thereof.B Monomer UnitsThe copolymers of the present invention comprise from about 1% to about 40%, preferablyfrom about 5% to about 30%, and more preferably from about 10% to about 25%, by weight of thecopolymer, of B monomer units.CA 02264769 1999-03-03wo 93/09597 PCT/US97/15549ll'fhe B monomer unit is selected from hydrophilic, copolymerizable monomers, preferablyethylenically unsaturated monomers, comprising at least one monomer copolymerizable with the Amonomer unit. Either a single type of B monomer unit or combinations of two or more B monomerunits can be utilized. The B monomers are selected to meet the requirements of the copolymer. By"copolymerizable", as used herein, is meant that the B monomer can be reacted with or polymerizedwith the A monomers or C rnacromonomers in a polymerization reaction using one or moreconventional synthetic techniques, such as ionic, emulsion, dispersion, Ziegler-Natta, free radical,group transfer or step growth polymerization. In the present invention, monomers andrnacromonomers that are copolymerizable using conventional free radical initiated techniques arepreferred. The tenn "ethylenically unsaturated" is used herein to mean a material that contains atleast one polymerizable carbon-carbon double bond. which can be monoâ, di-, tri- or tetra-substituted.The B monomer units are selected from hydrophilic monomers wherein at least 1% by weight basedon the weight of the copolymer, of the copolymer, comprises hydrophilic monomers having at leastone acid functional group. The hydrophilic monomers preferably are selected such that a polymer ofthese monomers has a Tg or a Tm above about -20°C.Preferred hydrophilic B monomers are copolymerizable with the A and C monomers, and areselected from the group consisting of unsaturated organic mono- and poly- carboxylic acids,unsaturated (meth)acrylates. unsaturated (meth)acrylarnides, unsaturated (meth)acrylate alcohols,unsaturated arninoalkylacrylates, unsaturated organic acid anhydrides, unsaturated esters of organicacid anhydrides. hydrophilic unsaturated vinyl compounds, hydrophilic unsaturated allyl compounds,hydrophilic unsanirated imides, salts of the foregoing compounds, and mixtures thereof.Representative examples of B monomers include acid functional compounds such as acrylicacid, methacrylic acid, maleic acid, crotonic acid and itaconic acid as well as non-acid functionalcompounds such as N,N-dimethylacrylamide, dimethylaminoethyl methacrylate, quatemizeddimethylaminoethyl methacrylate, methacrylamide, N-t-butyl acrylamide, maleic anhydride and itshalfesters, acrylamide, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride, vinyl pyrroli-done, vinyl ethers (such as methyl vinyl ether), maleimides. vinyl pyridine, vinyl irnidazole, otherpolar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (produced by the hydrolysis ofvinyl acetate aï¬er polymerization) and mixtures thereof. More preferred are B monomers selectedfrom the group consisting of acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethyl-arninoethyl methacrylate, vinyl pyrrolidone, and mixtures thereof. It is remains critical, however, thatat least 1% by weight, based on the weight of the copolymer. comprises 3 monomers having at leastone acid functional group.C Macromonomer UnitsThe copolymers of the present invention can comprise from about 0% to about 50%,preferably from about 5% to about 40%, and more preferably from about 15% to about 30%, byweight of the copolymer of C macromonomer units.CA 02264769 1999-03-03W0 93/09507 PCT/US97/1554912The C macromonomer units are hydrophobic macromonomers copolymerizable with the Aand B monomers, said C macromonomers preferably having an ethylenically unsaturated moiety.Either a single type of C macromonomer unit or combinations or two or more C macromonomer unitscan be utilized herein. The C macromonomers are selected to meet the requirements of thecopolymer. By "copolymerizable", as used herein, is meant that the C macromonomers can be reactedwith or polymerized with the A and B monomers in a polymerization reaction using one or moreconventional synthetic techniques, as described above.C macromonomers that are useful herein contain a polymeric portion and a copolyemiizablemoiety which is preferably an ethylenically unsaturated moiety. Typically, the preferred Cmacromonomers are those that are endcapped with the ethylenically unsaturated moiety. By"endcapped" as used herein is meant that the ethylenically unsaturated moiety is at or near a terminalposition of the macromonomer.The C macromonomers can be synthesized utilizing a variety of standard syntheticprocedures familiar to the polymer chemist of ordinary skill in the art. Furthermore, thesemacromonomers can be synthesized starting from commercially available polymers. The Cmacromonomer has a number average molecularâ weight from about l500 to about 50,000, preferablyfrom about 5000 to about 50,000, more preferably from about 5,000 to about 30,000, and mostpreferably from about 8,000 to about 25,000.Preferably, the C macromonomer units are selected from the group consisting of polysiloxanemacromonomers, polyalkylene macromonomers, and mixtures thereof.Polysiloxane C macromonomers are exemplified by the general formula:X(Y)..Si(R)3.nZ...wherein X is an ethylenically unsaturated group copolymerizable with the A monomers, such as avinyl group; Y is a divalent linking group; R is a hydrogen, hydroxyl, lower alkyl (e.g. C,-C4),phenyl, C1-C4 alkyl-substituted aryl, C1-C4 alkoxy, or C1-C4 alkyl or dialkylamino; Z is amonovalent siloxane polymeric moiety having a number average molecular weight of at least about1500, is essentially unreactive under copolymerization conditions, and is pendant from the vinylpolymeric backbone described above; it is 0 or 1; and m is an integer from t to 3.Preferably, the C macromonomer has a formula selected from the following fonnulas:X (CH2 );â35(Râ)3-rn-Zm(RzlnorX âC H2""(C H2)sâ5 i(Râ )3-mâZmOfCA 02264769 1999-03-03WO 93419507 PCT/US97/1 5549130IIX-C-0-(CH2)q-(0)1,-Si(Râ)3_mZmIn these structures s is an integer from 0 to 6, preferably 0, 1, or 2, more preferably 0 or l; in is aninteger from I to 3, preferably l; p is O or I; q is an integer from 2 to 6; R2 is selected from the groupconsisting of C1-C10 alkyl or C1-C4 alkyl-substituted aryl, preferably C1-C5 alkyl or C1-C4 alkyl-substituted aryl, more preferably C1-C2 alkyl; n is an integer selected from 0 to 4, preferably 0 or 1,more preferably 0; Râ is hydrogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl amino ordialkylamino, phenyl, C1-C4 alkyl substituted aryl, preferably Râ is C1-C4 alkyl; X isCH=C-I lR3 RâR3 is hydrogen or -COOH, preferably R3 is hydrogen; Râ is hydrogen, methyl or -CI-I2COOH,preferably Râ is methyl; Z isR6IR5-(-Si-0-)r;IR7R5, R5, and R7, independently are C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl or dialkylamino, phenyl,C1-C4 alkyl-substituted aryl, hydrogen or hydroxyl, preferably R5, R5, and R7 are C1-C4 alkyl; and ris an integer of from about 20 to about 900, preferably about 20 to about 673, more preferably r isfrom about 100 to about 325. Most preferably, Râ, Râ, and R7 are methyl, p=0, and q=3.Polyalkylene macromonomers are exempliï¬ed by the general formula:llln-lWlm-Ewherein I is an optionally present initiator (i.e. n = 0 or 1), W is a hydrophobic monomer unit, E is anendcapping group, and m is an integer from about 10 to about 2000.I is an optionally present chemical initiator moiety. Without being limited by theory, I can bederived from a chemical initiator or solvent used in the synthesis of the C macromonomer.Nonlirniting examples of such initiators from which I can be derived include hydrogen ion, hydrogenradical, hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxide anion, Cl-C20carbocations, Cl-C20 carbanions, Cl-C20 carbon radicals, Cl-C20 aliphatic and aromatic alkoxyanions, ammonium ion. and substituted ammonium ions (e.g.. C l-C20 alkyl and Cl-C20 alkoxysubstituted), and mixtures thereof. 1 can be derived from any useful solvent, nonlimiting examples ofwhich include water, methanol, ethanol, propanol, isopropanol. acetone, hexane, dichloromethane,chlorofonn, benzene, toluene, and mixtures thereof.CA 02264769 1999-03-03wo 98/09607 PCT/US97/1554914W is selected from one or more hydrophobic monomer units. Nonlimiting classes of suchmonomers include Cl-C18 acrylate esters, Cl-C18 (alk)acrylate esters, C2-C30 straight and branchedchain alkenes, styrenes, Cl-C30 vinyl ethers, C4-C30 straight and branched chain dienes, andmixtures thereof.Nonlimiting examples of W groups include those selected from the group consisting of n-butyl acrylate, dodecyl acrylate, ethyl acrylate, 2-ethybutyl acrylate, n-heptyl acrylate, n-hexylacrylate,iso-butyl acrylate, iso-decyl acrylate, iso-propyl acrylate, 3-methylbutyl acrylate, 2-methylpentylacrylate, nonyl acrylate, octyl acrylate, l-propyl acrylate, 2-ethylhexyl methacrylate, octylmethacrylate, n-dodecyl methacrylate, n-octadecyl mcthacrylate, n-decyl methacrylate, n-pentylmethacrylate, isobutylene, isoprene, 1,2-butadiene, 1,3-butadiene, 5-methyl-l-hexene, 6-methyl-l-heptene, 4,4-dimethyl-1-pentene, iso-butyl vinyl ether, styrene, 2âmethyl styrene, 3-methylstyrene, 4-methyl styrene, 2-t-butyl styrene, 3-t-butyl styrene, 4-t-butyl styrene, and mixtures thereof.E is a copolymerizable moiety or "endcappingâ group. Preferably E is an ethylenicallyunsaturated moiety. More preferred is when E is selected from the group consisting of vinyl, allyl,acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, l-propenyl, isobutenyl, cyclohexenyl, cyclopentenyl, andmixtures thereof. Even more preferred is when E is selected from the group consisting of vinyl, allyl,acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, and mixtures thereof. Most preferred is when E is selected from thegroup consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, andmixtures thereof.Nonlimiting examples of polysiloxane and polyalkylene C macromonomer units usefulherein include those selected from the group consisting of acryloyl, methacryloyl, or 3-, or 4-vinylbenzyl endcapped polymers of polydimethylsiloxane, polydiethylsiloxane,polyphenylmethylsiloxane, polyphenylethylsiloxane, poly(n-butyl acrylate), poly(dodecyl acrylate),poly(2-ethylhexyl acrylate), poly(2~ethylbutyl acrylate), poly(ethyl acrylate), poly(n-heptyl acrylate),poly(n-hexyl acrylate), poly(iso-butyl acrylate), poly(iso-decyl acrylate, poly(iso-propyl acrylate),poly(3-methylbutyl acrylate), poly(2-methylpentyl acrylate), poly(nonyl acrylate), poly(octyl acrylate),poly(propyl acrylate), poly (2-ethylhexyl methacrylate), poly(tridecyl methacrylate), poly (hexylmethacrylate), poly(decyl methacrylate), poly(octyl methacrylate), poly(octadecyl methacrylate),poly(dodecyl methacrylate), poly(n-pentyl methacrylate), poly(isobutylene), poly(isoprene),hydrogenated poly(l,2-butadiene). hydrogenated poly(l,4-butadiene). hydrogenated poly(isoprene),poly(l,2-butadiene), poly(l-butene), poly(5-methyl-1-hexene). poly(6-methyl-l-heptene), poly(4,4-dimethyl-l-pentene), poly(iso-butyl vinyl ether), poly[4-t-butyl vinyl benzene-co-2-ethylhexylacrylate], poly[2-ethylhexyl acrylate-co-octyl acrylamide), po|y[2-ethyl vinyl benzene-co-octylmethacrylate)], and mixtures thereof. ."Copolymer" type C macromonomers containing two or more different randomly repeatingmonomer units are useful herein. Nonlimiting examples of these "copolymer" type ofCA 02264769 1999-03-03WO 93/09507 PCT/U S97/ 1554915macromonomers include acryloyl endcapped poly[co(4-I-butyl vinyl benzene)(2,4-dimethyl vinylbenzene)], poly[co(4ât-butyl vinyl benzene)(2-ethylhexyl acrylate)], poly[co(2,4-dimethyl vinylbenzene)(2-ethylhexyl acrylate)], poly[co(2-ethyl vinyl benzene)(octylmethacrylate)], and the like.Nonlimitinrz» Examples Of Polvmers Of The Present InventionNonlimiting examples of polymers useful for making the complexes of the present inventioninclude those selected from the group consisting of poly[(I-butylacrylate-co-acrylic acid)-grampoly(dimetliylsiloxane)], polyl(4-I-butylstyrene-co-acrylic acid)-graï¬-poly(dimethylsiloxane)], poly[t-butylacrylate-co-acrylic acid)-graï¬-poly(isobutylene)], poly[(4-I-butylstyrene-co-acrylic acid)-graï¬-poly(isobutylene)], poly[(t-butylstyrene-co-acrylic acid)-graï¬-poly(2-ethylhexyl methacrylate)],poly[(4-I-butylacrylate-co-styrene-co-acrylic acid)-graï¬-poly(isobutylene)], poly[(t-butylacrylate-co-methacrylic acid)-graft-poly(dimethylsiloxane)], poly[(4-I-butylstyrene-co-methacrylic acid)-graï¬-poly(dimethylsiloxane)],poly[I-butylacrylate-co-methacrylic acid)-graï¬-poly(isobutylene)], poly[(4-t-butylstyrene-co-methacrylic acid)-graï¬-poly(isobutylene)], poly[(t-butylstyrene-co-methacrylic acid)-graï¬-poly(2-ethylhexyl methacrylate)], polyl(4-I-butylacrylate-co-styrene-co-methacrylic acid)-grampoly(isobutylene)], and mixtures thereof.The following more specific nonlimiting examples of polymers useful for making thecomplexes of the compositions of the present invention include the following. The weight percentsrefer to the amount of monomer and macromonomer reactants added in the polymerization reaction,not necessarily the amount in the finished polymer.(I) a copolymer prepared from the polymerization reaction of i0 weight percent acrylic acid, 70weight percent isobutylmethacrylate and 20 weight percent polydimethylsiloxane macromonomerhaving a weight average molecular weight of about 20,000.(II) a copolymer prepared from the polymerization reaction of 20 weight percent acrylic acid, 62weight percent t-butyl acrylate and 18 weight percent polydimethylsiloxane macromonomer having aweight average molecular weight of about 15,000.(III) a copolymer prepared from the polymerization reaction of 50 weight percent t-butylacrylate,10 weight percent t-butyl methacrylate, 10 weight percent acrylic acid, 10 weight percent ethylhexylmethacrylate and 20 weight percent polydimethylsiloxane macromonomer having a weight averagemolecular weight of about 10,000. A(IV) a copolymer prepared from the polymerization reaction of 60 weight percent t-butylacrylate,15 weight percent acrylic acid, l0 weight percent ethylhexyl methacrylate and 15 weight percentpolydimethylsiloxane macromonomer having a weight average molecular weight of about 10,000.(V) a copolymer prepared from the polymerization reaction of 70 weight percent tâbutylacrylate,10 weight percent methacrylic acid, and 20 weight percent polyisobutylene macromonomer having aweight average molecular weight of about 10,000.(VI) a copolymer prepared from the polymerization reaction of 75 weight percent t-butylacrylate,5 weight percent acrylic acid. and 20 weight percent polydimethylsiloxane macromonomer having aweight average molecular weight of about 10,000.CA 02264769 1999-03-03WO 93/09607 PCT/US97/1554916(VII) a copolymer prepared from the polymerization reaction of 70 weight percent tâbutylacrylate,10 weight percent acrylic acid, and 20 weight percent ethylhexyl methacrylate.(VIII) poly[(t-butyl acrylate-co-acrylic acid)-graft-polydimethylsiloxane)] having a weight averagemolecular weight of about 700,000, comprising about 67% I-butyl acrylate, about 3% acrylic acid, andabout 30% dimethylsiloxane macromonomer with a weight average molecular weight of about 11,000.Fam AmineThe copolymer component of the present invention comprises from about 1% to about 65%,preferably from about 10% to about 60%, and more preferably from about 30% to about 50%, basedon the weight of the copolymer complex, of a complexing, fatty amine and derivatives thereof andsalts thereof.Fatty amines useful to compositions of the present invention include primary, secondary andtertiary amines, quaternary ammonium salts, alkyl substituted heterocyclic amines, and polyarninessuch as diamines and triamines. Also useful herein are salts of these amines and quaternizedderivatives of these amines.It is critical to the present invention that copolymer complex formed by the acid functionalmonomer and the complexing amine be soluble or dispersible in the volatile, hydrophobic solventcomponent discussed below. Without being limited by theory, it is believed that the fatty aminesassociate with the acid functional monomers of the copolymer backbone so as to shield thehydrophilic, acid functional group from the hydrophobic solvent, improving the stability of thesolubilized and/or dispersed copolymer complexPrimary amines or salts thereof having the formula R1-NI-I2 wherein R1 is a C 1-C22 straightor branched chain aliphatic, hydroxyalkyl, amidoalkyl, carboxyallcyl, cyclic, alkoxy, polyalkoxy, orhydroxypolyalkoxy group function as useful fatty amines.Secondary amines or salts thereof having the formula RIRZ-NH wherein R1 and R2 areindependently a C1-C22 straight or branched chain aliphatic, hydroxyalkyl, amidoalkyl, carboxyalkyl,cyclic, alkoxy, polyalkoxy, or hydroxypolyalkoxy group also function as useful fatty amines.Additionally, tertiary amines or salts thereof having the fonnula RlR2R3N wherein R1, R2and R3 are independently a C I-C22 straight or branched chain aliphatic, hydroxyalkyl, amidoalkyl,carboxyalkyl, cyclic, alkoxy, polyalkoxy, or hydroxypolyalkoxy group function well as fatty amines.Other preferred complexing amines are quatemary ammonium compounds having theformula R1R2R3R4N"' [Xâ] wherein R1, R2, R3 and R4 are independently a C1-C3 straight orbranched chain aliphatic, hydroxyalkyl, amidoalkyl, carboxyallcyl, cyclic, alkoxy, polyalkoxy, orhydroxypolyalkoxy group and X is an anion. Examples of quaternary ammonium complexing aminesinclude C 12-C 13 alkyl dimethylammonium chloride, octadecyltrimethylammonium chloride,cetyltrimethylammonium bromide, n-dodecyltrimethylammonium hydroxide, tallow trimoniumchloride and n-octadecyltri-n-butylammonium nitrate.Polyamines or salts thereof are also suitable for use in the present invention. Suitablepolyamines are those having the formula R1R2-N((CH3)xN)n-RIR2 wherein R1 and R2 areCA 02264769 1999-03-03wo 93/09507 PCT/US97/1554917independently a hydrogen atom or a C1-C3 straight or branched chain aliphatic, hydroxyalkyl,amidoalkyl, carboxyalkyl, cyclic, alkoxy, polyalkoxy or hydroxypolyalkoxy group, x is an integer of lto 3, and n is an integer from 1 to 5. Representative polyamines are ethylenediaminc,diethylenetriamine triethylenetetraamine, tetraethylenepentamine, pentaethyienehexamine, tallowpropylenediarnine, 1,2-propanediamine, 1,3,5-pentanetriamine, and ethylenediarninetetraacetic acid(EDTA).I-leterocyclic amines or salts thereof having C1-C22 straight or branched chain alkylsubstituted imidazolines. morpholines, or piperidincs are also useful in the present invention. Typicalheterocyclic amines include aminoethyl hexadecylimidazoline, N-ethyl morpholine, and N-ethylpiperidine.Mixtures of the above fatty amines may also be used. Preferred for use in forming thecopolymer complexes of the present invention are tertiary amines or salts thereof.The copolymers of the present invention can be complexed with the fatty amines eitherduring the polymerization process or alter the polymerization process as part of a ï¬nal complexingstep preferably at a weight ratio of copolymer to fatty amine of from about 50:1 to about 1:1, morepreferably from about 3:1 to about l0:7, more preferably from about 15:7 to about 10:7.Volatile, Hydrophobic Solvent componentThe compositions of the present invention further comprises from about 1% to about 99.75%,preferably from about 4% to about 50%, and more preferably from about 4% to about 20%, based onthe weight of the composition, of a volatile, hydrophobic solvent for the copolymer complex.The term "solvent", as used herein, means a liquid suitable for solubilizing or dispersing oneor more of a variety of substances. The term "solvent component" as used herein means a liquidcomprised of a single solvent or a mixture of solvents. The term "volatile", as used herein, means thatthe solvent exhibits a significant vapor pressure at ambient conditions (e.g., 1 atmosphere at 25°C), asunderstood by those skilled in the scientific arts. Specially, the solvent component has a boiling pointat one atmosphere of about 260°C or less, preferably about 230°C or less, more preferably about215°C or less, and most preferably about 210°C or less and a solubility parameter of about 8.5(cal/cm3)lâ2 or less. In addition, the boiling point of the solvent will generally be at least about 50°C,preferably at least about 90°C. The solvent component should also be acceptable for topicalapplication to the hair and the skin. The copolymers composed of the monomer and/or rnacromerunits of the present invention must be soluble or dispersible in the volatile, hydrophobic solventcomponent once complexed with the fatty amine complexing agent of the present invention.Hydrophobic solvents suitable for use in the volatile, hydrophobic solvent component areselected from the group consisting of branched chain hydrocarbons, silicones, and mixtures thereof.Preferred hydrophobic branched chain hydrocarbons useful as the solvent component hereincontain from about 7 to about 14, more preferably from about 10 to about 13, and most preferablyfrom about ll to about 12 carbon atoms. Saturated hydrocarbons are preferred, although it is notintended to exclude unsaturated hydrocarbons. Examples of such preferred branched chainCA 02264769 1999-03-03W0 98/09507 PCTIUS97/15549l8hydrocarbons include isoparaï¬ins of the above chain sizes. lsoparaffms are commercially availableform Exxon Chemical Co; examples include Isopar E (C3~C9 isoparaï¬ins), IsoparTM H and K (C1 1-C12 isoparafï¬ns), and lsoparTM L (C â-C 13 isoparaï¬ins) or mixtures thereof. Other suitablebranched chain hydrocarbons are isododecane and isoundecane. Isododecane is preferred and iscommercially available from Presperse, Inc. (South Plainfield, NJ, USA) as PermethylTM 99A.Preferred silicones useful as the volatile hydrophobic solvent component include volatilesiloxanes such as phenyl pentamethyl disiloxane, phenylethylpentamethyl disiloxane, hexamethyldisiloxane, methoxy propylheptamethyl cyclotetrasiloxane, chloropropyl pentamethyl disiloxane,hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane,and mixtures thereof. More preferred among the silicones are cyclomethicones, examples of whichinclude hexamethyl disiloxane, octamethyl cyclo tetrasiloxane and decamethyl cyclopentasiloxane,which are commonly referred to D4 and D5 cyclomethicone, respectively.Small amounts of hydrophilic solvents such as water, the C1-C5 alcohols, or mixturesthereof may also be incorporated herein so long as the solubility parameter of the volatile,hydrophobic solvent component is about 8.5 (cal/cm3)1/2 or less.The copolymer complexes of the present invention are soluble or dispensable in the volatile,hydrophobic solvent component at a concentration by weight of about 0.2%, preferably of about 0.5%,and more preferably of about 1%.In the case of the improved hair styling embodiments, the copolymer complex and thevolatile, hydrophobic solvent are preferably mixed such that the copolymer complex/solvent mixturehas a viscosity above about 5,000 cps, preferably from about 7,000 cps to about 250,000 cps and morepreferably from about 7,000 cps to about l5,000 cps. All viscosities are measured at 25°C and at ashear rate of 10 secâ1 using a Bohlin cone and plate viscometer Model VOR (cone diameter: 30mm;cone angle: 2.5°) and are expressed in centipoise. Without being limited by theory, it is believed thatthese higher viscosity embodiments improve polymer deposition eï¬iciency and/or improve the weldmorphology of polymer droplets leading to improved hair style and hold.Qazrï¬Hair Care and Topical Skin Care CommsitionsThe copolymers of the present invention can be fonnulated into a wide variety of producttypes, including mousses, gels. lotions, creams, ointments, tonics, sprays, aerosols, shampoos,conditioners, rinses, bar soaps, hand and body lotions, facial moisturizers. solid gel sticks, sunscreens,anti-acne preparations, topical analgesics, mascaras, antiperspirants, deodorants and the like.Carriers optionally used to fonnulate such product types should be immiscible with the volatilehydrophobic solvent component. The tenn "immiscible" as used herein means the volatile,hydrophobic solvent component has a solubility in the carrier of less than 2% by weight, preferablyless than 1%, most preferably less than 0.1% such that at least two liquid phases are formed uponcombining the volatile, hydrophobic solvent component with the carrier. The optional Carriers andCA 02264769 1999-03-03wo 93/09507 PCTIUS97/1554919additionalcomponents vary with the product type and can be routinely chosen by one skilled in theart. The following is a description of some of these carriers and additional components.Hair Care CompositionsThe hair care compositions of the present invention can comprise a carrier, or a mixture ofsuch carriers, which are suitable for application to the hair. The carriers are preferably present atfrom about 0.5% to about 99.5%, preferably from about 5.0% to about 99.5%, more preferably fromabout 10.0% to about 98.0%, of the composition. As used herein, the phrase "suitable for applicationto hair" means that the carrier does not damage or negatively affect the aesthetics of hair or causeirritation to the underlying skin.Carriers stumble for use with hair care compositions of the present invention include, forexample, those used in the formulation of hair sprays, mousses, tonics, gels, shampoos, conditioners,and rinses. The choice of appropriate carrier will also depend on the particular copolymer to be used,and whether the product fonnulated is meant to be left on the surface to which it is applied (e.g., hairspray, mousse, tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner, rinse).The carriers used herein can include a wide range of components conventionally used in haircare compositions. The carriers can contain a solvent to dissolve or disperse additional copolyrnersbeing used, with water, the Cl-C6 alcohols, and mixtures thereof being preferred; and water,methanol, ethanol, isopropanol, and mixtures thereof being more preferred. The carriers can alsocontain a wide variety of additional materials including, but not limited to acetone, hydrocarbons(such as isobutane. hexane, decene), halogenated hydrocarbons (such as Freons), linalool, esters (suchas ethyl acetate, dibutyl phthalate), and volatile silicon derivatives (especially siloxanes such asphenyl pentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane, chloropropylpentamethyl disiloxane, hydroxypropyl pentamethyl disiloxane, octamethyl cyclotetrasiloxane,decamethyl cyclopentasiloxane, cyclomethicone, and dimethicone having for example, a viscosity at25°C of about 2.5 centipoise or less). and mixtures thereof. When the hair care composition is a hairspray, tonic, gel, or mousse the preferred solvents include water, ethanol, volatile silicone derivatives,and mixtures thereof. The solvents used in such mixtures may be miscible or immiscible with eachother. Mousses and aerosol hair sprays can also utilize any of the conventional propellants to deliverthe material as a foam (in the case of a mousse) or as a fine, uniform spray (in the case of an aerosolhair spray). Examples of suitable propellants include materials such as triclilorofluoromethane,dichlorodiï¬uoromethane, diï¬uoroethane, dimetliylether, propane, n-butane or isobutane. A tonic orhair spray product having a low viscosity may also utilize an emulsifying agent. Examples of suitableemulsifying agents include nonionic, cationic, anionic surfactants, or mixtures thereof.Fluorosurfactants are especially preferred, particularly if the product is a hair spray composition andmost especially if it is a spray composition having relatively lowâ levels of volatile organic solvents,such as alcohols, and relatively high levels of water (e.g., in excess of about 10%, by weight water). Ifsuch an emulsifying agent is used, it is preferably present at a level of from about 0.01% to about7.5% of the composition. The level of propellant can be adjusted as desired but is generally fromCA 02264769 1999-03-03wo 93/09507 PCT/US97l1554920about 3% to about 30% of mousse compositions and from about 15% to about 70% of the aerosol hairspray compositions.Suitable spray containers are well known in the art and include conventional, non-aerosolpump sprays i.e., "atomizers," aerosol containers or cans having propellant, as described above, andalso pump aerosol containers utilizing compressed air as the propellant. Pump aerosol containers aredisclosed, for example, in U.S. Patents 4,077,441, March 7, 1978, Olofsson and 4,850,577, July 25,1989, TerStege, both incorporated by reference herein, and also in U.S. Serial No. 07/839,648,Gosselin, Lund, Sojka, and Lefebvre, ï¬led February 21, 1992, "Consumer Product PackageIncorporating A Spray Device Utilizing Large Diameter Bubbles. Pump aerosols hair sprays usingcompressed air are also currently marketed by The Procter & Gamble Company under theirtradename VIDAL SASSOON AIRSPRAY® hair sprays.Where the hair care compositions are conditioners and rinses, the carrier can include a widevariety of conditioning materials. Where the hair care compositions are shampoos, the carrier caninclude surfactants, suspending agents, thickeners etc. Various additional components useful in haircare compositions are described in U.S. Patent No. 5,106,609, to Bolich, Jr. et 211., issued April 21,1992; and U.S. Patent No. 4,387,090, to Bolich, Jr. issued June 7, 1983; which are incorporated byreference herein. Some of these additional components are described below.Topical Skin Care CompositionsThe topical cosmetic and phamtaceutical compositions of the present invention can comprisea carrier. The carrier should be "cosmetically and/or pharmaceutically acceptableâ, which means thatthe carrier is suitable for topical application to the skin, has good aesthetic properties, is compatiblewith the copolymers of the present invention and any other components, and will not cause anyuntoward safety or toxicity concerns.The carrier can be in a wide variety of forms. For example, emulsion carriers, including, butnot limited to, oil-in-water, water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions,are useful herein. These emulsions can cover a broad range of viscosities, e.g., from about 100 cps toabout 200,000 cps. These emulsions can also be delivered in the form of sprays using eithermechanical pump containers or pressurized aerosol containers using conventional propellants. Thesecarriers can also be delivered in the fonn of a mousse. Other suitable topical carriers include an-hydrous liquid solvents such as oils, alcohols, and silicones (e.g., mineral oil, ethanol, isopropanol,dirnethicone, cyclomethicone, and the like); aqueous-based single phase liquid solvents (e.g., hydro-alcoholic solvent systems); and thickened versions of these anhydrous and aqueous-based single phasesolvents (e.g., where the viscosity of the solvent has been increased to fonn a solid or semi-solid bythe addition of appropriate gums, resins, waxes, polymers, salts, and the like). Examples of topicalcarrier systems useful in the present invention are described in the following four references all ofwhich are incorporated herein by reference in their entirety: "Sun Products Formularyâ Cosmetics QToiletries vol. 105, pp. 122-139 (December 1990); "Sun Products Fonnulary", Cosmetics & CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554921Toiletries vol. 102, pp. 117-136 (March 1987); U.S. Patent No. 4,960,764 to Figueroa et al.. issuedOctober 2, 1990; and U.S. Patent No. 4,254,105 to Fukuda et al.. issued March 3, 1981. The carriers of the skin care compositions preferably comprise from about 50% to about 99%by weight of the compositions of the present invention, more preferably from about 75% to about99%, and most preferably from about 85% to about 95%.Preferred cosmetically and/or phannaceutically acceptable topical carriers include hydro-alcoholic systems and oil-in-water emulsions. When the carrier is a hydro-alcoholic system, thecarrier can comprise from about 1% to about 50% of ethanol, isopropanol, or mixtures thereof, andfrom about 40% to about 99% of water. More preferred is a carrier comprising from about 5% toabout 60% of ethanol, isopropanol, or mixtures thereof, and from about 40% to about 95% of water.Especially preferred is a carrier comprising from about 20% to about 50% of ethanol, isopropanol, ormixtures thereof, and from about 50% to about 80% of water. When the carrier is an oil-in-wateremulsion, the carrier can include any of the common excipient ingredients for preparing theseemulsions. Additional components useful in formulating these topical compositions are furtherdescribed below.Additional CommnentsA wide variety of additional components can be employed in the hair care and topical skincompositions herein. Non-lirniting examples include the following:Pharmaceutical ActivesThe compositions of the present invention, especially the topical skin care compositions, cancomprise a safe and effective amount of a pharmaceutical active. The phrase "safe and effectiveamount", as used herein, means an amount of an active high enough to significantly or positivelymodify the condition to be treated, but low enough to avoid serious side eï¬ects (at a reasonablebeneï¬t/risk ratio), within the scope of sound medical judgment. A safe and effective amount of thepharmaceutical active will vary with the specific active, the ability of the composition to penetrate theactive through the skin, the amount of composition to be applied, the particular condition beingtreated, the age and physical condition of the patient being treated, the severity of the condition, theduration of the treatment, the nature of concurrent therapy, and like factors.The pharmaceutical actives which can be used in the compositions of the present inventionpreferably comprise from about 0.1% to about 20% âby weight of the compositions, more preferablyfrom about 0.1% to about'l0%, and most preferably from about 0.1% to about 5%. Mixtures ofpharmaceutical actives may also be used.Nonlirniting examples of pharmaceutical actives can include the following:Useful phamtaceutical actives in the compositions of the present invention include anti-acneactives. Anti-acne actives preferred for use in the present invention include the keratolytics such assalicylic acid, sulfur, lactic acid, glycolic, pyruvic acid, urea, resorcinol, and N-acetylcysteine;retinoids such as retinoic acid and its derivatives (e.g., cis and trans); antibiotics and antirnicrobialssuch as benzoyl peroxide, octopirox, erythrornycin, zinc, tetracyclin, triclosan, azelaic acid and itsCA 02264769 1999-03-03WO 98/09607 PCT/US97/ 1554922derivatives, phenoxy ethanol and phenoxy proponol, ethylacetate, clindamycin and meclocycline;sebostats such as flavinoids; alpha and beta hydro.\y acids; and bile salts such as scymnol sulfate andits derivatives, deoxycholate, and cholate. Preferred for use herein is salicylic acid.Useful pharmaceutical actives in the compositions of the present invention include analgesicactives. Analgesic actives suitable for use in the present compositions include salicylic acidderivatives such as methyl-salicylate, species and derivatives of the genus capsicum such as capsaicinand non-steroidal anti-inï¬ammatory drugs (NSAIDS). The NSAIDS can be selected from thefollowing categories: propionic acid derivatives; acetic acid derivatives; fenamic acid derivatives;biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDS are fully described in theU.S. Patent 4,985,459 to Sunshine et al., issued January 15, l99l, incorporated by reference herein.Most preferred are the propionic NSAIDS including but not limited to aspirin, acetaminophen,ibuprofen, naproxen, benoxaprofen, ï¬urbiprofen, fenoprofen, fenbufen, ketoprofen, indoprofen,pirprofen, carprofen, oxaprozin, pranoprofen. miroprofen, tioxaprofen, suprofen, alrninoprofen,tiaprofenic acid, ï¬uprofen and bucloxic acid. Also useful are the steroidal anti-inï¬ammatory dmgsincluding hydrocortisone and the like.Useful pharmaceutical actives in the compositions of the present invention includeantipruritic drugs. Antipruritic actives preferred for inclusion in compositions of the presentinvention include pharmaceutically-acceptable salts of methdilizine and trimeprazine. Usefulpharmaceutical actives in the compositions of the present invention include anesthetic actives.Anesthetic actives preferred for inclusion in compositions of the present invention includepharmaceutically-acceptable salts of lidocaine, bupivacaine, chlorprocaine, dibucaine, etidocaine,mepivacaine, tetracaine, dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxine and phenol.Useful pharmaceutical actives in the compositions of the present invention include antimicrobialactives (antibacterial, antifungal, antiprotozoal and antiviral drugs). Antimicrobial actives preferredfor inclusion in compositions of the present invention include phamiaceutically-acceptable salts of b-lactam dnigs, quinolone drugs, ciproï¬oxacin, norï¬oxacin, tetracycline, erythromycin, amikacin,triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline, oxytetracycline, clindamycin,ethambutol, metronidazole, pentamidine, gentamicin, kanamycin, lineomycin, methacycline, methen-amine, tninocycline, neomycin, netilmicin, paromomycin, streptomycin, tobramycin, miconazole andamanfadine. Antimicrobial dmgs preferred for inclusion in compositions of the present inventioninclude tetracycline hydrochloride, erythromycin estolate, erythromycin stearate (salt), amikacinsulfate, doxycycline hydrochloride, capreomycin sulfate, chlorhexidine gluconate, chlorhexidinehydrochloride, chlortetracycline hydrochloride, oxytetracycline hydrochloride, clindamycin hydro-chloride, ethambutol hydrochloride, metronidazole hydrochloride, pentamidine hydrochloride,gentarnicin sulfate, kanamycin sulfate, lineomycin hydrochloride, methacycline hydrochloride,methenamine hippurate, methenamine mandelate, minocycline hydrochloride, neomycin sulfate,netilmicin sulfate, paromomycin sulfate, streptomycin sulfate, tobramycin sulfate, rniconazoleCA 02264769 1999-03-03WO 93/09507 PCT/US97/1554923hydrochloride, amanfadine hydrochloride, ainanfadine sulfate, triclosan, octopirox, parachlorometaxylenol, nystatin, tolnaftate and clotrimazole.Also useful herein are sunscreening agents. A wide variety of sunscreening actives aredescribed in U.S. Patent No. 5,087,445, to I-laffey et 211., 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., at Chapter VIII, pages 189 et seq., of CosmeticsScience and Technology, all of which are incorporated herein by reference in their entirety.Preferred among those sunscreens which are useful in the compositions of the instant invention arethose selected from the group consisting of 2-ethylhexyl p~methoxycinnamate, 2-ethylhexyl N,N-dimethyl-pâarninobenzoate, p-aminobenzoic acid, 2-phenylbenzimidazole-5-sulfonic acid,octocrylene, oxybenzone, homomenthyl salicylate, octyl salicylate, 4,4'-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane, 3-benzylidene camphor, 3-(4-methylbenzylidene) carnphor, titanium dioxide, zinc oxide, silica, iron oxide, and mixtures thereof.Still other useful sunscreens are those disclosed in U.S. Patent No. 4,937,370, to Sabatelli,issued June 26, 1990; and U.S. Patent No. 4,999,186, to Sabatelli et al., issued March 12, 1991; thesetwo references are incorporated by reference herein in their entirety. The sunscreening activesdisclosed therein have, in a single molecule, two distinct chromophore moieties which exhibitdifferent ultra-violet radiation absorption spectra. One of the chromophore moieties absorbs pre-dominantly in the UVB radiation range and the other absorbs strongly in the UVA radiation range.These sunscreening actives provide higher eï¬icacy, broader UV absorption, lower skin penetrationand longer lasting eï¬icacy relative to conventional sunscreens. Especially preferred examples ofthese sunscreens include those selected from the group consisting of 4-N,N-(2-ethylhexyl)methyl-aminobenzoic acid ester of 2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoicacid ester with 4-hydroxydibenzoylmethane, 4âN,N- (2-ethylhexyl)methylaminobenzoic acid ester of2-hydroxy-4-(2-hydroxyethoxy)benzophenone, 4-N,N-(2-ethylhexyl)-methylaminobenzoic acid esterof 4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.Generally, the sunscreens can comprise from about 0.5% to about 20% of the compositionsuseful herein. Exact amounts will vary depending upon the sunscreen chosen and the desired SunProtection Factor (SPF). SPF is a commonly used measure of photoprotection of a sunscreen againsterythema. _S_e_e Federal Register, Vol. 43, No. 166, pp. 38206-38269, August 25, l978, which isincorporated herein by reference in its entirety.Also useful in the present invention are sunless tanning actives including dihydroxyacetone,glyceraldehyde, indoles and their derivatives, and the like. These sunless tanning actives may also beused in combination with the sunscreen agents.Other useful actives include skin bleaching (or lightening) actives including but not limitedto hydroquinone, ascorbic acid, kojic acid and sodium metabisulfite.Other useful actives which are especially useful for hair care compositions include anti-dandruï¬ actives such as zinc pyrithione, octopirox, selenium disulfide, sulfur, coal tar, and the like.CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554924Other useful actives include antiperspirant actives. Suitable for use herein are those whichcomprise any compound, composition or mixture thereof having antiperspirant activity. Astringentmetallic salts are preferred antiperspirant materials for use herein, particularly the inorganic andorganic salts of aluminum, zirconium and zinc. as well as mixtures thereof. Particularly preferred arethe aluminum and zirconium salts, such as aluminum halides, aluminum hydroxy halides, zirconyloxide halides, zirconyl hydroxy halides, and mixtures thereof.Additionally, deodorant actives in the form of bacteriostats may be incorporated into thepresent compositions. Suitable deodorant bacteriostats include 2,2'-methylenebis(3,4,6-trichlorophenol), 2,4,4â-trichloro-2'-hydroxy(diphenyl ether), zinc phenolsulfonate, 2,2'-thiobis(4,6-dichlorophenol), p-chloro-m-xylenol, dichloro-m-xylenol and the like. Most preferred is 2,4,4â-trichloro-2'-hydroxy(diphenyl ether), which is generically known as triclosan and available from theCiba-Geigy Corporation under the trademark, lrgasan DP-300 Registered TM. When triclosan isutilized it will be present in a range from about 0.05 to about 0.9%, preferably from about 0.1 to about0.5% by weight of the composition. Other types of bacteriostats include sodium N-lauroyl sarcosine,sodium N-palmitoyl sarcosine, lauroyl sarcosine, N-myristoyl glycine, potassium N-lauroyl sarcosineand aluminum chlorhydroxy lactate (sold by Reheis Chemical Company under trademark ofChloracel).ConditionersConditioning agents useful herein, and especially useful for hair care compositions, includehydrocarbons, silicone ï¬uids, and cationic materials.The hydrocarbons can be either straight or branched chain and can contain from about 10 toabout 16, preferably from about 12 to about 16 carbon atoms. Examples of suitable hydrocarbons aredecane, dodecane, tetradecane, tridecane, and mixtures thereof.Silicone conditioning agents useful herein can include either cyclic or linearpolydimethylsiloxanes, phenyl and alkyl phenyl silicones, and silicone copolyols. The linear volatilesilicones generally have viscosities of less than about 5 centistokes at 25°C, while the cyclic materialshave viscosities less than about 10 centistokes.Cationic conditioning agents useful herein include quaternary ammonium salts or the salts offatty amines. These additional cationic agents are used herein for the purpose of providingconditioning and are separate and apart from the complexing agents of the present invention.Preferred quaternary ammonium salts are dialkyl dimethyl ammonium chlorides, wherein the alkylgroups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids. Representativeexamples of quaternary ammonium salts include ditallow dimethyl ammonium chloride, ditallowdimethyl anunonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, and di(hydrogenatedtallow) ammonium chloride. Other quaternary ammonium salts useful herein are dicationics such astallow propane diammonium dichloride. Quaternary imidazolinium salts are also useful herein.Examples of such materials are those imidazolinium salts containing Cl2-22 alkyl groups such as l-methyl-1-[(stearoy|amide)ethyl]-2-heptadecyl-4, 5-dihydroimidazolinium chloride, l-methyl-l-CA 02264769 1999-03-03W0 93/09507 PCT/US97/ 1554925[(palmitoylarnide)ethyl]-2-octadecyl-4,5-dihydroimidazolinium chloride and l-methy1-l-[(tallowamide)-ethyl]-2âtallow~imidazolinium methyl sulfate. Also useful herein are salts of fattyamines. Examples of such compounds include stearylamine hydrochloride, soyamine hydrochloride,and stearylamine formate. Useful conditioning agents are disclosed in U.S. Patent No. 4,387,090, toBolich, issued June 7, 1983, which is incorporated by reference herein.I-Iumectants and MoisturizersThe compositions of the present invention can contain one or more humectant ormoisturizing materials. A variety of these materials can be employed and each can be present at alevel of from about 0.1% to about 20%, more preferably from about 1% to about 10% and mostpreferably from about 2% to about 5%. These materials include urea; guanidine; glycolic acid andglycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g.ammonium and quaternary alkyl ammonium); aloe vera in any of its variety of fonns (e.g., aloe veragel); polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol, propylene glycol, butylene glycol,hexylene glycol and the like; polyethylene glycols; sugars and starches; sugar and starch derivatives(e.g., alkoxylated glucose); hyaluronic acid; lactamide monoethanolamine; acetamidemonoethanolarnine; and mixtures thereof. Preferred humectants and moisturizers are glycerol,butylene glycol, hexylene glycol, and mixtures thereof.SurfactantsThe compositions of the present invention, especially the shampoo and conditionercompositions, can contain one or more surfactants. These surfactants are useful adjuncts for thecarriers of the present compositions, and are not required for solubilizing, dispersing or complexingthe copolymers of the present invention. For a shampoo, the level is preferably from about 10% toabout 30%, preferably from 12% to about 25%, of the composition. For conditioners, the preferredlevel of surfactant is from about 0.2% to about 3%. Surfactants useful in compositions of the presentinvention include anionic, nonionic, cationic. zwitterionic and amphoteric surfactants. A wide varietyof surfactants useful herein are disclosed in U.S. Patent No. 5,151,209, to Me Call et al., issuedSeptember 29, 1992; U.S. Patent No. 5,151,210, to Steuri et al., issued September 29, 1992; and U.S.Patent No. 5,120,532, to Wells et al., issued June 9, 1992, all of which are incorporated by referenceherein.Nonlimiting examples of these surfactants include anionic surfactants such as alkyl and alkylether sulfates. These materials typically have the respective âformulae ROSO3M andRO(C21-l4O)xSO3M, wherein R is alkyl or alkenyl of from about 10 to about 20 carbon atoms, x is 1to 10, and M is a water-soluble cation such as ammonium. sodium, potassium and triethanolamine.Another suitable class of anionic surfactants are the water-soluble salts of the organic, sulfuric acidreaction products of the formula:R 1 ââ S03 â- Mwherein R1 is chosen from the group consisting of a straight or branched chain, saturated aliphatichydrocarbon radical having from about 8 to about 24, preferably about 12 to about 18, carbon atoms;CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554926and M is a cation. Additional examples of anionic synthetic surfactants which come within the temtsof the present invention are the reaction products of fatty acids esteriï¬ed with isethionic acid andneutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil;sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example,are derived from coconut oil. Still other anionic synthetic surfactants include the class designated assuccinamates, olefin sulfonates having about 12 to about 24 carbon atoms, and b-alkyloxy alkanesulfonates. Many additional nonsoap synthetic anionic surfactants are described in McCutcheon's Detergents and Emulsiï¬ers, 1984 Annual, published by Allured Publishing Corporation, which isincorporated herein by reference. Also U.S. Patent 3,929,678, Laughlin et al., issued December 30,1975, discloses many other anionic as well as other surfactant types and is incorporated herein byreference.Nonionic surfactants useful herein are preferably used in combination with an anionic,amphoteric or zwitterionic surfactant. These nonionic surfactants can be broadly defined ascompounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.Cationic surfactants useful in compositions of the present invention are disclosed in thefollowing documents, all incorporated by reference herein: M.C. Publishing Co., McCutcheon's Detergents & Emulsifiers, (North American edition l979); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, New York: lnterscience Publishers, 1949; U.S. Patent 3,155,591,I-lilfer, issued November 3, 1964; U.S. Patent 3,929,678, Laughlin, et al., issued December 30, 1975;U.S. Patent 3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Patent 4,387,090, Bolich, Jr.,issued June 7, 1983. If included in the compositions of the present invention, the cationic surfactantis present at from about 0.05% to about 5%.Zwitterionic surfactants are exemplified by those which can be broadly described asderivatives of aliphatic quatemary ammonium, phosphonium, and sulfonium compounds, in whichthe aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group,e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Other zwitterionics such as betaines arealso useful in the present invention. Examples of betaines include the high alkyl betaines, such ascoco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxyethyl)carboxymethyl betaine, stearyl bis-(2-liydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2âhydroxypropyl)alpha-carboxyethyl betaine, coco dimethylsulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxyethyl) sulfopropyl betaine, and amidobetaines and arnidosulfobetaines (wherein theRC0NH(CH2)3 radical is attached to the nitrogen atom of the betaine).Examples of amphoteric surfactants which can be used in the compositions of the presentinvention are those which are broadly described as derivatives of aliphatic secondary and tertiaryCA 02264769 1999-03-03wo 98/09607 PCT/US97/1554927amines in which the aliphatic radical can be straight or branched chain and wherein one of thealiphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionicwater solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples ofcompounds falling within this definition are sodium 3-dodecyl-aminopropionate, sodium 3-dodecylarninopropane sulfonate, N-alkyltaurines such as the one prepared by reacting dodecylairiinewith sodium isethionate according to the teaching of U.S. Patent 2,658,072, N-higher alkyl asparticacids such as those produced according to the teaching of U.S. Patent 2,438,091, and the productssold under the trade name "Miranol" and described in U.S. Patent 2,528,378.Carbo iic Acid 0 I er ThickenersAnother component useful in the compositions herein is a carboxylic copolyrner thickener.These crosslinked polymers contain one or more monomers derived from acrylic acid, substitutedacrylic acids, and salts and esters of these acrylic acids and the substituted acrylic acids, wherein thecrosslinking agent contains two or more carbonâcarbon double bonds and is derived from a polyhydricalcohol. The preferred polymers for use herein are of two general types. The first type of polymer is acrosslinked homopolyrner of an acrylic acid monomer or derivative thereof (e.g., wherein the acrylicacid has substituents on the two and three carbon positions independently selected from the groupconsisting of Cl_4 alkyl, -CN, -COOH, and mixtures thereof). The second type of polymer is acrosslinked copolyiner having a first monomer selected from the group consisting of an acrylic acidmonomer or derivative thereof (as just described in the previous sentence), a short chain alcohol (i.e. aC14) acrylate ester monomer or derivative thereof (e.g., wherein the acrylic acid portion of the esterhas substituents on the two and three carbon positions independently selected from the groupconsisting of C14 alkyl, -CN, -COOH, and miiaures thereol), and mixtures thereof; and a secondmonomer which is a long chain alcohol (i.e. C340) acrylate ester monomer or derivative thereof(e.g., wherein the acrylic acid portion of the ester has substituents on the two and three carbonpositions independently selected from the group consisting of C 1_4 alkyl, -CN, -COOH, and mixturesthereof). Combinations of these two types of polymers are also useful herein.In the first type of crosslinked homopolymers the monomers are preferably selected from thegroup consisting of acrylic acid, methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylicacid being most preferred. In the second type of crosslinked copolymers the acrylic acid monomer orderivative thereof is preferably selected from the group consisting of acrylic acid, methacrylic acid,ethacrylic acid, and mixtures thereof, with acrylic acid, methacrylic acid, and mixtures thereof beingmost preferred. The short chain alcohol acrylate ester monomer or derivative thereof is preferablyselected from the group consisting of C]_4 alcohol acrylate esters, C1_4 alcohol methacrylate esters,Cl_4 alcohol ethacrylate esters, and mixtures thereof, with the C14 alcohol acrylate esters, C14alcohol methacrylate esters, and mixtures thereof, being most preferred. The long chain alcoholacrylate ester monomer is selected from C340 alkyl acrylate esters, with C1030 alkyl acrylate estersbeing preferred.CA 02264769 1999-03-03WO 93/09507 PCT/US97/1554928The crosslinking agent in both of these types of polymers is a polyalkenyl polyether of apolyhydric alcohol containing more than one alkenyl ether group per molecule, wherein the parentpolyhydric alcohol contains at least 3 carbon atoms and at least 3 hydroxyl groups. Preferredcrosslinkers are those selected from the group consisting of allyl ethers of sucrose and allyl ethers ofpentaerythritol, and mixtures thereof. These polymers useful in the present invention are more fullydescribed in U.S. Patent No. 5,087,445, to Haffey et a1., issued February 11, 1992; U.S. Patent No.4,509,949, to Huang et a1., issued April 5, 1985; U.S. Patent No. 2,798,053, to Brown, issued July 2,1957; which are incorporated by reference herein. See also. CTFA International Cosmetic IngredientDictionag, fourth edition, 1991, pp. 12 and 80; which are also incorporated herein by reference.Examples of commercially available homopolymers of the first type useful herein include thecarbomers, which are homopolymers of acrylic acid crosslinked with allyl ethers of sucrose orpentaerytritol. The carbomers are available as the Carbopol® 900 series from B.F. Goodrich.Examples of commercially available copolymers of the second type useful herein include copolymersof C10_30 alkyl acrylates with one or more monomers of acrylic acid, methacrylic acid, or one of theirshort chain (i.e. C1_4 alcohol) esters, wherein the crosslinking agent is an allyl ether of sucrose orpentaerytritol. These copolymers are known as acrylates/C10-30 alkyl acrylate crosspolymers and arecommercially available as Carbopol® 1342, Pemulen TR-1, and Pemulen TR-2, from B.F. Goodrich.In other words, examples of carboxylic acid polymer thickeners useful herein are those selected fromthe group consisting of carbomers, acrylates/C10-C30 alkyl acrylate crosspolymers, and mixturesthereof.The compositions of the present can comprise from about 0.025% to about 1%, morepreferably from about 0.05% to about 0.75% and most preferably from about 0.10% to about 0.50% ofthe carboxylic acid polymer thickeners.Emulsiï¬ersThe compositions herein can contain various emulsifiers. These emulsifiers are useful foremulsifying the various carrier components of the compositions herein, and are not required forsolubilizing or dispersing the copolymers of the present invention. Suitable emulsifiers can includeany of a wide variety of nonionic, cationic, anionic. and zwitterionic emulsiï¬ers disclosed in the priorpatents and other references. _S_e_e McCutc1ieon's, Detergents and Emulsifrers, North AmericanEdition (1986), published by Allured Publishing Corporation; U.S. Patent No. 5,011,681 to Ciotti etal., issued April 30, 1991', U.S. Patent No. 4,421,769 to Dixon et al., issued December 20, 1983; andU.S. Patent No. 3,755,560 to Dickert et al., issued August 28, 1973; these four references areincorporated herein by reference in their entirety.Suitable emulsiï¬er types include esters of glycerin, esters of propylene glycol, fatty acidesters of polyethylene glycol, fatty acid esters of polypropylene glycol, esters of sorbitol, esters ofsorbitan anhydrides, carboxylic acid copolymers, esters and ethers of glucose, ethoxylated ethers,ethoxylated alcohols, alkyl phosphates, polyoxyethylene fatty ether phosphates, fatty acid amides, acyllactylates, soaps and mixtures thereof.CA 02264769 1999-03-03wo 98/09507 PCTIUS97/1554929Suitable emulsiï¬ers can include, but are not limited to, polyethylene glycol 20 sorbitanmonolaurate (Polysorbate 20), polyethylene glycol 5 soya sterol, Steareth-20, Ceteareth-20, PPG-2methyl glucose ether distearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetylphosphate, diethanolamine cetyl phosphate, Polysorbate 60, glyceryl stearate, PEG-100 stearate, andmixtures thereof. The emulsifiers can be used individually or as a mixture of two or more and cancomprise from about 0.1% to about 10%, more preferably from about 1% to about 7%, and mostpreferably from about 1% to about 5% of the compositions of the present invention.EmollientsThe compositions useful in the methods of the present invention can also optionally compriseat least one emollient. Examples of suitable emollients include, but are not limited to, volatile andnon-volatile silicone oils, highly branched hydrocarbons, and non-polar carboxylic acid and alcoholesters, and mixtures thereof. Emollients useful in the instant invention are further described in U.S.Patent No. 4,919,934, to Deckner et al., issued April 24 1990, which is incorporated herein byreference in its entirety.The emollients can typically comprise in total from about 1% to about 50%, preferably fromabout 1% to about 25%, and more preferably from about 1% to about 10% by weight of thecompositions useful in the present invention.Additional CommnentsA variety of additional components can be incorporated into the compositions herein. Non-limiting examples of these additional components include vitamins and derivatives thereof (e.g.,ascorbic acid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids, and the like); low pHthickening agents (e.g. polyacrylamide and C1344 isoparaï¬in and laureth-7, available as Sepigelfrom Seppic Corporation; polyquaternium and mineral oil, available as Salcare SC92, from AlliedColloids; crosslinked methyl quatemized dimethylaminomethacrylate and mineral oil, available asSalcare SC95 from Allied Colloids; resins; gums and thickeners such as xanthan gum, carboxymethylcellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, alkyl-modiï¬ed hydroxyalkyl celluloses(e.g. long chain alkyl modified hydroxyethyl celluloses such as cetyl hydroxyethylcellulose), andmagnesium aluminum silicate; cationic polymers and thickeners (e.g.. cationic guar gum derivativessuch as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimoniumchloride, available as the Jaguar C series from Rhone-Poulenc; polymers for aiding the film-formingproperties and substantivity of the composition (such as a copolymer of eicosene and vinylpyrrolidone, an example of which is available from GAF Chemical Corporation as Ganex® V-220);suspending agents such as ethylene glycol distearate and the like; preservatives for maintaining theantimicrobial integrity of the compositions; skin penetration aids such as DMSO, 1-dodecylazacycloheptan-2-one (available as Azone from the Upjohn Co.) and the like; antioxidants;chelators and sequestrants; and aesthetic components such as fragrances, colorings, essential oils, skinsensates, astringents, skin soothing agents, skin healing agents and the like, nonlimiting examples ofthese aesthetic components include panthenol and derivatives (e.g. ethyl panthenol), pantothenic acidCA 02264769 1999-03-03W0 93,095.37 PCT/US97/1554930and its derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazeldistillate, allantoin, bisabalol, dipotassium glycyrrhizinate and the like.Method of Using Hair and Skin Care CompositionsThe hair care and skin care compositions of the present invention are used in conventionalways to provide the desired beneï¬t appropriate to the product such as hair styling, holding, cleansing,conditioning and the like for hair care compositions and benefits such as moisturization, sunprotection, anti-acne, anti-wrinkling, artiï¬cial tanning, analgesic, and other cosmetic andpharmaceutical beneï¬ts for skin care compositions. Such methods of use depend upon the type ofcomposition employed but generally involve application of an effective amount of the product to thehair or skin, which may then be rinsed from the hair or skin (as in the case of shampoos and someconditioning products) or allowed to remain on the hair (as in the case of spray, mousse, or gelproducts), or allowed to remain on the skin (as in the case of the skin care compositions). By"eifective amount" is meant an amount suï¬icient to provide the beneï¬t desired. Preferably, hair rinse,mousse, and gel products are applied to wet or damp hair prior to drying and styling of the hair.Aï¬er such compositions are applied to the hair, the hair is dried and styled in the usual ways of theuser. Hair sprays are typically applied to dry hair after it has already been dried and styled. Cosmeticand pharmaceutical topical skin care compositions are applied to and rubbed into the skin.â EXAMPLESThe following examples further illustrate preferred embodiments within the scope of thepresent invention. The examples are given solely for the purposes of illustration and are not to beconstrued as limitations of the present invention as many variations of the invention are possiblewithout departing from its spirit and scope.Ingredients are identiï¬ed by chemical or CTFA name.The following synthetic procedure is exemplary of the methods useful for synthesizing thecopolymers of the present invention.EXAMPLE ISmthesis of Poly|(t-bug! acglate)-(acgglic acig)-graï¬-mlydimethylsiloxane)IPlace 60 parts of I-butyl acrylate, 20 parts acrylic acid and 20 parts of polydimethylsiloxanemacromonomer (13,000 MW) (commercially available from 3M, St. Paul, MN) in a ï¬ask. Addsufï¬cient acetone as the reaction solvent to produce a final monomer concentration of 20%. Purge thevessel with an inert atmosphere, preferably nitrogen or argon. Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate for the desired molecular weight. Typically this is in therange of about 0.5% to about 1.0% by weight relative to the amount of monomer. Heat to 60°C andmaintain this temperature for 6 hours while agitating. Terminate the reaction by cooling to roomtemperature. The polymer is purified by drying 011â the reaction solvent in an oven.CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554931EXAMPLE 2Synthesis of Polvllt-butvl acrvlate)-(me!/mcrv/ic acid )-graft-polydimethvlsiloxa;1e_)_1Place 70 pans of r-butyl acrylate. 10 pans methacrylic acid and 20 pans ofpolydimethylsiloxane macromonomer (13,000 MW) (commercially available from 3M, St. Paul, MN)in a ï¬ask. Add suï¬icient acetone as the reaction solvent to produce a final monomer concentration of20%. Purge the vessel with an inert atmosphere, preferably nitrogen or argon. Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate for the desired molecular weight. Typically this is in therange of about 0.5% to about 1.0% by weight relative to the amount of monomer. Heat to 60°C andmaintain this temperature for 6 hours while agitating. Terminate the reaction by cooling to roomtemperature. The polymer is purified by drying oi? the reaction solvent in an oven.EXAMPLE 3Synthesis of Poly[(t-bugl acglate)-(methacr_-ylic acid )-(2-ethylhexylmethacrylate)|Place 70 parts of I-butyl acrylate, 10 parts methacrylic acid and 20 parts of 2-ethylhexylmethacrylate in a ï¬ask. Add sufficient acetone as the reaction solvent to produce a ï¬nalmonomer concentration of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen orargon. Add initiator, (2,2'-azobisisobutyronitrile) to a level appropriate for the desired molecularweight. Typically this is in the range of about 0.5% to about 1.0% by weight relative to the amount ofmonomer. Heat to 60°C and maintain this temperature for 6 hours while agitating. Terminate thereaction by cooling to room temperature. The polymer is purified by drying oï¬ the reaction solvent inan oven.EXAMPLE 4Smthesis of Polyltt-bug! acglate)-(acgglic acig)-graï¬-polyisobugleng)|Place 60 parts of !~butyI acrylate, 20 pans acrylic acid and 20 parts of polyisobutylenemacromonomer in a ï¬ask. Add sufficient acetone as the reaction solvent to produce a ï¬nal monomerconcentration of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen or argon. Addinitiator, (2,2â-azobisisobutyronitrile) to a level appropriate for the desired molecular weight.Typically this is in the range of about 0.5% to about 1.0% by weight relative to the amount ofmonomer. Heat to 60°C and maintain this temperature for 6 hours while agitating. Terminate thereaction by cooling to room temperature. The polymer is purified by drying off the reaction solvent inan oven.EXAMPLE 5Synthesis of Polylgt-bug! acglalc)-(me!/mcgylic acig)-graï¬-polyisgbugyleng)IPlace 70 parts of I-butyl acrylate, 10 parts methacrylic acid and 20 parts of polyisobutylenemacromonomer in a ï¬ask. Add sufficient acetone as the reaction solvent to produce a ï¬nal monomerconcentration of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen or argon. Addinitiator, (2,2'-azobisisobutyronitrile) to a level appropriate for the desired molecular weight.Typically this is in the range of about 0.5% to about 1.0% by weight relative to the amount ofmonomer. Heat to 60°C and maintain this temperature for 6 hours while agitating. Tenninate theCA 02264769 1999-03-03WO 98/09607 PCT/US97/1554932reaction by cooling to room temperature. The polymer is puriï¬ed by drying off the reaction solvent inan oven.EXAMPLE 6S thesis of Pol t-bu l ac late - melhac Iic acid ~ 2-eth lhe. lmethac latePlace 70 pans of t-butyl acrylate, 10 pans methacryiic acid and 20 parts of 2-ethylhexylmethacrylate in a ï¬ask. Add sufficient acetone as the reaction solvent to produce a finalmonomer concentration of 20%. Purge the vessel with an inert atmosphere, preferably nitrogen orargon. Add initiator, (2.2â-azobisisobutyronitrile) to a level appropriate for the desired molecularweight. Typically this is in the range of about 0.5% to about 1.0% by weight relative to the amount ofmonomer. Heat to 60°C and maintain this temperature for 6 hours while agitating. Terminate thereaction by cooling to room temperature. The polymer is purified by drying oï¬â the reaction solvent inan oven.By varying the monomers and macromonomers used, the general procedures given above inExamples 1-6, is used to prepare other copolymers of the present invention.EXAMPLE 7The following is a hair conditioner composition representative of the present invention.Component Weight %Water Q.S. to 100%Hydrophobically Modiï¬ed Hydroxyethylcellulose [11 0.25 %Stearalkonium Chloride 0.87 %Cetyl Alcohol 1.85 %Stearyl Alcohol 0.21 %Stearamidopropyl Dimethylamine 0.50 %CFl2l3o (21 2.33%Methylchloroisothiazolinone Methylisothiazolinone 0.03 %Perfume 0.33 %Copolyrner 3 [3] 2.00 %Dimethylmyristamine (ARMEEN DMl4D) I41 0.56 %Cyclomethicone D4 9.63 %I11 Polysurf 670 supplied by Aqualon[21 Dimethicone Gum in D5 cyclomethicone; commercially available from GE[31 Poly|(t-bugl acrylate)-gmethacgylic acid H2-ethylhexylmethacglate)|[41 Commercially available from AkzoThis product is prepared by dispersing the copolymer in Cyclomethicone D4 (solventcomponent) then adding the dimethylmyristamine. Heat the solution to 65°C and use an appropriatehomogenizer to facilitate incorporation of the copolymer into the solvent component. The othercomponents (except Kathon and perfume) are mixed in a separate vessel at a temperature highenough (80°C) to melt the solids. The polymer/solvent component mixture and the CF 1213:» areWO 98/09607CA 02264769 1999-03-0333PCT/US97/15549added separately to the other components after those have been cooled to at least 45°C. Finally,Kathon and perfume are added, and the product cooled to ambient. This composition is useful forapplication to the hair to provide conditioning, styling and hold benefits.Weight %EXAMPLE 8The following is a hair conditioner composition representative of the present invention.ComponentWaterHydrophobically Modified Hydroxyethylcellulose [11Stearalkonium ChlorideCetyl AlcoholStearyl AlcoholStearamidopropyl DimethylamineCF12 13¢ [21Methylchloroisothiazolinone MethylisothiazolinonePerfumeCopolymer l [31dimethyllaumnune(ARMEENDMl2D)l4lIsododecaneHexamethyl disiloxane[11 Polysurf67® supplied by Aqualon[2] Dimethicone Gum in D5 cyclometliicone; commercially available from GE[31 Poly[(t-butyl acrylate)-(acrylic acid)âgraft-polydimethylsiloxane)][41 Available from AkzoThis product is prepared by dispersing the copolymer in Isododecane and hexamethylQ.S. to 100%0.50 %0.87 %1.85 %0.21 %0.50 %2.33%0.03 %0.33 %2.00 %1.18 %4.81 %4.81%disiloxane (solvent component) then adding the dimethyllauramine. Heat the solution to 65°C and usean appropriate homogenizer to facilitate incorporation of the copolymer into the solvent component.The other components (except Kathon and perfume) are mixed in a separate vessel at a temperaturehigh enough (80°C) to melt the solids. The polymer/solvent component mixture and the dimethiconegum are added separately to the other components after those have been cooled to at least 45°C.Finally, Kathon and perfume are added, and the product cooled to ambient. This composition isuseful for application to the hair to provide conditioning, styling and hold benefits.WO 98/09607CA 02264769 1999-03-03PCT/US97/15549Weight %34EXAMPLE 9The following is a hair shampoo composition representative of the present invention.ComponentWater[11 Poly[(tâbutyl acrylate)-(methacrylic acid)-graï¬-polydimethy|siloxane)]Ammonium Lauryl SulfateAmmonium Laureth SulfateCetyl AlcoholStearyl AlcoholCoco Monoethanol AmideEthylene Glycol DistearateTricetyl Methyl Ammonium ChlorideMethylchloroisothiazolinone MethylisothiazolinonePerfumeCopolymer 2 I llStearamine (ARMEEN is)l2lIsododecane[21 Commercially available from AkzoQ.S. to 100 %3.14 %13.56 %0.45 %0.19 %3.00 %2.00 %0.50 %0.03 % _0.20 %4.00 %l.25 %7.40 %This product is prepared by dispersing the copolymer in isododecane (solvent component)then adding the stearamine. Heat the solution to 65°C and use an appropriate homogenizer tofacilitate incorporation of the copolymer into the solvent component. The other components aremixed in a separate vessel at a temperature high enough to melt the solids. The polymer/solventcomponent mixture is added to the other components aï¬er those have been cooled. This compositionis useful for application to the hair to provide cleansing, styling and hold beneï¬ts.EXAMPLE l0The following is a hair shampoo composition representative of the present invention.ComponentWaterCocoamidopropyl BetaineAmmonium Lauryl SulfateAmmonium Laureth SulfateCoco Monoethanol AmideI-lydroxypropyl Methocellulose (K15)Ethylene Glycol DistearateTricetyl Methyl Ammonium ChlorideMethylchloroisothiazolinone MethylisothiazolinonePerfumeWeight %Q.S. to 100 %8.30 %2.12 %6.35 %l.50 %0.25 %1.50 %0.50 %0.03 %0.20 %CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554935Copolymer 4 in 3.00 %dimethylstearamine (ARMEEN oM1sD)l2l 2.48 %Isododecane 5.00 %Cyclomethicone 5.00 %[11 Poly[(t-butyl acrylate)-(acrylic acid)-graft-polyisobutylene)1[21 Commercially available from AkzoThis product is prepared by dispersing the copolymer in isododecane and cyclomethicone(solvent component) then adding the dimethylstearamine. Heat the solution to 65°C and use anappropriate homogenizer to facilitate incorporation of the copolymer into the solvent component. Theother components are mixed in a separate vessel at a temperature high enough to melt the solids. Thepolymer/solvent component solution is added to the other components aï¬er those have been cooled.EXAMPLE llThe following is a hair styling gel composition representative of the present invention.Component Weight %Polymer-Solvent component MixCopolymer 5 [11 l.25 %dimethylpalmitamine 0.39 %Isopar H09 [2] 3.75 %1Water 43.00 %Hydrogenated Ditallowditnonium Chloride l.00 %(Quatemium 18)Main MixWater 48.47 %Carbopol 940:: 0.75 %Triethanol Amine 1.00 %Panthenol 0.05 %Perfume 0.20 %Ill Poly[(t-butyl acrylate)-(methacrylic acid)-graft-polyisobutylene)][2] C, 1-C12 lsoparaï¬in, available from Exxon Chemical Co.This product is prepared by dispersing the copolymer in Isopar H0 (solvent component) thenadding the dimethylpalmitamine. Heat the solution to 65°C and use an appropriate homogenizer tofacilitate incorporation of the copolymer into the solvent component. Quatemium 18 is mixed withwater at 80°C. The polymer-solvent component mixture is added to the Quatemium 18 containingpremix at either high or low temperature. The other components are mixed in a separate vessel atambient temperature. The Quatemium l8 premix with the polymer/solvent component mixture iscooled (if needed) and added to the other components. This composition is useful for application tothe hair to provide conditioning, styling and hold benefits.CA 02264769 1999-03-03wo 93/09597 PCT/US97/1554936EXAMPLE 12The following is a spray-on gel hair composition representative of the present invention.Component Weight %Water Q.S. to 100 %Tallowtrimonium Chloride 0.10 %Hydrogenated Ditallowdimonium Chloride 0.90 %(Quatemium 18)Panthenol 0.05 %Perfume 0.20 %Copolymer 6 [1] 1.00 %myristamine 0.25 %Hexamethyl disiloxane 3.00 %[11 Poly[(t-butyl acrylate)-(methacrylic acid)-(2-ethy|he>.ylmethacrylate)]This product is prepared by dissolving the copolymer in hexamethyl disiloxane (solventcomponent) then adding the myristamine. Heat the solution to 65°C and use an appropriatehomogenizer to facilitate incorporation of the copolymer into the solvent component. The othercomponents are mixed in a separate vessel at a temperature high enough (70°C) to melt the solids.The polymer/solvent component solution is added to the other components at either high or lowtemperature. This composition is useful for application to the hair to provide conditioning, stylingand hold beneï¬ts.EXAMPLE 13The following is a hair styling rinse composition representative of the present invention.Component Weight %Premix AWater 8.14 %.Ditallowdimonium Chloride (Varisoï¬ 470) 1.43 %CFl2l3@[11 2.33 %Amodimethicone 0.10 %Premix BWater 5.45 %Stearalkonium Chloride 0.30 %Panthenol DL 0.225 %Pantyl Ethyl Ether 0.025 %Main Mixwage: 66.02 %Hydrophobically Modified I-Iydroxyethylcellulose I21 1.23 °/..Xanthan Gum 0.25%Citric Acid 0.02 %CA 02264769 1999-03-03WO 93/09507 PCTIUS97/1554937Sodium Citrate 0.09 %Cetyl Alcohol 0.12 %Stearyl Alcohol 0.08 %Polymer-Solvent component MixtureCopolymer l [3] 2.00 %Cyclomethicone D4 5.00 %I-lexamethyl disiloxane 5.00 %Dimethylmyristamine (ARMEENDMMD) [41 1.33 %Methylchloroisothiazolinone Methylisothiazolinone 0.03 %Perfume 0.33 %Benzyl Alcohol 0.50 %[11 Dimethicone Gum in D5 cyclomethicone; commercially available from GE[21 Polysurf 670 supplied by Aqualon[3] Poly[(!-butyl acrylate)-(acrylic acid)-graï¬-polydimetliylsiloxane)][4] Commercially available from AkzoThis product is prepared by dispersing the copolymer in the cyclomethicone D4 andhexamethyl disiloxane (solvent component) then adding the dimethylmyristamine. Heat the solutionto 65°C and use an appropriate homogenizer to facilitate incorporation of the copolymer into thesolvent component. Premixes A and B are prepared by combining materials at 70°C. Premix A goesthrough a colloid mill and is cooled to 38°C. Materials in âMain Mixâ, except benzyl alcohol, aremixed at 65°C. The polymer solution is then added to the âMain Mixâ. Main mix goes through acolloid mill and is cooled to 38°C. Premixes and âMain Mix are combined at 38°C. Then the benzylalcohol is added. This composition is useful for application to the hair to provide conditioning,styling and hold benefits.EXAMPLE 14The following is a hair styling mousse composition representative of the present invention.Component Weight %Water Q.S. to 100 %Tallowtrimonium Chloride 0.10 %Hydrogenated Ditallowdimonium Chloride 0.90 %(Quatemium i8)Lauramine Oxide 0.20 %Panthenol 0.05 %Perfume 0.20 %Copolymer i [11 1.00 %lauramine 0.51 %Hexamethyl disiloxane 3.00 %Isobutane 7.00 %CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554938Iâ Poly[(-t-butyl acrylate)-(acry/ic acid)-graft-polydimethylsi1oxane)]This product is prepared by dispersing the copolymer in hexamethyl disiloxane (solventcomponent) then adding the lauramine. Heat the solution to 65°C and use an appropriatehomogenizer to facilitate incorporation of the copolymer into the solvent component. The othercomponents (except isobutane) are mixed in a separate vessel at a temperature high enough (70°C) tomelt the solids. The polymer/solvent component solution is added to the other components aï¬er thosehave been cooled. Aluminum aerosol cans are then filled with 93 parts of this batch, aï¬ixed with avalve which is crimped into position, and lastly pressure filled with 7 parts Isobutane. Thiscomposition is useful for application to the hair to provide conditioning, styling and hold beneï¬ts.EXAMPLE 15The following is a hair styling spray composition representative of the present invention.Component Weight %Water Q.S. to 100 %Panthenol 0.05 %Perfume 0.20 %Copolymer 4 [11 2.00 °/..Dimethylmyristamine 1.33 %Cyclomethicone D4 7.00 %Isobutane 25.00 %[11 Poly[(!-butyl acrylate)-(acrylic acid)-graï¬-polyisobutylene)]This product is prepared by dispersing the copolymer in Cyclomethicone D4 (solventcomponent) then adding the dimethylmyristamine. Heat the solution to 65°C and use an appropriatehomogenizer to facilitate incorporation of the copolymer into the solvent component. The othercomponents (except isobutane) are mixed in a separate vessel. The polymer/solvent componentsolution is added to the other components. Aluminum aerosol cans are then filled with 75 parts ofthis batch, aï¬ixed with a valve which is crimped into position, and lastly pressure filled with 25 partsIsobutanc. This composition is useful for application to the hair to provide conditioning, styling andhold beneï¬tsWhen the compositions defined in Examples 4 - 12 are applied to hair in the conventionalmanner, they provide effective hair conditioning and styling/hold benefits without leaving the hairwith a sticky/stiï¬' feel.WO 98/09607CA 02264769 1999-03-03PCT/US97/15549The following is a hair styling rinse composition representative of the present invention.39EXAMPLE 16ComponentPremix AWaterDitallowdimonium Chloride (Varisoï¬ 470)CFl2l3® (Dimethicone Gum) [2]AmodimethiconePremix BWaterStearalkonium ChloridePanthenol DLPantyl Ethyl EtherMain MixWaterHydrophobically Modified Hydroxyethylcellulose [1]Xanthan GumCitric AcidSodium CitrateCetyl AlcoholStearyl AlcoholPolymer-Solvent MixtureCopolymer # lCyclomethicone D4Dimethylmyristamine (ARMEENDMMD)Methylchloroisothiazolinone MethylisothiazolinonePerfumeBenzyl Alcohol[1] Polysurf 670 supplied by Aqualon[2] Commercially available from GEThis product is prepared by dispersing the copolymer #1 in the cyclomethicone D4(solvent)Weight %8.14 %.1.43 %2.33 %0.10 %5.45 %0.30 %0.225 %0.025 %71.35 %1.23 %0.25%0.02 %0.09 %0.12 %0.08 %2.00 %4.67 %1.33 %0.03 %0.33 %0.50 %then adding the dimethylmyristamine. Heat the solution to 65 C and use an appropriate homogenizerto facilitate incorporation of the copolymer into the solvent. Premixes A and B are prepared bycombining materials at 70°C. Premix A goes through a colloid mill and is cooled to 38°C. Materialsin 'Main Mixâ, except benzyl alcohol, are mixed at 65°C. The polymer solution is then added to the'Main Mixâ. Main mix goes through a colloid mill and is cooled to 38°C. Premixes and âMain Mixare combined at 38°C. Then the benzyl alcohol is added. This composition is useful for applicationto the hair to provide conditioning, styling and hold benefits.WO 98/09607CA 02264769 1999-03-03PCT/U S97/ 15549The following is a hair styling rinse composition representative of the present invention.40EXAMPLE 17ComponentPremix AWaterDitallowdimonium Chloride (Varisoft 470)CFl2l3® (Dimethicone Gum) [2]AmodimethiconePremix BWaterStearalkonium ChloridePanthenol DLPantyl Ethyl EtherMain MixWaterI-Iydrophobically Modiï¬ed Hydroxyethylcellulose [1]Xanthan GumCitric AcidSodium CitrateCetyl AlcoholStearyl AlcoholPol_v_n_ier-Solvent MixtureCopolymer # lCyclomethicone D4Dimethylmyristamine (ARMEENDMMD)Methylchloroisothiazolinone MetliylisothiazolinonePerfumeBenzyl Alcohol[1] Polysurf 67o supplied by Aqualon[2] Commercially available from GEThis product is prepared by dispersing the copolymer #1 in the cyclomethicone D4(solvent)Weight %8.14 %.1.43 %2.33%0.l0 %5.45 %0.30 %0.225 %0.025 %70.46 %1.23 %0.25%0.02 %0.09 %0.12 %0.08 %2.00 %5.56 %1.33 %0.03 %0.33 %0.50 %then adding the dimethylmyristamine. Heat the solution to 65 C and use an appropriate homogenizerto facilitate incorporation of the copolymer into the solvent. Premixes A and B are prepared bycombining materials at 70°C. Premix A goes through a colloid mill and is cooled to 38°C. Materialsin âMain Mixâ, except benzyl alcohol, are mixed at 65°C. The polymer solution is then added to the'Main Mixâ. Main mix goes through a colloid mill and is cooled to 38°C. Premixes and 'Main Mixare combined at 38°C. Then the benzyl alcohol is added. This composition is useful for applicationto the hair to provide conditioning, styling and hold beneï¬ts.WO 98/09607CA 02264769 1999-03-03PCTlUS97I15549The following is a hair styling rinse composition representative of the present invention.41EXAMPLE 18ComponentPremix AWaterDitallowdimonium Chloride (Varisoï¬ 470)CFl2l3® (Dimethicone Gum) [2]AmodimethiconePremix BWaterStearalkonium ChloridePanthenol DLPantyl Ethyl EtherMain MixWaterHydrophobically Modiï¬ed Hydroxyethylcellulose ll]Xanthan GumCitric AcidSodium CitrateCetyl AlcoholStearyl AlcoholPolymer-Solvent MixtureCopolymer # llsododecaneDimethyllauramine (ARMEENDMIZD)Methylchloroisothiazolinone MethylisothiazolinonePerfumeBenzyl Alcohol[1] Po1ysurf67o supplied by Aqualon[2] Commercially available from GEThis product is prepared by dispersing the copolymer #1 in the cyclomethicone D4(solvent)Weight %8.14 %.1.43 %2.33%0.10 %5.45 %0.30 %0.225 %0.025 %72.08 %1.23 %0.25%0.02 %0.09 %0.12 %0.08 %2.00 %4.09 %1.18 %0.03 %0.33 %0.50 %then adding the dimethylmyristamine. Heat the solution to 65 C and use an appropriate homogenizerto facilitate incorporation of the copolymer into the solvent. Premixes A and B are prepared bycombining materials at 70°C. Premix A goes through a colloid mill and is cooled to 38°C. Materialsin 'Main Mixâ, except benzyl alcohol, are mixed at 65°C. The polymer solution is then added to theâMain Mixâ. Main mix goes through a colloid mill and is cooled to 38°C. Premixes and âMain Mixare combined at 38°C. Then the benzyl alcohol is added. This composition is useful for applicationto the hair to provide conditioning, styling and hold benefits.WO 98/09607CA 02264769 1999-03-0342EXAMPLE [9PCT/U S97] 15549The following is a sunscreen composition representative of the present invention.An oil-in-water emulsion is prepared by combining the following components utilizingconventional mixing techniques.InggedientsPhase AWaterCarbomer 954[ 1]Carbomer l342[2]Disodium EDTAHIASJQIsoarachidyl NeopentanoatemPVP Eicosene CopolymermOctyl MethoxycinnamateOctocryleneOxybenzoneTitanium DioxideCetyl PalrnitateStearoxytrimethylsilane (and)Stearyl A1coholl5lGlyceryl Tribehenate 0.75DimethiconeTocopheryl AcetateDEA-Cetyl Phosphate2111WaterTliethanolamine 99%Phase DWaterButylene GlycolDMDM Hydantoin (and) Iodopropynyl ButylcarbamateléldL PanthenolE1_1as_e.§Cyclomethicone D4Copolytner 6 [71stearamine[11 Available as Calbopol® 954 from B.F. Goodrich.[21 Available as Carbopol® i342 from 3.1:. Goodrich.Weight %QSl000.240.160.052.002.007.504.001.002.000.750.50[.000.100.202.000.602.002.000.251.004.001.001.25CA 02264769 1999-03-03wo 93/09607 PCT/US97/1554943[3] Available as Ganex V-220 from GAF Corporation.[4] Available as DC 580 Wax from Dow Corning.[51 Available as Synchrowax I-{RC from Croda.[5] Available as Glydant Plus from Lonza.[71 Poly[(t-butyl acrylate)-(melhacrylic acid)-(2-ethylhexylmethacry1ate)]In a suitable vessel the Phase A ingredients are dispersed in the water and heated to 75-85°C.In a separate vessel the Phase B ingredients (except DEA-Cetyl Phosphate) are combined and heatedto 85-90°C until melted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B and stirreduntil dissolved. This mixture is then added to Phase A to form the emulsion. The Phase Cingredients are combined until dissolved and then added to the emulsion. The emulsion is thencooled to 40-45°C with continued mixing. In another vessel, the Phase D ingredients are heated withmixing to 40â45°C until a clear solution is formed and this solution is then added to the emulsion.The emulsion is cooled to 35°C. The Phase E ingredients are combined at 65°C, use an appropriatehomogenizer to facilitate incorporation of the copolymer into the solvent component. Phase E is thecooled to 35°C, added and mixed.This emulsion is useful for topical application to the skin to provide protection from theharmful eï¬ects of ultraviolet radiation.EXAMPLE 20The following is a facial moisturizing composition representative of the present invention.A leave-on facial emulsion composition containing a cationic hydrophobic surfactant isprepared by combining the following components utilizing conventional mixing techniques.In re ient Weight %Phase AWater QS100Glycerin 3.00Cetyl Palmitate 3.00Cetyl Alcohol 1.26Quaterniumâ22 1.00Glyceryl Monohydroxy Stearate 0.74Dimethicone 0.60Stearic Acid 0.55Octyldodecyl Myristate 0.30Potassium Hydroxide 0.20Carbomer 1342 0.125Tetrasodium EDTA 0.10DMDM Hydantoin and lodopropynyl Butyl Carbamate 0.10Carbomer 951 0.075Phase BCA 02264769 1999-03-03wo 93/09507 PCT/US97/1554944lsododecane 4.00Copolymer 2 [1] 1.00stearamine â 0.3 l[11 Poly[(!-butyl acrylate)-(methacrylic acid)-graï¬-polydimethylsiloxane)]In a suitable vessel the Phase A ingredients are combined to fonn an emulsion. Phase B isprepared by dispersing the copolymer in Isododecane (solvent component) then adding thestearamine. Heat the solution to 65°C and use an appropriate homogenizer to facilitate incorporationof the copolymer into the solvent component. Cool the Phase B and mix into Phase A usingconventional mixing techniques. .This emulsion is useful for application to the skin as a moisturizer.EXAMPLE 2!The following is an anti-perspirant composition representative of the present invention.Component Weight %PPG 2 Myristyl Propionate 34.00 %Glyceryl C13 - C36 Wax Acid Ester 0.40 %Cyclomethicone 32.75 %Copolymer I W 1.00 %Dimethylmyristamine 0.67 %Aluminum Chlorohydrate l9.00 %PPG 5 Ceteth 20 7.50 %Water 1.50 %[11 Pol t-bu lac late ac Iic actâ - raï¬- ol dimeth lsiloxaneMix PPG 2 Myristyl Propionate and Glyceryl C13 - C35 Wax Acid Ester, heat to 75°C.Disperse the Chlorohydrate. Disperse the copolymer in Cyclomethicone (solvent component) thenadd the dimethylmyristamine. Heat the solution to 65°C and use an appropriate homogenizer tofacilitate incorporation of the copolymer into the solvent component. Add the cyclomethiconemixture to the Chlorohydrate dispersion. Mix PPG 5 Ceteth 20 and the water. the add to oils, perfmneand cool.CA 02264769 1999-03-03wo 93/09507 PCT/US97/1554945EXAMPLE 22The following is an anti-acne composition representative of the present invention.Component Weight %Copolymer-Solvent component MixCopolymer 5 [H 1.00 %dimethylpalmitamine 0.31 %Isopar He: [2] 3.75 %Main MixWater Q.S. to 100 %Ethanol (SDA 40) 40.00 %Carbopol 940:» 0.75 %Triethanol Amine 1.00 %Salicylic Acid 2.00 %[11 Poly[(t-butyl acrylate)-(methacrylic acid)-graft-polyisobutylene)][21 Câ-C12 lsoparafï¬n, available from Exxon Chemical Co.This product is prepared by dispersing the copolymer in Isopar Ho (solvent component) thenadding the dimethylpalmitamine. Heat the solution to 65°C and use an appropriate homogenizer tofacilitate incorporation of the copolymer into the solvent component. The other components aremixed in a separate vessel at ambient temperature. The copolymer-solvent component premix iscooled (if needed) and added to the other components. This composition is useful for application tothe skin to provide improve water resistance and is useful in the treatment of acne.EXAMPLE 23The following is a topical analgesic composition representative of the present invention.Component Weight %Cgmlmger-Solvent component MixCopolymer l [1] 1.00 %dimethylpalmitamine 0.74 %Isopar Ho I21 3.75 %Mai MixWater Q.S. to 100 %Ethanol (SDA 40) 20.00 %Carbopol 9400 0.75 %Triethanol Amine 1.00 %Ibuprofen 2.00 %[11 Poly[(t-butyl acrylate)-(acrylic acid)-graft-polydimethylsiloxane)][21 C, 1-Câ Isoparaï¬in, available from Exxon Chemical Co.This product is prepared by dispersing the copolymer in Isopar Ho (solvent component) thenadding the dimethylpalmitamine. Heat the solution to 65°C and use an appropriate homogenizer toCA 02264769 1999-03-03wo 98/09607 PCT/US97/1554946facilitate incorporation of the copolymer into the solvent component. The other components aremixed in a separate vessel at ambient temperature. The copolymer-solvent component premix iscooled (if needed) and added to the other components. This composition is useful for application tothe skin to provide improve water resistance and is useful for the analgesic effects.
